BATTERY TECHNOLOGY HANDBOOK Second Edition edited by H. A. KIEHNE Technical Consultant Breckerfeld, Germany MARCEL MARCEL DEKKER, INC. ⃝ Extensive information on battery technology ⃝ Preview your personal ' Download bag' of the files papers with detailed insights into battery technology. Download Citation on ResearchGate | Battery Technology Handbook | This book discusses batteries in various applications as rechargeable secondary.
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This practical reference remains the most comprehensive guide to the fundamental theories, techniques, and strategies used for battery operation and design. but batteries are the best choice for most applications. .. Pb–acid batteries are a relatively old technology that maintain 40–45% of the in bq20zxx product family, Texas Instruments Inc., longmogedwapor.tk [ 84] Ehrlich, G.M. () Lithium ion batteries, in Handbook of Batteries (eds D. For today, we'll focus on batteries for portable energy storage. •Drag feet on carpet. •Pet a cat .. Handbook of Batteries 3e, Eds Linden and Reddy. Rate effects.
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However, it is reported that standard alkaline batteries can often be recharged a few times typically not more than ten , albeit with reduced capacity after each charge; chargers are available commercially.
Results are not consistent; consumer organisation Which? Yadav published papers reporting that alkaline batteries made by interleaving the interlayers with copper ions could be recharged for over 6, cycles due to the theoretical second electron capacity of manganese dioxide. All batteries gradually self-discharge whether installed in a device or not and dead batteries will eventually leak. Extremely high temperatures can also cause batteries to rupture and leak such as in a car during summer as well as decrease the shelf life of the battery.
The reason for leaks is that as batteries discharge — either through usage or gradual self-discharge — the chemistry of the cells changes and some hydrogen gas is generated.
This out-gassing increases pressure in the battery. Eventually, the excess pressure either ruptures the insulating seals at the end of the battery, or the outer metal canister, or both.
In addition, as the battery ages, its steel outer canister may gradually corrode or rust, which can further contribute to containment failure. Once a leak has formed due to corrosion of the outer steel shell, potassium hydroxide absorbs carbon dioxide from the air to form a feathery crystalline structure of potassium carbonate that grows and spreads out from the battery over time, following along metal electrodes to circuit boards where it commences oxidation of copper tracks and other components, leading to permanent circuitry damage.
The leaking crystalline growths can also emerge from seams around battery covers to form a furry coating outside the device, that corrodes any objects in contact with the leaking device. Disposal[ edit ] With the reduction in mercury in , alkaline batteries are allowed to be disposed of as regular domestic waste in some locations.
However, older alkaline batteries with mercury, and the remaining other heavy metals and corrosive chemicals in all batteries new and old , still present problems for disposal—especially in landfills. Disposal varies by jurisdiction. Radio Receiver Design, Robert C.
Dixon Electrical Contacts: Principles and Applications, edited by Paul G. Slade Phadke LaCombe Embedded Systems Design with Microcontrollers: Pilot Protective Relaying, edited by Walter A. Elmore High-Voltage Engineering: EM1 Filter Design: Electromagnetic Compatibility: Gieras and Mitchell Wing Ganon High Reliability Magnetic Devices: Design and Fabrication, Colonel Wm.
Hriatek Basfos and Nelson Sadowski Battery Technology Handbook: Second Edition, edited by H. There were also changes in the group of contributors of this book.
Some former contributors are no longer with us, while others retired and were replaced by younger experts. All the chapters have been revised, and some chapters are completely new. Berndt, one of the leading battery experts. Sassmanhausen and E. Nann, describing the coming volt technology for cars.
Dustmann, based on the former chapter by W. A new author and an expert on lithium battery technology, W. Fricke and N. I thank all the authors for their contributions, and the patience of the publishers, Expert Verlag and Marcel Dekker, Inc. I also thank my wife, Renate Kiehne, who assisted me in correcting the translation of the original German manuscripts. Preface to the First Edition Batteries in various applications as rechargeable secondary batteries or as nonrechargeable primary batteries have to be adapted to steadily changing demands.
Improvements to the existing and well-established systems, e.
All you need to know about batteries
Increased energy density and maintenance-free operation, as well as an extended temperature range, are the main aims of development. At the same time, research and development on new systems, e.
Furthermore, miniaturized batteries, such as lithium batteries, are needed as power sources for appliances and electronic watches. The origins of this book go back to two-day seminars on batteries taught at the Technical Academy of Esslingen. By , a revised second edition was necessary. The chapters dealing with primary batteries and small rechargeable batteries lead-acid and nickelcadmium batteries were published at the same time as a separate book, Portable Batteries, which now constitutes the second half of this volume.
Updated editions of Batteries and Portable Batteries appeared in It is hoped that this present English edition will be of help to those who want an extensive survey on the technical level of commercial batteries as well as insight into their emerging applications. I would like to thank all the contributors and the translator for their cooperation and the Technical Academy of Esslingen for lecture materials. My thanks also to Expert Verlag, the original publisher.
Handbook for Stationary Lead-Acid Batteries
Berndt 1. Kiehne 2. Preuss 3. Kiehne 4. Willmes 6. Franke 7. Stahl 8. Sassmannhausen and E. Nann 9. Dustmann The Solar Generator General Requirements and Selection of Chargers E. Wehrle Will Kiehne Kiehne, D. Spahrbier, D. Sprengel, and W. Raudzsus Kiehne and W. Tuphorn Jacobi Energy Density Knudsen Contributors Dr. Berndt Kronberg, Germany Dr. Franke Ennepetal, Germany Dr. Kiehne Breckerfeld, Germany N.
Nann Brilon, Germany Dr. Sassmannhausen Brilon, Germany Dr. Spahrbier Kelkheim, Germany Dr. Stahl Berlin, Germany Dipl. Wehrle Eschbach Germany Dipl. Will Erlangen, Germany Dipl. It can universally be applied and easily be converted into light, heat or mechanical energy. A general problem, however, is that electrical energy can hardly be stored. Capacitors allow its direct storage, but the quantities are small, compared to the demand of most applications.
In general, the storage of electrical energy requires its conversion into another form of energy. In batteries the energy of chemical compounds acts as storage medium, and during discharge, a chemical process occurs that generates energy which can be drawn from the battery in form of an electric current at a certain voltage.
For a number of battery systems this process can be reversed and the battery recharged, i. As a consequence, two different battery systems exist: Primary batteries that are designed to convert their chemical energy into electrical energy only once. Secondary batteries that are reversible energy converters and designed for repeated discharges and charges.
They are genuine electrochemical storage systems. There is no clear border between them, and some primary battery systems permit charging under certain conditions. Usually, however, their rechargeability is limited. Rechargeable batteries usually are the choice in such applications, since primary batteries would be too expensive for the required rather high capacity.
The second part Chapters 15 to 19 regards batteries mainly in portable applications and concerns smaller capacities. When the battery is discharged, chemical compounds of higher energy content are converted by this reaction into compounds of lower energy content.
Usually the released energy would be observed as heat.
Thus the generation or consumption of energy that is connected to the cell reaction is directly converted into an electric current. This is achieved in the electrochemical cell, sketched in Fig. A positive and a negative electrode are immersed in the electrolyte and the reacting substances the active material usually are stored within the electrodes, sometimes also in the electrolyte, if it participates in the overall reaction.
During discharge, as shown in Fig. This direct conversion of the current into chemical energy characterizes batteries and fuel cells. Figure 1. S N red and S P ox are the components of the negative and the positive electrode respectively. Fuel cells are also based on an electrochemical cell as shown in Fig. Therefore, fuel cells cannot directly be compared with batteries. The arrangement shown in Fig. Chemical reactions do not occur and the physical structure of the electrodes is not affected.
But the amount of stored energy per weight or volume is comparatively small. In batteries such a double layer also exists, and the large surface area of the active material gives rise to a high double layer capacitance when impedance measurements are made. The real battery capacity, however, is much higher and based on chemical reactions. In the following, a brief survey is given of the most important rules.
For details and derivations, the reader is referred to textbooks of electrochemistry or fundamental books on batteries e. Thermodynamic or equilibrium parameters describe the system in equilibrium, when all reactions are balanced. This means that these parameters represent maximum values that only can be reached under equilibrium. Kinetic parameters appear when the reaction occurs.
Kinetic parameters include mass transport by migration or diffusion that is required to bring the reacting substances to the surface of the electrode. The thermodynamic parameters describe the possible upper limit of performance data. The thermodynamic parameters of an electrochemical reaction are 1.
Enthalpy of reaction DH represents the amount of energy released or absorbed. Entropy of reaction DS characterizes the reversible energy loss or gain connected with the chemical or electrochemical process. DS, is called reversible heat effect. DS can be positive or negative. Otherwise, T? DS contributes additional heat cf. Uo describes the generated electrical energy kJ.
Thermodynamic parameters describe the fundamental values of a battery, like the equilibrium voltage and the storage capability. Some examples are listed in Table 1. Section 1. Thermodynamic quantities like DH and DG depend on the concentrations or more accurately activities of the reacting components, as far as these components are dissolved.
Table 1. The difference between these values and those observed in practice Column 9 is caused by kinetic parameters. H2 SO4 , 2? Depends on acid concentration cf. Combination of Eq. The lead-acid battery may be taken as an example: When this value is inserted into Eq. The special battery systems, listed in the lines 11 and 12 in Table 1. The dependence of the equilibrium voltage on the concentration of dissolved components is given by the Nernst equation Eq.
It is independent of the present amount of lead, lead dioxide or lead sulfate, as long as all three substances are available in the electrode. The result of this equation is plotted in Fig. In battery practice, mostly the approximation is used: Actually not the true equilibrium voltage but only the open circuit voltage can be measured with lead-acid batteries.
Due to the unavoidable secondary reactions of hydrogen and oxygen evolution and grid corrosion, mixed potentials are established at both electrodes, which are a little different from the true equilibrium potentials cf. But the differences are small and can be ignored. The discrepancy between the theoretical value and that in practice Column 9 is caused by all the passive components that are required in an actual cell or battery.
In battery practice, hydrogen reference electrodes are not used. Instead, a number of reference electrodes are used, e. In lithium ion batteries with organic electrolyte the electrode potential is mostly referred to that of the lithium electrode cf. Chapter This means that electron transfer has to be forced into the desired direction, and mass transport is required to bring the reacting substances to the electrode surface or carry them away. The overvoltage, caused by electrochemical reactions and concentration deviations on account of transport phenomena.
The ohmic voltage drops, caused by the electronic as well as the ionic currents in the conducting parts including the electrolyte.
The sum of both is called polarization, i. Overvoltage can only be separated by special electrochemical methods. Usually the reaction path consists of a number of reaction steps that precede or follow the actual charge transfer step as indicated in Fig. The slowest partial step of this chain is decisive for the rate of the overall reaction. As a consequence, overvoltages, or even limitations of the reaction rate, often are not caused by the electron-transfer step itself, but by preceding or following steps.
Some of these steps include mass transport, since the reaction would soon come to a standstill, if ions would no longer be available at the surface of the electrode or if reaction products would not be cleared away and would block the reacting surface. In a number of electrode reactions, the reaction product is dissolved. This applies, for example, to some metal electrodes, like zinc, lithium, cadmium, and also to lead.
Furthermore, chemical reactions may precede or follow the electron transfer step. Double-lined arrows mark the charging reaction. A corresponding number of electrons is removed from the electrode as negative charge.
The discharging reaction at the positive electrode proceeds in a similar manner: During charging of the battery, these reactions occur in the opposite direction, as indicated by the double-line arrows in Fig. The electrochemical reaction, the transfer step, can only take place where electrons can be supplied or removed, which means that this conversion is not possible on the surface of the lead sulfate, as lead sulfate does not conduct electric current. If the product of the discharge is highly soluble, during discharge the electrode will to a large extent be dissolved and will lose its initial structure.
This leads to problems during recharge because the redeposition of the material is favored where the concentration of the solution has its highest value. As a consequence, the structure of the electrode will be changed as demonstrated in the upper row of Fig. Connected to the shape change is a further drawback of the high solubility, namely the tendency that during recharging the precipitated material forms dendrites that may penetrate the separator and reach the opposite electrode, thus gradually establishing a short circuit.
Zinc electrodes are therefore not used in commercial secondary batteries, with the exception of the rechargeable alkaline zinc manganese dioxide battery RAM 6 which is a battery of low initial cost, but also limited cycle life. The metallic lithium electrode is another example where cycling causes problems due to its high solubility that causes shape change cf.
Chapter 18 and the lithium-ion system in Fig. Extremely low solubility of the reaction products leads to a more or less dense covering layer lower row in Fig. Thus only a thin layer of the active material reacts.
To encounter such a passivation, the active material in technical electrodes, e. The advantage of the low solubility is that the products of the reaction are precipitated within the pores of the active material, close to the place of their origin, and the structure of the electrode remains nearly stable.
This mechanism is illustrated in Fig. Here the reaction product is not dissolved, but the nickel ions are oxidized or reduced while they remain in their crystalline structure that of course undergoes certain changes. When the nickel electrode is charged oxidized , these protons have to leave the crystal lattice. Otherwise, local space charges would immediately bring the reaction to a standstill. Here oxidation and reduction occur within the solid state, and it depends on the potential of the electrode how far the material is oxidized.
Float charging at a comparatively low voltage, as it is normal for standby applications, does not preserve full capacity and requires regular equalizing charges or corresponding oversizing of the battery. During discharge, lithium ions are intercalated into the oxide from Ref. Another reaction mechanism that in a certain aspect resembles to the above one characterizes lithium-ion batteries cf.
The course of the cell reaction is illustrated in Fig. These positive electrodes intercalate the lithium when discharged, i. As a consequence, the problems caused by solution of a metallic lithium electrode as indicated in Fig.
Electron Transfer The electron transfer reaction denotes the central reaction step where the electrical charge is exchanged cf. EA actually depends on temperature, but often can approximately be treated like a constant.
In electrode reactions, n? F between mass transport and current i; U is the electrode potential; and cj the concentration of the reacting substance that releases or absorbs electrons.
Electron transfer, however, does not occur in only one direction: Thus, Eq. T where addend 1 describes the anodic reaction e. Electron transfer according to Eq. This leads to the usual form of Eq. T where io is the exchange current density that characterizes the dynamic equilibrium, as shown in Fig. The resulting current is represented in Fig. According to Eq. In practice polarization is always determined. The reaction of the lead electrode is inserted as an example. Electrode Polarization Polarization has been introduced as the deviation of the actual voltage from equilibrium by Eq.
Polarization of the single electrode in a battery is a very important parameter. Tafel Lines If the potential is shifted far enough from the equilibrium value, in Eq. The constant b represents the slope of the Tafel line and means the potential difference that causes a current increase of one decade. Tafel lines are important tools when reactions are considered that occur at high overvoltages, since such a linearization allows quantitative considerations.
They are often used with lead-acid batteries, since polarization of the secondary reactions hydrogen evolution and oxygen evolution is very high in this system cf. This dependence is described by the Arrhenius equation, which already has been introduced as Eq. The logarithmic form of Eq. Very often the approximation holds true that a temperature increase of 10 K or C doubles the reaction rate.
In electrochemical reactions, this means that the equivalent currents are doubled, which denotes a quite strong temperature dependence. A temperature increase of 20 K means a current increase by a factor of 4; a rise in temperature of 30 K corresponds to a factor of 8. Transport of the reacting species is achieved by two mechanisms: F qx zj?
Addend 1 of the right-hand part of this equation describes transport by diffusion that always equalizes concentration differences. When transport by diffusion of reacting neutral particles like that of O2 in the internal oxygen cycle Fig. If cj reaches zero, a further increase of the current is not possible.
Such a situation is called a diffusion limiting current, which according to Eq. Addend 2 in the right-hand part of Eq. It is characterized by the transference number. In binary salt solutions they are fairly close to 0. For diluted solutions of sulfuric acid given in Ref. For potassium hydroxide true for a wide concentration range given in Ref. This is one reason to aim at conducting salts with large anions cf.
The dashed curve shows the equilibrium voltage according to the Nernst equation. Flooded traction cell with tubular plates Ah at 5-hour rate. The dashed curve at the top represents the changing equilibrium voltage due to the gradually decreasing acid concentration, according to the Nernst equation Eq.
If all the partial-reaction steps were fast enough, i. So, with increasing load, the dischargeable share of the capacity is more and more reduced by the impact of kinetic parameters, and the current amount that can be drawn from the battery is markedly reduced, although the end-of-discharge voltage is lowered with increased load. Mainly acid depletion at the electrode surface reduces the rate of the reaction.
Furthermore, some of the undischarged material may be buried underneath the growing PbSO4 layer. This layer grows very fast at high loads, resulting in a thin but compact covering layer that prevents further discharge very early.
It is related to the thermodynamic equilibrium parameters of the concerned reaction, and is strictly connected with the amount of material in electrochemical equivalents that reacts. Thus, the reversible heat effect does not depend on discharge or recharge rates. When the cell reaction is reversed, the reversible heat effect is reversed too, which means it gets the opposite sign.
Thus, energy loss in one direction means energy gain when the reaction is reversed, i. Ucal is a hypothetical voltage that includes the reversible heat effect, and is used instead of the equilibrium voltage for caloric calculations.
Combination with Eqs. This heat is called the Joule effect; it always means loss of energy. Strictly speaking, the negative absolute value should be used in Eq. Then the Joule effect reads according to Eq. For heat effects this is not relevant, since heat generation is proportional to polarization.
Wh, or as work per time unit: Strictly speaking, Eq. The thermodynamic data that determine the equilibrium values are listed in Table 1. The table also Table 1. Section 5. Assumed internal resistance 4.
Sections 1. This is illustrated in Fig. In a vented lead-acid battery heat effects during charging are caused by the charging reaction itself and by water decomposition that accompanies the charging process at an increasing rate with increasing cell voltage. The charging reaction is a very fast one which means that overvoltage is small. At an assumed internal resistance of 4. The reversible heat effect, on the other hand, is determined by the amount of converted material formula mass that is proportional to current and amounts to 0.
Most of the energy that is employed for water decomposition escapes from the cell as energy content of the generated gases. This energy consists of the two components: Both shares are proportional to the amount of decomposed water, which again is only determined by the current i as the product Ucal? The portion of heat that remains within the cell is generated by Joule heating and determined by polarization of the water-decomposition reaction, i.
As an example Fig. The current-limited initial step of charging is followed by a constant-voltage period at 2. Equalizing charging up to 2.
Lead-acid with tubular positive plates Varta PzS , Ah. Heat-generation values referred to Ah of nominal capacity. The sum of the whole charging period amounts to Internal resistance 4. The center part of Fig.
Only when the voltage approaches the 2. The broken horizontal line marks the average voltage during this initial step. When subsequently the cell voltage remains at 2. During the equalizing step, nearly all the current is used for water decomposition on account of the progressively reduced charge acceptance.
During discharge, water decomposition again can be neglected because of the reduced cell voltage.
At the bottom of Fig. The distribution between reversible heat effect, charging, and water decomposition is marked by different patterns of the areas concerned. The value above each block is the total heat generation in Wh. The heat is mainly generated by the Joule effect, on account of the high current and the rather high internal resistance of 4. But the reversible heat effect also contributes noticeably to heat generation, on account of the converted active material.
When the internal oxygen cycle is established, almost all the overcharging current is consumed by the internal oxygen cycle center bar in the graph. The bar on the right corresponds to a vented battery.
Internal resistance assumed as 0.
When 2. During the equalizing step, gas evolution required for mixing of the electrolyte dominates. During discharge, due to the small overvoltage, heat generation is also small, and further reduced by the reversible heat effect that now causes cooling.
Heat generation in a valve-regulated lead-acid battery VRLA battery is mainly determined by the internal oxygen cycle that characterizes this design. It means that the overcharging current is almost completely consumed by the internal oxygen cycle formed by oxygen evolution at the positive electrode and its subsequent reduction at the negative electrode cf.
As a consequence, the cell voltage in total means polarization that produces heat. For this reason, overcharging of valveregulated lead-acid batteries must be controlled much stronger than that of vented ones to avoid thermal problems. The charging behavior of a valve-regulated type is shown in Fig. In the center of Fig. The sum of charging current and internal oxygen cycle represents the charging current hydrogen evolution and grid corrosion equivalents are not considered, since they are two orders of magnitude smaller than that of the internal oxygen cycle.
Actually, the current would slightly be increased by heating of the battery. This increase also is not considered in Fig. The bottom part of Fig.
At the beginning, the reversible heat effect dominates heat generation due to the high amount of material that is converted. The relation between the reversible heat effect and Joule heating is determined by the internal resistance of the battery.
Internal resistance 0. Heating of the battery during charging is not considered. Heat generation: This applies, for example, to Fig. When the charging voltage is reached, the current decreases and this applies also to heat generation due to the reversible heat effect and Joule heating, while heat generation by the internal oxygen cycle remains constant, according to the constant cell voltage which actually would slightly be increased by heating up.
But the total heat generation is largely determined by the internal oxygen cycle, especially during the equalizing step that in Fig. Actually, an even larger heat generation is to be expected, since, as already mentioned, the calculation did not consider the heat increase within the cell during charging that again would increase the rate of the internal oxygen cycle. Due to the uncertain thermodynamic data, these calculations are only rough approximations, but correspond with practical experience.
During the initial two sections of the charging period, slight cooling is observed on account of the reversible heat effect that consumes heat at a constant rate proportional to the current. With increasing cell voltage, Joule heating is increased, and when the charging voltage exceeds 1.
In total The main reason is that the reversible heat effect generates additional heat during discharge, while it compensates for heat generation during charging. The voltage curve at the top shows the gradual increase of charging voltage with charging time. The generated heat is calculated as an average value for different sections of this curve.
The numbers beside the charging curve are the average voltages V per cell for the corresponding section. The numbers are the heat in kJ for comparison, converted to Ah of nominal capicity. Charging with constant current I5 5 hour rate until 1. Discharge also with I5. In the top part, sections are shown that were used to calculate the average heat generation, shown in the bottom part.
So the number for this section is written below the zero line. When the charging process approaches completion, nearly all the current is used for the internal oxygen cycle, which causes much heat generation. Since this cycle can attain extremely fast rates, the situation is very dangerous in regard to thermal runaway.
Altogether The charging factor for the lead-acid battery in Fig. For comparison, all values are converted to Ah of nominal capacity. Rapid charging methods, as described in Section 13, are always based on this principle. Equation 42 points out that heat generation and heat dissipation are parameters of equal weight, which means that possibilities to dissipate heat are to be considered as thoroughly as the problem of heat generation.
The rate of the temperature change is determined by the heat capacity of the battery CBatt. Heat dissipation increases with a growing temperature difference DT between the battery and its surroundings, and a stable temperature of the battery is reached at a certain DT when heat generation balances heat dissipation, i.
If heat generation within the battery increases faster with increasing battery temperature than heat dissipation, such a thermal balance is not reached and temperature increase continues unlimited. For the emission of heat these ways are sketched in Fig. A corresponding situation with all the arrows reversed would apply for heat absorption from a warmer surroundings. Three mechanisms are involved in this heat exchange: Heat radiation. Heat transport by a cooling or heating medium.
Usually they occur in combination.
The bottom surface usually is in contact with the basis that attains the same temperature as the battery itself, except the battery is equipped with cooling channels in the bottom. The upper surface usually is of little importance for heat exchange, since the lid has no direct contact to the electrolyte, and the intermediate layer of gas hinders heat exchange because of its low heat conductivity cf.
Moreover, in monobloc batteries the cover often consists of more than one layer. Cooling through the terminal occasionally has been applied with submarine batteries which are equipped with massive copper terminals For batteries with aqueous electrolyte the internal resistance can be determined by this method only for the discharge, but not during charging because of the high overvoltage of the gassing reactions. Regalia A survey of alloys that especially are applied in valve-regulated lead-acid batteries is given in Ref.
Thus hydrogen evolution on the lead surface would enormously be increased by the precipitation of traces of other metals, like those shown in Fig.
EA actually depends on temperature, but often can approximately be treated like a constant. Thus, Eq. The latter would be equivalent to a selfdischarge of the negative of 1. When the electrode is polarized to more negative values, hydrogen evolution is increased according to the curves shown in Fig. The title will be removed from your cart because it is not available in this region.
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