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ONEMISCON CEPTION:We often thought that Li Ion and Li batteries are same but this is not true at all.

A Li Battery generally uses a Lithium metal or Li compound as the anode material but a Li Ion battery does not uses Li metal or a lithium compound as the anode material rather a Carbon material where Li ions get intercalated during charging. DEFINITION:A lithium ion battery is a family of rechargeable battery types in which Li ion moves from the negative electrode to the positive electrode during discharging and back when charging. DEFINITIONOFSOMEBATTER YCHARECTERISTICS: Battery Characteristics Open circuit voltage Current Definition Maximum voltage in the charged state at zero current. Low currents are characterized by activation losses, while the maximum current is normally determined by mass transfer limitations. The energy that can be derived per per litre unit volume of the weight of the cell. Unit Volt (V) Ampere (A)

Energy density

watt-hours per kilogram (Wh/dm3)

specific energy density

The energy that can be derived Watt-hours per kilogram per kilogram unit weight of the (Wh/kg) cell (or sometimes per unit weight of the active electrode material). The power that can be derived Watt per kilogram (W/kg) per kilogram unit weight of the cell. The theoretical capacity of a battery is the quantity of electricity involved in the electrochemical reaction Ampere-hours per gram (Ah/g)

Power density

Capacity

Shelf-life

The time a battery can be stored Years inactive before its capacity falls to 80%. The time a battery can be used at various loads and temperatures. Hours (usually normalized for ampere per kilogram (A/kg) and ampere per litre (A/Lt^3)

Service life

Cycle life

The number of Cycles charge/discharge it can undergo before capacity falls to 80%.

Ref: IntroductiontoElectrochemicalCells-R. Vasant Kumar and Thapanee Sarakonsri....page-6 http://en.wikipedia.org/wiki/Lithium-ion_battery

Advantages of Lithium Ion Battery:

* High energy density -High energy density with volumetric energy density 1.5 times higher and gravimetric energy density 2 times higher than that of high capacity model of Ni-Cd battery. This means that Lithium-ion battery is much more suitable for lighter or smaller portable applications.

* Voltages are high with average operating voltages at 3.6 to 3.7V and these are approximately the same as three cells in series of Ni-Cd or Ni-MH batteries. It means that using Lithium-ion batteries reduces the number of cells in actual use.

* Discharge curves are flat because of highly crystallized carbon graphite used as the anode.

* Does not need prolonged priming when new. One regular charge is all that's needed.

* Long cycle life normally 300 to 500 charge discharge cycles can be achieved.

* Relatively low self-discharge - self-discharge is less than half that of nickel-based batteries.

* Low Maintenance - no periodic discharge is needed; there is no memory.

* Speciality cells can provide very high current to applications such as power tools.

* Safety is high due to no metallic lithium content and improved structures.

Limitations of lithium ion Battery: * Requires protection circuit: If overheated or overcharged, Li-ion batteries may suffer thermal runaway and cell rupture. In extreme cases this can lead to combustion. Deep discharge may shortcircuit the cell, in which case recharging would be unsafe. To reduce these risks, Lithium-ion battery packs contain fail-safe circuitry that shuts down the battery when its voltage is outside the safe range of 34.2 V per cell. When stored for long periods the small current draw of the protection circuitry itself may drain the battery below its shut down voltage; normal chargers are then ineffective. Many types of lithium-ion cell cannot be charged safely below 0C.

Other safety features are required in each cell:

* Shut-down separator (for over temperature) * Tear-away tab (for internal pressure) * Vent (pressure relief) * Thermal interrupt (over current/overcharging)

These devices occupy useful space inside the cells, add additional points of failure and irreversibly disable the cell when activated. They are required because the anode produces heat during use, while the cathode may produce oxygen. These devices and improved electrode designs reduce/eliminate the risk of fire or explosion.

These safety features increase costs compared to nickel metal hydride batteries, which require only a hydrogen/oxygen recombination device (preventing damage due to mild overcharging) and a back-up pressure valve.

* Internal resistance:The internal resistance of standard (Cobalt) lithium-ion batteries is high compared to both other rechargeable chemistries such as nickel-metal hydride and nickel-cadmium, and LiFePO4 and lithium-polymer cells. Internal resistance increases with both cycling and age. Rising internal resistance causes the voltage at the terminals to drop under load, which reduces the maximum current draw. Eventually increasing resistance means that the battery can no longer operate for an adequate period. To power larger devices, such as electric cars, connecting many small batteries in a parallel circuit is more effective and efficient than connecting a single large battery.

* Cell life: Charging forms deposits inside the electrolyte that inhibit ion transport. Over time,

the cell's capacity diminishes. The increase in internal resistance reduces the cell's ability to deliver current. This problem is more pronounced in high-current applications. The decrease means that older batteries do not charge as much as new ones (charging time required decreases proportionally). High charge levels and elevated temperatures (whether from charging or ambient air) hasten capacity loss. Charging heat is caused by the carbon anode (typically replaced with lithium titanate which drastically reduces damage from charging, including expansion and other factors). A Standard (Cobalt) Li-ion cell that is full most of the time at 25 C (77 F) irreversibly loses approximately 20% capacity per year. Poor ventilation may increase temperatures, further shortening battery life. Loss rates vary by temperature: 6% loss at 0 C (32 F), 20% at 25 C (77 F), and 35% at 40 C (104 F). When stored at 40%60% charge level, the capacity loss is reduced to 2%, 4%, and 15%, respectively. In contrast, the calendar life of LiFePO4 cells is not affected by being kept at a high state of charge.

* Subject to ageing, even if not in use - storage in a cool place at 40% charge reduces the ageing effect.

* Transportation restrictions - shipment of larger quantities may be subject to regulatory control. This restriction - does not apply to personal carry-on batteries. Introduction to the basics of electrochemical cell:

Terminology
Anode: Electrode in an electrochemical cell on which the oxidation reaction occurs. Cathode: Electrode in an electrochemical cell on which the reduction reaction occurs Electro chemistry: A field of chemistry that focuses on the inter-change between electrical and chemical energy Electricity: Flow of electrons over a wire that is affected by the presence and flow of electric charge. Electrolysis: The decomposition of a substance by means of electric current. This method pushes push a redox reaction toward the non-spontaneous side. Electrolytic cell: Electrochemical cell that is being pushed toward the nonspontaneous direction by electrolysis. Electromotive force, EMF (or Cell Potential): Difference of potential energy of electrons between the two electrodes. .Oxidation number: Charge on an atom if shared electrons where assigned to the more electronegative atom. Oxidation: Lose of electrons, can occur only in combination with reduction. [remember: Oxidation Is Loss, Reduction Is Gain = OIL RIG] Reduction: Gain of electrons, can occur only in combination with oxidation. [remember: OIL RIG] Redox reaction: Short hand for reduction-oxidation reaction. Voltaic cell or Galvanic cell: An electrochemical cell that uses redox reaction to produce electricity spontaneously.

In 1793, Alessandro Volta discovered that electricity could be produced by placing different metals on the opposite sides of a wet paper or cloth. He made his first battery by placing Ag (later it was replaced by low cost Cu)and Zn on the opposite sides of a moistened cloth with salt or weak acid solution. Therefore, these batteries got the name Voltaic Cells. Voltaic (Galvanic) Cells are electrochemical cells which contain a spontaneous reaction, and always have a positive voltage. The electrical energy released during the reaction can be used to do work. A voltaic cell consists of two compartments called half-cells . The half-cell where oxidation occurs is called anode. The other half-cell where reduction occurs is called cathode. The Electrons in voltaic cells flow from the negative electrode to the positive electrode, which flows from anode to cathode. (See, figure below) (Note: electrodes=where the oxidation/reduction reactions occur). Red Cat and An Ox Reduction Cathode and Anode Oxidation is a helpful way to remember which reaction occurs on which half cell. In order for oxidation-reduction reaction to occur, the two substances in each respective half-cell are connected by closed circuit so that electrons can flow from the reducing agent to the oxidizing agent. It also needs a salt bridge so that reaction can keep proceeding. Galvanic Cell Needs electrical current from outside for it to work:

The figure above shows that Zn(s) is continuously oxidized, producing Zn2+ into the solution. Zn(s)--> Zn2+(aq)+2e-. Conversely, in the cathode, Cu2+ is reduced and continuously deposits on to the Cu(s) metal bar Cu2+(aq)+2e--->Cu(s). As a result, the solution containing Zn(s) becomes more positively charged while the solution containing Cu(s) becomes more negatively charged. In order for the voltaic cell to work, the solutions in the two half-cells must remain electrically neutral. Therefore, a salt bridge containing KNO3 is added to keep the solutions neutral by adding NO3-, an anion into the anode solution and K+, a cation into the cathode solution. As oxidation and reduction proceed, ions from the salt bridge migrate to neutralize charge in the cell compartments. The diagram of this electrical cell : Zn(s) Zn2+(aq) Cu2+(aq) Cu(s)
Cell Potential

The oxidation of Zn(s) into Zn2+ and the reduction of Cu2+ to Cu(s) occur spontaneously. In other words, the redox reaction between Zn and Cu2+ is spontaneous. This is caused by the difference in potential energy between the two substances. The difference in potential energy between the anode and cathode dictates the direction of electrons movement. Electrons move from area of higher potential energy to area of lower potential energy. In this case, the anode has a higher potential energy so electrons move from anode to cathode. The potential difference between the two electrodes is measured in units of volts. One volt (V) is the potential difference necessary to generate a charge of 1 coulomb (C) from 1 Joule (J) of energy. For a voltaic cell, this potential difference is called the cell potential, and is denoted Ecell. For a spontaneous reaction, Ecell is positive and G (Gibbs free energy that can be used to determine if a reaction occurs spontaneously) is negative. Thus, when G is negative the reaction is spontaneous. By merging electro chemistry with thermodynamics we get this formula: G = n F Ecell(or EMF). EMF= Electromotive Force. Cell potential is different for each voltaic cell, its value depends upon the concentrations of specific reactants and products as well as temperature of the reaction.

For standard cell potential, temperature of the reaction is assumed to be at 25 o Celsius, the concentration of the reactants and products is 1M and reaction occurs at 1 atm pressure. The standard cell potential is denoted Eo .The can be written= oxidation potential + reduction potential. For Voltaic cells it will be
cell o E =Eo(cathode)-Eo(Anode). cell cell

So in order to calculate the standard cell potential Eo

, we need to find out which substance is

being oxidized, then subtract the standard reduction potential of the oxidation reaction from the standard reduction potential of the reducing reaction. Zn(s) + Cu2+
(aq)

Zn2+

(aq)

+ Cu(s)

From the equation above, we know that Zn is being oxidized, and Cu is being reduced. For the redox reaction above, the potential for the two half reaction is given in the reduction form: Zn(s) Zn2+ Cu2+
(aq) (aq)

+ e-

+ e- Cu(s)

By looking at it's cell potential we can know which one is anode and cathode. Cathode has a more positive potential energy, thus Cu is the cathode .
Zn is the anode. In order to calculate Eo
cell

, subtract Zn of the oxidized species from the Cu of the reduced species,

E which is Eocell = (cathode)-E(Anode) (Note: Keep Cell potential in reduction form).


Oxidation: Zn(s) Zn2+ Reduction: Cu2+
(aq) (aq)

+ e-------> -Eo= +0.763V

+ e- Cu(s) ------> Eo= +0.340V


(aq)

Net: Zn(s) + Cu2+

Zn2+

(aq)

+ Cu(s)

Eocell = +0.34 V (0.76 V)= 1.10 V

The cell reaction is spontaneous in the forward direction if Ecell>0, G<0


The cell reaction is not spontaneous in the forward direction if Ecell<0, G>0 Nernst equation
Equation: EMF = EMFo (-RT/nF)ln Q EMF = cell potential at current conditions EMF = cell potential at standard state (usually at 25 degree Celsius)

R = 8.31 J/moleK T = Kelvin temperature n = mole of electron F = 1 Faraday . Q = reaction quotient (Product/Reactant) relates cell potential and reaction quotient. Using Boltzmann factors

Derivation:

For simplicity, we will consider a solution of redox-active molecules that undergo a one-electron reversible reaction

and that have a standard potential of zero. The chemical potential of this solution is the difference between the energy barriers for taking electrons from and for giving electrons to the working electrode that is setting the solution's electrochemical solution. The ratio of oxidized to reduced molecules, [Ox]/[Red], is equivalent to the probability of being oxidized (giving electrons) over the probability of being reduced (taking electrons), which we can write in terms of the Boltzmann factors for these processes:

Taking the natural logarithm of both sides gives

If

at [Ox]/[Red] = 1, we need to add in this additional constant.

Dividing the equation by e to convert from chemical potentials to electrode potentials, and remembering that kT/e = RT/F, we obtain the Nernst equation for the one-electron process :

Using entropy and Gibbs energy:


Quantities here are given per molecule, not per mole, and so Boltzmann constant k and the electron charge e are used instead of the gas constant R and Faraday's constant F. To convert to the molar quantities given in most chemistry textbooks, it is simply necessary to multiply by Avogadro's number : and The entropy of a molecule is defined as where is the number of states available to the molecule. The number of states must vary linearly with the volume V of the system, which is inversely proportional to the concentration c, so we can also write the entropy as The change in entropy from some state 1 to another state 2 is therefore

so that the entropy of state 2 is

If state 1 is at standard conditions, in which C1 is unity (e.g., 1 atm or 1 M), it will merely cancel the units of C2 We can, therefore, write the entropy of an arbitrary molecule A as where S^0 is the entropy at standard conditions and [A] denotes the concentration of A. The change in entropy for a reaction. is then given by

We define the ratio in the last term as the reaction quotient:

where the numerator is a product of reaction product activities, a j, each raised to the power of a stoichiometric coefficient j, and the denominator is a similar product of reactant activities. All activities refer to a time t. Under certain circumstances (see chemical equilibrium) each activity term such as aj^vj may be replaced by a concentration term, [A]. In an electrochemical cell, the cell potential E is the chemical potential available from redox reactions E=c/e.E is related to the Gibbs Energy change G only by a constant:

The Gibbs energy is related to the entropy by G=H-TS,where H is the enthalpy and T is the temperature of the system. Using these relations, we can now write the change in Gibbs energy, and the cell potential,

This is the more general form of the Nernst equation. For the redox reaction and we have:

Ref: Physical chemistry by Peter Atkins--------------------------------------chapter 7 http://chemwiki.ucdavis.edu/Analytical_Chemistry/Electrochemistry/Basics_of_Electrochemistry http://en.wikipedia.org/wiki/Nernst_equation Which factor determine the maximum attainable output voltage of a electrochemical cell ? The output voltage of a battery is given by V=Voc -I*Rb Voc is the open circuit voltage(I=0) given by

And Rb is the internal resistance of the Battery. In the above equation n is the number of electronic charges carried by the working ion and F is the Faraday's constant. The magnitude of the open circuit voltage is constrained to Voc < 5 v not only by the attainable difference (a-c) of the electrochemical potentials of the anode reductant and the cathode oxidant, but also by the energy gap Eg between the HOMO (highest occupied molecular orbital) and the LUMO (lowest unoccupied molecular orbital) of a liquid electrolyte or by the gap Eg between the top of the valence band and the bottom of the conduction band of a solid electrolyte. As illustrated in Fig below the chemical potential a which is the Fermi energy f of a metallic reductant anode or the HOMO of a gaseous or liquid reductant, must lie below the

LUMO of a liquid electrolyte or the conduction band of a solid electrolyte to achieve

thermodynamic stability against reduction of the electrolyte by the reductant. Similarly the

chemical potential pc, which is the LUMO of a gaseous or liquid oxidant or the Fermi energy of a metallic oxidant cathode, must lie above the HOMO of a liquid electrolyte or the valence band of a solid electrolyte to achieve thermodynamic stability against oxidation of the electrolyte by the oxidant. Thermodynamic stability thus introduces the constraint

as well as the need to match the window Eg of the electrolyte to the energies of the reactants to maximize V ,

a and c

Traditional batteries use aqueous electrolytes. Protonic conductivity H 5 0.1 S-cm-1can be achieved in aqueous solutions that are either strongly acidic, e.g., H2S04, or strongly alkaline, e.g., KOH. An acidic solution provides protonic conduction at an H30+/H20 couple, an alkaline solution at an H20/0H- couple. The HOMO and LUMO for an aqueous solution are, respectively, the 02/H20 and the H+/H2 couples; they are separated by an energy Eg= 1.23 eV. Therefore thermodynamic stability limits the voltage of an aqueous system to 1.23 V. However, a kinetic energy barrier at an electrode/electrolyte interface may allow realization of an aqueous battery having a voltage V> 1.23 V, as in the case of the lead-acid auto mobile battery with a

Vm = 2 V. However, kinetic barriers are not compatible with a long shelf life.

The principal motivation for turning from the proton to Li+ as the working ion is the voltage limitation of a proton cell. Lithium is much more electro positive than hydrogen, which allows the realization of significantly higher voltages. However, to realize the higher voltages possible with a lithium battery, a non-aqueous electrolyte having a large energy-gap window between its HOMO and its LUMO must be used. Practical quantities of very ionic lithium salts such as LiCl04, LiBF4 and LipF6 can be dissolved in empirically optimized mixtures of propylene carbonate (PC), ethylene carbonate (EC), or dimethyl carbonate (DMC), for example. Voltages approaching 4.5 V have been sustained in an electrolyte of LiPF6 in a 1 : 2 DMC : EC mixture. The (Cl04)- anion is explosive and not suitable for commercial applications. A commonly used electrolyte is LiBF4 in PC, but it is restricted to a Voc <4.2 V vs. Li. An improved Li+ ion electrolyte would be welcome.

Ref :1) Lithium_Ion_Batteries-Fundamentals_and_Performance_(1998)-------page 13 2) Lithium ion batteries-principle & performances----------------------- page 16

Construction of lithium Ion Battery:The three primary functional components of a lithium-ion battery are the 1) Negative electrode, 2) Positive electrode, and the 3) Electrolytes. The negative electrode of a conventional lithium-ion cell is made from carbon The positive electrode is a metal oxide and the Electrolytes are the lithium salts in a organic solvent. DETAILS : Negative electrode(anode) materials:main advantage of Li ion battery is their high energy density,which comes from the fact that Lithium is most electropositive as well as the lightest metal. However lithium dendrite growth after charge and discharge cycles easily will lead to a short circuit of the cell and an explosion hazard . Substituting Lithium metal for alloy with aluminium,silicon,zinc and so forth could solve the problem. Nevertheless the Lithium storage capacity of the alloy drops down quickly after merely several charge and discharge cycle. Because the big volume change causes great stress in alloy crystal lattice and thus gives rise to cracking and crumbling of the alloy particles. Alternatively, Sony Corporation in the early 1990s invented that by the application of lithiated carbon in place of a lithium metal electrode, any lithium metal plating process and the conditions for the growth of irregular dendritic lithium could be considerably eliminated, which shows promise for reducing the chances of shorting and overheating of the batteries. This kind of lithium-ion battery, which possessed a working voltage as high as 3.6 V and gravimetric energy densities between 120 and 150 Wh/kg,rapidly found applications in high-performance portable electronic devices. Thus the research on reversible lithium storage in carbonaceous materials became very popular in the battery community worldwide. In fact, the ability of layer-structured carbon to insert various species was well known by the latter half of the 1800s. The ability of graphite to intercalate anions promoted exploration into the use of a

graphite cathode for rechargeable batteries. Staging Phenomenon of Li-GIC: Graphite intercalation compounds have one significant feature: the staging phenomenon,which is characterized by a periodic sequence of intercalant layers (say, lithium cations) between graphite layers. The nth-stage compound consists of intercalant layers arranged between every n graphite layers. The first-stage lithium graphite intercalation compound has the stoichiometry of LiC 6 with the specific capacity of 372 mAh/g (850 mAh/cm 3), a theoretical saturated value of lithium storage for graphite under normal pressure. Solid Electrolyte Interface Film Formation: Another important feature for lithium graphite intercalation compounds in Li + containing electrolytes is the formation of solid electrolyte interface (SEI) film. During the first-cycle discharge of a lithium/carbon cell, a part of lithium atoms transferred to the carbon electrode electrochemically will react with the non aqueous solvent, which contributes to the initial irreversible capacity. The reaction products form a Li + -conducting and electronically insulating layer on the carbon surface. Peled named this film as SEI. Once SEI formed, reversible Li + intercalation into carbon, through SEI film, may take place even if the carbon electrode potential is always lower than the electrolyte decomposition potential, whereas further electrolyte decomposition on the carbon electrode will be prevented. Li + Diffusion in Carbon: Since the slow solid-state diffusion of Li + in the bulk of carbon may control the rate-determining step of the intercalation process and consequently affect the power density of Li + -ion batteries, the chemical diffusion coefficient of Li + ( D Li+ ) becomes a very key kinetic parameter. Carbon with Extra-High Capacity: Recently, much enthusiasm and effort have been concentrated on the development of high-capacity carbonaceous materials that are synthesized at relative low temperatures (from 500 to 1,100C) and deliver reversible capacities over 372 mAh/g. Thermal Safety of Lithiated Carbon: Most abusive conditions like short-circuit, crushing, nail-piercing, overcharge/discharge, and so forth will lead to heating of the batteries. Safety problems arise if the batteries exceed a critical temperature, above which thermal runaway occurs. So the thermal stability of the entire Li + -ion battery and various combinations of battery components are necessary for understanding and improving battery safety. Accelerating rate calorimetry (ARC) and differential scanning calorimetry(DSC)are generally used to investigate the causes of thermal run away in Li x C. [Thermal Runaway: It refers to a situation where an increase in temperature changes the conditions in a way that causes a further increase in temperature, often leading to a destructive result. It is a kind of uncontrolled positive feedback. In other words, the term "thermal runaway" is used whenever a process is accelerated by increased temperature, in turn releasing energy that further increases temperature. In chemical engineering this risk is associated with strongly exothermic reactions that are accelerated by temperature rise.

] Structure Modification of Carbon: Several modification on carbon materials has been done in the recent year. One series of the carbon modification examples is ascribed to doping foreign elements into carbon bulk matrix (carbon alloy). For instance, Dahn and his co-workers have occluded silicon into carbon by pyrolyzed silicon-containing resins, since each silicon can bond with four lithium atoms, the resultant silicon-containing carbon demonstrated very high reversible capacity. Effects of phosphorus, sulphur, and nitrogen doping also have been investigated widely. The most prominent doping element for carbon matrix is boron because the boron atom can be considerably dissolved into graphene layers and decreases the structure strain. Boron doping into a carbon matrix can facilitate diffusion of carbon atoms, increase the crystallite size, and thus improve the crystallinity of carbon in the heat treatment. These factors can increase the reversible capacity of lithium storage. Another series in contrast is the modification of the surface. Takamura and his collaborators have done extensive studies on this, since they realized that initial Li + insertion through carbon surface is the prerequisite for the overall intercalation process. The simplest way to modify the carbon surface is focused on the effect of functional groups, such as removing some detrimental functional groups such as OH from the carbon surface 155 or grafting some groups like COOH, I, which are facile for the build up of SEI film and Li + intercalation. Actually, more a popular trend for surface modification is to coat a layer onto carbon surface, which is called the core-shell structure. The core material is generally graphite because of its sensitivity to the electrolyte, while the shell materials may be diversified, including metals or alloys, metal oxides, conducting polymers, and some other kinds of carbons. The shell materials may be active or inactive for Li + storage. The former type seems more valuable in view of the reversible capacity. Carbon is one of the most promising coating materials partly because it is akin to the core material. Another interesting case is the hybrid effect of graphite-cokes and graphite-hard carbon mixtures. The most attractive advantage of graphite anode material is its very low and flat working potential, which also can be considered to a disadvantage from another viewpoint since at the end of Li + de intercalation process from graphite (corresponding to a discharge process of a Li + -ion battery), the working voltage of graphite anode will rise abruptly after the three plateaus, which cause the sharp drop down of the whole working voltage of Li + -ion batteries. This can cause at least one inconvenience for battery users if they are unaware of how much capacity is left inside a Li + -ion battery. Thus, disordered carbons with a sloping working voltage are superior to graphitic carbons in this respect. A trade-off was to mix graphite with disordered carbon in proper ratios. Practical Carbon Anode Materials: Among so many kinds of carbonaceous materials, the practical anode materials most widely used in commercialized lithium-ion batteries can be roughly classified into three categories: hard carbon, and natural and synthetic graphite.

Natural Graphite: Now, natural graphite is becoming one of the most promising candidates as lithium ion battery anode materials mainly because of its low cost, low and flat potential profile, high coulombic efficiency in proper electrolytes, and relatively high reversible capacity (330350 mAh/g). On the other hand, it has two main shortcomings: its low rate capacity and incompatibility with PC-based electrolytes. The low rate capacity of natural graphite actually comes from its high anisotropy. To solve this problem, mechanical milling have been applied to tear the natural graphite flakes into small pieces.

The incompatibility of graphite with PC-based electrolytes has been widely studied. There generally are two ways to solve this problem. One is to modify the electrolytes by additives. The other is to modify the graphite by coating. Synthetic Graphite: Synthetic graphite has many properties that are the same as those of natural graphite. Besides, it has many unique merits such as high purity, variety of structures suitable or smooth Li + intercalation and diffusion, and so forth. Nevertheless, it is more expensive because of the high-temperature treatment (> 2,800C) on soft carbon precursor, and its reversible capacity is a little smaller than natural graphite. precursors, and its reversible capacity is a little smaller than natural graphite. Graphitized MCMB, mesophase-pitch-based carbon fibre (MCF), and vapour grown carbon fibre (VGCF) are the representatives of benchmark synthetic graphite anode materials for Li + -ion batteries in the market today. Graphitized MCMB has many advantages: 1. High packing density that guarantees high-energy density. 2. Small surface area that decreases the irreversible capacity corresponding to electrolyte decomposition. 3. Most of the surfaces of MCMB spheres are composed of edge-plane surfaces, thus Li + intercalation becomes easier and the rate capacity increases. 4. MCMB can be easily spread onto copper foil. . Hard Carbon:

Hard carbons can deliver high capacity at low potential ranges (<0.2 V vs. Li/Li +).if they can be adequately charged with lithium. Generally, it is very difficult to fulfil this point in normal time periods. The random alignment of small-dimensional raphene layers in hard carbons provides many voids to accommodate lithium. nevertheless, the manner in which lithium diffusion occurs inside hard carbons looks like a maze, and thus makes lithium diffusion become very sluggish. So the rate capacity of the carbon usually is very poor. The voids inside hard carbons also account for certain volume occupations. Although the gravimetric capacity of hard carbon seems very high compared with graphite, the volumetric capacity falls far behind this expectation, indeed. Of course, hard carbon still has some superiority over graphite. For example, its sloping voltage profile vs. capacity at the end of discharge may be very valuable for indicating the residue capacity.

Ref: Lithium Ion Batteries: science and Technology Lithium ion batteries-Principle and Performance. Positive Electrode (Cathode) Materials: The lithium-ion battery generates a voltage of more than 3.5 V by a combination of a cathode material and carbonaceous anode material, in which the lithium ion reversibly inserts and extracts. Such electrochemical reaction proceeds at a potential of 4 V vs. Li/Li + electrode for cathode and ca. 0 V for anode. Since the energy of a battery depends on the product of its voltage and its capacity, a battery with a higher energy density is obtained for a material with a higher voltage and a higher capacity. Therefore, when the same anode material is used, the higher the cathode potential and the larger the capacity of the cathode material, the higher the energy of the battery. The cathode and anode were packed into a vessel with constant dimensions, so the capacity for unit volume is more important than for weight. The volumetric specific capacity of LiCoO 2 is 808 mAh/cm3 , which is high enough to be used as a cathode material. Nickel-based cathode materials deliver higher capacity of 870 970 mAh/cm 3 . Safety problems for this material are overcome by the simultaneous doping of cobalt and aluminium. SAFT Co. has adopted Li Ni 0.8 Co 0.15 Al 0.05 O 2 supplied by Toda Kogyo Co. (formerly Fuji Chemical Industry Co.) as a cathode material in the lithium-ion battery for an electric vehicle (EV) application. An analogous compound is used in Japan. A press release announced that the capacity of it is 20% higher than that of LiCoO 2 and it is safer than LiCoO 2 in terms of overcharge problems. Manganese spinel cathode materials, although inferior to layered compounds, are cheap and rich in resources. Therefore, it is suitable as a cathode material in large-scale use of lithium-ion batteries. The Structure of Cathode Material: Many of the lithium battery cathode materials have a layered structure, which enables the two-dimensional diffusion of the lithium ion, or a spinel structure, which enables the three-dimensional diffusion. The basic compounds with a layered structure are LiCoO2 , LiNiO2 , LiCrO2 , Li2MoO3, and Li0.7MnO2 . The initial three compounds have a rhombohedral structure.

As shown in Fig the rhombohedral unit cell has a geometric feature that has three axes of an equal length,and that each angle between any two axes is the same. Electrochemical Characteristics and Structural Changes during Charge/Discharge: Layered Material: The charge/discharge curves of LiCoO2 and LiNiO2 are shown in Fig.below When the cut-off voltage is selected to be 4.3 V, LiCoO 2 has a comparatively smooth curve, while LiNiO 2 has a complicated curve with some voltage plateaus. In the following,

the composition of the LiNiO 2 -type compound during the charge/discharge will be expressed as Li1 xNiO2 . The origin of this complicated curve is attributed to the structural transformation Li1 x NiO2 keeps its original structure initially; however, it transforms the monoclinic phase in the range of 0.22 < x < 0.64. Further delithiation causes the formation of the NiO 2 phase in the range of x > 0.70 or more. For LiCoO2 two crystal phases with R3m (original LiCoO 2 and Li 0.75 CoO2) appears in the range of x < 0.25. The second rhombohedral phase continues except for a narrow range around Li0.5CoO2, which is a monoclinic phase the same as Li1 xNiO2.However, this phase transforms the rhombohedral phase by increasing the temperature. However, lithium excess LiCoO2 shows different behaviour from stoichiometric LiCoO2..It does not have the two-phase range of x < 0.25 and the monoclinic phase at around x = 0.5, which also is easily judged from the shape of its simple charge/discharge curves. The electrochemical reaction of lithium excess LiCoO2 proceeds in one phase, where the length of the c -axis continuously increases and that of the a -axis decreases as the degree of the delithiation.

Spinel: Manganese, whose resource is abundant and inexpensive, is used worldwide as an environmentally friendly and inexpensive dry battery material. Moreover, when a spinel-type manganese-based material is used as the electrode material of a lithium ion battery, the battery has the advantages of greatly improved safety and an inexpensive battery control circuit. The market trend for the manganese-based cathode material in a lithium-ion battery is roughly divided into two categories. The first category is materials used in portable electronic devices such as the mobile phone. The spinel lithium manganate has been used for the power source of the mobile phone for many years because of its excellent safety and cheaper control circuit, although its market share is low. Moreover, it is said that the capacity fading of the graphite anode during the cycling is prevented by the use of LiNixCo1 xO2 LiMn2O4 mixed cathode because of lower manganese deposition on the anode even at elevated temperatures. The second category is the cathode materials for large-size lithium-ion batteries as power sources for electric vehicles, hybrid vehicles, and so forth. High power, safety, and low cost are strongly required among their performances, so manganese-based cathode materials are suitable for such applications. It overwhelmingly excels in the power density compared to cheaper iron-based cathode material(LiFePO4) and it is used in a large-sized battery.

Problems of Cathode Materials (Safety Problem of Layered Material and Spinel LiMn2O4 Type Materials) Layered Materials: The cathode materials of lithium batteries have a strong oxidative power in the charged state as expected from their electrode potential. Then, charged cathode materials may be able to cause the oxidation of solvent or self-decomposition with the oxygen evolution. Finally, these properties highly relate to the battery safety. The thermal decomposition reaction of electrochemically delithiated Li1 y CoO2 (0.4< y < 0.6)is simple. On the other hand, it is more complicated in LiNiO2 .
Li0.5 CoO2 = 1/2 LiCoO2 + 1/6Co3 O4 + 1/6O2 Li0.5 NiO2 = (1/2 LiNi2 O4 ) = 3/2 Li0.33 Ni0.67 O + 1/4O2

The main difference between the above two equations is the amount of evolved oxygen gas. Since Li0.5NiO2 release 1.5 times of O2 than Li0.5CoO2,LiNiO2 has a greater possibility to generate heat than LiCoO2 . Recent Progress in Practical Cathode Materials for Lithium-Ion Batteries: The LiCoO2 has more than a 90% share in the market of cathode material for the lithium-ion battery, which is applied to cellular phones and portable computers. Manganese-based materials have a share of residual several percent. The capacity of lithium-ion batteries has been increased by the improvement of the carbon anode in the initial stage; however, recent improvements in capacity are achieved by the increased charge voltage. Doping foreign ions into LiCoO2 allows the use of a higher charge voltage without capacity fading. The current 18650- type battery with aluminium- or magnesium-doped LiCoO2 cathode can deliver the capacity of higher than 2.4 Ah. The practical application of nickel-based materials with large capacity per unit volume has been delayed from the viewpoint of safety; however, the safety of the foreign metal-doped LiNiO2 was confirmed and the practical use of the nickel based cathode started in fiscal year 2004. By the way, spinel LiMn2O4type materials exhibit excellent safety, so it is considered to be a promising candidate for large-sized batteries such as for hybrid electric vehicles (HEV) and electric vehicles (EV). Recent Cobalt-Based Materials: Recently, the properties of LiCoO2 have been considerably improved to fit the pulse discharge with high current, which is demanded for recent cellular phones. It is considered to be important to control the atomic ratio of Li/Co in the production of LiCoO2 because it control the physical property of LiCO2 . One of the features of this product is that its ratio is generally less than one. The specific surface area (SSA) also is one of the guidelines, since the reaction area is large when the surface area is large. It is obvious that cathode materials with a high SSA have improved rate performance for high-current discharge. Finally, there is a limitation in enlarging the SSA. Of course, if nano particles are used as an electrode-active material, it causes an extreme decrease in density. Further, the battery safety might be seriously ruined even if the rate performance is improved. Therefore, nano sized cathode material could not be recommended. Such materials are not used practically because they have a high possibility of firing in the nail penetration test (a type of battery short-circuit test) and the hot box test (battery heating test in air bath at 150C). SSA decreases with increases in Li/Co.

Recent layered Nickel based cathode materials are also very promising.

Ref: Lithium Ion Batteries: science and Technology. Lithium ion batteries-Principle and Performance. Lithium Ion Batteries Fundamentals and Performance.

Electrolytes: The role of liquid electrolytes in lithium-ion cells is to act as an ionic


conductor to transport lithium ions back and forth between positive and negative electrodes as the cells are charged and discharged. Since the electrodes in lithium-ion cells are the porous composite electrodes, consisting of an active material [carbon in the negative electrode and lithium transition metal (Co, Ni, Mn) oxide in the positive electrode, respectively], a conductive material (carbon black), and a polymer binder as depicted in Fig. 4.1 , the liquid electrolyte must seep into the porous electrodes and transfer lithium ions smoothly at the interfaces between the liquid and solid phases. Most lithium-ion cells available in the market utilize non aqueous electrolyte solutions, where lithium salts are dissolved in aprotic(A solvent that does not yield or accept a proton.) organic solvents. The gelled electrolytes used in lithium-ion polymer cells also are regarded as a liquid electrolyte immobilized with a high molecular weight polymer. Therefore, the same functions are required for the liquid and gelled electrolytes to greater or lesser degrees. Most of the liquid electrolytes used in the commercial lithium-ion cells are the non aqueous solutions, in which roughly 1 mol dm3 (M) of lithium hexafluorophosphate (LiPF6 ) salt is dissolved in the mixture of carbonate solvents selected from cyclic carbonates ethylene carbonate (EC), and propylene carbonate (PC) , and linear carbonates dimethyl carbonate (DMC), ethyl methyl carbonate (EMC),and diethyl carbonate (DEC). Recently, another type of liquid electrolyte based on 1.5 M LiBF 4 / g -butyrolactone (GBL) + EC came onto the market for the laminated thin lithium-ion cells with an excellent safety performance.

These can be called role assigned electrolytes: 1. Anode passivation film forming agents 2. Cathode protection agents 3. Overcharge protection agents 4. Wetting agents 5. Flame retardant agents 6. Others

Anode passivation film forming Agents: It is well known that the solid electrolyte inter phase (SEI) formed on the carbon anode determines the important cell performances such as reversible capacity, storage life, cycle life, and safety. This SEI originates from the electrolyte decomposition during the charging process. The electrolyte (particularly EC) begins to decompose around a potential E = 1.4 V vs . Li + /Li during the first charge, which results in the creation of an irreversible capacity Q irr (the difference in capacity Q between the charge and discharge) as shown in Fig. From the second cycle, this irreversible capacity becomes smaller and the constant reversible capacity Q rev is obtained during charge and discharge cycles. When PC is used as a solvent, the electrolyte continues to decompose at about 0.9 V vs . Li + /Li, as shown in Fig. 4.4 , and graphitic (crystalline) carbons cannot be charged due to their ex foliation caused by the solvent cointercalation. This is the reason why EC is dominantly used instead of PC, which was adopted for the first commercial lithium-ion cells with a nongraphitic (amorphous) carbon anode. However, the addition of some compounds such as vinylene carbonate (VC) prevents the graphite ex foliation and enables the charge of graphitic carbons, as shown in Fig.

Besides this there are several new compounds are being used .They are mentioned below. 1.Unsaturated Carbon Bond Compounds. 2.Sulphur-Containing Organic Compounds. 3.Halogen-Containing Organic Compounds. 4.Inorganic Compounds. 5.Ionic Compounds Cathode Protection Agents: There is by far less information available on the cathode interface than the anode interface. However, the reports appeared recently, which insisted that there is a film on the cathode, which may be called a SEI as well as the anode.Since the oxidative reactions on the cathode cannot immobilize reaction products like the reductive reactions on the anode, the amount of SEI on the cathode is much smaller than that on the anode. Overcharge Protection Agents: Non aqueous electrolyte solutions enable the lithium-ion cells to attain high voltage up to about 4 V, however, no overcharge protection mechanism is included in principle, as the aqueous electrolyte solutions in rechargeable cells such as Pb-acid, Ni Cd, and NiMH have overcharge protection mechanisms, which are the electrolysis of H2O to H2+O2 and their recombination to H2O. Present lithium-ion cells in the market are sold as a battery pack, where safety devices such as a control integrated circuit and a positive temperature coefficient (PTC) are attached. However, demands for higher safety, higher capacity, and lower cost have been accelerating the movement that safety functions should be included in the battery materials themselves. The overcharging degrades electrodes, current collectors, electrolytes, and separators,which can result in cell failure due to internal shorting and/or gas evolution. When lithium-ion cells are overcharged, extra lithium ions are subtracted from the cathode and extra lithium metal is deposited on the anode. Then both electrodes become thermally unstable and the input energy is consumed for the Joule heat of the cells, which causes thermal runaway, eventually resulting in fire and explosion, as illustrated in Fig.below . The overcharge protection agent is an additive that prevents the overcharge reactions of the both electrodes by its sacrificial reactions. Therefore,it must be inactive at normal use and work only under overcharged conditions.

Redox Shuttle-Type Compounds:

They following properties are required for this type of compounds: 1. The redox potential should be slightly positive (0.10.2 V) to the formal potential of the cathode at the end-of-charge. 2. The redox reactions during overcharge should be kinetically reversible on the negative and positive electrodes (the electrochemical rate constants should be greater than 10 5 cm s 1 ). 3. Redox species should be chemically stable and should not react with other components. 4. The diffusion coefficients and solubilities of redox species should be as high as possible. Non-Redox Shuttle-Type Compounds: There is a group of aromatic compounds that shows no reversible electrochemical behaviour but gives overcharge protection effects. The first proposed compound of this group is bi phenyl. It polymerizes on the cathode during overcharge and the liberated protons migrate to the anode generating hydrogen gas. These phenomena are being used for the overcharge protection. Ref: Advances in Lithium-Ion Batteries. Lithium-lon Batteries Solid-Electrolyte Inter phase. Lithium Ion Batteries: science and Technology. Lithium ion batteries-Principle and Performance. Lithium Ion Batteries Fundamentals and Performance.

Separators: Major function of battery separators is to insulate positive and negative electrodes

retain the electrolyte and transmit lithium ions. To ensure functionality the separator needs to have the following characteristics 1. Electrical insulation. 2. Chemical and thermal stability against electrolyte. 3. Capability of holding electrolyte. 4. Porous for transmission of Li ions. 5. Thinness and mechanical strength. Polyethylene and polypropylene porous thin films are generally used as suitable materials for above mentioned requirements. The pores of these films melt and prevent the lithium ions from passing through the separators at certain temperature which makes a major contribution to safety of the lithium batteries.
Structure of a Li ion battery: The three participants in the electrochemical reaction in a

lithium ion battery are the anode, cathode and electrolyte. We have discussed in details of these three components. Another important component for the cell to work properly is the separator which we have also discussed previously. Now let us look into the structure of a Li ion battery

Fig shows the structure of SANYOS cylindrical type Li ion cell. Standard cylindrical types have shorter width (diameter) and more capacity than prismatic types. This is why cylindrical types are very preferred when high capacity is needed for long tube shaped space, such as hinge of notebook pc. As we can see electrodes are spirally wound roll consisting of very thin sheets of positive and negative electrode and high polymer separators. Therefore cylindrical cell have an efficient structure which allows for a good performance for energy density. In order to keep safety in case of abnormal use the cell has some protective parts such as PTC

devices, gas release vent, or special separator.PTC has a combined function of current fuse and thermal fuse .when over current flows through the PTC self heating increases its resistance. This controls the abnormal large current. In addition the cell is equipped with a current interrupt device combined with a gas release vent. This will stop charging when pressure increases in the cell and cell will vent in case of further increases in pressure. Charge Discharge mechanism of Li ion cell:

Anode Reactions: The electrochemical potential of Li metal lies above the LUMO of preferred
electrolytes, and reaction with the electrolyte results in the formation of a passivating surface layer. Although Li ions pass through the layer on discharge, the Li redeposited on charge tends to form dendrites that traverse the electrolyte and separator to give electronic pathways that short-circuit the cell Lack of reliable reversibility of a Li-meta. Anode motivated development of oxide cathodes of high V, vs. a Li-metal anode so as to enable development of Li anodes having a lower electrochemical potential than metallic lithium. A candidate insertion host having Fermi energy only about 0.5 eV below that of Li is carbon. Li can be inserted reversibly into graphite to LiG. However, the bonding between graphite layers is too strong to give a high Li, and a quasi-amorphous petroleum coke was developed to give the now commercial battery.
Li1+xCoO2 non-aqueous Li+/ LiC

Having the anode reaction

y=

in general

Cathode Reaction: materials containing ions and which can be used as the active cathode materials must be capable of deintercalation of Lithium ions during charge and intercalation of Li ions during discharge. Lithium cobaltate (LiCoO2) is mainly used in the market place as the active cathode material and it is well known that Lithium nickelet (LiNiO2) and Lithium manganate (LiMn2O4) are also used for the cathode. The positive electrode half-reaction when Lithium Cobaltate is the active material (with charging being forwards) is

So the overall reaction of the Lithium ion battery can be shown as below

Electrical representation of a Li ion battery during discharge:

Ref: 1> http://en.wikipedia.org/wiki/Lithium-ion battery 2> Documents of Li ion battery from SANYO corporation. 3> Lithium_Ion_Batteries-Fundamentals_and_Performance. 4> Next generation lithium ion batteries.

Different Electrical Characteristics And their explanation Of A Li Ion Battery:


Load Current Vs output voltage: If we assume that in a given situation output current is I then out put voltage is given by the following equation V=Voc-I*Rb where Rb is the series resistance (called the internal resistance of the battery) as shown in the figure previously and Voc is called the open circuit voltage of the battery (output voltage when load current is zero). Now Rb can be expressed by the following equation Rb
=

Re1 + Rin(A)

Rin(C)

+ Rc(A) +Rc(C)

The electrolyte resistance

to the ionic current is proportional to the ratio of the effective thickness L to the geometrical area A of the inter electrode space that is filled with an electrolyte of ionic conductivity i. Since ions move diffusively, i.e., with a mobility i = qD/ kT where the diffusion coefficient D= DO exp(Gm/kT) contains a motional free energy Gm and i=niqi is proportional to the density ni of carriers of charge q.

increases with temperature T, and a i 0.1 S-cm-1(the maximum i represents the room temperature protonic conductivity H in a strong acid) at an operating temperature To dictates the use of a membrane separator of large geometrical area A and small thickness L. The resistance to transport of the working ion across the electrolyte-electrode interfaces is proportional to the ratio of the geometrical and inter facial areas at each electrode: Rin =A/Ain Where the chemical reaction of the cell involves ionic transport across an interface, above equation dictates the construction of a porous, small-particle electrode as illustrated in Fig. below. Achievement and retention of a high electrode capacity, I. e . , utilization of a high fraction of the electrode material in the reversible reaction, requires the achievement and retention of good electronic contact between particles over many discharge/charge cycles.

Finally, current from the large-area electrodes must be collected to the negative and positive posts, and a clever geometrical design is needed to allow assembly of the cell into a small package that minimizes the current-collector resistance RC of each electrode.

l is the mean distance an electron (or hole) travels through the thickness of the electrode of electronic conductivity e to reach the current-collector of conductivity m and d is a geometrical parameter having units of length.

The battery voltage V vs. the current I delivered across a load is called the polarization curve. The voltage drop ( Voc- V)= (I) of a typical curve, Fig. 1.4, is a measure of the battery resistance On charging, (Z) = (Vapp- Voc) is referred to as an overvoltage. The inter facial voltage drops saturate in region (i) of Fig. 1.4; therefore in region (ii) the slope of the curve is

Region (iii) is diffusion-limited; at the higher currents I, normal processes do not bring ions to or remove them from the electrode/electrolyte interfaces rapidly enough to sustain an equilibrium reaction. Typical discharge characteristics of a Li ion battery: The battery voltage V vs. the state of charge, or the time during which a constant current I has been delivered, is called a discharge curve. Typical curves are shown in Fig. Below for the solid solution reactions

In the first, illustrated schematically in Fig. 1.6, a complete solid solution 0x1 is obtained, and V(x) is described by the Nernst equation

where the standard potential V0 for the Ti4+/Ti3+ redox couple is independent of x and corresponds to x= 0.5. It is interesting that above eq.is obeyed even though the electrons donated to the TiSz array occupy a narrow Ti-3d band rather than a localized Ti3+: T2g configuration. In the second reaction the insertion of Li into the spinel Li[Mn2]O4 induces a cooperative Jahn-Teller distortion from cubic to tetragonal symmetry that stabilizes the localized Mn3+Eg configuration of a cubic octahedral site. The solid solution within the tetragonal phase begins at x0.8; and in accordance with the Gibbs phase rule, the voltage remains flat, independent of x, over the extended two-phase region 0 <x<0.8. LiCoO2 is mainly used for the cathode in present lithium ion batteries. It is relatively easy to prepare.LiCoO2 is rock salt-structured materials based on a closepacked network of oxygen atoms with Li+ ions ordering on alternating (1 1 1) planes of the cubic rock salt structure. This (1 1 1) ordering introduces a slight distortion of the lattice to

hexagonal symmetry. Hence, LiCoO2 crystallizes in the space group (R3m) with cell constants a = 2:816 A and c = 14:08 A. The lithium ion intercalates into or deintercalates from the van der Waals gap between CoO2 layers (3a site) reversibly. The discharge curve is shown below

In general, the a-axis changes little, but the c axis changes from 14.1 to 14.6 A with lithium deintercalation. Since a new phase appears near x=0.5 the voltage begin to be remain flat for the next discharge period. Ref:Lithium_Ion_Batteries-Fundamentals_and_Performance. Recent developments in lithium ion batteries - journal-Materials Science and Engineering R33 (2001) 109-134 . Performance Characteristics of Cathode Materials for Lithium-Ion Batteries: A Monte Carlo Strategy -Journal of The Electrochemical Society, 155 12 A875-A878 2008 A875 0013-4651/2008/155 12 /A875/4/23.00 The Electrochemical Society . Temperature dependence of Li Ion Battery:Batteries function best at room temperature, and any

deviation towards hot and cold changes the performance and/or longevity. Operating a battery at elevated temperatures momentarily improves performance by lowering the internal resistance: The internal resistance Rb of a battery is given by the following equation. Rb = Re1 Rin(A) Rin(C) Now the electrolyte resistance

+ Rc(A) +Rc(C)

It is proportional to the ratio of the effective thickness L to the geometrical area A of the inter

electrode space that is filled with an electrolyte of ionic conductivity i. Since ions move diffusively, i.e., with a mobility i = qD/ kT where the diffusion coefficient D= DO exp(- Gm/kT) contains a motional free energy Gm and i=niqi is proportional to the density ni of carriers of charge q.

so we see that conductivity increases i.e. internal resistance decreases with temperature. The collector resistance also decreases with increase in temperature which helps to decrease the cell resistance faster with temperature. speeding up the chemical metabolism:Rates of most reactions are very sensitive to temperature. Most increase rapidly with increasing temperature. If we recall the kinetic molecular theory (which was discussed in the previous semester of this course), one finds that the average speed of molecules increases with temperature. In fact, the average speed is related to the square root of the absolute temperature. For a reaction to occur, the participants need to collide with each other. Hence, one may suggest that as the temperature rises, the relative speeds of molecules with respect to one another increase (as the distribution of molecules among various velocities expands as the temperature is raised), leading to an increase in collision frequency. However, this is only a root (a very mild) dependence on temperature. It does not explain why rates can double by simply raising the temperature by 10 degrees. In 1889 Svante Arrhenius (Univ. of Stockholm) found an empirical relation that accurately describes the T dependence of k.

The specific mathematical form is k = Ae-(Ea/RT) where A pre-exponential factor E a Arrhenius activation energy Typically, we find for unimolecular reactions A ~ 1012 - 1015 sec-1 and for bimolecular reaction's A ~ 1011 l/mole. sec and Ea ~ 50 to 300 kJ/mole . Better performance of a battery at a elevated temperature has some drawback also. It shorten service life if allowed to continue for a long period of time. Cold temperature increases the internal resistance,and reduce the reaction rate which in tern diminishes the capacity. Batteries that would provide 100 percent capacity at 27C (80F) will typically deliver only 50 percent at 18C (0F). The Graph below shows the Li ion battery characteristics at different temperature.

Ref: http://batteryuniversity.com/learn/article/discharging_at_high_and_low_temperatures http://bouman.chem.georgetown.edu/S02/lect4/lect4.htm Documents on Li Ion Battery by Sanyo corporation. Lithium_Ion_Batteries-Fundamentals_and_Performance. Capacity Deterioration with Cycling: Chemical Changes: Batteries are electrochemical devices which convert chemical energy into electrical energy or vice versa by means of controlled chemical reactions between a set of active chemicals. Unfortunately the desired chemical reactions on which the battery depends are usually accompanied by unwanted chemical reactions which consume some of the active chemicals or impede their reactions. Even if the cell's active chemicals remain unaffected over time, cells can fail because unwanted chemical or physical changes to the seals keeping the electrolyte in place. Decrease in effective electrode area:If the reversible reaction involves a first-order phase change,

the particles may fracture or lose contact with one another on cycling to break a continuous electronic pathway to the current collector. Where there is a two-phase process (or even a sharp guest-species gradient at a diffusion front) without fracture of the particles, the area of the interface (or diffusion front) decreases as the second phase penetrates the electrode particle. Loss of inter particle electrical contact results in an irreversible loss of capacity. Temperature effects: Chemical reactions internal to the battery are driven either by voltage or temperature. The hotter the battery, the faster chemical reactions will occur. High temperatures can thus provide increased performance, but at the same time the rate of the unwanted chemical reactions will increase resulting in a corresponding loss of battery life. The shelf life and charge retention depend on the self discharge rate and self discharge is the result of an unwanted chemical reaction in the cell. Similarly adverse chemical reactions such as passivation of the electrodes, corrosion and gassing are common causes of reduced cycle life. Temperature therefore affects both the shelf life and the cycle life as well as charge retention since they are all due to chemical reactions. Pressure effects: These problems related to sealed cells only. Increased internal pressure within a cell is usually the consequence of increased temperature. Several factors can play a part in causing the temperature and pressure rise. Excessive currents or a high ambient temperature will cause the cell temperature to rise and the resulting expansion of the active chemicals will in turn cause the internal pressure in the cell to rise. Overcharging also causes a rise in temperature, but more seriously, overcharging can also cause the release of gases resulting in an even greater build up in the internal pressure. Unfortunately increased pressure tends to magnify the effects of high temperature by increasing the rate of the chemical actions in the cell, not just the desired Galvanic reaction but also other factors such as the self discharge rate or in extreme cases contributing to thermal runaway. Excessive pressures can also cause mechanical failures within the cells such as short circuits between parts, interruptions in the current path, distortion or swelling of the cell case or in the worst case actual rupture of the cell casing. All of these factors tend to reduce the potential battery life. Depth Of Discharge (DOD):At a given temperature and discharge rate, the amount of active chemicals transformed with each charge - discharge cycle will be proportional to the depth of discharge. The relation between the cycle life and the depth of discharge appears to be logarithmic as shown in the graph below. In other words, the number of cycles yielded by a battery goes up exponentially the shallower the DOD. This holds for most cell chemistries. This is because rapid change in the charge/discharge potential of graphite electrode at a lower voltage region in li ion battery introduces several side reactions such as electrolytic decomposition due to non uniform potential difference across the Graphite Electrode.

Charging Rate: Battery life is also influenced by the charging rate. The capacity reduction at high discharge rates occurs because the transformation of the active chemicals cannot keep pace with the current drawn. The result is incomplete or unwanted chemical reactions and an associated reduction in capacity as noted in the paragraph on Chemical Changes above. This may be accompanied by changes in the morphology of the electrode crystals such as cracking or crystal growth which adversely affect the internal impedance of the cell. Similar problems occur during charging. There is a limitation as to how quickly the Lithium ions can enter into the intercalation layers of the anode. Trying to force too much current through the battery during the charging process results in surplus ions being deposited on the anode in the form of Lithium metal. Known as Lithium plating, this results in an irreversible capacity loss. At the same time, maintaining the higher voltages needed for fast charging can lead to breakdown of the electrolyte which also results in capacity loss. From the above we can expect that with each charge/discharge cycle the accumulated irreversible capacity loss will increase. Although this may be imperceptible, ultimately the capacity reduction will result in the cell being unable to store the energy required by the specification. In other words it reaches the end of its useful life and since the capacity loss is brought on by high current operation, we can expect that battery cycle life will be shorter, the higher the current it carries. The graph below demonstrates that this is the case in practice.

Voltage effects Rechargeable batteries each have a characteristic working voltage range associated with the particular cell chemistry employed. The practical voltage limits are a consequence of the onset of undesirable chemical reactions which take place beyond the safe working range. Once all the active chemicals have been transformed into the composition associated with a fully charged cell, forcing more electrical energy into the cell will cause it to heat up and to initiate further unwanted reactions between the chemical components breaking them down into forms which can not be recombined. Thus attempting to charge a cell above its upper voltage limit can produce irreversible chemical reactions which can damage the cell. The increase in temperature and pressure which accompanies these events if uncontrolled could lead to rupture or explosion of the cell and the release of dangerous chemicals or fire. Similarly, discharging a cell below its recommended lower voltage limit can also result in permanent, though less dangerous, damage due to adverse chemical reactions between the active chemicals. Protection circuits are designed to keep the cell well within its recommended working range with limits set to include a safety margin. This is discussed in more detail in the section on Protection . Cycle life estimations normally assume that the cells will only be used within their specified operating limits, however this is not always the case in practice and while straying over the limits for short periods or by a minor margin will not generally cause the immediate destruction of the cell, its cycle life will most likely be affected. Ref:http://www.mpoweruk.com/life.htm Documents on Li Ion Battery by Sanyo corporation. Lithium_Ion_Batteries-Fundamentals_and_Performance.

Why does the reduction potential of a Li ion is -3.01 v ?


To describe this we need to find out the actual energy of a electron residing at the outermost orbital of Li ion. So we first find out the expression for the total energy of a electron at n th orbital for the hydrogen like atom and then modify that to find out the same expression for the Li atom.

The RutherfordBohr model of the hydrogen(Z = 1) like atom. According to them the angular momentum L of a electron is restricted to be an integer multiple of a fixed unit:

where n = 1, 2, 3, ... is called the principle quantum number and = h/2. According to Classical mechanics

The electron is held in a circular orbit by electrostatic attraction. The centripetal force is equal to the coulomb force. where me is the electron's mass, e is the charge of the electron, ke is coulomb's constant and Z is the atom's atomic number. This equation determines the electron's speed at any radius:

It also determines the electron's total energy at any radius:

Now according to Quantum rule

The angular momentum L = mevr is an integer multiple of :

Substituting the expression for the velocity gives an equation for r in terms of n:

so that the allowed orbit radius at any n is:

The energy of the n-th level for any atom is determined by the radius and quantum number:

Now this expression is only valid for the hydrogen like atom i.e. those atom which have only one electron(like He+,Be+++). For atom with multiple number of electron we will modify the equation by changing the Z by Zeff where Zeff =Z- Ze Z is due to the Z number of proton in the nucleus where as Ze is the effective number of other electron engaged in repelling the electron of interest. To find out Ze we have to solve the Schrdinger's wave equation because according to quantum theorem there are hardly any discreet electron moving around the nucleus in it's orbital rather they are forming a cloud like environment where we cant find out there relative position accurately at a time. we can only find out the probability of being at a certain a position at a time

using Schrdinger's wave equation. based on that For Li ion Zeff has been calculated to be 1.26.

So for lithium total energy of the electron at nth(n=2 as from the figure) stage En= -Zeff2*13.6 /n2 eV = -(1.26)^2 * 13.6/4 eV = - 5.4 eV reduction potential = - (5.4 eV/e-)v=-3.3 V practically we get it as - 3.01 V. Ref :http://en.wikipedia.org/wiki/Bohr_model Correlation energy of many-electron systems: a modified Colle-Salvetti approach

http://electron6.phys.utk.edu/phys250/modules/module%203/Multi-electron %20atoms.htm Why do we need the electronic conductivity (e) of a electrolyte to be zero ? If the electrolyte has a finite e then there will exist a finite drift current through the electrolyte in a direction opposite to the diffusion current. This is highly undesirable because it will causes a continuous self discharge of the battery potential. Why does the normal charger are inefficient when the battery gets over discharged? Li-ion should never be discharged too low, and there are several safeguards to prevent this from happening. The equipment cuts off when the battery discharges to about 3.0V/cell, stopping the current flow. If the discharge continues to about 2.70V/cell or lower, the batterys protection circuit puts the battery into a sleep mode. This renders the pack unserviceable and a recharge with most chargers is not possible. To prevent a battery from falling asleep, apply a partial charge before a long storage period. Battery manufacturers ship batteries with a 40 percent charge. The low charge state reduces aging-related stress while allowing some self-discharge during storage. To minimize the current flow for the protection circuit before the battery is sold, advanced Li-ion packs feature a sleep mode that disables the protection circuit until activated by a brief charge or discharge. Once engaged, the battery remains operational and the on state can no longer be switched back to the standby mode. When the battery voltage begins to fall below the rated voltage of fully discharged state i.e. as it begins to go to the over discharged state the copper current collector of anode begins to dissolve into the electrolyte. This increase the self discharge current and it may causes a partial short circuit situation in extreme case. As discharge current is higher now so the trickle charge(this is the first stage charging of the Li ion battery) can't recover the cell potential rather due to the higher current follow through the cell; battery temperature begins to increase which may causes thermal runaway. So in this stage we need to give a current boost one minute to force the electrode to recover their potential and dissolved copper to precipitate in the current collector. But this precipitation is not 100% effective because some dissolved copper may precipitate somewhere else other than the anode current collector. so there is always a irreversible capacity loss due to the over discharge. In this technique if cell potential of a over discharged battery does not recover after a one minute of boosted current charge then we have to reject that battery because it has damaged permanently. Also it is better to reject and not to recharge a lithium-ion if a cell has stayed at or below 1.5V for more than a week. Copper shunts may have formed inside the cells that can lead to a partial or total electrical short. If recharged, the cells might become unstable, causing excessive heat or showing other anomalies. Li-ion packs that have been under stress are more sensitive to mechanical abuse, such

as vibration, dropping and exposure to heat. Charging Lithium-Ion Batteries : The rate of charge or discharge is often expressed in relation to the capacity of the battery. This rate is known as the C-Rate. The C-Rate equates to a charge or discharge current and is defined as: I = M x Cn where: I = charge or discharge current, A M = multiple or fraction of C C = numerical value of rated capacity, Ah n = time in hours at which C is declared.

A battery discharging at a C-rate of 1 will deliver its nominal rated capacity in one hour. For example, if the rated capacity is 1000mAhr, a discharge rate of 1C corresponds to a discharge current of 1000mA. A rate of C/10 corresponds to a discharge current of 100mA.

So how is energy properly restored to a Li-Ion battery? The preferred charge algorithm for LiIon battery chemistries is a constant, or controlled, current -- constant voltage algorithm that can be broken up into four stages: trickle charge, constant current charge, constant voltage charge, and charge termination. Refer to Figure below.

Stage 1: Trickle Charge -- Trickle charge is employed to restore charge to deeply depleted cells. When the cell voltage is below approximately 3V, the cell is charged with a constant current of 0.1C maximum.

Stage 2: Constant Current Charge -- After the cell voltage has risen above the trickle charge threshold, the charge current is raised to perform constant current charging. The constant current charge should be in the 0.2C to 1.0C range. The constant current does not need to be precise and semi-constant current is allowed. Often, in linear chargers, the current is ramped-up as the cell voltage rises in order to minimize heat dissipation in the pass transistor. Charging at constant current rates above 1C does not reduce the overall charge cycle time and should be avoided. When charging at higher currents, the cell voltage rises more rapidly due to over-voltage in the electrode reactions and the increased voltage across the internal resistance of the cell. The constant current stage becomes shorter, but the overall charge cycle time is not reduced because the percentage of time in the constant voltage stage increases proportionately. Stage 3: Constant Voltage -- Constant current charge ends and the constant voltage stage is invoked when the cell voltage reaches 4.2V. In order to maximize performance, the voltage regulation tolerance should be better than +1%.

Stage 4: Charge Termination -- Unlike nickel-based batteries, it is not recommended to continue to trickle charge Li-Ion batteries. Continuing to trickle charge can cause plating of metallic lithium, a condition that makes the battery unstable. The result can be sudden, automatic, and rapid disassembly. Charging is typically terminated by one of two methods: minimum charge current or a timer (or a combination of the two). The minimum current approach monitors the charge current during the constant voltage stage and terminates the charge when the charge current diminishes in the range of 0.02C to 0.07C. The second method determines when the constant voltage stage is invoked. Charging continues for an additional two hours, and then the charge is terminated. Charging in this manner replenishes a deeply depleted battery in roughly 2.5 to 3 hours.

Ref: Documents on Li ion battery charger by Microchip Corporation. Documents on Pulse Mode Li ion battery charger by Texas Instrument. http://batteryuniversity.com/learn/article/how_to_prolong_lithium_based_batteri es

Lithium Ion Battery Model


Ideal battery properties and discharge time estimates : The two most important properties of batteries from the viewpoint of someone using them are voltage and capacity. An ideal battery has 1.>An ideal battery has a constant voltage throughout a discharge, which drops instantaneously to zero when the battery is fully discharged . 2.> It has has constant capacity for all values of the load, as shown in Figure 1.

The charge capacity of the battery is typically given in terms of Amphours or milliamp-hours and is called the batterys C rating. The advantage of C ratings is that it allows battery manufacturers to present one graph of discharge curves for batteries of similar construction but different capacities. Loads are then measured relative to the C rating, e.g. a 10 mA load on a battery with a rated capacity of 100 mAh is a load of 0.1C

For mobile systems, the discharge time T is usually estimated to be the batterys rated voltage V multiplied by the charge capacity C , divided by the average power P of the system, or T = (CV)/P . Non-ideal battery properties: While ideally a battery has constant
voltage and capacity,in practice both vary widely. Figure 2a shows the battery voltage as a function of discharge time for two different loads. Load 1 is smaller than load 2. Because of resistance and other losses, the voltage throughout the discharge is lower for load 2 than load 1. The voltage for each load also drops over the course of the discharge due to changes in the batterys active materials and reactant concentrations. The capacity also varies with the value of the load. The two major ways in which it varies are loss of capacity with increasing load, and an effect called recovery where an intermittent load may have a larger capacity than a continuous load. Figure 2b shows the loss of capacity with increasing load current for a typical NiCd battery. The capacity decreases by about 40% over a range of discharge rates of 0.1C to 10C. (Note that the capacity in Figure 2b exceeds 100% at low rates because the C rating is specified as the capacity for a given time of discharge. The capacity in Figure 2b was measured at the 2 hour rate, since 100% capacity occurs at 0.5C. If the capacity had been measured at the 10 hour rate, 100% would have occurred at 0.1C.) The second non-ideal capacity property, recovery, is shown in Figure 2c. A reduction of the load for periods of time results in an increase in battery capacity. The voltage rises while the load is reduced, and the overall time of discharge increases. This phenomena occurs because, during the time when load is reduced, reactants in the battery diffuse to the reaction location, allowing more of them to be used during the life of the battery. The degree to which the battery recovers depends on the discharge rate and the length of time the load is reduced, as well as the details of the battery construction.

Some Battery Model:

All about the current from a Battery: ButlerVolmer equation The ButlerVolmer equation is one of the most fundamental relationships in electrochemical kinetics. It describes how the electrical current on an electrode depends on the electrode potential, considering that both a cathodic and an anodic reaction occur on the same electrode:

Mass-transfer control
The previous form of ButlerVolmer equation is valid when the electrode reaction is controlled by electrical charge transfer at the electrode (and not by the mass transfer to or from the electrode surface from or to the bulk electrolyte). Nevertheless, the utility of the ButlerVolmer equation in electrochemistry is wide, and it is often considered to be "central in the phenomenological electrode kinetics".[1] In the region of the limiting current, when the electrode process is mass-transfer controlled, the value of the current density is:

D is the diffusion coefficient; is the diffusion layer thickness; C* is the concentration of the electroactive (limiting) species in the bulk of the electrolyte. The more general form of the Butler Volmer equation, applicable to the mass transfer-influenced conditions, can be written as:[2]

The limiting cases


There are two limiting cases of the ButlerVolmer equation:

the low over potential region (called "polarization resistance", i.e., when E Eeq), where the ButlerVolmer equation simplifies to:

the high overpotential region, where the Butler Volmer equation simplifies to the Tafel equation:

where a and b are constants (for a given reaction and temperature) and are called the tafel equation constants. The theoretical values of a and b are different for the cathodic and anodic processes.

References

[1] J. O'M. Bockris, A.K.N.Reddy, and M. Gamboa-Aldeco, "Modern Electrochemistry 2A. Fundamentals of Electrodics.", Second Edition, Kluwer Academic/Plenum Publishers, p.1083, 2000. [2] Allen Bard and Larry Faulkner, "Electrochemical Methods. Fundamentals and Applications". 2nd edition, John Wiley and Sons, Inc., 2001.

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