A818

Journal of The Electrochemical Society, 152 ͑4͒ A818-A829 ͑2005͒
0013-4651/2005/152͑4͒/A818/12/$7.00 © The Electrochemical Society, Inc.

Cyclable Lithium and Capacity Loss in Li-Ion Cells
John Christensen*,z and John Newman**
Department of Chemical Engineering, University of California, Berkeley, California 94720, USA In lithium-ion cells, there are several different classes of capacity loss, both reversible and irreversible, that limit the cell’s exploitable specific capacity and can lead to eventual cell failure. We attempt to clarify what is meant by capacity loss and cyclable lithium loss by defining these terms in the context of electrode state-of-charge restrictions. We define irreversible capacity loss as that associated with active material loss and define two types of reversible capacity loss associated with balanced and unbalanced side reactions. We also examine several methods of compensating for cyclable lithium loss associated with passive-film formation and calculate the effect each has on a cell’s specific energy. Preforming the negative electrode, adding cyclable lithium to the positive electrode, and introducing lithium powder into the negative electrode appear to be the most attractive methods in terms of specific energy, but practical constraints such as fabrication cost must be evaluated to determine which is superior. © 2005 The Electrochemical Society. ͓DOI: 10.1149/1.1870752͔ All rights reserved. Manuscript submitted July 13, 2004; revised manuscript received October 19, 2004. Available electronically March 14, 2005.

Cyclable lithium is consumed to form passivating films on electrode materials during the formation cycles of the lithium-ion cell, which consist of one to several charge-discharge cycles. The source of cyclable lithium is that which is initially contained in the positive and negative electrode insertion materials, as well as that which is added to either electrode via side reactions from the lithium salt in the electrolytic solution. The latter source typically accounts for a small but significant fraction ͑less than 15%͒ of the total amount of lithium in the cell.1 Because some lithium is consumed irreversibly ͑a process that is often misleadingly referred to as “irreversible capacity loss”͒ during the first few cycles, it is common practice to include excess capacity in the positive electrode when manufacturing low-power cells, thereby allowing full utilization of the negative electrode’s capacity.2 Such “mismatched” cells have a lower overall specific energy than an idealized cell would have, in which there is no loss of cyclable lithium. One means of avoiding this ostensibly necessary evil is to introduce cyclable lithium by some means other than those already mentioned. FMC Corporation has demonstrated the successful introduction of passivated lithium powder into the composite negative electrode of a lithium-ion cell.3 This additional cyclable lithium compensates for that which is lost in passive-film formation, while minimizing the addition of mass to the cell. Furthermore, the optimally balanced cell that results can be operated over a higher average cell-voltage range. In the present work, we attempt to clarify what is meant by capacity loss and loss of cyclable lithium, the two being equivalent only when a loss of lithium effectively limits the cycling range of the cell. Perhaps counter to intuition, increasing the amount of lithium contained in the positive and negative electrodes can also lead to capacity loss. To elucidate these concepts, we evaluate several methods for balancing the loss of lithium during passive-film formation. We also examine capacity loss due to loss of active material and distinguish between “reversible” and “irreversible” capacity loss. Conceptual Framework An earlier paper introduced the state-of-charge ͑SOC͒ operating window used to examine capacity fade and capacity balance phenomena.1 We summarize the pertinent equations here. Let x be the negative electrode SOC, or amount of lithium in LixN, where N represents the electrochemically active negative electrode material ͑e.g., C6͒; let y be the positive electrode SOC, or amount of lithium in LiyP, where P represents the positive electrode material ͑e.g., Mn2O4͒. The capacity ratio is defined as

z=

ˆ L ␧ ␳ ⌬x C + + + + = ˆ L ␧ ␳ ⌬y C − − − −

͓1͔

ˆ is the specific capacity of the active material in the elecwhere C i trode i, ␧i is the volume fraction of active material, Li is the electrode thickness, and ␳i is the active-material density. The optimum capacity ratio, in which the entire capacity range of both electrodes is realized, is zopt = ⌬xmax ⌬y max ͓2͔

where the maximum cycling range is set by physical considerations ͑e.g., Li deposition at high x and Jahn-Teller distortion at y Ͼ 1, for some materials͒.2 Figure 1 is a schematic SOC operating window, with cycle paths drawn for a perfectly balanced cell and a mismatched cell that has excess positive electrode capacity. ⌬xmis is the cycling range of negative electrode SOC for the mismatched cell, and in this case it is equal to ⌬xmax. Likewise, ⌬y mis is the range of positive electrode SOC, which is less than ⌬y max when there is excess positive electrode capacity. In the absence of side reactions and capacity loss, the precise limits of the positive electrode cycling range depend entirely on the initial SOCs of both electrodes. For instance, if we were to build the same cell with additional lithium in the positive electrode material, the mismatched cell’s cycle path would be shifted upward in the operating window. However, the slope of the path would remain the same, because it is dictated by the relative capacity of the two electrodes. Figure 2 is an alternative representation of capacity balance, using open-circuit potential ͑OCP͒ curves for positive and negative electrodes. Figure 2a illustrates the case in which the two electrode capacities are perfectly balanced. In Fig. 2b, the additional positive electrode capacity, which may be introduced by increasing the thickness of the positive electrode or the volume fraction of active material, is represented by stretching the positive electrode curve relative to that of the negative electrode. By shifting the two curves relative to one another along the capacity axis, we explore different portions of the positive electrode curve, and therefore different positive electrode SOC’s and cell potentials, while maintaining the capacity ratio. To examine capacity-fade and side-reaction phenomena, we must introduce equations for the amount of lithium contained in different parts of the cell. At any given time, the amount of lithium contained in the negative electrode active material, per unit separator area, is nLi,− = ˆ L ␧ ␳ x C − − − − F ͓3͔

* Electrochemical Society Student Member. ** Electrochemical Society Fellow.
z

E-mail: jake@newman.cchem.berkeley.edu

where F is Faraday’s constant. Similarly, the amount contained in the positive electrode material is

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Journal of The Electrochemical Society, 152 ͑4͒ A818-A829 ͑2005͒

A819

Figure 1. The SOC operating window, with limits on x and y corresponding to a typical LixC6 /LiyMn2O4 cell. The optimum cycle path, a, has a slope of −1/zopt = − ⌬y max /⌬xmax, while the cycle path for a mismatched cell, b, has a slope of −1/zmis = − ⌬y mis /⌬xmis. The shaded areas represent unutilized positive electrode capacity for the mismatched cell.

nLi,+ =

ˆ L ␧ ␳ y C + + + + F

͓4͔

We refer to the sum of these two amounts as the total cyclable lithium. By our definition, lithium corresponding to y Ͻ y min and x Ͻ xmin is called cyclable, even though it is never accessed during cell operation. There is also “noncyclable” lithium contained in other parts of the cell, most notably the electrolyte, which can become cyclable lithium through the occurrence of a side reaction. The area-specific quantity of lithium in the electrolyte is given by nLi,E = cLiX͑L−␧E,− + L+␧E,+ + LS␧E,S͒ ͓5͔
Figure 2. OCP functions of positive and negative electrodes for ͑a͒ a perfectly balanced cell and ͑b͒ a mismatched cell with excess positive electrode capacity. The empirical fits shown here are for Lonza KS6 graphite ͑from Belcore͒ and spinel Mn2O4 ͑upper plateau͒, taken from the program Dualfoil, available on our website at http://www.cchem.berkeley.edu/ϳjsngrp/

where cLiX is the concentration of lithium salt in the electrolyte, LS is the separator thickness, and ␧E,−, ␧E,+, and ␧E,S are the volume fractions of electrolyte in the negative electrode, positive electrode, and separator, respectively. This typically accounts for less than 15% of the total lithium in the cell. Lithium can also be present in the form of reduction or oxidation products that make up passivating films on the electrodes or are otherwise insoluble. Passivated lithium powder is another source of lithium, which becomes cyclable when it is introduced into the active electrode material. Cyclable lithium can be added or destroyed via side reactions at either the positive or negative electrode. The main reaction at the negative electrode is xLi+ + xe− + N and a generic side reaction is S+e

ˆ L ␧ ␳ i = −C − − − −

dx + isn dt

͓10͔

where isn is the combined current density of side reactions at the negative electrode and is negative for the forward direction of Reaction 7. At the positive electrode, the total superficial current density is ˆ L ␧ ␳ dy − i i=C + + + + sp dt ͓11͔

LixN

͓6͔

S

͓7͔

Similarly, the main reaction at the positive electrode is LiyP and a generic side reaction is S S +e
+ −

where isp is the combined current density of side reactions at the positive electrode and is positive for the forward direction of Reaction 9. From Eq. 3, 4, 10, and 11, the rate of change in cyclable lithium is dnLi dt d = dt ͑nLi,+ + nLi,−͒ = isn + isp F ͓12͔

y Li+ + y e− + P

͓8͔

͓9͔

Here S is any species ͑e.g., solvent, anion, additive, or binder͒ that can be oxidized or reduced. The total superficial current density at the negative electrode is

We have here neglected the introduction or loss of cyclable lithium by diffusion between solids. As we demonstrate, such nonelectrochemical changes can be accounted for by modification of Eq. 10-12. Before proceeding with specific examples, we define cell capacity, reversible capacity loss, and irreversible capacity loss as they are

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A820

Journal of The Electrochemical Society, 152 ͑4͒ A818-A829 ͑2005͒

Figure 4. Extensive-capacity operating window for a perfectly balanced cell, before and after 25% of the positive electrode active material is lost. In this representation, active material loss is represented by shrinkage of the window, and, in the absence of side reactions, the cycle path does not move or change slope. The dotted area represents negative electrode capacity that is still available but not utilized. This figure corresponds to the change from the optimum cycle path to cycle path c represented in Fig. 3. Figure 3. Different types of capacity loss encountered in lithium-ion cells: ͑a͒ cycle path after “restricted cycling loss” corresponding to a loss of cyclable lithium, ͑b͒ reversible capacity loss due to balanced side reactions at the two electrodes, and ͑c͒ cycle path after irreversible capacity loss associated with the loss of positive electrode active material. All losses are relative to an ideally balanced cell, represented by the dashed cycle path.

used throughout the paper. We define the “full cell capacity” as the ˆ L ␧ ␳ ⌬x ͒ and minimum of the negative electrode capacity ͑ C − − − − max ˆ positive electrode capacity ͑ C+L+␧+␳+⌬y max͒, because the two are not necessarily equal. The “effective cell capacity,” defined as the actual discharge capacity of the cell, is lower than the full cell capacity if the SOC cycling ranges are limited by running the cell into a corner of the operating window. Capacity loss ͑or gain͒ occurs only if there is a change in capacity from one discharge to the next. Figure 3 depicts three classes of capacity loss. The first, represented by cycle path a, is reversible capacity loss due to imbalanced side reactions ͑ isn − isp͒, which lead to a change in cyclable lithium. This class could also be called a “restricted cycling loss,” and is manifested in the SOC operating window as translation of the cycle path toward the upper right or lower left corner. This capacity loss is a change in the effective cell capacity, but not the full cell capacity. An example is the formation of a passivating film, called the solid electrolyte interphase ͑SEI͒, at the negative electrode, in which cyclable lithium is consumed, and the cycle path moves into the lower left corner of the SOC window ͑see Fig. 3, path a͒. The slope of the cycle path at the end of this process ͑provided that the side reaction ceases͒ is the same as the initial cycle path slope. Side reactions could also add cyclable lithium to the cell, moving the cycle path into the upper right corner and resulting in restricted cycling loss. Whether this type of capacity loss is truly reversible depends on the nature of the side reactions that cause it ͑are they reversible?͒ and how the cell is put together ͑are there lithium reservoirs that can replenish the cyclable lithium that is lost?͒. We call this capacity loss reversible in the sense that a hypothetical external lithium source ͑or sink͒ could be used to bring the cell back into balance, although we do not have the luxury of opening the cell in most practical applications. We stress that loss or addition of cyclable lithium need not result in capacity loss at all. Mismatched cells may shift position, within limits, without restricting the cycling range of the cell ͑see the section on excess positive electrode capacity under Capacity Balancing͒. The second type of reversible capacity loss ͑shown in Fig. 3 as arrow b͒ is reversible capacity loss due to balanced side reactions ͑ isn = − isp͒, which do not change the amount of cyclable lithium. This is manifested in the operating window as movement along the initial cycle path, in which useful energy is not obtained from the

cell ͑e.g., during self-discharge of the cell͒. This would be encountered when a redox couple in the system removes some lithium from the negative electrode and inserts a commensurate amount of lithium into the positive electrode as it is shuttled across the separator. This type of capacity loss is reversible in a classical sense; it is a temporary drop in the effective cell capacity and should be recovered on a subsequent discharge. If the cell is charged, then discharged immediately at a rate high enough to make the fraction of current due to side reactions insignificant, the full capacity should be realized. ͑A caveat to this statement is that, at high discharge rates, high cell impedance can limit the extent of discharge.1 Thus, we may not be able to observe the full capacity of the cell.͒ In terms of the variables defined previously, reversible capacity loss is purely restricted cycling loss when either isn or isp is nonzero, and the other is zero. From Eq. 12, it is clear that reversible capacity loss is entirely of the second variety if isn = − isp 0. In general, isn − isp, and both side-reaction currents are nonzero, in which case the cell may undergo a combination of both types of reversible capacity loss. Finally, our definition of irreversible capacity loss applies only to loss of active material, manifested as a change in the cycle path slope ͑see Fig. 3, path c͒. In this case, the full cell capacity is diminished only if the active material is lost from the limiting electrode. Active material loss has a number of possible causes, including dissolution, exfoliation, or particle isolation. This process can be shown more clearly on an extensive-capacity operating window. Let ˆ L ␧ ␳ x C− = FnLi,− = C − − − − and ˆ L ␧ ␳ y C+ = FnLi,+ = C + + + + ͓14͔ Then, for a perfectly balanced cell, ⌬C+ = ⌬C− and dC+ /dC− = −1. If active material is lost, the size of the window changes, but the slope of the cycle path does not change. In Fig. 4, we show an example of this, in which positive electrode material is lost ͑⌬C+ decreases͒. This effectively limits the negative electrode SOC range, while maintaining the positive electrode SOC range, and is equivalent to the cycle path change, from the optimum path to cycle path c, shown in Fig. 3. In summary, irreversible capacity loss results from a change in the size of the ͑extensive-capacity͒ box, while reversible capacity loss comes from a change in cell balance, so that cycling reaches the constraint ͑of y or x͒ on one electrode before the other, or from movement along the cycle path due to balanced side reactions. This can be compared and contrasted with the traditional view of reversible and irreversible capacity loss. If a charged battery is left on open circuit, it may lose capacity in the sense that a discharge, after ͓13͔

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Journal of The Electrochemical Society, 152 ͑4͒ A818-A829 ͑2005͒ stand, shows less capacity. If the battery is recharged, some of this capacity may be recovered. The capacity not recovered would be called irreversible capacity loss. Irreversible capacity loss ͑or simply “irreversible capacity”͒ has also been used extensively to mean the difference between the first charge capacity and first discharge capacity, often associated with SEI formation. Our definition of effective cell capacity rejects the use of the term irreversible capacity in this sense. Depending on how the cell is designed ͑i.e., whether it is purposefully mismatched͒, SEI formation may or may not result in capacity loss, and it does not result in irreversible capacity loss unless it actually isolates or destroys active electrode material. We prefer to classify SEI formation as consumption of cyclable lithium.
Table I. Typical cell parameters. Negative electrode Li ͑ ␮m͒ ␧i ␧E ␳i ͑ g/cm3͒ ␳E ͑ g/cm3͒ ␳b ͑ g/cm3͒ ˆ ͑ mAh/g͒ C
i

A821

Separator 25 0.4 1.3 1.8

Positive electrode 61.24 0.4 0.596 4.5 ͑ P = Mn2O4͒ 1.3 1.8 148 ͑ P = Mn2O4͒ 1.0 0.17 3 12.5 2.71

70 0.4 0.596 2 ͑ N = C 6͒ 1.3 1.8 372 ͑ N = C6͒ 0.65 0 5 12.5 8.95

xmax ͑or y max͒ xmin ͑or y min͒ ri ͑ ␮m͒ Lcc ͑ ␮m͒ ␳cc ͑ g/cm3͒ Other parameters ⌬xSEI rLi ͑ ␮m͒ ␳SEI ͑ g/cm3͒ ␳Li2CO3 ͑ g/cm3͒ ␳Li ͑ g/cm3͒ cLiX ͑ mol/L͒ MwLi ͑ g/mol͒ MwX ͑ g/mol͒

Capacity Balancing An optimum balance between negative and positive electrode capacities can be achieved after formation-cycle lithium loss by several means. We discuss here ͑i͒ the building of excess capacity in the positive electrode, ͑ii͒ the manufacture of positive electrodes with high lithium content ͑ y Ͼ 1͒, ͑iii͒ the use of pretreated carbon in the negative electrode, ͑iv͒ the inclusion of passivated lithium powder in the negative electrode, and ͑v͒ the use of a high salt concentration in the electrolyte. We compare the influence of each method on the cell’s specific energy and examine practical difficulties that may preclude the use of some methods in manufacturing commercial cells. Some clarification should be given about capacity balancing and the intended application. Because of transport limitations in carbonaceous materials, the concentration of lithium may be much higher at the particle surface than the average concentration in the particle. Thus, lithium tends to plate at the surface at a much lower average SOC in high-power applications than in low-power applications. To avoid this plating, which leads to further SEI formation and loss of cyclable lithium, one should actually design the cell with excess negative capacity. An alternative way of stating this is that xmax should be lowered as the peak power requirements are increased. From this perspective, all of the following discussion of “capacity balancing” is valid for both low-power and high-power cells. Excess positive electrode capacity.—Lithium-ion cells are typically manufactured with enough excess capacity in the positive electrode to compensate for the amount of lithium that is consumed in formation of the SEI on the graphitic negative electrode. The required increase in mass of positive electrode material, beyond that of a perfectly balanced cell, is proportional to the fraction of cyclable lithium that is consumed in SEI formation. This increase in loading, in units of mass per unit area, can be achieved by increasing either the thickness of the composite electrode or the volume fraction of active material. Thus, we have ⌬ ͑ L +␧ +͒ = ˆ L ␧ ␳ ⌬x C − − − − SEI ⌬y max ˆ ␳ C
+ +

0.065 0.5 2 2.1 0.534 1.0 6.941 144.9642 ͑ X = PF6͒

⌬m = ⌬L+͓␧E,+␳E + ␧+␳+ + ͑1 − ␧E,+ − ␧+͒␳b͔

͓16͔

where ␳E is the electrolyte density and ␳b is the volume-average density of any polymeric binder or conductive filler contained in the positive electrode. The specific energy of an electrochemical cell is directly proportional to the average cell voltage and inversely proportional to the mass of the cell. Thus, the decrease in specific energy of a properly “mismatched” cell below that of a “balanced” cell is m0 ˆ =E ˆ ⌬E 0 ⌬Vav − ⌬m Vav m0 + ⌬m

͓17͔

͓15͔

where ⌬xSEI is the amount of cyclable lithium consumed during SEI formation, expressed in terms of x. This amount depends on active material particle size, carbon type,4,5 chemical and thermal treatment,4,6 electrode porosity,7 and the choice of electrolyte,8 but is typically around 8-15% of ⌬xmax for graphitic negative electrodes.4-8 Because we can vary thickness and volume fraction independently, the required increase in cell mass is not uniquely determined by the predicted SEI-related cyclable lithium loss, but depends on how we add active material to the cell. We would select the value of these two parameters to optimize the cell for a particular application ͑e.g., electric vs. hybrid electric vehicles͒. Assuming that only the thickness is changed, the mass increase per unit separator area is given by

ˆ is the specific energy of an idealized balanced cell, with no where E 0 side reactions, m0 is its mass, Vav is the average voltage that the idealized cell supplies between its cycle limits, and ⌬Vav is the change in the average cell voltage between the mismatched and idealized cells. The average cell voltage can be roughly estimated from the difference in OCPs of the positive and negative electrodes. Comparison of Fig. 2a and b reveals that there is a slight difference in Vav between the two cells because the cycle limits of the positive electrode have changed. Table I contains parameters and properties of a typical lithiumion cell. From the preceding equations, we calculate that the cell’s mass must be increased by 15.8 g/m2 ͑3.50%͒ to account for film formation, and that the average cell voltage would increase by 29.5 mV ͑0.759%͒, resulting in a specific energy loss of 4.70 Wh/kg ͑2.65%͒. Although the mass of the positive electrode increases 10% in this case, the cell’s mass increase is much smaller due to the additional weight of the negative electrode, separator, and current collectors. Furthermore, even though the difference in average cell voltage is small, it can have a big impact on the specific capacity ˆ would be 28% change ͑i.e., if we neglected ⌬Vav in Eq. 17, ⌬E larger͒. The mass increase and specific energy decrease for each method discussed here are summarized in Table II. ⌬Vav is zero for each of the other methods because the ultimate cycle path is the same as that of the idealized balanced cell. We can quantitatively determine the path traced out in the SOC operating window for a mismatched cell that undergoes passivation

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A822

Journal of The Electrochemical Society, 152 ͑4͒ A818-A829 ͑2005͒

Table II. Changes in cell mass and specific energy. Idealized cell m0 = 474.8 g/m2 Vav0 = 3.86 V ˆ = 177.8 Wh/kg E 0 ⌬m ͑ g/m2͒ ͑%͒ ⌬Vav ͑ mV͒ ͑%͒ ˆ ͑ Wh/kg͒ ⌬E 0 ͑%͒ Method ͑i͒ 15.8 3.50 29.5 0.759 −4.70 −2.65 Method ͑ii͒ 0.351 0.0776 0 0 −0.138 −0.0775 Method ͑iii͒ 0.336 0.0743 0 0 −0.132 −0.0743 Method ͑iv͒ 0.355 0.0785 0 0 −0.139 −0.0784 Method ͑v͒ 7.67 1.70 0 0 −2.97 −1.67 No compensation 0 0 7.14 0.185 −17.5 −9.83

The methods of capacity balancing entail ͑i͒ excess capacity in the positive electrode, ͑ii͒ excess Li in the positive electrode, ͑iii͒ pretreated carbon in the negative electrode, ͑iv͒ passivated Li powder in the negative electrode, and ͑v͒ high salt concentration. Changes in specific energy are calculated by Eq. 17 for ˆ =E ˆ ͑ 0.9 Vav0+⌬Vav − 1͒. the five methods of capacity balancing. Change in specific energy when the cell is not compensated is given by ⌬E 0 0 Vav0

with the use of Eq. 1, 10, and 11. In this case we assume that isp = 0 and that the only side reactions at the negative electrode are those that contribute to SEI formation. Combining the equations, we have dy = − 1 i dx z i − isn ͓18͔

a−L−K exp − isn = −

ͩ

F ͑ ␾ e − ␾ f͒ RT

ͪ

1 LSEI + FDe F Fkcexp − ␣ c͑ ␾ f − ␾ s͒ RT

ͩ

ͪ

͓22͔

in which isn is a function of the negative electrode potential. This dependence can be garnered from cyclic voltammograms or discharge curves. The side reaction of interest is reduction of the solvent at the film-solution interface, which we assume to be the result of electron transfer through the film. To calculate the side reaction current density, we must examine charge transfer at the electrode-film and filmsolution interfaces, as well as the transport of electrons through the film. For the sake of this example, let us assume that charge transfer at the electrode-film interface is fast, so that the equilibrium electron concentration at that interface is ce,ef F = K exp − ͑ ␾ e − ␾ f͒ RT

where the dimensionless factor a−L− is the electrochemical surface area per unit separator area. We assume further that the potential drop across the electrode-film interface is independent of the electrode SOC, and is equal to the constant ⌽. If the main reaction is fast and the rate of the side reaction is small compared to the cathodic contribution to the main reaction, then we can assume that the film-solution potential drop roughly follows the OCP of the main reaction, minus the constant ⌽ ␾f − ␾s Ϸ U͑x͒ − ⌽ ͓23͔

ͩ

ͪ

͓19͔

where U͑ x͒ is an experimentally determined function of the SOC. Note that the constant, ⌽, in Eq. 23 can be absorbed into the equilibrium constant K and the cathodic rate constant kc in Eq. 22. For graphite ͑see Fig. 2 caption͒, we use U͑x͒ = 0.7222 + 0.13868x + 0.028952x1/2 − 0.017189x−1 + 0.001914x−3/2 + 0.28082 exp͓15͑0.06 − x͔͒ − 0.79844 exp͓0.44649͑x − 0.92͔͒ ͓24͔ The rate of change in film thickness is proportional to the side reaction current density dLSEI = ␥isn dt ͓25͔

where K is the ratio of anodic and cathodic rate constants, R is the gas constant, T is the temperature, ␾e is the potential of the electrode, ␾f is the potential of the film, and the subscript ef refers to the electrode-film interface. The current through the film is given as ifilm FDe =− ͑ce,ef − ce,fs͒ LSEI ͓20͔

where De is the diffusion coefficient of electrons in the film, LSEI is the film thickness, and the subscript fs refers to the film-solution interface. Note that the current density is inversely proportional to the film thickness, in accordance with previous SEI models.9-11 We have assumed here that the potential drop through the film, and therefore migration of electrons, is negligible. Finally, we assume that solvent reduction at the film-solution interface is irreversible and follows a Tafel dependence ifs = − Fkcce,fs ␣ cF exp − ͑ ␾ f − ␾ s͒ RT

where ␥ depends on the composition and density of the film. Combining Eq. 10 and 25, we have dLSEI = − ␥C−L−␧−␳− isn dx i − isn ͓26͔

ͩ

ͪ

͓21͔

Combining Eq. 22, 23, and 26, we have the first-order differential equation dLSEI =

where kc is the cathodic rate constant, ␣c is the cathodic transfer coefficient, and ␾s is the potential in the solution. The superficial side-reaction current density is equal to the electronic current density through the film and at each interface, corrected by a factor which relates the electrochemical surface area of the negative electrode to the superficial area of the cell. Thus, combining Eq. 19-21, we have

LSEI ␣ cF 1 + I exp U͑x͒ + RT ␤ where

ͫ ͩ

␥ C −L −␧ −␳ −

ͪ

ͬ

dx

͓27͔

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Journal of The Electrochemical Society, 152 ͑4͒ A818-A829 ͑2005͒

A823

Figure 5. Cycle paths for a mismatched cell with a cyclable lithiumconsuming side reaction at the negative electrode and an initial capacity ratio of 0.861. Intermediate curves a, b, and c are first-charge paths with dimensionless superficial current densities of −0.01, −0.025, and −0.07, respectively.

Figure 6. Cycle paths for an initially balanced cell ͑ z = 0.65/0.83͒ that goes out of balance and loses capacity due to a cyclable lithium-consuming side reaction at the negative electrode. Intermediate paths a, b, and c represent dimensionless superficial current densities of −0.01, −0.025, and −0.07, respectively. ⌬xL and ⌬y L represent the losses in negative electrode and positive electrode cycling range, respectively.

I=

F⌽ a−L−FKkc exp ͑␣c − 1͒ RT

ͩ

i

ͪ

͓28͔

is the dimensionless total current density, and we define the parameter ␤= De F⌽ exp − ␣c kc RT

ͩ

ͪ

͓29͔

Depending on the exact mechanism for film formation, one may end up with a result somewhat different from Eq. 27. These equations are readily solved on a spreadsheet by stepping through values of x. Figure 5 is a representation of passive-film formation in the SOC operating window, in which we have used the 1 values z = 1.1⌬xmax /⌬y max = 0.861, ␤ = 0.05 nm, ␣c = 2 , and ˆ ␥C−L−␧−␳− = −155 nm. We assume that the film stops growing once it has reached a thickness of 10 nm. This is an idealized scenario; cells may be cycled several times before growth tapers off, and some small degree of side reaction, possibly involving continuous film growth, can occur throughout the life of the cell. The three solid curves in the figure correspond to three different dimensionless current densities, −0.01, − 0.025, and −0.07. At a higher current density, the current efficiency ͑ =1 − isn /i͒ is higher, which is why the film does not reach a thickness of 10 nm until the negative electrode has attained a higher SOC. Regardless of the particular path taken, once the film has stopped growing, the cell cycles along the lower curve in Fig. 5. Notice that this curve has the same slope as the dashed curve, which would be traced out if there were no film formation. The slope is dictated by the invariant capacity ratio, z. The mismatched cell does not lose any capacity after film formation; it cycles between the same limits of x and with the same ⌬y as in a hypothetical cell that does not undergo passivation. In both cases, the negative electrode capacity is the limiting capacity of the cell, and this capacity has not been diminished in forming an SEI, even though some cyclable lithium has been consumed. One must be careful when using the term “irreversible capacity loss” in conjunction with SEI formation, because in this case, the utilized capacity of both positive and negative electrode, proportional to ⌬y and ⌬x, respectively, remains constant. Alternatively, if a cell were manufactured without excess positive electrode capacity, SEI formation would result in capacity loss, spe-

cifically restricted cycling loss, as shown in Fig. 6. In this case, the cycling ranges of both the positive and negative electrode are diminished as we run into a corner of the cycling window. Note that the cycling window losses, ⌬xL and ⌬y L, are not necessarily equal, but the capacity losses in the two electrodes are. Even in this case, the capacity loss cannot be termed “irreversible,” as it is conceivable that cyclable lithium can be added to either electrode from some lithium reservoir within the cell, as described in later subsections. This could negate a portion or all of the capacity loss exhibited in Fig. 6. Because of the cyclable lithium loss, the uncompensated cell has 10% less capacity than an idealized cell, and 9.83% less specific energy. The specific energy does not scale precisely with the cell capacity because there is a slight increase in the average cell voltage ͑7.14 mV͒. In Table II, we clearly see that any compensated cell design is far superior to the uncompensated cell design. Excess lithium in the positive electrode.—Rather than increase the entire positive electrode mass, it has been demonstrated that enough additional lithium can be inserted into the active material before cell assembly to account for the lithium consumed during SEI formation at the negative electrode.12 For instance, if it is believed that 10% of the cyclable lithium would otherwise be consumed, the positive electrode material could be fabricated with a stoichiometry of y = 1.083. The operating window and cycle path for this cell are shown in Fig. 7. The benefit of this technique is that much less mass must be added to the cell to achieve post-formation balance. The additional lithium mass is ⌬mLi = C−L−␧−␳−⌬xSEIMwLi F ͓30͔

where MwLi is the molar mass of lithium. From the parameters listed in Table I, the additional lithium mass is 0.351 g/m2 ͑0.0776%͒. Because only lithium is added, this is equal to the additional cell mass. Thus, according to Eq. 17 ͑with ⌬Vav = 0͒, the specific energy decrease is only 0.138 Wh/kg ͑0.0775%͒, or 2.93% of the decrease for the method involving excess positive electrode active material. One drawback of using this method is that some positive electrode materials undergo phase changes when additional lithium is inserted in the host matrix. For instance, LiyMn2O4 undergoes JahnTeller distortion when y increases above 1,2,13-15 although this dis-

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Figure 7. Cycle paths for a perfectly balanced cell that is fabricated with a 10% excess of cyclable lithium in the positive electrode and loses capacity due to a cyclable lithium-consuming side reaction at the negative electrode. Intermediate paths a, b, and c represent dimensionless superficial current densities of −0.01, −0.025, and −0.07, respectively.

Figure 8. Schematic of lithium transport in a porous negative electrode that contains passivated lithium powder. Lithium can ͑a͒ enter the negative electrode by ͑i͒ diffusing through the lithium-carbonate film into an adjacent graphite particle or ͑ii͒ dissolving into solution and intercalating into the graphite, with the negative electrode matrix providing an electronic pathway; or ͑b͒ enter the positive electrode by dissolving and migrating across the separator. The former may occur under any condition, including open circuit, and is driven by the difference in electrochemical potential between the lithium metal and LixC6. The latter can occur only during cell discharge, or if there is a corroding side reaction at each electrode.

tortion is diminished when the original starting material has y Ͼ 1.05.2,12,16 Strain between the surface tetragonal Li2Mn2O4 phase and bulk cubic LiMn2O4 phase can lead to particle fracture and loss of particle contact.15 Furthermore, some authors suggest that LiyMn2O4 may be more susceptible to manganese dissolution at low potentials when trace acid is present in the electrolyte.17-20 There is evidence that the dissolution also occurs when the cell is fully charged.21,22 Pretreated carbon.—Another means of avoiding cyclable lithium consumption in the cell is to preform the negative electrode, that is, form an SEI on the active material before assembling the cell. This results in a cell of slightly higher mass than a balanced cell that is not preformed. The additional mass depends on the density and thickness of the SEI and the electrochemical surface area of the negative electrode ⌬m = ␳SEIa−L−LSEI ͓31͔ where a− = 3␧− /r− is the electrochemical surface area per unit volume of the composite electrode and r− is the radius of active material particles. For the set of parameters we consider here, the mass increase is 0.336 g/m2 ͑0.0743%͒, and the decrease in specific energy is 0.132 Wh/kg ͑0.0743%͒. As there are no film-formation side reactions in the preformed cell, the operating window would be that of Fig. 1, with cycle path a. Although this appears to be an attractive solution to the loss of cyclable lithium, there are several practical considerations that preclude its widespread implementation. If the carbon particles were somehow preformed before a composite negative electrode was pressed, the electronically insulating SEI surrounding them would prevent the establishment of a conducting matrix. Therefore, one must first build a composite uncharged electrode, then charge it in a temporary cell, and finally remove the preformed electrode from this cell and use it as the negative electrode of a perfectly balanced commercial cell. This additional processing step could prove costly, and the increase in specific energy over the method of excess positive electrode capacity may not offset the additional cost. Lithium powder.—A fourth alternative was presented at a recent symposium in Berkeley. FMC Corporation has been able to produce a passivated lithium powder by exposing grains of lithium metal to a carbon dioxide atmosphere.3 The powder does not corrode in air and can be included during the fabrication of composite negative

electrodes. Figure 8 is a diagram of a portion of the composite electrode. Because the lithium particles are passivated, they are not in electrical contact with the active electrode material. However, There is a pathway for lithium transport through the Li2CO3 SEI. The excess lithium contained in the powder can thus become cyclable lithium if it diffuses into the graphitic host material ͓Fig. 8a ͑i͔͒. The additional mass requirement should be much less than that of the method of excess positive electrode capacity and is dependent upon the total surface area of the lithium particles and thickness of the Li2CO3 film surrounding them. The additional mass of the actual lithium is given by Eq. 30. The ratio of Li2CO3 mass to lithium mass is approximately mLi2CO3 mLi = 3␳Li2CO3LLi2CO3 ␳LirLi ͓32͔

where rLi is the radius of the lithium particles and LLi2CO3 is the thickness of the Li2CO3 film. Thus, the total additional mass is ⌬m = 3␳Li2CO3LLi2CO3 C−L−␧−␳−⌬xSEIMwLi 1+ F ␳LirLi

ͩ

ͪ

͓33͔

Given the parameters listed in Table I, the mass of the cell would increase by 0.355 g/m2 ͑0.0785%͒, and the specific energy would decrease by 0.139 Wh/kg ͑0.0784%͒. There are several mechanisms for transport of lithium to the negative or positive electrode material. Depending on the time constants and driving forces that are involved, one mechanism may dominate, or they could occur simultaneously. One such mechanism is diffusion of lithium from the powder, through the lithiumcarbonate coating, and into the graphitic host material. Presumably, the lithium diffuses more rapidly into the graphite when it is vacant. If this is the case, the transport could take place as soon as the composite electrode is manufactured, resulting in a preformed cell much like that examined in the method of pretreated carbon. The lithium powder method has an advantage over the method of pretreated carbon only if the additional step of manufacturing passivated lithium powder is more economical than the other means of preforming the negative electrode. The difference in specific energy between the two cells is small. Perhaps the diffusion process is slow enough that it does not proceed fully until the cell is already in use. In this case, we must modify Eq. 10 to account for diffusion

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Journal of The Electrochemical Society, 152 ͑4͒ A818-A829 ͑2005͒ dx + isn − NLiFa−L− dt

A825

i = − C −L −␧ −␳ −

͓34͔

Here, NLi is the flux, per unit electrochemical surface area, of lithium from the powder to the active material. It depends, among other things, on the area of contact between the powder and the active material. If the Li2CO3 coating has a high enough electrical conductivity that the lithium metal can be electrochemically oxidized, the lithium dissolves into solution. A shorted electrochemical cell can be set up between the lithium metal and graphite, in which electrons are carried through the conductive matrix, including lithium particles, graphite particles, and current collector ͓Fig. 8a ͑ii͔͒. This may occur during charge or discharge, or at open circuit. Alternatively, the dissolved lithium could migrate to the positive electrode during discharge ͑Fig. 8b͒. Then the addition of cyclable lithium to the system may occur during the first discharge, rather than before the first charge. The dissolved lithium could be intercalated into the positive electrode material, thereby rebalancing the cell’s capacity after SEI formation during the charge step. In this case, the negative electrode side reaction is dissolution of Li, and Eq. 18 becomes dy = − 1 i dx z i − iLi ͓35͔

where iLi is the current density due to lithium dissolution. Neglecting concentration gradients in the solution, the rate of dissolution should be relatively constant. Therefore, we get a straight line in the operating window during discharge, with a slope that differs from −1/z by i /͑ i − iLi͒. Once the lithium has completely dissolved, the slope returns to −1/z. If the proper amount of lithium powder has been added to the negative electrode, the optimum cycle path is reached, and the capacity of the cell is perfectly balanced. The cycle path traced out during cell operation in this case is depicted in Fig. 9a. Clearly, if we have too much lithium powder, the cycle path overshoots the optimal path and runs into the upper right corner of the operating window, as shown in Fig. 9b. This effectively limits the cycling range in both x and y , reducing the capacity of both electrodes equally. Thus, the cell can experience capacity loss even when cyclable lithium is added to the electrode material. This counterintuitive example underscores the confusion that can result if capacity is not defined carefully. This capacity loss is considered reversible, as there is the possible existence of a side reaction that consumes cyclable lithium. If one does exist, it is likely for the cycle path to again overshoot the optimal path and run into the lower left corner of the operating window. This sort of “capacity fade” is usually exhibited in lithiumion cells. Even if no such side reaction exists, we still refer to any process that limits capacity through a change in cyclable lithium as “reversible capacity loss.” High lithium-salt concentration.—We have already suggested that there is insufficient lithium in the electrolytic solution to replace the cyclable lithium that is lost during SEI formation.1 Depending on the cell design and type of SEI that is formed, there may be enough to balance the cell, but not without severely diminishing the conductivity of the electrolyte. A technique that may be tried is to increase the concentration of lithium salt in the solution by enough to compensate for the loss of cyclable lithium that occurs during formation. There are several immediate difficulties with this approach. First, increasing the salt concentration may decrease the conductivity in the short term. Lithium-salt concentrations between 1 and 2 M are typically chosen because they result in a conductivity maximum.23 Too high a concentration can increase the solution’s viscosity to a point where the conductivity is adversely affected. It would seem that if the lithium in solution is intercalated as cyclable lithium, this issue would be resolved. But for cyclable

Figure 9. Cycle path for a perfectly balanced cell, in which cyclable lithium lost during film formation is replaced by passivated lithium metal that dissolves during discharge. Plot ͑a͒ shows the cell returning to the optimal path when the correct amount of lithium powder is contained in the negative electrode, while ͑b͒ shows the cycle path running into the upper right corner when there is too much lithium powder. The dashed line in ͑b͒ is the optimum cycle path.

lithium to be created, a side reaction is required, as per Eq. 12. Oxidation of the solvent or some additive at the positive electrode would yield a cation that could replace the lithium removed from solution. This probably would not help decrease the solution’s viscosity, unless the new salt precipitated as a solid. Even then, it could affect transport by plugging pores or forming surface layers. Another possibility is that the anions themselves are oxidized or even intercalated irreversibly into a host material in one of the electrodes. A number of electrochemically active polymers can be oxidized with the concomitant insertion of anions,24 including poly͑3butyl thiophene͒ ͑P3BT͒, which has been used in lithium-ion cells for overcharge protection.25,26 Typical lithium-ion battery anions such as PF− 6 can be inserted into P3BT, which is oxidized at potentials above the normal operating potential of the positive electrode. Thus, additional cyclable lithium could be generated at the negative electrode while anions are inserted into P3BT in the positive electrode if the battery is overcharged. However, as anion insertion into the polymer is reversible, so is the addition of cyclable lithium at the negative electrode. In any case, the system becomes much more complicated when increasing the salt concentration is chosen as a strategy to balance the cell. The components must be chosen such that the desired side

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reactions occur, and if they do occur, there must be some mechanism for stopping them once the lithium salt falls to the desired concentration. One can imagine that tailoring the negative electrode SEI, an endeavor that has been the focus of intense research over the past several decades, would be a simpler task. Furthermore, it is unclear exactly how much extra mass must be added to the cell to achieve the appropriate side reactions. In the ideal case, only the additional salt must be added. For the salt Li␯+X␯−, the additional mass would be ⌬m = C−L−␧−␳−⌬xSEIMwLi ␯−MwX 1+ F ␯+MwLi

ͩ

ͪ

͓36͔

where ␯+ and ␯− are the numbers on cations and anions, respectively, into which the salt dissociates. Even this minimum value is large for 2 ˆ a heavy anion like PF− 6 , for which ⌬m is 7.67 g/m ͑1.70%͒ and ⌬E is −2.97 Wh/kg ͑ −1.67%͒. These values are smaller than, but of the same order of magnitude as, those calculated for the method of excess positive electrode capacity. A specific side reaction mechanism is required to determine the cycle path traced out in the operating window. Just imagining a few possible paths makes evident the challenge of ending up on the desired optimal path. Using lithium powder is much simpler because the side reaction ͑or diffusion process͒ can be allowed to continue until the reactant ͑Li͒ is completely consumed. In the method of high salt concentration, we do not want to consume all of the lithium salt. Loss of Active Material So far we have examined processes that involve changes in the amount of cyclable lithium, which can lead to cell imbalance and reversible capacity loss. We have already defined “irreversible capacity loss” as capacity loss associated with the loss of active electrode material. In terms of an electrode’s capacity, this loss of active material manifests itself as a reduction in active material volume fraction. The full capacity of each electrode can be obtained from Eq. 13 and 14 ˆ L ␧ ␳ ⌬x ⌬C− = C − − − − ˆ L ␧ ␳ ⌬y ⌬C+ = C + + + + ͓37͔ ͓38͔

Figure 10. Cycle path of a cell that loses positive electrode active material, but maintains its cyclable lithium, while it is stored in the discharged state. The dashed line is the optimum cycle path.

of balance, and the slope of the cycle path becomes steeper than the optimal slope. Upon cycling, the cell follows the cycle path in Fig. 11. In this case, there is no chance of going outside the operating window without further side reactions, which replace the cyclable lithium that has been lost, resulting in the cycle path drifting to the right. Notice that the value of ⌬x over which the negative electrode is cycled may be the same regardless of whether cyclable lithium is lost along with the active material. However, the actual limits of x are different, meaning the cell potential that is achieved may be somewhat different in the two cases. A variation on Reaction 39 which has been proposed for lithium dissolution is2,29 12LiMn2O4 → Li2MnO3 + 5Li2Mn4O9 + 3Mn2+ + 6e− ͓41͔ Li2MnO3 is electrochemically inert and Li2Mn4O9 has very limited capacity at the potential over which the positive electrode is cycled; therefore, cyclable lithium is effectively lost from the positive electrode in the dissolution process. However, because electrons are generated at the positive electrode, there must be a commensurate intercalation of lithium into the negative electrode. Because 12 lithi-

Thus, any decrease in the volume fraction of active material yields a proportional decrease in capacity. We can illustrate the effect this type of capacity loss has on the cycle path through a few examples. We first examine positive electrode material loss while the cell is held in the discharged state ͑i.e., y = 1͒. Two possible electrochemical reactions are 2LiP + A+ → Li2P + P+ + A
+ +

͓39͔

where A is a cation in solution that can be reduced ͑e.g., H ͒, and, for P = Mn2O4 4H+ + 2LiMn2O4 → 2Li+ + Mn2+ + 3␭-MnO2 + 2H2O ͓40͔ The latter is known as Hunter’s reaction, and it is a well-studied mechanism for manganese dissolution in the presence of trace acid.2,18,22,27,28 In Eq. 39, the amount of cyclable lithium in the positive electrode remains constant ͑assuming the lithiumcontaining product can still deintercalate lithium͒, but y increases above 1. The loss of active material results in an increase in the slope of the cycle path, according to Eq. 1. During charge, it would appear as though no capacity has been lost, but on the subsequent discharge, the capacity is limited by the maximum value of y in the operating window. One could conceivably discharge the cell above this value and recover the full capacity, but this may have a deleterious impact on the intercalation host ͑e.g., via Jahn-Teller distortion͒. The cycle path for this type of capacity loss is shown in Fig. 10. In Reaction 40, both the active material and cyclable lithium are consumed. The value of y does not change, but the cell still falls out

Figure 11. Cycle path of a cell that loses positive electrode active material, as well as cyclable lithium, while stored in the discharged state. The dashed line is the optimum cycle path.

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Journal of The Electrochemical Society, 152 ͑4͒ A818-A829 ͑2005͒

A827

Figure 12. Cycle path ͑represented by the solid line͒ of a cell that loses positive electrode active material via an electrochemical side reaction before the cell is charged, according to Reaction 41. The dashed line is the optimum cycle path; the dotted lines indicate the cycle paths of ͑a͒ a cell that loses positive electrode active material and cyclable lithium in the discharged state, ͑b͒ a cell in which the lithium-containing products in Reaction 41 are completely inert, and ͑c͒ a cell that loses the same amount of positive electrode active material in the charged state. These paths are chosen with a particular capacity ratio to serve as a frame of reference for the solid cycle path, which would shift to the left or the right depending on the ratio of LiMn2O4 that is lost to the electrons that are generated.

Figure 13. Cycle path followed due to manganese dissolution from the positive electrode and deposition at the negative electrode, according to Reactions 42 and 44. The process illustrated here occurs at open circuit, with y Ͼ y min. The dashed line is the optimum cycle path.

ums are consumed and only 6 electrons are generated in Reaction 41, roughly half of the cyclable lithium lost at the positive electrode is recovered at the negative electrode. The Mn2+ ions replace the Li+ that is intercalated from the electrolyte into the negative electrode. Overall this active material consumption leads to an increase in cycle path slope that limits that charge capacity of the negative electrode, accompanied by a shift in x that divides the loss into two nearly equal portions of the negative electrode capacity. Because a very small amount of Li in the Li2Mn4O9 product is still cyclable lithium, y actually increases slightly, and the cycle path is shifted so that it passes just to the right of the operating window’s center. This scenario is shown in Fig. 12. If we combine the preceding side reaction ͑Reaction 41͒ with the positive electrode main reaction ͑Reaction 8͒, we can eliminate the electrons to yield 6 LiyMn2O4 + 6Li+ → Li2MnO3 + 5Li2Mn4O9 + 3Mn2+ y + 6͑1 − 2 y ͒ Mn2O4 y ͓42͔

cyclable lithium is lost if y Ͼ y min, whereas if y = y min, the lithium that is lost is inert. The overall SOC of the positive electrode does not change during this process, whereas the SOC of the negative electrode decreases, driving the potential higher. Thus, the cycle path is shifted toward the left within the operating window to compensate for the loss in positive electrode active material, as shown in Fig. 13. Line a of Fig. 14 is the cycle path for a cell in which positive electrode active material is consumed when the cell is in the charged state. This could occur if oxidation of solvent at high potentials forms a film that electronically isolates active material or if dissolution proceeds in the charged cell. As with Reaction 39, no cyclable lithium is lost in this case, and although the slope of the cycle path increases, the cell could recover its full capacity if lithium were inserted into the positive electrode above y = 1. Electronic isolation may also occur in the negative electrode, especially in the charged state. In this case, both active material and cyclable lithium contained therein are made unavailable. The slope of the cycle path decreases from the optimal value, as shown in Fig.

At the negative electrode, manganese cations are reduced Mn2+ + 2e− → Mn ͓43͔ Combining this with the negative electrode main reaction ͑Reaction 6͒, we have 2 2 LixC6 + Mn2+ → 2Li+ + C6 + Mn x x ͓44͔

We can see that, at open circuit, Reactions 42 and 44 describe a self-discharge of the cell that involves the dissolution of active material in the positive electrode. Overall, there is one lithium atom lost ͑if we assume Li2MnO3 and Li2Mn4O9 to be inert͒ for each Mn2O4 unit that is consumed in Reaction 42. It is interesting that, although this set of equations describes a self-discharge process, it is necessary that some lithium be present in the positive electrode ͑i.e., the positive electrode cannot be fully charged͒. We can say that

Figure 14. Cycle paths for capacity loss due to electronic isolation of active material in ͑a͒ the positive electrode and ͑b͒ the negative electrode, while the cell is in the charged state. The cycle path directions are given as ͑i͒ first charge, ͑ii͒ first discharge, and ͑iii͒ second charge.

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14, line b. Because cyclable lithium is lost, there is no chance of overshooting the maximum value of x unless side reactions carry the cycle path upward ͑in the direction of positive y ͒. The danger in charging past the upper limit on x is that lithium metal can deposit at the electrode surface, leading to rapid reduction of the solvent and altering the character of the SEI. Loss of active material in an actual cell is probably even more complicated than in the examples discussed already. Active material may be lost as part of a side reaction that occurs during charge or discharge. Take, for instance, Reactions 41 and 43, in which side reactions decrease the amount of active material in the positive electrode. Let Rdis be the net rate of Reaction 41. In terms of Rdis, the rate of the side reaction is isp = 6FRdis ͓45͔

and the corresponding decrease in the volume fraction of active material is d␧+ Mw+ Rdis = − 12 dt L +␳ + d␧+ d␧+ dx Mw+ =−2 isp = dt dx dt FL+␳+ Combining this equation with Eq. 10, we have ␧+0 d␧+ = 2 I s␪ z0 dx ͓48͔ ͓46͔
Figure 15. Cycle path that is followed according to Eq. 52, with ␪ = 0.96 and Isp = 0.5. As indicated in the figure, we assume that the side reaction suddenly ceases, after which the cycle path obeys the relationship dy /dx =−1/z. The dashed line is the optimum cycle path.

where Mw+ is the molecular weight of the active material. Hence ͓47͔

where z0 is the initial capacity ratio, ␧+0 is the initial volume fraction of active material in the positive electrode, Is = isp /͑ i − isn͒, and ␪ ˆ /F. We could assume that i = − i ͑i.e., every Mn atom = Mw+C + sn sp that dissolves from the positive electrode is plated at the negative electrode͒, although this is not necessarily true, because some manganese cations can remain in solution. Equation 12 implies that cyclable lithium is not consumed when isn = − isp. However, Eq. 12 does not account for changes in active material mass, and a more rigorous derivation shows that ˆ L ␳ x d␧ ˆ L ␳ y d␧ dnLi isn + isp C C + − + + + − − − + = + dt dt dt F F F ͓49͔

tures, this might correspond to abruptly lowering the temperature of the cell. The elementary but important point brought forth by these examples is that a change in the amount of active material leads to a permanent change in the slope of the cycle path, whereas side reactions that do not consume active material change the slope only while they occur. If such a side reaction stops, the slope returns to that dictated by the capacity ratio of the cell. Side reactions that do consume active material create a combination of temporary and permanent slope changes. Conclusions Capacity loss occurs whenever the cycle path is moved further away from its optimum, either through changes in cyclable lithium or loss of active material. The former is termed “reversible,” because side reactions or appropriate lithium sources and sinks may help rebalance the cell. The capacity loss in this case manifests itself as the cycle path running into a corner of the SOC operating window, the lower left if cyclable lithium is consumed, and the upper right if cyclable lithium is generated. Loss of active material is termed “irreversible capacity loss”, although it is possible to maintain the initial capacity if the cell is cycled beyond its normal operating limits. This capacity loss manifests itself as a change in the slope of the cycle path. There are several techniques that may be used to replace cyclable lithium that is lost when forming the SEI during the first several cycles. Because the current collector’s mass is a significant portion of the overall cell mass, compensating for a 10% cyclable lithium loss increases the cell mass by at most a few percent. However, addition of lithium by increasing the active mass of the positive electrode or the concentration of electrolyte has a much greater impact on the mass and specific energy than the other methods discussed. Preforming the surface of the negative electrode, adding lithium powder, and increasing the initial lithium content in the positive electrode material all have a negligible influence ͑ca. 0.08% increase for a typical cell͒ on the cell mass. The main practical consideration in choosing among these latter methods is the cost of additional steps in the cell fabrication process. Acknowledgments The authors thank Venkat Srinivasan for helpful discussions regarding high-power applications and passivated lithium powder. This work was supported by the Assistant Secretary for Energy Ef-

To minimize the complexity of our example, let us assume that Is is constant. Then Eq. 48 can be integrated to yield ␪ ␧+ = ␧+0 1 + 2Is ͑x − x0͒ z0 1 + Is dy =− dx z 0 + 2 I s␪ ͑ x − x 0͒

ͫ

ͬ

͓50͔

Substituting this expression into Eq. 11, we have ͓51͔

where we have again made use of Eq. 10 to eliminate the time derivative. Integrating once more yields y = y0 − 1 + Is I s␪ ln 1 + 2 ͑x − x0͒ 2 I s␪ z0

ͫ

ͬ

͓52͔

Figure 15 shows the cycle path that is followed according to Eq. 52, with ␪ = 0.96 ͑using the molecular weight and upper-plateau specific capacity of Mn2O4͒ and Is = 1/3 ͑i.e., isp = − isn = i /2͒. As indicated in the figure, we assume that the side reaction suddenly ceases, after which the cycle path obeys the relationship 1 dy =− dx z ͓53͔

z being the new capacity ratio after Mn2O4 has stopped dissolving. The point at which the side reaction stops has been chosen arbitrarily. Because Mn2O4 dissolves more readily at higher tempera-

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Journal of The Electrochemical Society, 152 ͑4͒ A818-A829 ͑2005͒ ficiency and Renewable Energy, Office of FreedomCAR and Vehicle Technologies of the U.S. Department of Energy under contract no. DE-AC03-76SF00098.
The University of California at Berkeley assisted in meeting the publication costs of this article.
ct E ef fs i Li Li2CO3 max min mis S SEI X + −

A829

List of Symbols
a ce specific electrode area, cm2 /cm3 concentration of electrons in the SEI, mol/m3 concentration of salt in the electrolytic solution, mol/m3 separator area-specific capacity of electrode, mAh/cm2

cLiX C ˆ mass-specific capacity of active material, mAh/g C De diffusion coefficient for electrons in the SEI, m2 /s ˆ specific energy of cell, Wh/kg E ˆ E 0 F i ifilm isn isn0 isp I Is kc K L LSEI m m0 Mw nLi N NLi P r Rdis S t U V V0 Vav x y z z0 zopt Greek ␣c ␤ ␥ ␧ ␧+0 ␩ ␪ ␯ ␳ ⌽ ␾e ␾f ␾s Subscripts b polymeric binder/conductive filler property

charge transfer electrolyte property electrode-film interface film-solution interface species index lithium property lithium carbonate property maximum stoichiometry, dictated by electrode properties, or maximum stoichiometric range, dictated by electrode properties minimum stoichiometry, dictated by electrode properties stoichiometric range for mismatched cell separator property SEI property anion property positive electrode property negative electrode property

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specific energy of idealized balanced cell, Wh/kg Faraday’s constant, F = 96,487 C/mol superficial current density, A/cm2 electronic current density through the SEI, A/cm2 superficial current density of all side reactions at the negative electrode, A/cm2 exchange current density of a side reaction at the negative electrode, A/cm2 superficial current density of all side reactions at the positive electrode, A/cm2 dimensionless total current density dimensionless side-reaction current density cathodic rate constant, m/s equilibrium constant, mol/m3 electrode thickness, cm SEI thickness, nm cell mass, g/cm2 mass of idealized balanced cell, g/cm2 molar mass, g/mol amount of cyclable lithium in cell ͑or electrode͒, mol/cm2 negative electrode chemical formula flux of Li from powder to active material, mol/cm2-s positive electrode chemical formula particle radius, cm rate of positive electrode dissolution, mol/cm2-s electrolyte species time, s OCP, V potential, V equilibrium potential for SEI formation, V average cell potential, V stoichiometry of lithium in negative electrode stoichiometry of lithium in positive electrode negative-to-positive capacity ratio initial capacity ratio optimum capacity ratio

cathodic transfer coefficient of side reaction proportionality constant, nm proportionality constant, cm3 /C volume fraction initial volume fraction of active material in positive electrode surface overpotential, V dimensionless positive electrode capacity electrolyte dissociation number density of active electrode material, g/cm3 ␾ e − ␾ f, V potential of the electrode, V potential of the film, V potential of the solution, V

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