Journal of The Electrochemical
`Society
`
`Rechargeable LiNiO2 / Carbon Cells
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`To cite this article: J. R. Dahn et al 1991 J. Electrochem. Soc. 138 2207
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`, TECHNICAL PAPERS ELECTROCHEMICAL SCIENCE AND TECHNOLOGY Rechargeable LiNiO2/Carbon Cells J. R. Dahn Department of Physics, Simon Fraser University, Burnaby, British Columbia, Canada, V5A 1S6 U. von Sacken, M. W. Juzkow,* and H. Al-Janaby Moli Energy (19g0) Limited, Burnaby, British Columbia, Canada, V5C 4G2 ABSTRACT Rechargeable cells can be made using two different intercalation compounds, in which the chemical potential of the intercalant differs by several eV, for the electrodes. We discuss the factors that play a role in the selection of appropriate lithium intercalation compounds for such cells. For ease of cell assembly the cathode should be stable in air when it is fully intercalated, like LiNiO2. For the anode, the chemical potential of the intercalated Li should be close to that of Li metal, like it is in Li=Cs. We discuss the intercalation of Li in LiNiO2 and then in petroleum coke. Then, we show that LiNiO2/coke cells have high energy density, long cycle life, excellent high-temperature performance, low self-discharge rates, can be repeatedly discharged to zero volts without damage, and are easily fabricated. In our opinion this type of cell shows far more promise for widespread applications than traditional secondary Li cells using metallic Li anodes. Rechargeable Li batteries like Li/MnO2 (1) have several advantages over conventional secondary systems like NiCad or new technologies like Ni-metal hydride. Second- ary Li cells promise higher energy, higher voltage, and longer shelf life than competitive technologies (2). How- ever, secondary Li batteries also have numerous disadvan- tages which may preclude their widespread acceptance in the marketplace. Secondary Li batteries generally have a lower cycle life than NiCad cells. This results from the inability of at- taining 100% Li cycling efficiency. Even in commercial Li/ MoS2 cells (3) there is a three-to fourfold stoichiometric ex- cess of Li compared to that needed to fully intercalate the cathode. If the Li cycling efficiency is 99%, then 1% of the cycled Li is lost on each cycle. Therefore, to obtain 200 deep discharge cycles, at least a three-fold excess of Li is required. The excess Li in these cells can cause other problems if the cells are allowed to discharge to low voltages outside their normal operating range. Many intercalation cathodes decompose (e.g., to form Li2S or Li20) if allowed to react with excess lithium (4). The cells are then only poorly re- chargeable because of irreversible chemical and structural changes in the cathode. In addition, the reactions that occur at low voltage can often totally consume the Li anode, making charging difficult. The relatively~ poor cycling efficiency of the Li anode arises because it is not thermodynamically stable in typi- cal nonaqueous electrolytes. The surface of the Li is covered with a film of the reaction products between the Li and the electrolyte (5, 6). Every time the Li is stripped and plated, some new Li surface is exposed and hence passivated, consuming Li. Much effort has been expended to improve the cycling efficiency of the Li anode through changes to the electrolyte (7, 8) or through the application of uniaxial pressure to the Li surface (9, 10). Practical cells use both optimum electrolYtes and pressures of about 1.4 MPa on the Li electrode to achieve efficiencies of up to 99% (3): Special separators which can withstand high uni- axial pressures and which have a pore size smaller than the diameter of typical Li dendrites must be used in these cells. These separators, generally polypropylene or poly- ethylene microporous films, are relatively expensive and contribute significantly to the raw materials cost of a spiral * Electrochemical Society Active Member. wound secondary Li cell. As long as Li metal anodes are used, the uniaxial pressure requirement precludes the construction of flat or prismatic cells with thin-walled cases. Secondary Li cells with Li metal anodes require thin electrode technologies. Generally, the anode and cathode thicknesses are about 100 ~m. Thin electrodes are required because: (i) The thickness of the stripped and plated Li de- posit is proportional to the cathode thickness; electrode thicknesses are kept thin to minimize the risk of dendrite penetration of the separator during the plating of the Li. (ii) The conductivity of nonaqueous electrolytes are typi- cally two orders of magnitude less than the aqueous elec- trolytes used in NiCad cells. To obtain reasonable rate cap- ability, electrode separations and thicknesses must be roughly an order of magnitude less than in NiCad. The thin electrode technology, the excess Li, the need for assembly equipment to be located in dry rooms, and the relatively expensive separators all contribute to the relatively high cost of secondary Li cells compared to NiCad. Secondary Li cells typically use recharge currents which correspond to C/10 (10 h for full recharge) rates (3). This is because the risk of dendrite penetration of the separators increases as the recharge current is increased and because the Li cycling efficiency is improved when the current density used for plating the Li is substantially less than that used for stripping (1, 3). This represents a major disad- vantage for secondary Li cells since NiCad cells and Ni- metal hydride cells can be charged in one hour or less. The safety of AA size secondary Li cells with metallic Li anodes is presently less than satisfactory (11, 12). There have been reported incidents of fires involving equipment powered by secondary Li/MoS2 cells which led to a prod- uct recall (13, 14). There have even been similar recalls in- volving primary Li/MnO~ cells (15) suggesting that safety is a central issue which must be resolved to make this a via- ble technology. It is clear that although the use of metallic Li leads to higher energies, higher voltages, and longer shelf life than conventional cells, the many disadvantages of this tech- nology severely limit its application. Here we show that cells using two different Li intercalation compounds, in which the chemical potential of the intercalated Li differs by several eV, for the electrodes eliminate most Of the dis- advantages discussed above while retaining the essential advantages of secondary Li cells. There is, of course, a J. Electrochem. Soc., Vol. 138, No. 8, August 1991 (cid:14)9 The Electrochemical Society, Inc. 2207
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`2208 J. Electrochem. Soc., Vol. 138, No. 8, August 1991 (cid:14)9 The Electrochemical Society, Inc. small penalty to be paid in cell voltage and in cell energy. Cells of this design are often called "rocking chair cells" (16) because the Li shuttles or "rocks" between the elec- trodes as the cell is charged or discharged. At least one Japanese company announced its plans to commercialize this technology (17). First we discuss the selection of appropriate materials for the electrodes of "rocking chair" cells and show that LiNiO~ and petroleum coke are good candidates for the cathode and anode, respectively. Next, we review the elec- trochemical intercalation of Li in these two materials. Then we describe the construction of 1225 coin cells using LiNiO2 and petroleum coke as electrode materials. The re- sults of cycle testing these cells under a variety of condi- tions demonstrate that most of the disadvantages associ- ated with secondary Li cells are eliminated. Finally, we summarize our work and comment on the key problems remaining in the further development of rocking chair cells. Electrode Materials for "Rocking Chair Cells" The voltage, V, of an electrochemical cell based on the intercalation of Li into a host electrode, relative to Li metal, is V = -~/e [1] where ~ is the chemical potential of the Li intercalated in the host and e is the magnitude of the electron charge (18). Normally, the voltage varies with the composition of the intercalation compound. Figure 1 shows the chemical po- tential ranges of intercalated Li in a variety of compounds. Clearly it is possible to find materials where the chemical potential differs by several eV. In a practical rocking chair cell it is necessary to ensure that one of the electrodes is loaded with lithium prior to cell assembly. Most powdered intercalation compounds are pyrophoric when loaded with Li. However, the Li will not deintercalate to react with air or moisture if it is suffi- ciently tightly bound in the intercalation compound. When the chemical potential is less than about -3.5 eV, lithium intercalation compounds are generally observed by x-ray diffraction to be air stable. Fortunately, there are several well-known Li insertion compounds which have < -3.5 eV even when the material is loaded with sub- stantial Li. Of these, Lil_yNiO2 (0 < y < 0.8) (19, 20), Lil_~CoO2 (0 < y < 0.8) (21), and Lil_~Mn~O4 (0 < y < 1) (22) are currently the most studied. Li~_yNiO2 was selected for the cathode in our studies be- cause it has a lower voltage vs. Li than either Li~_~CoO2 or Li~_yMn204. At sufficiently high voltages (generally greater 4.2 3.8 o > 3.4 ~9 ~D O 3.0 2.6 0 0.1 0.2 0.3 0.4 0.5 0.6 y in IA(l_y)Ni0 2 Fig. 2. Voltage of Li/Lil_vNiOz cells vs. y for the first charge and dis- charge of the cell. The current was chosen so that a change hy = 1 oc- curred in 40 h. than 4.0 V) the oxidation of the nonaqueous electrolytes used in secondary Li cells can occur (23). This electrolyte oxidation is to be avoided if long cycle life cells are to be made. The voltage-composition profile for Li/Lil_~NiO2 cells is shown in Fig. 2. The cells cycle reversibly for hy = 0.5 below 4.0 V. The anode should be selected from those materials which have chemical potentials close to that of lithium metal. Of these, carbons like graphite and petroleum coke are especially well suited (24, 25). Graphite and petroleum coke can intercalate Li to composition limits of LiC6 (cor- responding to 0.37 Ah/g) and Li0.sC~, respectively (25). The voltage-composition profile for Li/petroleum coke cells is shown in Fig. 3. Li/graphite cells have a much "flatter" voltage-composition profile, which varies from about 0.25 V near x = 0 to about 0.70 V near x = 1 in LixC6 (25). For reasons discussed below, we chose petroleum coke over graphite for our electrodes even though graphite gives twice the specific capacity. In earlier studies of Li/graphite and Li/coke cells (24) we showed that during the first electrochemical intercalation of Li into carbon, some Li is irreversibly consumed. The I A S I T R A B L E o eV -I eV -2 eV -3 eV -4 eV -5 eV LI metal LlxGraphite LixCoke LixWO 2 I LIxMoO L1T15 L1MOS2 I L1 MnO (0<x<l.0) x 2 I '11_72 Li 1 _~o0 2 Fig. 1. Showing the chemical potential ranges of intercalated Li in a variety of compounds. Chemical potentials are measured relative to Li metal. 0 o 1.6' 1.4 1.2: 1.01 0.8 0.4, 0.21 0 0 Discharge 0.1 0.2 0.3 0.4 0.5 x in LixC 6 Fig. 3. Voltage of Li/LixC6 cells vs. x for the second discharge and charge of the cell. The carbon in the positive electrode is petroleum coke. The current was chosen so that a change Ax = 1 occurred in 8O h.
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`J. Electrochem. Soc., Vol. 138, No. 8, August 1991 (cid:14)9 The Electrochemical Society, Inc. 2209 amount of Li consumed was shown to be proportional to the surface area of coke electrodes, suggesting that a passi- vating film of constant thickness was being formed. In the case of graphite electrodes, there was additional irrever- sible consumption of Li. This was thought to be associated with electrolyte reduction occurring on fresh surfaces of graphite exposed during partial exfoliation of graphite caused by the cointercalation of electrolyte solvent. Since the amount of Li in a rocking chair celt is entirely supplied by that initially loaded into the cathode, it is very impor- tant to minimize any possible loss of Li to film forming or other irreversible reactions. Therefore, we decided to use low surface area petroleum coke electrodes in our first cells. Experimental LiNiO2 was prepared as outlined in Ref. (20). The mate- rial used in the 1225 coin cells had an actual stoichiometry of Li0.96NiL0402. Top premium petroleum needle coke des- ignated XP was obtained from Conoco, Incorporated (Houston, Texas) in the form of lumps about 1 cm 3. This material is about 99.5 weight percent (w/o) carbon with sul- fur (0.3 w/o) as the major impurity. The spacing between carbon planes, d(002) = 3.46 A is typical for needle cokes. The petroleum coke was ground and then sized using standard sieves. The coke used to fabricate electrodes was -200/+400 mesh (i.e., 75 ~m > particle diameter > 38 ~m). Stainless steel 1225 coin cell hardware (12 mm outside diameter and 2.5 mm thickness) obtained from Rayovac Corporation (Madison, WI) was used. A polypropylene gas- ket is used to make the seal. Leak tests of coin cells filled only with dimethyoxyethane (DME) (about 70 mg) showed no measureable weight loss (<0.1 mg) after 1 week at 55~ in a vacuum oven, proving that the leak rates at these tem- peratures are negligible. Disk-shaped tablet electrodes were prepared from a mixture of the active powders with binder and carbon black followed by pressing. A laboratory scale rotary tablet press (Stokes 511) was used to press tablets with uni- form thickness and mass. The tablet thickness and mass were adjusted so that: (i) The thickness of the tablets plus separator was equal to the inside height to the cell. Each tablet was approximately 1.0 mm thick. (ii) The masses are adjusted so that at the completion of the first charge of the cell the cathode stoichiometry is Li0.sNiO2 while the anode stoichiometry is simultaneously Li0.sC6. The calculation ac- counts for that Li irreversibly consumed by the carbon anode. Typical active masses for the LiNiO~ and petroleum coke electrodes were 93 and 61 mg, respectively. LiN(CF3SO2)2 was obtained from 3M Corporation (Min- neapolis, MN) and was dried under vacuum at 140~ before use. Typical electrolytes used in these cells were 1M solu- tions of this salt in a 50:50 mixture of propylene carbonate (PC) and DME or in a 50:50 mixture of ethylene carbonate and DME. We observed no difference in performance be- tween cells using PC or EC as a cosolvent. PC and EC (Texaco) were purified by vacuum distillation. DME from Aldrich was used as received or was repurified from Li benzophenone ketyl solutions. Electrolytes were not used if the moisture content determined by Karl-Fisher titration exceeded 100 ppm. Celanese No. 2502 microporous films were used as sepa- rators in most cells. In some cells we used nonwoven poly- propylene separators and observed similar results. All cells reported here were assembled in a dry room with RH < 0.5%. Cells were charged and discharged using com- puter-controlled battery cyclers capable of constant cur- rent cycling between fixed voltage limits, constant capac- ity cycling, or discharge through a fixed load followed by a charging to a voltage cutoff. These chargers were designed and built at Moll Energy (1990) Limited. Results and Discussion Figure 4 shows the first cycles of a LiNiO~/coke 1225 coin cell. During the first charge, Li is deintercalated from Lil-~NiO2 and is intercalated into LixC6. The capacity of the first charge is about 18% larger than that of the subsequent cycles. The Li which has been consumed is thought to be now incorporated into the passivation film on the surface v 3, r~ o LiNiOz/COKE 1225 CELL 0.5 mA at 21~ 0 | i o z'o 4'o 6'o 80 TIME (HOURS) Fig. 4. First cycles of a LiNiOz/coke 1225 coin cell at 21 ~ The cell is charging and discharging between 3.9 and 0.7 V using a constant current of 0.5 mA. of the intercalated coke (24) and is hence unavailable for the next discharge of the cell. The cell capacity on the sec- ond cycle is about 10 mAh when the cell is charged to 4.0 V. Figure 5 shows the capacity vs. cycle number for a cell at room temperature. On the scale of Fig. 5 the charge and discharge capacities are indistinguishable after the first cycle. Apart from a small amount of early capacity fade, these cells exhibit good reversibility. Since there is no excess Li in these cells, each Li atom lost to an irrevers- ible reaction will be unavailable for cycling and capacity loss will result. The data in Fig. 5 prove that the interca- lation of Li in Lil_~NiO2 and in Li=C~ is nearly 100% revers- ible. Once the capacity loss associated with the first charg- ing of the cell has been eliminated, very little further loss is seen. At the time of this writing cells have been tested con- tinuously for 11 months and show no sign of impending failure as evidenced by increases in charge or discharge overvoltages or by capacity loss. These rocking chair cells have no excess Li in the anode or cathode, so they should be tolerant to repeated dis- charges to zero volts. At zero volts, all the available Li has been removed from Li=C6 and inserted into Lil_yNiO2. Fig- ure 6 shows the voltage vs. time for cycles 10 and 11 and for 0.010 /--,0.008 J~ I ~'~0.006 E~ ~ 0.004 ~9 0.002 0.000 1.0mA DISCHARGE 0.7V TO 3.7V 21"C 0.SmA CHARGE Fig. 5. Capacity vs. cycle number for LiNiO2/coke 1225 coin cells cy- cled at 21~ using constant current (0.5 mA). The voltage limits are in- dicated in the figure. o ,do ~do 860 4oo CYCLE NUMBER
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`2210 J. Electrochem. Soc., Vol. 138, No. 8, August 1991 (cid:14)9 The Electrochemical Society, Inc. 3 v 0 <2 1 1 2o 4'o TIME (HOURS) / 0.012 ,~ 0.010 ~ 0.008 ~ 0.006 ~ 0.004 0.002 o.0oo LINiOs/COKE 1~5 cells 1.0 mA at 55"C solid - 3.7V to 0.7V small dash - 3.85V to 0.TV large dash - 4.0V to 0.7V 6b o do ' CYCLE NUMBER Fig. 6. Voltage vs. time for a LiNiO2/coke 1225 coin cell discharged through a 3 kD. load and then charged to 3.8 V. The 10th, 1 lth (solid), and 110th, and 11 lth (dashed) cycles are shown. The cell was at 21~ 100 Fig. 8. Capacity vs. cycle number for LiNiO2/coke 1225 coin cells cy- cled at 55~ The cycling current was 1.0 mA. The voltage limits are given in the figure. cycle 110 and 111 of a cell discharged through a 3 kft resis- tor and then charged to 3.8 V. The charge is initiated 10 h after the cell voltage drops below 0.1 V. Thus, the cell spends 10 h near zero volts on every cycle. Figure 7 shows the capacity fade for the cell of Fig. 6 and for an identical cell discharging through a 1 kt) resistor. Both of these cells have cycled to zero volts hundreds of times without signif- icant capacity loss. Again, at the time of writing these cells have been tested for 11 months with no signs of impending failure. Figure 8 shows capacity vs. cycle number for 3 LiNiO~/ coke cells cycling at 55~ using a current of 1 mA for both charge and discharge. The rate of capacity loss increases when the upper voltage limit is raised, presumably be- cause the electrolyte oxidation rate increases at the higher voltages. Nevertheless, the cell charged to 3.7 V shows ex- cellent cycling behavior even at 55~ At the time of this writing, the cell charging to 3.7 V has reached over 300 cy- cles and shows no signs of impending failure. 0.010 /-~0.008 ~C I < "~-JO.O06 ~ 0004 O~ < <.) 0.002 0,000 " 16o 260 CYCLE NUMBER 300 Fig. 7. Capacity vs. cycle number for LiNiO2/coke 1225 coin cells discharged through 1 and 3 k~ resistors. The lower capacity data are for the 3 k~ load. The cell voltage remains below 0.1 V for 10 h before each recharge (see text). LiNiOJcoke cells were discharged to a fixed capacity at 85~ and then recharged to 3.7 V. Figure 9 shows the volt- age reached at the end of each constant capacity discharge plotted vs. cycle number for cells discharged to 1, 2, 4, and 6 mAh. The tests were stopped when the cell voltage reached 2.0 V. Over 1000 cycles were obtained for the 1 mAh discharge (10% DOD). These cells were weighed be- fore and after testing and a small weight loss, corre- sponding to about 15% of the weight of the DME, was ob- served. The boiling point of DME is 85~ and the permeability of the polypropylene seal increases with temperature. Therefore it is likely that cell leakage contrib- uted to the failure of the cells cycled at 85~ The data in Fig. 9 proves the suitability of this chemistry for high-tem- perature applications. The cells also show excellent storage properties. Fig- ure 10 shows the capacity vs. cycle number for a cell charged to 3.9 V and stored for 30 days at room tempera- ture after every ten cycles. After storage, the cells were dis- charged first. The first discharge after the storage period does not show appreciable capacity loss. The cells were cy- ~4.0 L 3.s ~z.5 4 =~ z ~ ~ z.o ~ ~.5 ~ 1.O rj r.~ o.5 0.0 o 'zdo '460 '860 '860 ',obo',2oo CYCLE NUMBER Fig. 9. End of discharge voltage vs. cycle number for constant capac- it}, discharges (1.0 mA) at 85~ The LiNiO2/cake cells were charged to 3.7 V at 1.0 mA following each discharge. Four cells were tested using discharge capacities of 1, 2, 4, and 6 mAh.
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`J. Electrochem. Soc., Vol. 138, No. 8, August 1991 (cid:14)9 The Electrochemical Society, Inc. 2211 0.012 0.010 I 0.008 ,.~0.006 ~o.oo4 0.002 0.000 o i o u [ I ~iaw I I I ooo~ Discharge ++++§ Recharge l'0 2'0 3'0 4'0 Cycle Number 50 Fig. 10. Capacity vs. cycle number for LiNiO2/coke 1225 coin cells with 30 day storage periods after every 10 cycles. The storage periods occurred after each vertical bar in the graph. The cycling currents are indicated in the figure. The cells were cycled between 3.9 and 2.5 V. cled using 1 mA currents for the first five cycles and 0.5 mA currents for the other five cycles of all but the first cycling period. The capacity loss shown by these cells is low even though they have been repeatedly stored and cy- cled. Other cells were charged to 3.9 V and then left open circuit. Their voltage was monitored daily. Within a few days the rate of cell voltage loss (-dV/dt) was less than 1 mV/day. After 100 days storage we found -dV/dt < 0.5 mV/day. Since the cell voltage varies by more than 1 V over the useful capacity of the cell, this corresponds to a shelf life of order 2000 days. Conclusions We have shown that LiNiO2/coke cells have long cycle life, excellent high-temperature performance, low self- discharge rate, can be repeatedly discharged to zero volts without harm, and can be made with electrodes at least 1 mm thick. It is our opinion that this technology is well suited for consumer applications in coin, prismatic, spiral- wound cylindrical, and small diameter (e.g., AAA) bobbin- type cells. We are presently studying the reactivity of Li interca- lated carbon with nonaqueous battery electrolytes using an accelerating rate calorimeter. These are similar to our studies of Li metal which were recently described (12). These preliminary results suggest that the safety of rock- ing chair cells will be greatly improved over secondary cells using Li metal. In addition, the absence of dendritic Li and excess Li in the LiNiOJcoke cells will also contrib- ute to increased cell safety. More work is required to further increase the capacity and energy of rocking chair cells. New materials with higher specific capacities for both the anode and cathode are needed. The approach discussed in Fig. 1 associated with the selection of electrodes for rocking chair cells should be extended to sodium intercalation compounds. Sodium is more abundant than Li and it is possible that the reactivity of sodium compounds with nonaqueous electrolytes could be significantly different than that of Li so that fundamentally safer cells might be obtained. Fi- nally, the rocking chair approach should be coupled to cells with polymer electrolytes as this again may lead to safer cells. It is our opinion that rocking chair cells show far more promise than traditional secondary cells using metallic Li. Acknowledgments We thank Sid Megahed of Rayovac Corporation for sup- plying the 1225 coin cell hardware. Manuscript submitted Nov. 19, 1990; revised manuscript received Feb. 21, 1991. This was Paper 42 presented at the Seattle, WA, Meeting of the Society, Oct. 14-19, 1990. Moli Energy (1990) Limited assisted in meeting the publi- cation costs of this article. REFERENCES 1. M. W. Juzkow, Paper 48 presented at The Electro- chemical Society Meeting, Seattle, WA, Oct. 14-19, 1990. 2. For example see the articles in "Proceedings of the 4th International Meeting on Lithium Batteries," Van- couver, B.C. (1988), R. R. Haering, Editor; also pub- lished as J. Power Sources, 26 (1989). 3. F. C. Laman and K. Brandt, J. Power Sources, 24, 195 (1988). 4. L. S. Selwyn, W. R. McKinnon, U. Von Sacken, and C. A. Jones, Solid State Ionics, 22, 337 (1987). 5. E. Peled, This Journal, 126, 2047 (1979). 6. D. Aurbach, M.L. Daroux, P. W, Faguy, and E.B. Yeager, This Journal, 134, 1611 (1987). 7. S. Tobishima, M. Arakawa, and J. Yamaki, Electro- chim. Acta, 35, 383 (1990). 8. Y. Matsuda, J. Power Sources, 20, 19 (1987). 9. D. Wainwright and R. Shimizu, ibid., To be published. 10. D. P. Wilkinson, in "Proceedings of 5th International Meeting on Lithium Batteries," May 1990, Beijing, China, In press. 11. D. P. Wilkinson, J. R. Dahn, U. Von Sacken, and D. T. Fouchard, Paper 53 presented at The Electrochemi- cal Society Meeting, Seattle, WA, Oct. 14-19, 1990. 12. U. Von Sacken and J. R. Dahn, Paper 54, ibid. 13. For example, see "Cellular Phone Recall May Cause Setback for Moli," Toronto Globe and Mail, August 15, 1989 (Toronto, Canada). 14. For example, see Adv. Bart. Technol., 25, No. 10, 4 (1989). 15. For example, "Duracell Product Recall," The Times (London, England) Friday, July 7, 1989, and Adv. Bart. Technol., 25, No. 9, 5 (1989). 16. J. J. Auborn and Y. L. Barberio, This Journal, 134, 638 (1987). 17. T. Nagaura, "A Lithium Ion Rechargeable Battery," presented at the 4th International Rechargeable Bat- tery Seminar in Deerfield Beach, FL (March, 1990). 18. W. R. Mckinnon and R. R. Haering, in "Modern Aspects of Electrochemistry," No. 15, R. E. White, J. O'M. Bockris, and B. E. Conway, Editors, p. 235, Plenum, New York (1983). 19. M. G. S. R. Thomas, W. I. F. David, J. B. Goodenough, and P. Groves, Mat. Res. Bull., 20, 1137 (1985). 20. J. R. Dahn, U. Von Sacken, and C. A. Michal, Solid State Ionics, To be published. 21. E. Plicta, M. Salomon, S. Slane, M. Uchiyama, D. Chua, W. B. Ebner, and H. W. Lin, J. Power Sources, 21, 25 (1987). 22. T. Ohzuku, M. Kitagawa, and T. Hirai, This Journal, 137, 769 (1990). 23. S. A. Campbell, C. Bowes, and R. S. McMillan, J. Elec- troanal. Chem., 284, 195 (1990). 24. Rosamaria Fong, U. von Sacken and J. R. Dahn, This Journal, 137, 2009 (1990). 25. J. R. Dahn, Rosamaria Fong, and M. J. Spoon, Phys. Rev. B, 42, 6424 (1990).
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