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Batteries/Lithium- air Page 071204
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From the 42nd Power Sources Conference...
Lithium Primary Continues to Evolve
by Donald Georgi
The common denominator for military primary batteries has to be the BA 5590, a rectangular box with groups of cylindrical cells which can be connected as a 15 or 30 Volt battery. It has been in production for over 20 years and is used in at least 50 different military devices, the most popular being the ANC PRC 119 SINCGARS (Single Channel Ground and Radio Systems)
 The BA 5590/ 5390/2590 Battery is the workhorse of military batteries. The latest Li-SO2 battery has increased energy density from 200 Wh/kg to 250 Wh/kg, beating even the BA5390 (Li-MnO2) which produces 214 Wh/kg.
During the period of 1999-2003, Saft alone produced 1,000,000 BA 5590s. (Photo from www.army-technology.com.) +
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During its history, millions of BA 5590s have been built and many improvements have resulted in great advances in capacity. First built with Lithium-sulfur dioxide chemistry, a later addition, designated the BA 5390, was constructed with Lithium-manganese dioxide chemistry. The sulfur cell has better low temperature performance to -400 C, whereas nominal manganese cells perform to -200 C, but the manganese cells have higher nominal energy density of 535 Wh/l compared to the sulfur cells with only nominal 415 Wh/l.+
(Without fanfare, let it be said that there is also a rechargeable BA 2590 using Lithium-ion chemistry which has been improving to the point that total performance allows replacement in some combat applications. Rechargebility allows top-off before a mission and eliminates primary pack dispositon. This rechargeable may provide even more energy to future field packs.)
High Capacity Li/Mno2 Primary D-cell... (session 4.4) As an example of the significant improvement in Lithium-manganese dioxide D-cells, Ultralife Batteries, Inc. presented the positive results of the improved cell which provides over twice the performance of the current cell at -400 C. An overall 27% capacity increase is also reported. When compared to the Lithium-sulfur dioxide D-cell, the Lithium-manganese dioxide cell produces about 50% more capacity.
In formulating the cathode material, SEM micrographs show much larger manganese dioxide particle size in the improved cell. The cells have completed safety and performance testing and are ready for integration into existing military battery designs.
High Capacity Li/MnO2... (Session 4.2) In the continual quest for greater power and energy density for the military, primaries have added the Lithium-manganese dioxide chemistry and Lithium-sulfur dioxide performance has been improved. An alternate path for the energy improvement is to look at the total package which has cylindrical cells stuffed in a rectangular box. Air gaps are left between the cells which, if filled, could result in greater volumetric energy density.
In pursuing the space utilization, Ultralife Batteries, Inc. has built a BA-7847 Lithium-manganese dioxide cell with rectangular pouch cell configuration, maximizing the space utilization in a rectangular housing. It has energy density of 400 Wh/kg, providing 70% more energy than the same battery constructed with D-cell Lithium-manganese dioxide, and 150% more energy than the same package constructed with Lithium-sulfur dioxide D-cells. The presentation focused on the successful electrical and transportation safety testing, but it did not address pouch swelling.
Lithium Fluorinated Carbons System... (Session 4.1) Despite the continual increase in performance of current BA-X590 batteries, there is a possibility for further energy density improvements with Lithium-fluorinated carbon (LI/CFx) chemistry. The presentation compared the volumetric and gravimetric energy densities of the Spectrum Brands, Inc’s. (previously known as Ray O Vac) D-size Lithium-Fluorinated carbon battery to operational sulfur and manganese based batteries. At 1 Amp to a 2 Volt cutoff, the fluorinated carbon improved the volumetric performance by 54% and the gravimetric performance by 103%.
The energy density improvement would suggest a change to the fluorinated carbon chemistry, but one major problem remains. The fluorinated carbon chemistry displays a Voltage delay at the beginning of operation. At activation at -200 C, the Voltage immediately drops from a nominal 2.5 Volts to 1.6 Volts and then exponentially rises. In the first 500 seconds, the terminal Voltage is only back to 2 Volts. According to the MIL spec, it should recover to 1.9 Volts in 60 seconds, leaving the fluorinated carbon performance in need of improvement.
Li(CF)n Battery for Low Temperature and High Power... (Session 4.5) Continuing with development in Lithium-carbon monofluoride (also Lithium-fluorinated carbon) is work presented by Quallion LLC. The reason for continuing to pursue the chemistry centers on its high capacity and excellent performance at high temperatures. Although well-known and utilized in some military batteries, Lithium-carbon monofluoride batteries have undesirable characteristics which include low power performance and poor low temperature performance. This work targeted the power problem with a configuration change of the active materials on electrodes from pellets to thin film layers. The impedance of the thin film was reduced to 0.0002 Ohms/mm2 from 0.5 Ohms/mm2 for the pelletized construction.
To address the poor low temperature performance, Quallion changed to a low viscosity electrolyte and a 25 micron microporous separator film.
Test data showed that the cell capacity doubled and performance at - 300 C improved approximately eight fold. The data suggests that the Voltage depression was also markedly improved with the addition of LiV3O8. Data on power density was not included.
BD
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Lithium-Air...the ‘Ultimate’ Battery?
by Donald Georgi
Life’s quest for the technological holy grail takes on many different aspects. To fly... to eliminate polio...to go to the moon, some of these pursuits have been achieved. But people are never satisfied and the quest continues. Battery people, utilizing technology, have their moments to hope, dream and pursue greater energy densities. Having been brought up in the era of nuclear energy, the technologist envisions the day when a battery the size of a pack of chewing gum will power a computer for years. While batteries do make modest gains in energy stored, technologies such as cell phones expand to capture the dollar of the consumer by adding features which require greater power, but result in devices with micro-sized, dim displays to match almost unuseable, tiny keyboards.
Thinking beyond the device of today, some see an ‘always-connected’ person who has the combination of computer, cell phone, PDA and entertainment center in a single device ready to make the business deal, cure the illness and make the next hotel reservation while living in a virtual reality of a galaxy far, far away. Forgetting the electronic challenges of this magic module, the energy storage device necessary to provide this power, with small package size to satisfy the user, lies within this holy grail.
As we are jolted back into the real world bounded by physical laws which encompass electrochemistry, battery people have to ask, “Where is the upper limit of energy density?” Despite extensive knowledge of chemical fundamentals, that question has not been, and may never be, completely answered because the realm of practicality must be included. The practical answer includes acceptable safety, a dependence on the application, the environment of use, the economic factors and the admission that the battery for one application may not be the best choice for another.
 To identify the best posibilites for candidates to improve high energy density batteries, one may look at the theoretical energy density of the active materials in a particular chemistry. After that, the actual battery must be built and tested. A practical cell has from 15% to 40% of the energy density of the active material’s theoretical maximum. Shown above is a group of the most popular chemistries1 along with the theoretical/practical values for Lithium-air. The theoretical value for Lithium-air has been derived from the energy density of the lithium perchloride (3620 Wh/kg) found as the result of the battery’s discharge chemical reaction. Although practical Lithium-air batteries are not yet available from which to obtain data, the estimated value shown above, of 25% of the theoretical value, was selected. With technological improvements, one wonders if practical densities over 1000 Wh/kg are unreasonable to expect. (Staff graphic)+
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Just as the mountain climber would look to Mt. Everest as the pinnacle of peaks, an electrochemist, browsing the list of metals’ reduction potentials and electrochemical equivalents, sees one possibility in the combination of lithium with oxygen. Lithium metal, excluding oxygen, has the highest standard potential and electrochemical equivalence of all metals.
Between theory and practice is a reduction of that value which can be anywhere from 2:1 for Lithium-thionyl chloride to 7:1 for Lead-acid. Stated in another way, only a part of the theoretical maximum energy density can be recovered in a practical manufactured battery. The challenge is to get the most practical energy from the highest theoretical combination.
To that end, using a lithium anode with an air cathode to supply the oxygen (as is commonly done with the very popular Zinc-air hearing aid batteries) may result in the highest practical energy density possible in a metal-based battery which has an abundant air supply, environmental friendliness, and reasonable safety. Since the anode is lithium metal which reacts aggressively with water, a nonaqueous electrolyte is used with an organic polymer film separator to facilitate the supply of oxygen from the air. The cathode consists of a metal current collector surrounded by a layer of carbon which provides the platform for combining the oxygen with the lithium ion which moves from the electrolyte to form lithium peroxide or lithium oxide. Electrolytes can either be non-aqueous liquid or polymer electrolyte.3
The description of Lithium-air sounds so ideal that we might wonder why we are still stuck with the myriad of chemistries with ‘inferior’ energy densities. To better understand why it is not universally used, an understanding of the previously mentioned suitability criteria which includes the application, the environment of use, economics and practicality is needed. Much has been learned in how to build Zinc-air cells; some of this knowledge can be applied to the design of Lithium-air chemistry.
Reversability of the reaction to allow electrical recharge of Lithium-air is possible. Despite classifying the Lithium-air cell as a primary battery, the literature does include data on the performance of a rechargeable form, researched by Abraham, et. al.2 When the liquid electrolyte is replaced with a polymer electrolyte, the reaction of the lithium directly with oxygen forms lithium peroxide which can reoxidized to oxygen with externally applied current. This has been found to have major barriers in Zinc-air, so starting with the primary version of Lithium-air simplifies the goal tremendously.
As noted in the Zinc-air experience, a virtually unlimited amount of ambient air can be used to supply the oxygen, but as a result, it also adds the limitation of convenience limiting the operating life of about two weeks after exposing the cathode material to the air. Unlike Alkalines, which just ‘sit there’ when not used for days weeks or years, the Lithium-air battery cannot be put into a standby mode conveniently. The solution here is to choose the application which properly suits the continuous period after activation.
Very low power density is another constraint of the Lithium-air battery. Unlike the high power providers of chemistries such as Lead-acid, current densities of Lithium-air can be as much as 1,000 times lower in order to extract the maximum amount of energy. Low current may not be a problem if the application is tailored to the capability, but one does not look upon Lithium-air as a replacement car starting battery.
The problem of temperature range must be considered again because the performance of Lithium-air varies by a factor of 5 over the -20 0C to +40 0C range. It is important to note that the battery must be tuned to the application because Lithium-air batteries are not going to start Minnesota autos in January.
Rather than speculate on the future of Lithium-air batteries, the work being done now is a good indicator of where the technology stands and may suggest when a practical version may be built. The two presentations which describe this work were given at the 41st Power Sources Conference and are highlighted as follows:
Session 4.3 Non-aqueous Lithium-Air Batteries with an Advanced Cathode Structure. Yardney Technical Products, Inc./Lithion, Inc.
 The Diagram shows the layered carbon electrode used as an air cathode in the Lithion, Inc. Lithium-air cells. The PTFE is a Teflon membrane to repel water from the atmosphere. The “C” is the carbon layer that contains the metal catalysts. Nickel mesh is the current collector. (Graphic reproduction permission is by Lithion, Inc., facilitated by Arthur Dobley.)+
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Using non-aqueous electrolytes removes the problem of self-discharge parasitic corrosion due to lithium interaction with water. Non-aqueous electrolytes also remove the production of hydrogen, thus yielding a safer cell. The next barrier to maximizing performance is the low rate of oxygen diffusion in the air cathode. Taking experience from zinc and aluminum metal air batteries, new cathode structures were fabricated using a variety of metal catalysts added to a carbon with binder and deposited on a nickel current collector.4 A teflon film was placed over the structure to repel atmospheric water but to allow oxygen diffusion. Of all the catalysts, manganese was noticeably superior, extending the specific capacity of the air cathode to 3471 mAh/g. (Note: this is for the cathode only.) The carbon material provides the reactive surface for the reduction of the oxygen gas and must have a porous structure with highly distributed catalyst materials.
Several cells were constructed and tested at constant currents at 20 0C, yielding specific capacity of 3471 mAh/g. (Ed. note. With an average potential of 2.47 Volts, this would equate to 8573 Wh/kg. Assuming practical packaging requirements to triple the mass, a real battery might produce 1157 Wh/kg, which would be a wonderful achievement.)
4.4 Temperature Performance of the Non-aqueous Lithium/Air Battery. U.S. Army Research Laboratory, Adelphi, MD
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Theoretical and Practical?
The determination of the theoretical maximum capacity of a Lithium-air battery is complex, and there isn’t a flat statement of fact in the Handbook of Batteries , Third Edition as are many more well developed chemistries. To provide the most accurate value for the maximum capacity, BD asked Dr. Arthur Dobley to provide an expert opinion, which we quote as follows:
“Specific capacity:
n For lithium metal alone 13 kWh/kg.
n For the lithium and air, theoretical, 11,100 Wh/kg, not including the weight of oxygen, and 5,200 Wh/kg including the weight of oxygen. This was checked by calculation and agrees with K.M. Abrahams publication ,JECS 1996.
n For the Lithium air cell, practical, 3,700 Wh/kg, not including the weight of oxygen, and 1,700 Wh/kg with the weight of oxygen. These numbers are predictions and are made with the presumption that 33% of the theoretical energy will be obtained. The battery industry typically obtains 25% to 50% of the theoretical energy (Handbook of Batteries). Metal air batteries are higher in the range. Zinc-air is about 44% (Handbook of Batteries, 3rd Ed. pg 1.12 and 1.16 table and fig).
We selected a conservative 33%. You may quote these numbers above and make any comments with them. The theoretical numbers are similar to the numbers in the ECS 2004 abstract. ( The difference is due to mathematical rounding.)
Below are references you can use:
n The patent by K.M. on non-aqueous Li air: K.M. Abraham and Z. Jiang, U.S. Patent 5,510,209 (1996)
n The first paper on non-aqueous Li air: K.M. Abraham and Z. Jiang, J. Electrochemical Soc., 143, 1 (1996)
n The second paper on non-aqueous Li air: K.M. Abraham, Z. Jiang, and B. Carroll, Chem. Mater., 9 1978-1988 (1997)
n Read, J. J. Electrochem. Soc. 2002, 149, A1190-A1195
n Read, J.; Mutolo, K.; Ervin, M.; Behl, W.; Wolfenstein, J.; Drieger, A.;Foster, D. J. Electrochem. Soc. 2003, 150, A1351-A1356.
n Dobley, A.; DiCarlo, J.; Abraham, K.M. “Non-aqueous Lithium-Air Batteries with an Advanced Cathode Structure” 41st Power Sources Conference Proceedings, Philadelphia, PA, 2004, 61.
n Handbook of Batteries, 3rd ed.; Linden, D.; Reddy, T.B., Eds.; McGraw-Hill: New York, 2002.
BD will err on the conservative side and use the 5,200 Wh/kg theoretical value which includes the weight of oxygen and the 1,700 Wh/kg practical value, realizing that production cells may be something less. DKG
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Seeking combinations of battery support for the Land Warrior has opened up the possibility of including Lithium-air batteries. If radio batteries carried by the troops have rechargeable Lithium-ion batteries, they can be recharged for the next mission by a variety of sources which might not always be a large, heavy and noisy power source.
 The Lithium-air pouch cell is used by Lithion to test the air cathodes. Transitional metals were added as catalysts into the carbon electrode to increase the specific capacity of the cathode. Testing results showed a specific capacity of 3471 m Ah/g at 1 mA discharge. (Photo reproduction is by permission of Lithion, Inc., facilitated by Arthur Dobley.) +
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If Lithium-ion cells had energy densities approaching 200 Wh/kg, and Lithium-air cells had energy densities of 1000 Wh/kg, then 5 field packs could be recharged from a single Lithium-air battery weighing the same as one radio battery. Extending the concept, a combination (hybrid) Lithium-air and Lithium-ion might work together so that the Lithium-ion provided the talk power, and the Lithium-air constantly kept topping off the Lithium-ion resulting in total usability time increases and reduction in pack weight to carry.
 The specific capacity of a battery depends on the capacity of the lithium anode and the carbon cathode. Adding transition metals increases the specific capacity of the cathode; some materials are better than others. This graph shows the superiority of a manganese catalyst over others. Data is from the abstract of a paper to be given at the Fall 2004 meeting of the Electrochemical Society by Arthur Dobley. (Permission to use the data is from Lithion, inc., facilitated by Arthur Dobley.Graphic reproduction permission is from Lithion, Inc., facilitated by Arthur Dobley.)+
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But the Army realizes that major obstacles exist for Lithium-air, especially in the area of temperature range. The present study looks at liquid electrolyte and the carbon black coated anode current collector. Over temperature ranges from -30 0C to +40 0C, the cells were discharged at constant currents from 0.05 to 0.5 mA/cm2. Cells operated at +40 0C gave nominally 10 times more specific capacity than those at -30 0C.
 The combined effects of temperature and discharge rate on specific capacity show the rate effect to be greater for the high temperature operation. The rapid increase in discharge capacity at all rates with temperature indicates that the diffusion coefficient of oxygen tends to dominate performance. (Graphic reproduction is courtesy of the U.S. Army Research Laboratory facilitated by Jeff Read. )+
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It is projected that the temperature affects the diffusion of oxygen through the electrolyte. It is anticipated that future work should separate the effects of oxygen solubility from oxygen diffusion. The reformulation of the electrolyte may be the way to improve low temperature operation. Until then, Lithium-air will remain in the study category for the Army.
 Data from the Army Research Laboratory experimental cell made of Super P carbon black with PTFE and LiPF6 electrolyte shows strong reduction in performance at lower temperatures. The dependence is apparently the result of the temperature effect on oxygen difffusion through the electrolyte. Discharge current is 0.1 mA/cm2. (Graphic reproduction is courtesy of the U.S. Army Research Laboratory facilitaed by Jeff Read.) +
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Reference
1. Handbook of Batteries, Third Edition. pp. 1.12-1.13
2. Handbook of Batteries, Third Edition. pp.38.49-38.51
3. “A Polymer Electrolyte-Based Rechargeable Lithium/Oxygen Battery,” Abraham, K.M. J. Electrochem Soc., 1996, 143. 1-5
4. “High Capacity Cathodes for Lithium-air Batteries,” Yardney TechnicalProducts.
www2.electrochem.org/cgi-bin/abs?mtg=206&abs=0496
BD