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LITHIUM-SULFUR BATTERIES

William Lominac UNC Charlotte Department of Chemistry Dr. Daniel Rabinovich, Advisor CHEM 4696 Fall 2013

1 CONTENT I. ABSTRACT II. INTRODUCTION III. LITHIUM-SULFUR BATTERIES IV. COATING WITH GRAPHENE V. COMPOSITE CATHODES VI. A LITHIUM METAL-FREE CELL VII. CONCLUSION

ABSTRACT Lithium-Ion batteries offer higher energy densities, increased performance, and longer life than conventional alkaline and lead-acid batteries, are ubiquitous in consumer electronics, such as phones, computers, and cameras, and are an attractive choice of battery chemistry in automotive and other large-scale applications. However, the cathode materials of lithium-ion batteries can be toxic, hard to obtain, and expensive. Additionally, the electrolytes used in lithium-ion batteries are flammable and kept under pressure, which poses a concern for the safety of the batteries. Lithium-sulfur is a new type of cathode chemistry that has the potential to vastly improve rechargeable lithium batteries. The theoretical energy density of a lithium-sulfur cell nearly quadruples that of current lithium-ion chemistries, and sulfur benefits from being far more abundant, lighter, less toxic, and less expensive than typical cathode materials. However, the loss of polysulfides to side-reactions during battery cycling leads to very short cycle life for lithium-sulfur cells, which would be a major inhibitor to the use of this battery chemistry. To stem the loss of polysulfides, several new techniques have been proposed, which include grafting sulfur to electrolyte chains on a substrate, the use of a porous composite membrane that traps sulfur and prevents its dissolution, and using a recently isolated crystalline form of carbon, graphene, to embed the polysulfides and avoid side reactions in the cell. These techniques and others have been shown to increase cycle life of lithium-sulfur cells by increasing the retention of polysulfides during cycling.

2 INTRODUCTION Rechargeable batteries have permeated nearly every facet of modern life. Every day, a typical American will check a cell phone, use a laptop, and drive a vehicle to work. Some will ride in an electric cart during 9 holes of golf, or use a cordless power tool. Some may catch a flight to a business meeting; still more will have an important vital sign measured by a piece of medical equipment. Each of these applications uses a rechargeable battery1. The oldest type of rechargeable battery, the lead-acid battery, was developed by French physicist Gaston Plante in 1859. They are still widely used for automobile starters and other large backup power supplies. Lead-acid batteries have very low energy densities, and are susceptible to significant capacity loss if not charged regularly2.

PICTURE 1: French physicist Gaston Plante, pictured here on a 1957 stamp Waldemar Jungner, a Swedish engineer, developed nickel-cadmium, or Ni-Cd, batteries in 1899. These batteries offered much-improved cycle life and a significantly higher energy density than lead-acid cells. They still see use today in backup power applications, cordless power tools, and heavy-discharge applications. Ni-Cd cells have several key disadvantages, however: nickel and cadmium are both expensive, despite the trade-off in power versus lead-acid batteries. Cadmium is also highly toxic, making depleted Ni-Cd disposal a difficult process. Ni-Cd batteries suffer from capacity loss in the form of memory, where repeatedly failing to completely charge or discharge a battery will cause the upper or lower capacity limit to shrink, respectively3.

PICTURE 2: A Craftsman Nickel-Cadmium battery used in cordless drills. The 19.2 volts are derived from using six 3.2 volt cells The modern battery chemistry that shows the greatest cycle life, energy density, and adaptability to different applications is lithium-ion. Theoretical work on Lithium-ion originated in the 1970s and 1980s after M.Stanley Whittingham proposed an intercalated electrode concept. The first marketable prototype of a Li-ion cell was created by Japans Akira Yoshino and his research group in 1985. Modern lithium-ion batteries are used in myriad devices, vehicles, and equipment. The reason that lithium-ion, or li-ion, batteries can cover such a wide range of products is in their chemistry. Li-ion batteries can have a variety of different cathode and electrolyte chemistries, each having unique energy densities, performance characteristics, and safety levels4. For consumer electronics (CE), the most common cathode is lithium cobalt oxide, LiCoO2, which provides a high energy density at the expense of thermal stability, making them dangerous if handled improperly. In cellular phones, the predominant battery voltage is 3.7 volts, an example of this high-energy design. Larger CE batteries employ the use of multiple cells to achieve higher voltages. For example, the laptop battery shown below is a 3-cell, 11.1 volt battery5.

PICTURE 3: A LiCoO2 battery for a laptop, composed of three 3.7 V cells

4 In power tools, medical equipment, and other applications, lithium iron phosphate (LFP) and lithium manganese oxide (LMO) are widely used, due to their longer service lives, increased stability, and safety. These two chemistries are also less expensive to use, but have lower energy densities than LiCoO2 batteries. Commonly, these batteries are between 3.0 and 3.6 volts, 6. The leading contender for electric vehicle batteries is the lithium nickel manganese cobalt oxide chemistry, or NMC. NMC Batteries are generally 3.0 volts or lower, making them some of the lowest-energy Li-ion batteries. However, they are also among the safest, a necessity for large-scale use4. The basis of the chemistry that makes lithium-ion cells function is intercalation, or the insertion of one molecule of a component between two or more molecules of another. In this case, the intercalated components are lithium ions, which are transferred through the electrolyte between the anode and cathode. During discharging, lithium ions are removed from the anode and intercalated into the cathode. The reverse process, charging, is shown below.

FIGURE 1a: The cathode half reaction during charging. Lithium ions are extracted from the cathode material

FIGURE 1b: The anode half reaction during charging. Lithium ions are intercalated into the anode molecules The intercalation model for lithium-ion cells produces 41.7 kJ/g at 3 V, which is slightly higher than gasolines heat of combustion. However, care must be taken not to overcharge or over-discharge lithium-ion cells, as the intercalation reaction limits can overload the electrodes, causing irreversible side reactions that cause capacity loss. Leaving a lithium-ion battery in long-term storage at a fully or mostly discharged level can supersaturate lithium cobalt oxide, causing the following reaction to occur4:

FIGURE 2: Irreversible side reaction caused by over-discharge. Lithium oxide is formed from the reaction Though lithium-ion batteries are among the best available today in terms of energy density and cycle life, they do have several weaknesses that must be recognized. The non-lithium materials used in the various cathodes and anodes of li-ion batteries, such as cobalt, iron, manganese, and nickel, have high costs relative to that of lithium and electrolyte materials. Many are also highly toxic and dangerous to the environment, making storage, disposal, and recycling of the cells more difficult. The electrolytes

5 used in li-ion batteries are flammable and have to be kept under high pressure in the cells, which poses a risk to personal safety. In terms of cell performance, the comparatively heavy non-lithium materials used in the anode and cathode lower the actual energy-to-weight ratio of li-ion cells considerably. Several safety features have been introduced to lithium-ion cells to help circumvent these problems; smart chargers and charge-protection circuits in the cells themselves help to prevent overcharging and overdischarge during use. The cells themselves are required to contain pressure-relief vents and thermal protection from heat produced in an overcharge. These safety features, while necessary, add considerable production costs and add more potential areas for cell failure to occur4. For these reasons, cathode and anode materials with more favorable characteristics are a focal point of recent battery research. Sulfur has recently emerged as a potential new material for lithium battery cathode due to its high theoretical capacity, which is nearly three times that of current lithium-ion batteries. Sulfur as a cathode material would have a number of other advantages over current configurations; these include lower material cost and higher abundance, lower toxicity and environmental impact, and lower weight compared to current cathode materials. In essence, a lithium-sulfur cell would be cheaper, lighter, safer, and more powerful than current lithium-ion cells7. However, there are several obstacles to overcome before lithium-sulfur cells can become a reality outside of the laboratory. Among these are the tendency of polysulfide molecules in the cathode to undergo side reactions that produce insoluble intermediates that remove active material from the cell, and the low intrinsic conductivity of sulfur, which makes necessary the addition of other materials to augment this property. Recent research has focused on many unique solutions to these problems.

LITHIUM-SULFUR BATTERIES The achievable energy density of lithium-sulfur batteries has been estimated at around 2600 Wh/kg or more, far higher than that of modern lithium-ion batteries, which range between 300-400 Wh/kg11. When considered alongside sulfurs light molecular weight (compared with cobalt, nickel, and other common cathode materials), it becomes apparent that the ideal lithium-sulfur battery will allow much higher amounts of energy to be contained within even smaller cells than are currently used. In addition to the performance upgrade that a lithium-sulfur battery would provide, the use of sulfur is more environmentally friendly and less toxic than in lithium-ion batteries, making transportation and

6 handling safer for manufacturers, distributors, and end users. In addition, sulfur is less expensive than many current cathode materials, which would facilitate the adoption of lithium-sulfur chemistry in a wide range of applications. The chemistry of sulfur in Li-S batteries is fairly simple, and can be described in four phases, beginning with a pure polysulfide molecule.

FIGURE 3a: Solid-liquid reduction of sulfur into a liquid cathode During this phase, many voids are left in the cathode as liquid polysulfide material is removed by the electrolyte.

FIGURE 3b: Liquid-liquid reduction into low-order polysulfides The liquid electrolyte solution becomes more viscous as the length of the S-S chain decreases, reaching a maximum at the shortest chain length.

FIGURE 3c: Liquid-solid reduction to insoluble intermediates During this phase, the two reactions shown compete with each other. The majority of the capacity of the Li-S cell results from this phase. The highest capacity achievable with Li-S cells occurs when the second reaction in Figure 3c is predominant. When the first reaction of this phase is significantly present, an additional reduction occurs.

FIGURE 3d: Solid-solid reduction to the insoluble intermediate This side reaction contributes to capacity loss in the cell as active material is removed into the electrolyte and not cycled back into the cathode. This is called the shuttle effect. The voids created in phase one are the physical evidence of this lost capacity. This capacity loss, when repeated over several charge-discharge cycles, can drastically shorten the life of a lithium-sulfur cell10. In addition, the insoluble intermediates increase the internal resistance of the cell, which in turn lowers the capacity. Ergo, to prevent both capacity and cycle life loss in lithium-sulfur cells, it is necessary to find a way to protect

7 sulfur from undergoing these side reactions, either chemically or physically. Chemical methods of protecting sulfur typically involve combining it with one or more other components in a composite cathode, which hold polysulfide chains in place to prevent loss during electrode cycling. Composite cathodes are typically chosen for their ability to increase sulfurs conductivity, as well. Physical methods of preventing side reactions are fairly straightforward: a substance, usually a type of carbon (and oftentimes graphene), is used to surround or coat the polysulfide chain, literally shielding it from unwanted interaction with the electrolyte7,8,9,.

COATING WITH GRAPHENE Graphene, a crystalline form of carbon with a regular hexagonal pattern, was isolated for the first time in 2004 by Andre Geim and Konstantin Novoselov, who later won the 2010 Nobel Prize in Physics for their discovery8. In the nine years since it was first isolated, graphene has become a sort of wonder material, showing up in various fields of nanoscale chemistry, including the development of lithium-ion and lithium-sulfur batteries. Graphene has several properties that make it well-suited for battery applications; high thermal and electronic conductivity, a strong, self-repairing, lightweight structure, and facile functionalization to graphene oxide, which is a sheet of graphene with hydroxyl and epoxy groups along its edges and center9. In lithium-sulfur cells, graphene and graphene oxide are commonly used to surround and coat sulfur molecules, effectively limiting the dissolution of polysulfides into the electrolyte, which helps the cells retain capacity during cycling to prolong cell life. The electronic conductivity of graphene also counteracts the low conductivity of sulfur, which helps being the cell closer to its theoretical capacity limit. Though the use of graphene is now common in the cathode of lithium-sulfur cells, many variations of the graphene-coated cathode have met varying success. Sulfur-Polyacrylonitrile Composite with Graphene Coating Polyacrylonitrile has been shown to engage with a high percentage of sulfur in the cathode, and to stabilize the Li-S cell during cycling by limiting sulfur side reactions. When combined with sulfur, the resulting composite cathode is known as S/PAN. A drawback to this material is its somewhat low conductivity, which makes susceptible to failure during high-current cycling12. For this reason, the highlyconductive graphene is thought to be a good candidate to increase the conductivity of the S/PAN cathode.

FIGURE 4: Comparison of untreated S/PAN, S/PAN/Graphene, and S/Graphene As shown in the figure to the right, graphene alone does not yield a high-capacity cell, and has poor cyclability. S/PAN cathode shows good capacity initially, but loses almost 59% of its capacity by the 100th cycle. In contrast, S/PAN/graphene exhibits a high capacity, around 612 mAh/g, which is mostly retained over the first 100 charge cycles at 0.1 C (1/10 of the nominal current). The effect of graphene on the cathode composite is even more striking at 2C (twice the nominal current), where a reversible capacity of 285 mAh/g was maintained at almost 100% retention over an extended cycling test. It is therefore appropriate to suggest that graphene enhances the conductivity of the composite cathode, becoming especially effective in high-current applications, and that the combination of graphene and the cathode composite helps to increase the cycle life of lithium cells, more so than either by itself12. Graphene oxide over mesoporous carbon The primary limitation of lithium-sulfur batteries is the loss of active material due to polysulfide dissolution in the cathode; with each cycle, material is lost and the cells capacity drops. To prevent this, sulfur is often embedded in a porous material, such as mesoporous carbon, which helps to essentially hold polysulfides in place during the charge and discharge processes. These porous materials still leave sulfur accessible to the electrolyte, however, which can dissolve and carry away polysulfides. In effect, they can only slow down the loss of active material, not stop it. In order to eliminate the polysulfide loss, hybrid nanostructures have been employed that feature an additional compound, commonly graphene, to better trap the sulfur in the cathode area. Graphenes use, as previously stated, also helps to increase cell performance due to its high intrinsic conductivity13.

FIGURE 5: Structure of GO-wrapped, mesoporous carbon-implanted sulfur cathode A novel nanostructural hybrid partners mesoporous carbon with hydroxyl- and carboxylfunctionalized graphene oxide (GO). Here, mesoporous carbon provides space for sulfurs interaction with lithium ions during charging and discharging, while a GO skin has functional groups that interact with and capture excess polysulfides, as well as increase the cells electrochemical performance. The resulting composite cathode was measured to be 53% sulfur by weight13.

FIGURE 6: Right: CMK (Non-GO) versus RGO@CMK at 0.2 C. Left: Results for 0.5 and 1.0 C During high-current testing (at 1 C), the RGO-wrapped composite cathode exhibited a capacity of 1147 mAhg-1, about 68% of the theoretical capacity of Li-S. Additionally, cyclability was greatly improved, with almost 100% retention after 100 cycles. At 0.5 and 0.2 C, performance dropped dramatically; nearly 25% capacity loss was observed over 100 cycles. However, the capacity of RGO-wrapped cathode was higher than that of unwrapped cathode, likely a result of graphenes excellent conductivity. These data

10 suggest that, in high-current applications, the combination of a functionalized GO exterior and mesoporous carbon interior can produce a high-performance, stable-cycling lithium-sulfur cell13. Amylopectin-reinforced graphene coatings The limitation of graphene coatings for the sulfur cathode is in the physical stacking ability of the graphene sheets. No matter how close two graphene sheets are able to be positioned, there will remain some space between them that allows polysulfides to pass through nearly unimpeded. As a result, capacity fading of close to 50% had been observed during the first 20 cycles. To counteract this, aqueous binders (such as gelatin and cyclodextrin) had been introduced to the Li-S cells. Amylopectin is another favorable choice of polymer, as it contains many hydroxyl groups that will interact with those of graphene oxide (GO), filling gaps between GO layers. Being a natural polymer, amylopectin is also environmentally friendly, an attractive characteristic for use in Li-S cells7.

FIGURE 7: GO/S/Amy: Yellows are sulfur, blacks are carbon black, the substrate of Li-S cathode As can be seen in the structure of GO/S/Amy, spacing between graphene sheets is filled by amylopectin, forming a shield that prohibits polysulfides from escaping into the electrolyte. This amylopectin-wrapped structure was tested alongside a control, unwrapped GO-S.

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FIGURE 8: GO-S-Amy charge/discharge vs. GO-S control The GO-S compound performed as expected: graphenes high conductivity helped to produce a high initial capacity, roughly equivalent to the wrapped structures. However, after only 25 charge cycles, GO-S began to lose capacity, achieving only 38% of its initial capacity by the 100th cycle. Amylopectin wrapping appeared to have a major effect on cycling efficiency, however. At a C/8 (low current) rate, GOS-Amy showed over 90% retention between cycles, at several different loadings of sulfur. The most striking result of the GO-S-Amy cycling test was at a C/2 (high current) rate. Although the capacity of GOS-Amy was lower at C/2 than at C/8, there was no significant degradation of the cathode or capacity loss at C/2. Furthermore, a sample of the GO-S-Amy composite was collected after fifty cycles and examined via STEM, which produced the following image7.

FIGURE 9: (a) GO-S-Amy image via STEM dark field. (b) mapping for sulfur (c) mapping for carbon

12 The image of GO-S-Amy appears to overlap strongly with those of carbon and sulfur suggesting that the GO-S-Amy composite maintains its structure after fifty cycles. Ergo, it can also be concluded that active material loss is reduced by this composite. A possible explanation for the effectiveness of the composite is the crosslinking of amylopectin and graphene oxide sheets, which creates a barrier to contain polysulfides7.

COMPOSITE CATHODES Each of the previously discussed methods shares a common thread: sulfur is not alone in the cathode. The original design of Li-S cathode, a simple mixture of carbon and sulfur, has for the most part been replaced by sulfur-carbon composites. These composites help to increase cycle life, as sulfur is held by mesoporous silica or other materials to prevent diffusion and subsequent capacity loss. This function of these composites is vital for cell performance, but their other function is equally important: composites serve to increase the conductivity of the otherwise poorly-conducting sulfur. Composite cathodes are highly customizable, and much research has been dedicated to different types of composite cathodes and their effects on cell performance. One composite configuration, sulfur/polyaniline/carbon, or SPC, has shown promising results. SPC Composite Cathode Carbon nanostructures, including graphene, porous carbons, and carbon nanotubes have seen widespread use in lithium-sulfur composite cathodes. Their combination with other conducting polymers provides the sulfur in the cell with a matrix that both increases its poor conductivity and helps to counteract the diffusion of polysulfides into the electrolyte. Polymers such as polypyrole and polythiophene have seen some use; however, polyaniline, or PANi, is a more attractive option due to its relatively simple production and small environmental footprint. A combination of sulfur, PANi, and carbon, commonly known as SPC, begins as polyaniline-carbon black (PANi-C), a commercially available compound. PANi-C is heated in a container with elemental sulfur, which produces a composite with an interesting structure, as exhibited by scanning electron microscopy9.

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FIGURE 10: SEM image of sulfur/polyaniline/carbon cathode composite After thermal treatment at 320 oC, was calculated to be 58% sulfur by weight, indicating that a large amount of sulfur had been captured by the PANi-C composite. Three methods of creating the SPC composite were tested: The standard, a two-stage heating process at 280 oC. SPC-155 was created through a one-stage heating process at 155 oC. SPC-RT was produced by ball-milling at room temperature9.

FIGURE 11: Comparison of SPC production methods at 0.5 C Disregarding the high initial capacity of SPC-RT, the electrochemical performance of the SPC cells appears to be linked to the temperature at which the PANi-C is combined with sulfur. It is hypothesized that this is because sulfur penetrates the PANi-C structure more deeply at higher temperatures. The SPC

14 cathode has an initial capacity of around 1150 mAhg-1, about 68% of the Li-S theoretical capacity, which drops to 732 mAhg-1 after the first 100 cycles. Although some capacity loss was observed, the SPC composite retained its shape during cycling, PANi-C appears to absorb and constrain a large amount of sulfur in its porous structure, protecting it from extreme levels of diffusion. However, the SPC cathode did not seem to be as effective as other methods for preserving capacity during cycling9. High-performance, mesoporous TiO2 cathodes Although the carbon nanostructures in most composite cathodes do augment the electrochemical performance of sulfur, they become quite massive comparatively, occupying as much as 50% of the cathode by weight. In addition, carbon structures prevent polysulfide dissolution only by physical means, holding the sulfur in place, rather than by a chemical process. TiS2 has recently been shown to be a suitable replacement for these structures, helping to reduce the carbon content of the cathode composite. A similar compound, TiO2, is a semi-conductor that is chemically stable, conductive, and can confine sulfur effectively in its pores. An advantage that TiO2 has over carbon is that it can serve as a second active material, if polysulfide loss does occur. For these reasons, a TiO2 composite cathode was developed to determine what effect it would have on Li-S cycling performance14.

FIGURE 12: Comparison of TiO2/S composite and untreated sulfur cathodes at 0.5 C Obviously, TiO2/S cathode shows a dramatic increase in both cycling efficiency and capacity, with an initial and 100th cycle capacity of around 700 mAhg-1. The lower capacity of the TiO2/S cathode than most carbon/sulfur composites is most likely the result of TiO2 having a lower specific capacity than that of carbon. It can be concluded that this composite would be a good candidate for a low capacity, high cycle count application14.

15 A high-sulfur content composite cathode In order for lithium-sulfur batteries to be practical for large-scale applications, a high energy density is a must-have characteristic. Most composite cathodes in current publications have sulfur contents well below 50% by weight in the cathode. The highest capacities obtained experimentally have been with sulfur content around the 50% mark, and with sulfur loading at or below 2 mg/cm2. These two lows cause the energy density to drop dramatically, resulting in much bulkier batteries than what Li-S potential would suggest are possible. Few papers have been published using high-sulfur content and loading; however, the results from the few papers that have been released seem to suggest good potential for high-sulfur content cathodes15.

FIGURE 13: Preparation of P-AB@S For this experiment, the composite cathode prepared was a mixture of polyethylene glycol (PEG), acetylene black (AB), and sulfur. The cathode, known as P-AB@S, was 66% sulfur by weight, a figure higher than that of many composite cathodes. The P-AB@S cathode composite was inserted into a coin-type lithium battery and put through cycling tests. The initial capacity of the P-AB@S battery was 1221 mAhg-1, equivalent to 72% of sulfurs potential capacity15.

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FIGURE 14: Cycling of P-AB@S, 0-500 cycles Impressively, P-AB@S, after falling to around 718 mAhg-1 during its first few cycles, retained a capacity of 706 mAhg-1 after 100 cycles. After 500 cycles, P-AB@S still produced a capacity 577 mAhg-1, a retention of 80% from the 718 mAhg-1 it achieved during its first few cycles. The addition of PEG to the AB@S core structure seems to have drastically improved the cycle life of the cathode, likely by interacting with and binding the polysulfides to the surface of the cathode15.

A LITHIUM METAL-FREE CELL As lithium-sulfur battery technology inches closer to becoming a reality, talk of its potential applications has progressed as well. Battery-powered cars, which currently are growing in popularity and in production, have one caveat that could prevent them from becoming ubiquitous: current lithium-ion batteries do not have the charge density required to power the cars for very long distances. A Li-ion battery able to power an electric car for a distance of several hundred kilometers would have to be massive, likely too large and too heavy to be practical. Lithium-sulfur batteries on the other hand, with a charge density three to five times higher than Li-ion and a smaller, lighter form factor, would have the potential to be a major breakthrough in electric car technology. The advents of improved cathode composites, polymer-based electrolytes, and additives that prevent polysulfide diffusion have greatly improved the achievable cycle life of Li-S cells, and brought the capacity of lithium-sulfur cells closer to their potential. However, the safety of lithium-sulfur cells had not been specifically researched or improved upon. Though they are not inherently as dangerous as lithium-ion cells, there is still some

17 hazardous potential if lithium-sulfur is to be used in electric vehicles. Specifically, the lithium metal that constitutes the anode of lithium-sulfur cells is highly reactive, making it dangerous for use on the large scale that an automotive battery would require. It was hypothesized that by using a lithiated anode instead of the more reactive lithium metal that cells could be made safer for use in vehicles while retaining the increased performance of the Li-S platform8.

FIGURE 15: Formation of HCS-S as sulfur interacts with the surfaces of the carbon spherules To create this lithium-free battery, a composite cathode of mesoporous hard carbon spherules, or HCS, and sulfur was synthesized hydrothermally, achieving a sulfur composition of 42% by weight. Silicon/graphite/petroleum powders were heated to 1000 0C and lithiated by direct contact with lithium metal to create the anode. The electrolyte, LiCF3SO3-TEGDME (tetraglyme), was chosen for its conductivity. The lithium-free cells exhibited an initial capacity of around 1000 mAhg-1, equating to 60% of the Li-S cells theoretical capacity. This value dropped to 600 mAhg-1 after 100 cycles8.

FIGURE 16: Cycling data for HCS-S over first 100 cycles at 1C

18 The drop in capacity over the first 100 cycles can be attributed to several factors; of course, the possibility that some polysulfide dissolution still takes place in the cathode is very real. However, the drop may also be the result of an uneven mass balance between the two electrodes, causing a charge differential. The batterys performance could possibly be improved by stricter control on cycle time, or by optimizing the cell structure, in terms of materials and build method8.

CONCLUSIONS The evolution of the rechargeable battery started more than a century and a half ago, and is still continuing for now and the foreseeable future. As newer, better technologies are developed, batteries will become safer, cheaper, and more powerful. Lithium-sulfur batteries have the potential to revolutionize the rechargeable battery industry, due to their high capacity, inexpensive materials, and low toxicity and environmental impact. However, the technologys greatest asset, sulfur, is also its greatest liability. If the problems of polysulfide diffusion and the resulting capacity loss can be solved, lithium-sulfur batteries may hold the key to a brighter, greener future. Current research on lithium-sulfur batteries revolves primarily around either one of two strategies for overcoming the pitfalls of Li-S batteries; the sulfur cathode can either be physically embedded in a nanostructure, relying on sterics to prevent polysulfides from escaping into the electrolyte; or a material can chemically interact with sulfur, binding it to a surface so that it can react with lithium during the charge and discharge cycles, but wont be able to diffuse into the electrolyte afterwards. Perhaps the best strategy for improving lithium sulfur will be combining the two techniques, eventually striving to completely eliminate sulfur loss from the Li-S cell. Indeed, the most successful cycling of any cell discussed was the graphene-wrapped mesoporous carbon composite. Mesoporous carbon serves as the physical component, holding sulfur in its pores while allowing it to react with lithium and allowing the accompanying expansions and contractions in volume. Hydroxyl- and carboxylfunctionalized graphene oxide serves as the chemical part of the structure, interacting with sulfur as it leaves the mesoporous carbon and preventing it from escaping into the electrolyte, while also giving the cathode a boost in conductivity. This combination results in a near-perfect 100-cycle test at high current, in terms of cycling efficiency. Building off of the dual-technique approach, it would likely be illuminating to perform a reaction optimization, tweaking one part of the composite at a time to determine the ideal set of materials to give both a high capacity and a consistent cycling profile. Effectively, that is exactly

19 what most of these papers have done. Very few pieces of new research show experiments on composite cathodes without some kind of conductive carbon or silicon nanostructure involved as well. The reverse is also true, as most papers concerning the use of graphene or other nanostructures also made use of an established cathode composite. This makes one wonder what the ideal combination of materials will be, and who will find it. Certainly, whomever develops the first production-ready lithium-sulfur cell will go down as one of the greats, helping to bring the future one step closer to the present.

20 REFERENCES 1. Wikipedia, the free encyclopedia. Rechargeable Battery. http://en.wikipedia.org/wiki/rechargeable_battery (Accessed September 2013). 2. Wikipedia, the free encyclopedia. Lead-Acid Battery. http://en.wikipedia.org/wiki/lead_acid_battery (Accessed September 2013). 3. Wikipedia, the free encyclopedia. Nickel-Cadmium Battery. http://en.wikipedia.org/wiki/nickel-cadmium_battery (Accessed September 2013). 4. Wikipedia, the free encyclopedia. Lithium-Ion Battery. http://en.wikipedia.org/wiki/lithium-ion_battery (Accessed September 2013). 5. Wikipedia, the free encyclopedia. Lithium-Cobalt Oxide. http://en.wikipedia.org/wiki/lithium_cobalt_oxide (Accessed September 2013). 6. Wikipedia, the free encyclopedia. Lithium-Iron Phosphate. http://en.wikipedia.org/wiki/lithium_iron_phosphate (Accessed September 2013). 7. Zhou, W.; Chen, H.; Yu, Y.; Wang, D.; Cui, Z.; DiSalvo, F. J.; Abruna, H. D. Amylopectin Wrapped Graphene Oxide/Sulfur for Improved Cyclability of Lithium-Sulfur Battery ACS Nano 2013, 7, 8801-8808. 8. Hassoun, J.; Kim, J.; Lee, D. J.; Jung, H. G.; Lee, S. M.; Sun, Y. K.; Scrosati, B. A contribution to the progress of high energy batteries: A metal-free, lithium-ion, siliconsulfur battery J. Power Sources 2012, 202, 308-313. 9. Zhao, X.; Kim, J. K.; Ahn, H. J.; Cho, K. K.; Ahn, J. H. A ternary sulfur/polyaniline/carbon composite cathode for lithium sulfur batteries Electrochem. Acta 2013, 109, 145-152. 10. Zhang, S. S. Liquid electrolyte lithium/sulfur battery: Fundamental chemistry, problems, and solutions J. Power Sources 2013, 231, 153-162. 11. Doan, T. N. L.; Ghaznavi, M.; Konarov, A.; Zhang, Yongguang; Chen, P. Cyclability of sulfur/dehydrogenated polyacrylonitrile composite cathode in lithium-sulfur batteries J. Solid State Electrochem. 2014, 18, 69-76. 12. Zhang, Y.; Zhao, Y.; Bakenov, Z.; Babaa, M. R.; Konarov, A.; Ding, C.; Chen, P. Effect of Graphene on Sulfur/Polyacrylonitrile Nanocomposite Cathode in High Performance Lithium/Sulfur Batteries J. Electrochem. Soc. 2013, 160, 1194-1198. 13. Zhou, X.; Xie, J. K.; Yang, J.; Zou, Y.; Tang, J.; Wang, S.; Ma, L.; Liao, Q. Improving the performance of lithium-sulfur batteries by graphene coating J. Power Sources 2013, 243, 993-1000.

21 14. Ding, B.; Shen, L.; Xu, G.; Nie, P.; Zhang, X. Encapsulating sulfur into mesoporous TiO2 host as a high performance cathode for lithium-sulfur batteries Electrochem. Acta 2013, 107, 78-84. 15. Miao, L. X.; Wang, W. K.; Wang, A. B.; Yuan, K. G.; Yang, Y. S. A high sulfur content composite with core-shell structure as cathode material for Li-S batteries J. Mater. Chem. 2013, 1, 11659-11664.