Li-S Batteries

LITHIUM-SULFUR BATTERIES
William Lominac Chem 4696 Fall 2013 Dr. Rabinovich, Advisor
OUTLINE
Introduction Current Lithium-Ion Batteries Chemistry, benefits, and limitations Lithium-sulfur chemistry Advantages over Li-ion Drawbacks to usage Improving Li-S batteries Graphene embedding and coating Conductive coatings Composite cathodes A lithium-free cell Conclusions
INTRODUCTION
Rechargeable lead-acid batteries invented by Gaston Plante (1859) Still used in automobiles and for backup power sources Nickel-Cadmium batteries (Jungner, 1899): higher energy density/longer life, but expensive and highly toxic
Wikipedia, the free encyclopedia. Lead-Acid Battery. http://en.wikipedia.org/wiki/lead_acid_battery (Accessed September 2013). Wikipedia, the free encyclopedia. Rechargeable battery. http://en.wikipedia.org/wiki/rechargeable_battery (Accessed September 2013).
INTRODUCTION
Birth of Li-ion in 1985 by Akira Yoshino and his research group Today, Li-ion batteries dominate the consumer electronics market Increasing role in automotive and industrial applications
However, materials are expensive and some are very toxic
Wikipedia, the free encyclopedia. Lithium-Ion Battery. http://en.wikipedia.org/wiki/lithium-ion_battery (Accessed September 2013).
CURRENT LITHIUM-ION BATTERIES

Lithium-Cobalt Oxide (LiCoO2) consumer and handheld electronics Lithium-Iron Phosphate (LFP) and Lithium-Manganese Oxide (LMO) power tools and medical equipment Lithium-Nickel-Manganese-Cobalt Oxide (NMO) most popular battery for automotive use Special-use batteries such as lithium-titanate in power grids
CHEMISTRY IN THE LI-ION CELL

Cathode Half-Reaction: during cell charging, Li is extracted from the cathode Anode Half Reaction: Li is intercalated into the carbon-based anode
Overdischarging can cause an irreversible side reaction

Active material removed from electrodes Drastically reduces both the capacity and cycle life of the battery
LIMITATIONS OF LITHIUM-ION
Non-lithium materials are heavy, lowering the energy density of the batteries (150-250 Wh/kg) Pressurized, flammable electrolytes pose safety risks High toxicity of electrolytes and cathode materials High material costs (cobalt, iron, manganese, and nickel)
LITHIUM-SULFUR BATTERIES
High theoretical energy density (500-600 Wh/kg) due to higher lithium capacity in cell structure Low molecular weights of sulfur and lithium mean a more lightweight battery compared to current Li-Ion cells Sulfur is more abundant, cheaper, and safer than the cathode materials in current Li-Ion cells
Zhang, S. S. J. Power Sources 2013, 231, 153-162
CHEMISTRY IN THE LI-S CELL

Phase I: Sulfur reduction into a liquid cathode Phase II: Liquid-liquid reduction to form lower-order polysulfides Phase III: Two competing liquid-solid reductions that form insoluble sulfide structures; these produce the major portion of the Li-S cells capacity Phase IV: Solid-solid reduction of insoluble sulfides; this side reaction is the cause of capacity loss in the cell
When the second Phase III reaction dominates, Phase IV does not occur and active material loss is minimized
LIMITATIONS OF LITHIUM-SULFUR
Sulfur is intrinsically a poor conductor of heat and electricity
Sulfur undergoes side reactions in the electrolyte that form insoluble polysulfides
Cathode mass loss due to active material deposition during cycling Internal resistance is increased during each cycle due to aggregation of polysulfide intermediates in electrolyte
For lithium batteries to be practical, the development of a method of controlling the sulfur cathode loss is critical
IMPROVING LITHIUM-SULFUR
Though there are many potential ways to solve the problem of active material loss, two are quite common: Using composite cathodes of various materials to prevent polysulfide loss and increase capacity Coating, embedding, or otherwise surrounding the sulfur cathode (often with graphene)
Graphene Nobel Prize in Physics (2010) Andre Geim and Konstantin Novoselov
COATING SULFUR WITH GRAPHENE

Untreated sulfur/polyacrylonitrile (S/PAN) composite cathode and GO/S cathode as controls Graphene sheets were sandwiched around S/PAN molecules to observe their effects on capacity and cyclability of Li-S cells
Zhang, Y.; Zhao, Y.; Bakenov, Z.; Babaa, M. R.; Konarov, A.; Ding, C.; Chen, P. J. Electrochem. Soc. 2013, 160, 1194-1198
COATING SULFUR WITH GRAPHENE

Graphene had no negative effect on capacity, while increasing the retention of discharge capacity late in the cycling test S/PAN without graphene still shows large increases in performance over the S/Graphene cathode
Zhang, Y.; Zhao, Y.; Bakenov, Z.; Babaa, M. R.; Konarov, A.; Ding, C.; Chen, P. J. Electrochem. Soc. 2013, 160, 1194-1198
AMYLOPECTIN AND GRAPHENE

Amylopectin interacts with the hydroxyl groups of graphene oxide (GO) sheets to create a cross-linked structure and close gaps Chosen for its high capacity for H-bonding, insolubility, and small environmental impact
Zhou, W.; Chen, H.; Yu, Y.; Wang, D.; Cui, Z.; DiSalvo, F. J.; Abruna, H. D. ACS Nano 2013, 7, 8801-8808

The GO-S combination exhibited significant capacity loss beginning with the 25th cycle, as with untreated sulfur. Gaps between graphene sheets allowed polysulfides to diffuse fairly unimpeded

GO-S-Amy maintained over 80% capacity retention at a C/8 charge-discharge rate (1/8 of nominal current) GO-S-Amy did not experience significant capacity loss in the first 100 cycles at C/2 (1/2 of nominal current)
GRAPHENE OXIDE COATING

Highly conductive GO coatings over mesoporous carbon have a two-fold benefit in lithium-sulfur cells: The graphene skin traps polysulfide molecules, reducing active material loss Graphenes high conductivity negates sulfurs low conductivity
Zhou, X.; Xie, J. K.; Yang, J.; Zou, Y.; Tang, J.; Wang, S.; Ma, L.; Liao, Q. J. Power Sources 2013, 243, 993-1000
GRAPHENE OXIDE COATING

Combined effect: an Li-S cell with an initial capacity of 1147.7 mAhg-1, which is (68.3% of theoretical capacity), and better cycling performance at 1 C Performance was better at high current, with close to 100% cycling efficiency through 100 cycles
Zhou, X.; Xie, J. K.; Yang, J.; Zou, Y.; Tang, J.; Wang, S.; Ma, L.; Liao, Q. J. Power Sources 2013, 243, 993-1000
SPC COMPOSITE CATHODE

Composite cathodes made of sulfur, polyaniline, and carbon (SPC) serve two roles in Li-S batteries: Increasing conductivity Prevent polysulfide dissolution SPC maintained its structure after 100 cycles, unusual without graphene reinforcement Cycling with SPC produced an initial capacity of 1150 mAhg-1, and 732 mAhg-1 after 100 cycles
Zhou, X.; Kim, J. K.; Ahn, H. J.; Cho, K. K.; Ahn, J. H. Electrochem. Acta 2013, 109, 145-152
HIGH-SULFUR COMPOSITE CATHODE

In most Li-S cells, sulfur content is low, as higher amounts of sulfur often coincide with lower capacities However, low sulfur also means low potential capacity
Miao, L. X.; Wang, W. K.; Wang, A. B.; Yuan, K. G.; Yang, Y. S. J. Mater. Chem. 2013, 1, 11659-11664

Here, acetylene black (AB) is functionalized and reacted with polyethylene glycol (PEG), before sulfur is added. P-AB@S is the resulting cathode composite The PEG grafted onto the AB surface grabs sulfur to prevent unwanted side reactions

The P-AB@S composite produced an initial capacity of 1221 mAhg-1, which tapered to 718 mAhg-1 at 100 cycles

At 100 mAg-1, P-AB@S was able to maintain 577 mAhg-1 through 500 cycles, indicating that PEG can effectively stem the loss of polysulfide active material
A NOVEL SILICON-SULFUR CELL

Avoiding the use of lithium metal as anode material creates a safer high-energy battery Li anode replaced with a nanoscale silicon-carbon composite, then lithiated by a separate process
Hassoun, J.; Kim, J.; Lee, D. J.; Jung, H. G.; Lee, S. M.; Sun, Y. K.; Scrosati, B. J. Power Sources 2012, 202, 308-313

Lithium triflate, LiCF3SO3, in triglyme as an electrolyte
Low toxicity/reactivity, high conductivity
Hard carbon spherules, or HCS, were heated with sulfur to create HCS-S composite

HCS-S slowed capacity loss during cycling When combined with the LiSi-C anode, more consistent cycling, especially during first 20 cycles

Additionally, the combination of composite anode and cathode seems to have stabilized the charge and discharge voltages of the cell at various current levels
CONCLUSIONS
There are several effective methods of inhibiting the side reactions of sulfur in Li-S cathode Graphene, a relatively new material (discovered only in 2004), will play a significant role in the development of Li-S cathodes
Conductive composite cathodes offset sulfurs low conductivity, but will raise both the weight and cost of Li-S cells
As safer, cheaper, and higher-performing batteries, Li-S may represent a great step forward in battery technology
ACKNOWLEDGEMENTS
Dr. Rabinovich Advisor
Dr. Merkert
4695 and 4696 classes
Andre Geim and Konstantin Novoselov
Gaston Plante
Waldemar Jungner Akira Yoshino

Li-S Batteries

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LITHIUM-SULFUR BATTERIES

William Lominac Chem 4696 Fall 2013 Dr. Rabinovich, Advisor

However, materials are expensive and some are very toxic

CURRENT LITHIUM-ION BATTERIES

CHEMISTRY IN THE LI-ION CELL

Overdischarging can cause an irreversible side reaction

Zhang, S. S. J. Power Sources 2013, 231, 153-162

CHEMISTRY IN THE LI-S CELL

Zhang, S. S. J. Power Sources 2013, 231, 153-162

Zhang, S. S. J. Power Sources 2013, 231, 153-162

COATING SULFUR WITH GRAPHENE

COATING SULFUR WITH GRAPHENE

AMYLOPECTIN AND GRAPHENE

AMYLOPECTIN AND GRAPHENE

AMYLOPECTIN AND GRAPHENE

GRAPHENE OXIDE COATING

GRAPHENE OXIDE COATING

SPC COMPOSITE CATHODE

HIGH-SULFUR COMPOSITE CATHODE

HIGH-SULFUR COMPOSITE CATHODE

HIGH-SULFUR COMPOSITE CATHODE

HIGH-SULFUR COMPOSITE CATHODE

A NOVEL SILICON-SULFUR CELL

A NOVEL SILICON-SULFUR CELL

A NOVEL SILICON-SULFUR CELL

A NOVEL SILICON-SULFUR CELL

Andre Geim and Konstantin Novoselov

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