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Lithium-Sulfur Battery

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The Lithium-Sulfur Battery

Introduction

The lithium-sulfur battery is a promising technology due to its high theoretical specific capacity of Sulfur (cathode: 1675 mA·h·g−1) and theoretical energy density.

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High Gravimetric Energy Density of the Lithium-Sulfur Battery

In addition, the lithium-sulfur battery is the most competitive in gravimetric energy density with current technology, rather than volumetric energy density, compared with the lithium-ion battery. 

The Lithium-Sulfur Battery is abundant

Sulfur el desierto mine%2c san pablo de napa%2c daniel campos province%2c potos%c3%ad%2c bolivia
Crystalline Sulfur For Lithium-Sulfur Battery

Moreover, the lithium-sulfur battery conforms to the energy source demand for electric car and portable electronic products. Furthermore, the lithium-sulfur battery has other beneficial assets properties such as rich raw material sources, low cost and environment friendly.

The advantages of abundant reserves, low-cost and environmental friendliness are also attributed to sulfur. 

Lithium-sulfur-battery---logo

With growing attention paid to the application of Lithium Sulfur batteries, also new challenges at the practical cell level emerged.

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Capacity of the Sulfur cathode and Lithium anode

Between available anode and cathode materials, lithium metal has the highest theoretical specific capacity of 3,860 mA·h·g−1 and the lowest electrochemical potential of 3.04 V (vs. standard hydrogen). Sulfur, with low relative molecular mass and two electron transfer reaction, depicts the highest discharge capacity of 1,672 mA·h·g−1, which stands out among all solid cathode materials. 

Working Voltage Lithium-Sulfur Battery

When sulfur is paired with lithium metal, lithium-sulfur batteries provide an average working voltage of 2.15 V, which is much higher than that of the many commercial batteries but a bit lower than lithium-ion batteries. 

Pros and Cons of the Lithium-Sulfur Battery

Since its invention half a century ago, the Li-S battery has achieved key breakthroughs and innovations in its faltering development. There are pros and cons to the sulfur cathode’s conversion reaction mechanism, which is different from the intercalation chemistry.
The advantage is that sulfur reacts with Li-ion and goes through a two-electron transfer reaction that has a high specific discharge capacity. 
The disadvantage is that the conductivity of sulfur and the discharge product, lithium sulfide (Li2S) is extremely low.
The volumetric change is large, and the cyclic performance is unstable. Despite decades of research, Li-S batteries have been plagued by problems. 

Improvement of the capacity and stability

CMK-3 (ordered mesoporous carbon) with mesoporous channels can increase the specific discharge capacity a lot. After that discovery, there was an explosion in published literatures and the specific capacity and cyclic stability increased considerably.
But the shuttle effect of lithium polysulfides (LiPSs) caused by the wrong reaction kinetics results in poor long-cycle stability. The targeted strategies are subsequently designed, including LiPS limitation, regulation of sulfur redox reactions and electrocatalysts for sulfur redox reactions.

Strategies to overcome shuttle-effect

But the shuttle effect of lithium polysulfides (LiPSs) caused by the wrong reaction kinetics results in poor long-cycle stability. The targeted strategies are subsequently designed, i) including LiPS limitation, ii) regulation of sulfur redox reactions and iii) electro-catalysis for sulfur-redox reactions.

Lithium-dendrites in the lithium-sulfur battery

Lithium metal has been the “holy grail” in battery research. Recent advances in solid-state electrolytes promise to overcome the dendrite difficulty. 
 

Strategies to overcome the lithium-dendrite issue

The main strategies to overcome the lithium-dendrite issue are the
i) artificial solid electrolyte interface (SEI), ii) electrolyte design, and a iii) structured anode that increases the Coulombic efficiency (CE) and stops lithium dendrite growth.

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Issues that currently hamper industrial-ization of the Lithium-Sulfur Battery

1) The volume expansion

In addition, the density of sulfur and lithium sulfide is 2 g/cm3 and 1.7 g/cm3, respectively. The volume expansion and shrinking in the charge-discharge process is as high as 80%, resulting in the separation of the active sulfur-material from the conducting-none expanding material and the attenuation of capacity.

2) Dissolution of sulfur and sulfur compounds into the Lithium-sulfur battery cell

On the other hand, the suitability of lithium-sulfur battery is limited by the dissolution of a) elemental sulfur and b) intermediate product polysulfide ions in the liquid electrolyte.

The dissolution of polysulfides can result in the loss of the sulfur-cathode materials, which i) results in a rapid decrease in capacity and ii) deformation and subsequent mechanical instability of the sulfur-cathode.

4) The Problem with the Polysulfide-Shuttle

Polysulfide-shuttle-in-the-lithium-sulfur battery
Polysulfide-Shuttle In The Lithium-Sulfur Battery

Moreover, if lithium metals is used as the anode, the battery cell is to slowly but surely to self-discharge with soluble lithium polysulfides which diffuse to the Anode-side. Because of the high chemical reactivity of the lithium anode surface, the polysulfides are lithiated at the Lithium-Anode.

5) Bad performance at low temperatures

The decline in performance below 0 °C temperatures limits the application for certain situations. Under certain conditions, a working temperature above -10 °C can be sufficient. However, this problem can be solved by maintaining the operating temperature above 0 °C.

5) Dendrite formation at the lithium metal anode

If lithium metal is used as an anode, dendrites are formed rapidly. Dendrites are shorting the battery cell. Therefore, dendrite grow has to be mitigated to build a useful Lithium-sulfur battery cell.

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References and Readings

  1. Mori, R. Cathode materials for lithium-sulfur battery: a review. J Solid State Electrochem 27, 813–839 (2023). https://doi.org/10.1007/s10008-023-05387-z
  2. Shao Q, Zhu S, Chen J. A review on lithium-sulfur batteries: Challenge, development, and perspective. Nano Research, 2023
  3. Lithium–sulfur battery. From Wikipedia, the free encyclopedia. Read, February 2023
  4. Lithium-sulfur batteries are one step closer to powering the future, Argonne National Laboratory. Retrieved March 2023. 
  5. A Perspective toward Practical Lithium−Sulfur Batteries, ACS Cent. Sci. 2020, 6, 1095−1104.
  6. A high-energy sulfur cathode in carbonate electrolyte by eliminating polysulfides via solid-phase lithium-sulfur transformation. Nature Communications 9, 4509 (2018). https://doi.org/10.1038/s41467-018-06877-9

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