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The concept of all-solid-state lithium using INORGANIC SOLID-STATE ELECTROLYTES rechargeable batteries has attracted great attention due to their high safety (no solvents) and increased energy density. Solid-state lithium secondary batteries are considered the most promising future generation of high-energy density batteries. The most essential components are solid electrolytes for all-solid-state lithium metal batteries.
Liquid organic electrolytes are mostly used in commercial lithium-ion batteries, due to their advantages of high conductivity and excellent wetting of the electrode/electrolyte interface.
However, liquid electrolytes are flammable. This is a safety issue in current commercial lithium-ion batteries.
Inorganic Solid-state electrolytes enable several emerging technologies, such as solid-oxide fuel cells, sensors, and solid-state batteries for EV.
Recent discoveries have led to increased lithium-ion conductivity, with LISICON-type, argyrodites, lithium nitrides, lithium hydrides, perovskites, and lithium bromides, lithium chlorides, lithium Iodides – all having higher conductivities than liquid-solvent-based electrolytes. Structural and compositional tuning within a given family of structures can increase conductivities.
Lithium-ion conductors provide exciting opportunities for solid-state lithium-ion and lithium−air batteries for vehicle applications (Transportation, e-mobility) and large-scale stationary applications.
Solid-state electrolytes have a broad electrochemical stability window, improved thermal stability, and no flammability, but many are unstable against negative electrodes like lithium-metal.
Accelerated ion-conductors can react with positive active electrode materials, resulting in bad interfacial charge-transfer kinetics.
Monovalent ions have the highest diffusion coefficients and migration energies, when comparing M+ (Li+, Na+, K+), M2+ (Mg2+, Ca2+, Zn2+) (Tm3+ and Al3+) inLi2SO4 at 550 °C.
There are several structural families that have high lithium-conductivities in the range of 10−2 to 10−3 S/cm at room temperature, and lithium-ion conductivity can vary by up to 5−6 orders of magnitude within each family of compounds.
Increasing the lattice volume or lithium–ion diffusion bottleneck size has been exploited effectively to enhance the lithium-ion conductivity in LISICON-, NASICON-, perovskite-electrolytes.
Disordering lithium-atoms in tetrahedral and octahedral sites is a good way to achieve high lithium-ion conductivity in the garnet electrolytes.
Inorganic sulfide solid electrolytes for all-solid-state lithium secondary batteries,
J. Mater. Chem. A, 2019,7, 20540-20557
Atul Kumar Mishra et al., 2021, Review — Inorganic Solid State Electrolytes: Insights on Current and Future Scope, J. Electrochem. Soc. 168, 080536, DOI: 10.1149/1945-7111/ac1dc
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.
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.
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.
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.
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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