Dendrite initiation and propagation in lithium metal solid-state batteries.

All-solid-state batteries with a Li anode and ceramic electrolyte have the potential to deliver a step change in performance compared with today's Li-ion batteries1,2. However, Li dendrites (filaments) form on charging at practical rates and penetrate the ceramic electrolyte, leading to short circuit and cell failure3,4. Previous models of dendrite penetration have generally focused on a single process for dendrite initiation and propagation, with Li driving the crack at its tip5-9. Here we show that initiation and propagation are separate processes. Initiation arises from Li deposition into subsurface pores, by means of microcracks that connect the pores to the surface. Once filled, further charging builds pressure in the pores owing to the slow extrusion of Li (viscoplastic flow) back to the surface, leading to cracking. By contrast, dendrite propagation occurs by wedge opening, with Li driving the dry crack from the rear, not the tip. Whereas initiation is determined by the local (microscopic) fracture strength at the grain boundaries, the pore size, pore population density and current density, propagation depends on the (macroscopic) fracture toughness of the ceramic, the length of the Li dendrite (filament) that partially occupies the dry crack, current density, stack pressure and the charge capacity accessed during each cycle. Lower stack pressures suppress propagation, markedly extending the number of cycles before short circuit in cells in which dendrites have initiated.

Visualizing plating-induced cracking in lithium-anode solid-electrolyte cells.

Lithium dendrite (filament) propagation through ceramic electrolytes, leading to short circuits at high rates of charge, is one of the greatest barriers to realizing high-energy-density all-solid-state lithium-anode batteries. Utilizing in situ X-ray computed tomography coupled with spatially mapped X-ray diffraction, the propagation of cracks and the propagation of lithium dendrites through the solid electrolyte have been tracked in a Li/Li6PS5Cl/Li cell as a function of the charge passed. On plating, cracking initiates with spallation, conical 'pothole'-like cracks that form in the ceramic electrolyte near the surface with the plated electrode. The spallations form predominantly at the lithium electrode edges where local fields are high. Transverse cracks then propagate from the spallations across the electrolyte from the plated to the stripped electrode. Lithium ingress drives the propagation of the spallation and transverse cracks by widening the crack from the rear; that is, the crack front propagates ahead of the Li. As a result, cracks traverse the entire electrolyte before the Li arrives at the other electrode, and therefore before a short circuit occurs.

Computational design of graphitic carbon nitride photocatalysts for water splitting.

A series of structures based on graphitic carbon nitride (g-C3N4), a layered material composed of linked carbon-nitrogen heterocycles arranged in a plane, were investigated by density functional theory calculations. g-C3N4 is a semiconductor that absorbs UV light and visible light at the blue end of the visible spectrum, and is widely studied as a photocatalyst for water splitting; however, its photocatalytic efficiency is limited by its poor light-harvesting ability and low charge mobilities. Modifications to the g-C3N4 structure could greatly improve its optical and electronic properties and its photocatalytic efficiency. In this work, the g-C3N4 structure was modified by replacing the nitrogen linker with heteroatoms (phosphorus, boron) or aromatic groups (benzene, s-triazine and substituted benzenes). Two-dimensional (2D) sheets and three-dimensional (3D) multilayer structures with different stacking types were modelled. Several new structures were predicted to have electronic properties superior to g-C3N4 for use as water splitting photocatalysts. In particular, introduction of phosphorus, benzene and s-triazine groups led to band gaps smaller than in the standard g-C3N4 (down to 2.4 eV, corresponding to green light). Doping with boron in the linker positions dramatically reduced the band gap (to 1.6 eV, corresponding to red light); the doped material has the valence band position suitable for water oxidation. Our computational study shows that chemical modification of g-C3N4 is a powerful method to tune this material's electronic properties and improve its photocatalytic activity.

Critical stripping current leads to dendrite formation on plating in lithium anode solid electrolyte cells.

A critical current density on stripping is identified that results in dendrite formation on plating and cell failure. When the stripping current density removes Li from the interface faster than it can be replenished, voids form in the Li at the interface and accumulate on cycling, increasing the local current density at the interface and ultimately leading to dendrite formation on plating, short circuit and cell death. This occurs even when the overall current density is considerably below the threshold for dendrite formation on plating. For the Li/Li6PS5Cl/Li cell, this is 0.2 and 1.0 mA cm-2 at 3 and 7 MPa pressure, respectively, compared with a critical current for plating of 2.0 mA cm-2 at both 3 and 7 MPa. The pressure dependence on stripping indicates that creep rather than Li diffusion is the dominant mechanism transporting Li to the interface. The critical stripping current is a major factor limiting the power density of Li anode solid-state cells. Considerable pressure may be required to achieve even modest power densities in solid-state cells.

Temperature Dependence of Lithium Anode Voiding in Argyrodite Solid-State Batteries.

Void formation at the Li/ceramic electrolyte interface of an all-solid-state battery on discharge results in high local current densities, dendrites on charge, and cell failure. Here, we show that such voiding is reduced at the Li/Li6PS5Cl interface at elevated temperatures, sufficient to increase the critical current before voiding and cell failure from <0.25 mA cm-2 at 25 °C to 0.25 mA cm-2 at 60 °C and 0.5 mA cm-2 at 80 °C under a relatively low stack-pressure of 1 MPa. Increasing the stack-pressure to 5 MPa and temperature to 80 °C permits stable cycling at 2.5 mA cm-2. It is also shown that the charge-transfer resistance at the Li/Li6PS5Cl interface depends on pressure and temperature, with relatively high pressures required to maintain low charge-transfer resistance at -20 °C. These results are consistent with the plastic deformation of Li metal dominating the performance of the Li anode, posing challenges for the implementation of solid-state cells with Li anodes.

Sodium/Na ß″ Alumina Interface: Effect of Pressure on Voids.

Three-electrode studies coupled with tomographic imaging of the Na/Na-ß″-alumina interface reveal that voids form in the Na metal at the interface on stripping and they accumulate on cycling, leading to increasing interfacial current density, dendrite formation on plating, short circuit, and cell failure. The process occurs above a critical current for stripping (CCS) for a given stack pressure, which sets the upper limit on current density that avoids cell failure, in line with results for the Li/solid-electrolyte interface. The pressure required to avoid cell failure varies linearly with current density, indicating that Na creep rather than diffusion per se dominates Na transport to the interface and that significant pressures are required to prevent cell death, >9 MPa at 2.5 mA·cm-2.