The impact of magnesium content on lithium-magnesium alloy electrode performance with argyrodite solid electrolyte.

Solid-state lithium-based batteries offer higher energy density than their Li-ion counterparts. Yet they are limited in terms of negative electrode discharge performance and require high stack pressure during operation. To circumvent these issues, we propose the use of lithium-rich magnesium alloys as suitable negative electrodes in combination with Li6PS5Cl solid-state electrolyte. We synthesise and characterise lithium-rich magnesium alloys, quantifying the changes in mechanical properties, transport, and surface chemistry that impact electrochemical performance. Increases in hardness, stiffness, adhesion, and resistance to creep are quantified by nanoindentation as a function of magnesium content. A decrease in diffusivity is quantified with 6Li pulsed field gradient nuclear magnetic resonance, and only a small increase in interfacial impedance due to the presence of magnesium is identified by electrochemical impedance spectroscopy which is correlated with x-ray photoelectron spectroscopy. The addition of magnesium aids contact retention on discharge, but this must be balanced against a decrease in lithium diffusivity. We demonstrate via electrochemical testing of symmetric cells at 2.5 MPa and 30∘C that 1% magnesium content in the alloy increases the stripping capacity compared to both pure lithium and higher magnesium content alloys by balancing these effects.

A 3.2 V Binary Layered Oxide Cathode for Potassium-Ion Batteries.

Potassium-ion batteries (KIBs) can offer high energy density, cyclability, and operational safety while being economical due to the natural abundance of potassium. Utilizing graphite as an anode, suitable cathodes can realize full cells. Searching for potential cathodes, this work introduces P3-type K0.5Ni1/3Mn2/3O2 layered oxide as a potential candidate synthesized by a simple solid-state method. The material works as a 3.2 V cathode combining Ni redox at high voltage and Mn redox at low voltage and exhibits highly reversible K+ ion (de)insertion at ambient and elevated (40-50 °C) temperatures. First-principles calculations suggest the ground state in-plane Mn-Ni ordering in the MO2 sheets is strongly correlated to the K-content in the framework, leading to an interwoven and alternative row ordering of Ni-Mn in K0.5Ni1/3Mn2/3O2. Postmortem and electrochemical titration reveal the occurrence of a solid solution mechanism during K+ (de)insertion. The findings suggest that the Ni addition can effectively tune the electronic and structural properties of the cathode, leading to improved electrochemical performance. This work provides new insights in the quest to develop potential low-cost Co-free KIB cathodes for practical applications in stationary energy storage.

Mitigating Sodium Ordering for Enhanced Solid Solution Behavior in Layered NaNiO2 Cathodes.

The O-type layered nickel oxides suffer from undesired cooperative Jahn-Teller distortion stemming from Ni3+ ions and undergo multiple biphasic structural transformations during the insertion/extraction of large Na+ ions, posing a significant challenge to stabilize the structural integrity. We present here a systematic investigation of the impact of substituting 5 % divalent (Mg2+) or trivalent (Al3+ or Co3+) ions for Ni3+ to alleviate Na+ion ordering and perturb the Jahn-Teller effect to enhance structural stability. We gauge a fundamental understanding of the Mg-O and Na-O or Mg-O-Na bonding interactions, noting that the ionicity of the Mg-O bond deshields the electronic cloud of oxygen from Na+ ions. Furthermore, calculations of the Van Vleck distortion modes reveal a relaxation of NiO6 octahedra from Jahn-Teller distortion and a reduced electron density at the interlayer with Mg2+ substitution. Long-range (operando X-ray diffraction) and short-range (magic angle spinning nuclear magnetic resonance) structural analyses provide insights into reduced ordering, allowing a stable continuous solid solution. Overall, Mg-substitution results in a high-capacity retention of ~96 % even after 100 cycles, showcasing the potential of this strategy for overcoming the structural instabilities and enhancing the performance of sodium-ion batteries.

Uncovering the Interplay of Competing Distortions in the Prussian Blue Analogue K2Cu[Fe(CN)6].

We report the synthesis, crystal structure, thermal response, and electrochemical behavior of the Prussian blue analogue (PBA) K2Cu[Fe(CN)6]. From a structural perspective, this is the most complex PBA yet characterized: its triclinic crystal structure results from an interplay of cooperative Jahn-Teller order, octahedral tilts, and a collective "slide" distortion involving K-ion displacements. These different distortions give rise to two crystallographically distinct K-ion channels with different mobilities. Variable-temperature X-ray powder diffraction measurements show that K-ion slides are the lowest-energy distortion mechanism at play, as they are the only distortion to be switched off with increasing temperature. Electrochemically, the material operates as a K-ion cathode with a high operating voltage and an improved initial capacity relative to higher-vacancy PBA alternatives. On charging, K+ ions are selectively removed from a single K-ion channel type, and the slide distortions are again switched on and off accordingly. We discuss the functional importance of various aspects of structural complexity in this system, placing our discussion in the context of other related PBAs.

Potassium Cobalt Pyrophosphate as a Nonprecious Bifunctional Electrocatalyst for Zinc-Air Batteries.

Economic and sustainable (ecological) energy storage forms a major pillar of the global energy sector. Bifunctional electrocatalysts, based on oxygen electrolysis, play a key role in the development of rechargeable metal-air batteries. Pursuing precious metal-free economic catalysts, here, we report K2CoP2O7 pyrophosphate as a robust cathode for secondary zinc-air batteries with efficient oxygen evolution and oxygen reduction (OER||ORR) activity. Prepared by autocombustion, nanoscale K2CoP2O7 exhibited excellent oxygen reduction and evolution reactions among all phosphate-based electrocatalysts. In particular, the OER activity surpassed that of commercial RuO2 with low overpotential (0.27 V). First-principles calculations revealed that the bifunctional activity is rooted in the Co active site with the CoO5 local coordination in the most stable (110) surface. This nanostructured (tetragonal) pyrophosphate can be harnessed as an economic bifunctional catalyst for zinc-air batteries.

P3-type layered K0.48Mn0.4Co0.6O2: a novel cathode material for potassium-ion batteries.

P3-type layered K0.48Mn0.4Co0.6O2 was synthesized using a solid-state method. By stabilising into a rhombohedral structure [s.g. R3m (#160)], it delivers a reversible capacity of 64 mA h g-1 with a nominal voltage of ∼3.0 V (vs. K/K+) and it has good cycling stability. It involves a solid-solution redox mechanism, and forms an economical and stable oxide insertion material for potassium-ion batteries.

Electrochemical potassium-ion intercalation in NaxCoO2: a novel cathode material for potassium-ion batteries.

Reversible electrochemical potassium-ion intercalation in P2-type NaxCoO2 was examined for the first time. Hexagonal Na0.84CoO2 platelets prepared by a solution combustion synthesis technique were found to work as an efficient host for K+ intercalation. They deliver a high reversible capacity of 82 mA h g-1, good rate capability and excellent cycling performance up to 50 cycles.