Molecular Design of Solid Polymer Electrolytes with Enthalpy-Entropy Manipulation for Li Metal Batteries with Aggressive Cathode Chemistry.

Solid polymer electrolytes (SPEs) with high ion conductivity, high Li+ transference number, and a wide electrochemical window are promising for the next-generation high-energy Li metal batteries (LMBs). Here we describe an enthalpy-entropy manipulation strategy enabling a class of polycarbonate-based copolymeric electrolytes (PCCEs) with regulated cation/anion solvation via a molecular design of the polymer backbone. By integrating a weakly solvating linear carbonate with another strongly solvating cyclic carbonate segment in the polymer backbone, the cation-dipole coordination for Li+ ions (with two types of carbonyl groups) is weakened (low enthalpy penalty) and nondirectional (high entropy penalty), which enables a weak solvation and rapid diffusion of Li+. We further introduce a bis-acrylamide-based cross-linking segment which, other than imparting high mechanical strength, exhibits dihydrogen bonding with the difluoro(oxalate) borate anions, which is strong (high enthalpy penalty) and directional (low entropy penalty), thus restricting the migration of anions. As a result, the PCCE delivers a high ionic conductivity of 0.66 mS cm-1 with a high Li+ transference number (0.76) at 25 °C, as well as high oxidation stability. By an in situ polymerization approach, the PCCE enables LMBs using high-nikel LiNi0.8Co0.1Mn0.1O2 cathodes with a high capacity retention of 82.2% over 800 cycles with a cutoff voltage of 4.5 V and further LMBs using aggressive LiNi0.5Mn1.5O4 cathodes with a 96.4% capacity retention over 300 cycles with a cutoff voltage of 5.0 V. The described enthalpy-entropy manipulation approach offers a unique perspective for the molecular design of high-performance SPEs for high-energy Li metal batteries.

Tuning the Electrolyte and Interphasial Chemistry for All-Climate Sodium-ion Batteries.

Sodium-ion batteries (SIBs) present a promising avenue for next-generation grid-scale energy storage. However, realizing all-climate SIBs operating across a wide temperature range remains a challenge due to the poor electrolyte conductivity and instable electrode interphases at extreme temperatures. Here, we propose a comprehensively balanced electrolyte by pairing carbonates with a low-freezing-point and low-polarity ethyl propionate solvent which enhances ion diffusion and Na+-desolvation kinetics at sub-zero temperatures. Furthermore, the electrolyte leverages a combinatorial borate- and nitrile-based additive strategy to facilitate uniform and inorganic-rich electrode interphases, ensuring excellent rate performance and cycle stability over a wide temperature range from -45 °C to 60 °C. Notably, the Na||sodium vanadyl phosphate cell delivers a remarkable capacity of 105 mAh g-1 with a high rate of 2 C at -25 °C. In addition, the cells exhibit excellent cycling stability over a wide temperature range, maintaining a high capacity retention of 84.7 % over 3,000 cycles at 60 °C and of 95.1 % at -25 °C over 500 cycles. The full cell also exhibits impressive cycling performance over a wide temperature range. This study highlights the critical role of electrolyte and interphase engineering for enabling SIBs that function optimally under diverse and extreme climatic environments.

Rapid-charging aluminium-sulfur batteries operated at 85 °C with a quaternary molten salt electrolyte.

Molten salt aluminum-sulfur batteries are based exclusively on resourcefully sustainable materials, and are promising for large-scale energy storage owed to their high-rate capability and moderate energy density; but the operating temperature is still high, prohibiting their applications. Here we report a rapid-charging aluminium-sulfur battery operated at a sub-water-boiling temperature of 85 °C with a tamed quaternary molten salt electrolyte. The quaternary alkali chloroaluminate melt - possessing abundant electrochemically active high-order Al-Cl clusters and yet exhibiting a low melting point - facilitates fast Al3+ desolvation. A nitrogen-functionalized porous carbon further mediates the sulfur reaction, enabling the battery with rapid-charging capability and excellent cycling stability with 85.4% capacity retention over 1400 cycles at a charging rate of 1 C. Importantly, we demonstrate that the asymmetric sulfur reaction mechanism that involves formation of polysulfide intermediates, as revealed by operando X-ray absorption spectroscopy, accounts for the high reaction kinetics at such temperature wherein the thermal management can be greatly simplified by using water as the heating media.

Surface passivation for highly active, selective, stable, and scalable CO2 electroreduction.

Electrochemical conversion of CO2 to formic acid using Bismuth catalysts is one the most promising pathways for industrialization. However, it is still difficult to achieve high formic acid production at wide voltage intervals and industrial current densities because the Bi catalysts are often poisoned by oxygenated species. Herein, we report a Bi3S2 nanowire-ascorbic acid hybrid catalyst that simultaneously improves formic acid selectivity, activity, and stability at high applied voltages. Specifically, a more than 95% faraday efficiency was achieved for the formate formation over a wide potential range above 1.0 V and at ampere-level current densities. The observed excellent catalytic performance was attributable to a unique reconstruction mechanism to form more defective sites while the ascorbic acid layer further stabilized the defective sites by trapping the poisoning hydroxyl groups. When used in an all-solid-state reactor system, the newly developed catalyst achieved efficient production of pure formic acid over 120 hours at 50 mA cm-2 (200 mA cell current).

A solution-to-solid conversion chemistry enables ultrafast-charging and long-lived molten salt aluminium batteries.

Conventional solid-to-solid conversion-type cathodes in batteries suffer from poor diffusion/reaction kinetics, large volume changes and aggressive structural degradation, particularly for rechargeable aluminium batteries (RABs). Here we report a class of high-capacity redox couples featuring a solution-to-solid conversion chemistry with well-manipulated solubility as cathodes-uniquely allowed by using molten salt electrolytes-that enable fast-charging and long-lived RABs. As a proof-of-concept, we demonstrate a highly reversible redox couple-the highly soluble InCl and the sparingly soluble InCl3-that exhibits a high capacity of about 327 mAh g-1 with negligible cell overpotential of only 35 mV at 1 C rate and 150 °C. The cells show almost no capacity fade over 500 cycles at a 20 C charging rate and can sustain 100 mAh g-1 at 50 C. The fast oxidation kinetics of the solution phase upon initiating the charge enables the cell with ultrafast charging capability, whereas the structure self-healing via re-forming the solution phase at the end of discharge endows the long-term cycling stability. This solution-to-solid mechanism will unlock more multivalent battery cathodes that are attractive in cost but plagued by poor reaction kinetics and short cycle life.

Reversible Zn Metal Anodes Enabled by Trace Amounts of Underpotential Deposition Initiators.

Routine electrolyte additives are not effective enough for uniform zinc (Zn) deposition, because they are hard to proactively guide atomic-level Zn deposition. Here, based on underpotential deposition (UPD), we propose an "escort effect" of electrolyte additives for uniform Zn deposition at the atomic level. With nickel ion (Ni2+ ) additives, we found that metallic Ni deposits preferentially and triggers the UPD of Zn on Ni. This facilitates firm nucleation and uniform growth of Zn while suppressing side reactions. Besides, Ni dissolves back into the electrolyte after Zn stripping with no influence on interfacial charge transfer resistance. Consequently, the optimized cell operates for over 900 h at 1 mA cm-2 (more than 4 times longer than the blank one). Moreover, the universality of "escort effect" is identified by using Cr3+ and Co2+ additives. This work would inspire a wide range of atomic-level principles by controlling interfacial electrochemistry for various metal batteries.

Facile preparation of a MXene-graphene oxide membrane and its voltage-gated ion transport behavior.

Two-dimensional MXenes have become a crucial topic in the field of ion transportation owing to their excellent electrochemical performance. Herein, a strategy for preparing a layered MXene-graphene oxide (GO) membrane via vacuum filtration is proposed, which endows the delaminated two-dimensional MXene-GO membrane (MGOm) with excellent electrical conductivity and chemical stability, achieving an excellent voltage-gated ion transport behavior. Owing to the presence of charges or dipoles within the membrane's channel, the movement of electrons or dipoles under the influence of membrane potential is possible. By varying the transmembrane potential, the transition between the closed and open states of the voltage-gated ion channel can be adjusted. When a negative potential is applied at osmotic pressure, the force between the charged MGOm sheet and the cation (K+) is enhanced, promoting ion permeation. Conversely, the application of positive potential attenuates electrostatic attraction, resulting in a decrease in ion permeability. In addition, the effects of MXene and GO with different modulation ratios on the voltage-gated ion transport have shown that when the modulation ratio of MXene : GO is 7 : 3, the optimal ion permeation rate is achieved. In conclusion, the conductive film with voltage-gated nanochannels is a promising alternative for ion transportation, opening up new avenues for the further exploration of MXene materials in energy storage devices.

Dense T-Nb2O5/Carbon Microspheres for Ultrafast-(Dis)charge and High-Loading Lithium-Ion Batteries.

Orthorhombic niobium pentoxide (T-Nb2O5) is regarded as a potential anode material for lithium-ion batteries (LIBs) due to ultrafast charge/discharge and high safety. However, the poor electronic conductivity and low mass loading of nanostructured T-Nb2O5 limit its practical application in LIBs. Herein, we design and construct dense microspheres consisting of nanostructured T-Nb2O5 embedded in amorphous N-doped carbon (Nb2O5@NC) via a facile method to achieve fast ionic and electronic transport as well as a high mass loading. The dense micro-sized particles with an interconnected carbon network avoid the low mass loading and volumetric energy density of conventional nanostructures. Interconnected pores in the range of a few nanometers are also formed in the Nb2O5@NC microspheres. Notably, at a high mass loading of 12.8 mg cm-2, Nb2O5@NC can achieve a high specific capacity of 171.5 mAh g-1 and an areal capacity of 2.05 mAh cm-2, showing its high lithium storage capacity. The intercalation reaction mechanism with a small volume change during cycling at both crystal lattice and microsphere levels is confirmed by in situ X-ray diffraction and in situ high-resolution transmission electron microscopy. The elegant structure and the electrochemical reaction mechanism disclosed in the work is important for designing ultrafast-(dis)charge electrode materials.

Ultrahigh Stable Methanol Oxidation Enabled by a High Hydroxyl Concentration on Pt Clusters/MXene Interfaces.

Anchoring platinum catalysts on appropriate supports, e.g., MXenes, is a feasible pathway to achieve a desirable anode for direct methanol fuel cells. The authentic performance of Pt is often hindered by the occupancy and poisoning of active sites, weak interaction between Pt and supports, and the dissolution of Pt. Herein, we construct three-dimensional (3D) crumpled Ti3C2Tx MXene balls with abundant Ti vacancies for Pt confinement via a spray-drying process. The as-prepared Pt clusters/Ti3C2Tx (Ptc/Ti3C2Tx) show enhanced electrocatalytic methanol oxidation reaction (MOR) activity, including a relatively low overpotential, high tolerance to CO poisoning, and ultrahigh stability. Specifically, it achieves a high mass activity of up to 7.32 A mgPt-1, which is the highest value reported to date in Pt-based electrocatalysts, and 42% of the current density is retained on Ptc/Ti3C2Tx even after the 3000 min operative time. In situ spectroscopy and theoretical calculations reveal that an electric field-induced repulsion on the Ptc/Ti3C2Tx interface accelerates the combination of OH- and CO adsorption intermediates (COads) in kinetics and thermodynamics. Besides, this Ptc/Ti3C2Tx also efficiently electrocatalyze ethanol, ethylene glycol, and glycerol oxidation reactions with comparable activity and stability to commercial Pt/C.

Fast-charging aluminium-chalcogen batteries resistant to dendritic shorting.

Although batteries fitted with a metal negative electrode are attractive for their higher energy density and lower complexity, the latter making them more easily recyclable, the threat of cell shorting by dendrites has stalled deployment of the technology1,2. Here we disclose a bidirectional, rapidly charging aluminium-chalcogen battery operating with a molten-salt electrolyte composed of NaCl-KCl-AlCl3. Formulated with high levels of AlCl3, these chloroaluminate melts contain catenated AlnCl3n+1- species, for example, Al2Cl7-, Al3Cl10- and Al4Cl13-, which with their Al-Cl-Al linkages confer facile Al3+ desolvation kinetics resulting in high faradaic exchange currents, to form the foundation for high-rate charging of the battery. This chemistry is distinguished from other aluminium batteries in the choice of a positive elemental-chalcogen electrode as opposed to various low-capacity compound formulations3-6, and in the choice of a molten-salt electrolyte as opposed to room-temperature ionic liquids that induce high polarization7-12. We show that the multi-step conversion pathway between aluminium and chalcogen allows rapid charging at up to 200C, and the battery endures hundreds of cycles at very high charging rates without aluminium dendrite formation. Importantly for scalability, the cell-level cost of the aluminium-sulfur battery is projected to be less than one-sixth that of current lithium-ion technologies. Composed of earth-abundant elements that can be ethically sourced and operated at moderately elevated temperatures just above the boiling point of water, this chemistry has all the requisites of a low-cost, rechargeable, fire-resistant, recyclable battery.