Understanding the Cathode-Electrolyte Interfacial Chemistry in Rechargeable Magnesium Batteries.

Rechargeable magnesium batteries (RMBs) have garnered significant attention due to their potential to provide high energy density, utilize earth-abundant raw materials, and employ metal anode safely. Currently, the lack of applicable cathode materials has become one of the bottleneck issues for fully exploiting the technological advantages of RMBs. Recent studies on Mg cathodes reveal divergent storage performance depending on the electrolyte formulation, posing interfacial issues as a previously overlooked challenge. This minireview begins with an introduction of representative cathode-electrolyte interfacial phenomena in RMBs, elaborating on the unique solvation behavior of Mg2+, which lays the foundation for interfacial chemistries. It is followed by presenting recently developed strategies targeting the promotion of Mg2+ desolvation in the electrolyte and alternative cointercalation approaches to circumvent the desolvation step. In addition, efforts to enhance the cathode-electrolyte compatibility via electrolyte development and interfacial engineering are highlighted. Based on the abovementioned discussions, this minireview finally puts forward perspectives and challenges on the establishment of a stable interface and fast interfacial chemistry for RMBs.

Improving rechargeable magnesium batteries through dual cation co-intercalation strategy.

The development of competitive rechargeable Mg batteries is hindered by the poor mobility of divalent Mg ions in cathode host materials. In this work, we explore the dual cation co-intercalation strategy to mitigate the sluggishness of Mg2+ in model TiS2 material. The strategy involves pairing Mg2+ with Li+ or Na+ in dual-salt electrolytes in order to exploit the faster mobility of the latter with the aim to reach better electrochemical performance. A combination of experiments and theoretical calculations details the charge storage and redox mechanism of co-intercalating cationic charge carriers. Comparative evaluation reveals that the redox activity of Mg2+ can be improved significantly with the help of the dual cation co-intercalation strategy, although the ionic radius of the accompanying monovalent ion plays a critical role on the viability of the strategy. More specifically, a significantly higher Mg2+ quantity intercalates with Li+ than with Na+ in TiS2. The reason being the absence of phase transition in the former case, which enables improved Mg2+ storage. Our results highlight dual cation co-intercalation strategy as an alternative approach to improve the electrochemical performance of rechargeable Mg batteries by opening the pathway to a rich playground of advanced cathode materials for multivalent battery applications.

Long Cycle-Life Ca Batteries with Poly(anthraquinonylsulfide) Cathodes and Ca-Sn Alloy Anodes.

Calcium (Ca) batteries are attractive post-lithium battery technologies, due to their potential to provide high-voltage and high-energy systems in a sustainable manner. We investigated herein 1,5-poly(anthraquinonylsulfide) (PAQS) for Ca-ion storage with calcium tetrakis(hexafluoroisopropyloxy)borate Ca[B(hfip)4 ]2 [hfip=OCH(CF3 )2 ] electrolytes. It is demonstrated that PAQS could be synthesized in a cost-effective approach and be processed environmentally friendly into the electrodes. The PAQS cathodes could provide 94 mAh g-1 capacity at 2.2 V vs. Ca at 0.5C (1C=225 mAh g-1 ). However, cycling of the cells was severely hindered due to the fast degradation of the metal anode. Replacing the Ca metal anode with a calcium-tin (Ca-Sn) alloy anode, the PAQS cathodes exhibited long cycling performance (45 mAh g-1 at 0.5C after 1000 cycles) and superior rate capability (52 mAh g-1 at 5C). This is mainly ascribed to the flexible structure of PAQS and good compatibility of the alloy anodes with the electrolyte solutions, which allow reversible quinone carbonyl redox chemistry in the Ca battery systems. The promising properties of PAQS indicate that further exploration of the organic cathode materials could be a feasible direction towards green Ca batteries.

Anion Storage Chemistry of Organic Cathodes for High-Energy and High-Power Density Divalent Metal Batteries.

Multivalent batteries show promising prospects for next-generation sustainable energy storage applications. Herein, we report a polytriphenylamine (PTPAn) composite cathode capable of highly reversible storage of tetrakis(hexafluoroisopropyloxy) borate [B(hfip)4 ] anions in both Magnesium (Mg) and calcium (Ca) battery systems. Spectroscopic and computational studies reveal the redox reaction mechanism of the PTPAn cathode material. The Mg and Ca cells exhibit a cell voltage >3 V, a high-power density of ∼∼3000 W kg-1 and a high-energy density of ∼∼300 Wh kg-1 , respectively. Moreover, the combination of the PTPAn cathode with a calcium-tin (Ca-Sn) alloy anode could enable a long battery-life of 3000 cycles with a capacity retention of 60 %. The anion storage chemistry associated with dual-ion electrochemical concept demonstrates a new feasible pathway towards high-performance divalent ion batteries.

Long-Cycle-Life Calcium Battery with a High-Capacity Conversion Cathode Enabled by a Ca2+/Li+ Hybrid Electrolyte.

Calcium (Ca) batteries represent an attractive option for electrochemical energy storage due to physicochemical and economic reasons. The standard reduction potential of Ca (-2.87 V) is close to Li and promises a wide voltage window for Ca full batteries, while the high abundance of Ca in the earth's crust implicates low material costs. However, the development of Ca batteries is currently hindered by technical issues such as the lack of compatible electrolytes for reversible Ca2+ plating/stripping and high-capacity cathodes with fast kinetics. Herein, we employed FeS2 as a conversion cathode material and combined it with a Li+/Ca2+ hybrid electrolyte for Ca batteries. We demonstrate that Li+ ions ensured reversible Ca2+ plating/stripping on the Ca metal anode with a small overpotential. At the same time, they enable the conversion of FeS2, offering high discharge capacity. As a result, the Ca/FeS2 cell demonstrated an excellent long-term cycling performance with a high discharge capacity of 303 mAh g-1 over 200 cycles. Even though the practical application of such an approach is questionable due to the high quantity of electrolytes, we believe that our scientific findings still provide new directions for studying Ca batteries with long-term cycling.

Calcium-tin alloys as anodes for rechargeable non-aqueous calcium-ion batteries at room temperature.

Rechargeable calcium batteries possess attractive features for sustainable energy-storage solutions owing to their high theoretical energy densities, safety aspects and abundant natural resources. However, divalent Ca-ions and reactive Ca metal strongly interact with cathode materials and non-aqueous electrolyte solutions, leading to high charge-transfer barriers at the electrode-electrolyte interface and consequently low electrochemical performance. Here, we demonstrate the feasibility and elucidate the electrochemical properties of calcium-tin (Ca-Sn) alloy anodes for Ca-ion chemistries. Crystallographic and microstructural characterizations reveal that Sn formed from electrochemically dealloying the Ca-Sn alloy possesses unique properties, and that this in-situ formed Sn undergoes subsequent reversible calciation/decalciation as CaSn3. As demonstration of the suitability of Ca-Sn alloys as anodes for Ca-ion batteries, we assemble coin cells with an organic cathode (1,4-polyanthraquinone) in an electrolyte of 0.25 M calcium tetrakis(hexafluoroisopropyloxy)borate in dimethoxyethane. These electrochemical cells are charged/discharged for 5000 cycles at 260 mA g-1, retaining a capacity of 78 mAh g-1 with respect to the organic cathode. The discovery of new class of Ca-Sn alloy anodes opens a promising avenue towards viable high-performance Ca-ion batteries.

Dual Role of Mo6 S8 in Polysulfide Conversion and Shuttle for Mg-S Batteries.

Magnesium-Sulfur batteries are one of most appealing options among the post-lithium battery systems due to its potentially high energy density, safe and sustainable electrode materials. The major practical challenges are originated from the soluble magnesium polysulfide intermediates and their shuttling between the electrodes, which cause high overpotentials, low sulfur utilization, and poor Coulombic efficiency. Herein, a functional Mo6 S8 modified separator is designed to effectively address these issues. Both the experimental results and density functional theory calculations show that the electrochemically active Mo6 S8 layer has a superior adsorption capability of polysulfides and simultaneously acts as a mediator to accelerate the polysulfide conversion kinetics. Remarkably, the magnesium-sulfur cell assembled with the functional separator delivers a high specific energy density (942.9 mA h g-1 in the 1st cycle) and can be cycled at 0.2 C for 200 cycles with a Coulombic efficiency of 96%. This work demonstrates a new design concept toward high-performance metal-sulfur batteries.

Growth and Optical Properties of the Whole System of Li(Mn1-x,Nix)PO4 (0 ≤ x ≤ 0.5) Single Crystals.

A series of single crystals of Li(Mn1-x,Nix)PO4 (x = 0.00, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.08, 0.10, 0.15, 0.20, and 0.50) have been grown to large sizes up to 5 mm in diameter and 120 mm in length using the floating zone method for the first time. The comprehensive characterizations of the as-grown crystals were performed before further physical property measurements. The composition of the grown crystals was determined by energy-dispersive X-ray spectroscopy. The crystal structures were characterized by the X-ray powder diffraction method with a GSAS fitting for structural refinement, which reveals a high phase purity of the as-obtained crystals. The polarized microscopic images and Laue patterns prove the excellent quality of the single crystals. Oriented cuboids with sizes of 2.7 × 3.8 × 2.1 mm3 along the a, b, and c crystalline directions were cut and polished for further anisotropic magnetic and transparent measurements. We also first proposed a new potential application in the non-linear optical (NLO) and laser generation application for LiMPO4 (M = transition metal) materials. The optical and laser properties, such as the absorption spectra and the second harmonic generation (SHG), have been investigated and have furthermore confirmed the good quality of the as-grown single crystals.

New Insight into Desodiation/Sodiation Mechanism of MoS2: Sodium Insertion in Amorphous Mo-S Clusters.

Molybdenum disulfide (MoS2) is a promising anode material for sodium batteries due to its high theoretical capacity. While significantly improved electrochemical performance has been achieved, the reaction mechanism is still equivocal. Herein, we applied electron pair distribution function and X-ray absorption spectroscopy to investigate the desodiation/sodiation mechanism of MoS2 electrodes. The results reveal that Mo-S bonds are well preserved and dominant in the sodiation product matrix but do not convert to metallic Mo and Na2S even at deep sodiation. The MoS2 multilayer sheets break into disordered MoSx clusters with modified octahedral symmetry during discharging. The long-range order was not rebuilt during subsequent charging but with partial recovery of the Mo-S coordination symmetry. The mechanism of the reaction is independent of the carbon matrix, although it prevents the MoSx clusters from leaching into the electrolyte and thus contributes to an extended cycle life. This work refreshes the fundamental understanding of the desodiation/sodiation mechanism of MoS2 materials.

Modeling of Electron-Transfer Kinetics in Magnesium Electrolytes: Influence of the Solvent on the Battery Performance.

The performance of rechargeable magnesium batteries is strongly dependent on the choice of electrolyte. The desolvation of multivalent cations usually goes along with high energy barriers, which can have a crucial impact on the plating reaction. This can lead to significantly higher overpotentials for magnesium deposition compared to magnesium dissolution. In this work we combine experimental measurements with DFT calculations and continuum modelling to analyze Mg deposition in various solvents. Jointly, these methods provide a better understanding of the electrode reactions and especially the magnesium deposition mechanism. Thereby, a kinetic model for electrochemical reactions at metal electrodes is developed, which explicitly couples desolvation to electron transfer and, furthermore, qualitatively takes into account effects of the electrochemical double layer. The influence of different solvents on the battery performance is studied for the state-of-the-art magnesium tetrakis(hexafluoroisopropyloxy)borate electrolyte salt. It becomes apparent that not necessarily a whole solvent molecule must be stripped from the solvated magnesium cation before the first reduction step can take place. For Mg reduction it seems to be sufficient to have one coordination site available, so that the magnesium cation is able to get closer to the electrode surface. Thereby, the initial desolvation of the magnesium cation determines the deposition reaction for mono-, tri- and tetraglyme, whereas the influence of the desolvation on the plating reaction is minor for diglyme and tetrahydrofuran. Overall, we can give a clear recommendation for diglyme to be applied as solvent in magnesium electrolytes.

Establishing a Stable Anode-Electrolyte Interface in Mg Batteries by Electrolyte Additive.

Simple magnesium salts with high electrochemical and chemical stability and adequate ionic conductivity represent a new-generation electrolyte for magnesium (Mg) batteries. Similar to other Mg electrolytes, the simple-salt electrolyte also suffers from high charge-transfer resistance on the Mg surface due to the adsorbed species in the solution. In the current study, we built a model Mg cell system with the Mg[B(hfip)4]2/DME electrolyte and Chevrel phase Mo6S8 cathode, to demonstrate the effect of such anode-electrolyte interfacial properties on the full-cell performance. It was found that the cell required additional activation cycles to achieve its maximal capacity. The activation process is mainly attributed to the conditioning of the anode-electrolyte interface, which could be boosted by introducing an additive amount of Mg(BH4)2 to the Mg[B(hfip)4]2/DME electrolyte. Electrochemical and spectroscopic analyses revealed that the Mg(BH4)2 additive helps to remove the native oxide layer and promotes the formation of a solid electrolyte interphase layer on Mg. As a result, the full cell with the additive-containing electrolyte delivered a stable capacity from the second cycle onward. Further battery tests showed a reversible cycling for 600 cycles and an excellent rate capability, indicating good compatibility of the Mg(BH4)2 additive. The current study not only provides fundamental insights into the interfacial phenomena in Mg batteries but also highlights the facile tunability of the simple-salt Mg electrolytes.

Surface Engineering of a Mg Electrode via a New Additive to Reduce Overpotential.

In nonaqueous Mg batteries, inactive adsorbed species and the passivation layer formed from the reactive Mg with impurities in the electrolyte seriously affect the Mg metal/electrolyte interface. These adlayers can impede the passage of Mg2+ ions, leading to a high Mg plating/stripping overpotential. Herein, we report the properties of a new additive, bismuth triflate (Bi(OTf)3), for synthesizing a chlorine-free Mg electrolyte to enhance Mg plating/stripping from initial cycles. The beneficial effect of Bi(OTf)3 can be ascribed to Bi/Mg3Bi2 formed in situ on the Mg metal surface, which increases the charge transfer during the on-off transition by reducing the adsorption of inactive species on the Mg surface and enhancing the resistance of the reactive surface to passivation. This simple method provides a new avenue to improve the compatibility between the Cl-free Mg electrolyte and the Mg metal anode.

A Self-Conditioned Metalloporphyrin as a Highly Stable Cathode for Fast Rechargeable Magnesium Batteries.

Development of practical rechargeable Mg batteries (RMBs) is impeded by their limited cycle life and rate performance of cathodes. As demonstrated herein, a copper-porphyrin with meso-functionalized ethynyl groups is capable of reversible two- and four-electron storage at an extremely fast rate (tested up to 53 C). The reversible four-electron redox process with cationic-anionic contributions resulted in a specific discharge capacity of 155 mAh g-1 at the high current density of 1000 mA g-1 . Even at 4000 mA g-1 , it still delivered >70 mAh g-1 after 500 cycles, corresponding to an energy density of >92 Wh kg-1 at a high power of >5100 W kg-1 . The ability to provide such high-rate performance and long-life opens the way to the development of practical cathodes for multivalent metal batteries.

Rechargeable Calcium-Sulfur Batteries Enabled by an Efficient Borate-Based Electrolyte.

Rechargeable metal-sulfur batteries show great promise for energy storage applications because of their potentially high energy and low cost. The multivalent-metal based electrochemical system exhibits the particular advantage of the feasibility of dendrite-free metal anode. Calcium (Ca) represents a promising anode material owing to the low reductive potential, high capacity, and abundant natural resources. However, calcium-sulfur (Ca-S) battery technology is in an early R&D stage, facing the fundamental challenge to develop a suitable electrolyte enabling reversible electrochemical Ca deposition, and at the same time, sulfur redox reactions in the system. Herein, a study of a room-temperature Ca-S battery by employing a stable and efficient calcium tetrakis(hexafluoroisopropyloxy) borate Ca[B(hfip)4 ]2 electrolyte is presented. The Ca-S batteries exhibit a cell voltage of ≈2.1 V (close to its thermodynamic value) and good reversibility. The mechanistic studies hint at a redox chemistry of sulfur with polysulfide/sulfide species involved in the Ca-based system.

Multi-Electron Reactions Enabled by Anion-Based Redox Chemistry for High-Energy Multivalent Rechargeable Batteries.

The development of multivalent metal (such as Mg and Ca) based battery systems is hindered by lack of suitable cathode chemistry that shows reversible multi-electron redox reactions. Cationic redox centres in the classical cathodes can only afford stepwise single-electron transfer, which are not ideal for multivalent-ion storage. The charge imbalance during multivalent ion insertion might lead to an additional kinetic barrier for ion mobility. Therefore, multivalent battery cathodes only exhibit slope-like voltage profiles with insertion/extraction redox of less than one electron. Taking VS4 as a model material, reversible two-electron redox with cationic-anionic contributions is verified in both rechargeable Mg batteries (RMBs) and rechargeable Ca batteries (RCBs). The corresponding cells exhibit high capacities of >300 mAh g-1 at a current density of 100 mA g-1 in both RMBs and RCBs, resulting in a high energy density of >300 Wh kg-1 for RMBs and >500 Wh kg-1 for RCBs. Mechanistic studies reveal a unique redox activity mainly at anionic sulfides moieties and fast Mg2+ ion diffusion kinetics enabled by the soft structure and flexible electron configuration of VS4 .

Fast kinetics of multivalent intercalation chemistry enabled by solvated magnesium-ions into self-established metallic layered materials.

Rechargeable magnesium batteries are one of the most promising candidates for next-generation battery technologies. Despite recent significant progress in the development of efficient electrolytes, an on-going challenge for realization of rechargeable magnesium batteries remains to overcome the sluggish kinetics caused by the strong interaction between double charged magnesium-ions and the intercalation host. Herein, we report that a magnesium battery chemistry with fast intercalation kinetics in the layered molybdenum disulfide structures can be enabled by using solvated magnesium-ions ([Mg(DME)x]2+). Our study demonstrates that the high charge density of magnesium-ion may be mitigated through dimethoxyethane solvation, which avoids the sluggish desolvation process at the cathode-electrolyte interfaces and reduces the trapping force of the cathode lattice to the cations, facilitating magnesium-ion diffusion. The concept of using solvation effect could be a general and effective route to tackle the sluggish intercalation kinetics of magnesium-ions, which can potentially be extended to other host structures.

Surface modification of bacterial cellulose aerogels' web-like skeleton for oil/water separation.

The cellulose nanofibers of bacterial cellulose aerogel (BCA) are modified only on their surfaces using a trimethylsilylation reaction with trimethyichlorosilane in liquid phase followed by freeze-drying. The obtained hydrophobic bacterial cellulose aerogels (HBCAs) exhibit low density (≤6.77 mg/cm(3)), high surface area (≥169.1 m(2)/g), and high porosity (≈ 99.6%), which are nearly the same as those of BCA owing to the low degrees of substitution (≤0.132). Because the surface energy of cellulose nanofibers decreased and the three-dimensional web-like microstructure, which was comprised of ultrathin (20-80 nm) cellulose nanofibers, is maintained during the trimethylsilylation process, the HBCAs have hydrophobic and oleophilic properties (water/air contact angle as high as 146.5°) that endow them with excellent selectivity for oil adsorption from water. The HBCAs are able to collect a wide range of organic solvents and oils with absorption capacities up to 185 g/g, which depends on the density of the liquids. Hence, the HBCAs are wonderful candidates for oil absorbents to clean oil spills in the marine environment. This work provides a different way to multifunctionalize cellulose aerogel blocks in addition to chemical vapor deposition method.