A High-Rate and Long-Life Sodium Metal Battery Based on a NaB3H8 ⋠xNH3@NaB3H8 Composite Solid-State Electrolyte.

All-solid-state sodium metal batteries are promising for large-scale energy storage applications owing to their intrinsic safety and cost-effectiveness. However, they generally suffer from sodium dendrite growth or rapid capacity fading, especially at high rates, mainly due to poor wettability, sluggish ionic transport, or low interfacial stability of the solid electrolytes. Herein, we report a novel composite, NaB3H8 ⋅ xNH3@NaB3H8 (x<1), as a new class of solid electrolyte for high-rate batteries. NaB3H8 ⋅ xNH3@NaB3H8 is obtained from the sticky NaB3H8 ⋅ NH3 after removal of NH3 partially at room temperature. It delivers an ionic conductivity of 0.84 mS cm-1 at 25 °C and reaches 20.64 mS cm-1 at 45 °C after an order-disorder phase transformation. It also reveals a good capability of dendrite suppression and remarkable stability against sodium metal. These performances enable the all-solid-state Na//TiS2 battery with a high capacity of 232.4 mAh g-1 (97.2 % of theoretical capacity) and long-term cycling stability at 1 C. Notably, this battery shows superior long-life cycling stability even at 5 and 10 C, which has been rarely reported in all-solid-state sodium metal batteries. This work opens a new group of solid electrolytes, contributing to fast-charging or high-power-density sodium metal batteries.

Potassium Decahydrido-closo-Decaborane Urea Complex as a Potential Solid-State Electrolyte for Potassium Metal Batteries.

All-solid-state potassium metal batteries have been considered promising candidates for large-scale energy storage because of abundance and wide availability of K resources, elimination of flammable liquid organic electrolytes, and incorporation of high-capacity K metal anode. However, unideal K-ion conductivities of most reported K-ion solid electrolytes have restricted the development of these batteries. Herein, a novel K2B10H10·CO(NH2)2 complex is reported, forming by incorporating urea into K2B10H10, to achieve an enhanced K-ion conductivity. The crystal structure of K2B10H10·CO(NH2)2 was determined as a monoclinic lattice with the space group of C2/c (No. 15). K2B10H10·CO(NH2)2 delivers an ionic conductivity of 2.7 × 10-8 S cm-1 at 25 °C, and reaching 1.3 × 10-4 S cm-1 at 80 °C, which is about 4 orders of magnitude higher than that of K2B10H10. One possible reason is the anion expansion in size due to the presence of dihydrogen bonds in K2B10H10·CO(NH2)2, resulting in an increase in the K-H bond distance and the electrostatic potential, thereby enhancing the mobility of K+. The K-ion conductivity is also higher than those of most hydridoborate-based K-ion conductors reported. Besides, K2B10H10·CO(NH2)2 reveals a wide electrochemical stability window and remarkable interface compatibility with K metal electrodes, suggesting a promising electrolyte for all-solid-state K metal batteries.

KB3H8·NH3B3H7 Complex as a Potential Solid-State Electrolyte with Excellent Stability against K Metal.

All-solid-state potassium batteries are promising candidates in the fields of large-scale energy storage owing to their intrinsic safety, stability, and cost-effectiveness. However, a suitable solid-state electrolyte with high ionic conductivity and favorable interfacial stability is a major challenge for the design and development of these batteries. Herein, we report the synthesis of new KB3H8·nNH3B3H7 (n = 0.5 and 1) complexes to develop suitable solid-state K-ion conductors for batteries. Both the complexes undergo a reversible phase transition below the thermal decomposition temperature. The optimal KB3H8·NH3B3H7 delivers a solid-state K-ion conductivity of 1.3 × 10-4 S cm-1 at 55 °C with an activation energy of 0.44 eV after a transition from a monoclinic to an orthorhombic phase, which is the highest value of K borohydrides reported to date and places KB3H8·NH3B3H7 among the leading solid-state K-ion conductors. Moreover, KB3H8·NH3B3H7 reveals a K-ion transference number of nearly 0.93, an electrochemical stability window of 1.2 to 3.5 V vs K+/K, a good capability of K dendrite suppression, and a remarkable stability against the K metal anode due to the formation of the stable interface. These performances make KB3H8·NH3B3H7 a promising electrolyte for all-solid-state potassium batteries.

Synthesis of K[B3H7NH2BH2NH2B3H7] for a K-ion solid-state electrolyte.

All-solid-state K batteries are ideal energy storage devices for grid-scale applications of renewable energies. A novel electrolyte K[B3H7NH2BH2NH2B3H7] with weakly coordinating anions was synthesized. It has a high K+ conductivity of 1.01 × 10-4 S cm-1 at 75 °C, which is probably due to the increased electrostatic potential and size of the anions.

A safe and robust dual-network hydrogel electrolyte coupled with multi-heteroatom doped carbon nanosheets for flexible quasi-solid-state zinc ion hybrid supercapacitors.

Aqueous zinc ion hybrid supercapacitors (ZHSCs) are receiving increasing research interest because of their superiority in safety, economy, and high water compatibility. However, the corrosion problems coupled with dendrite growth in an aqueous system severely limit the potential use of zinc storage systems with long service life. To delicately address the above obstacles, a κ-carrageenan/polyacrylamide/Zn(CF3SO3)2 hydrogel electrolyte (denoted as κ-CG/PAAm/Zn(CF3SO3)2) with an ionically and covalently double crosslinked network was constructed, which possesses a high ionic conductivity of 2.3 S m-1, a high tensile strength of 34.6 kPa with a superior stretchability of 599.0%, and an excellent compression strength of 75.3 kPa at 75.0% strain. The double crosslinked polymer chains realize uniform zinc deposition. In addition, the intrinsic hydrophilic groups in the κ-carrageenan (κ-CG) and polyacrylamide (PAAm) chains can well immobilize water molecules, which favor electrolyte ion transport. Moreover, nitrogen and sulphur co-doped carbon nanosheets (denoted as ACNS) characterized by the rich amorphous phase associated with lots of short-range ordered microcrystalline regions were prepared as the cathode material in this work, which exhibits a high capacity of 116.4 mA h g-1 coupled with superior rate performance and long-term cycling stability (108.0% capacity retention over 10 000 cycles) for an aqueous Zn//ACNS ZHSC. A quasi-solid-state ZHSC based on ACNS and κ-CG/PAAm/Zn(CF3SO3)2 exhibits a specific capacity of 100.5 mA h g-1 at 0.25 A g-1 with a high capacity retention of 50.8% at 20 A g-1. The as-fabricated ZHSC also shows excellent cycling stability of 10 000 cycles as well as a superior energy density of 86.5 W h kg-1 at a power density of 215.3 W kg-1. The ZHSC can also be used as a reliable source to drive various kinds of electronics (e.g., mobile phones and electronic timers), which uncovers a feasible strategy for engineering the high-performance hydrogel electrolytes and cathode materials for ZHSC applications.

High Proton-Conductivity in Covalently Linked Polyoxometalate-Organoboronic Acid-Polymers.

The controlled bottom-up design of polymers with metal oxide backbones is a grand challenge in materials design, as it could give unique control over the resulting chemical properties. Herein, we report a 1D-organo-functionalized polyoxometalate polymer featuring a purely inorganic backbone. The polymer is self-assembled from two types of monomers, inorganic Wells-Dawson-type polyoxometalates, and aromatic organo-boronates. Their covalent linkage results in 1D polymer strands, which combine an inorganic oxide backbone (based on B-O and Nb-O linkages) with functional organic side-chains. The polymer shows high bulk proton conductivity of up to 1.59×10-1  S cm-1 at 90 °C and 98 % relative humidity. This synthetic approach could lead to a new class of organic-inorganic polymers where function can be designed by controlled tuning of the monomer units.

Iodine-Substituted Lithium/Sodium closo-Decaborates: Syntheses, Characterization, and Solid-State Ionic Conductivity.

Solid-state electrolytes based on closo-decaborates have caught increasing interest owing to the impressive room-temperature ionic conductivity, remarkable thermal/chemical stability, and excellent deformability. In order to develop new solid-state ion conductors, we investigated the influence of iodine substitution on the thermal, structural, and ionic conduction properties of closo-decaborates. A series of iodinated closo-decaborates, M2[B10H10-nIn] (M = Li, Na; n = 1, 2, 10), were synthesized and characterized by thermal analysis, powder X-ray diffraction, and electrochemical impedance spectroscopy; the stability and ionic conductivity of these compounds were studied. It was found that with the increase of iodine substitution on the closo-decaborate anion cage, the thermal decomposition temperature increases. All M2[B10H10-nIn] exhibit an amorphous structure. The ionic conductivity of Li2[B10H10-nIn] is higher than that of the Li2[B10H10] parent compound. An ionic conductivity of 2.96 × 10-2 S cm-1 with an activation energy of 0.23 eV was observed for Li2[B10I10] at 300 °C, implying that iodine substitution can improve the ionic conductivity. However, the ionic conductivity of Na2[B10H10-nIn] is lower than that of Na2[B10H10] and increases with the increase of iodine substitution, which could be associated with the increase of the electrostatic potential, mass, and volume of the iodinated anions. Moreover, Li2[B10I10] offers a Li-ion transference number of 0.999, an electrochemical stability window of 3.3 V and good compatibility with the Li anode, demonstrating its potential for application in high-temperature batteries.

Phosphate-modified Co-Ni phosphide heterostructure formed by interfacial and electronic tuning for boosted faradaic properties.

Rational structural and compositional modulation endows electrode materials with unique physicochemical characteristics due to their adjustable electronic properties. Herein, a phosphate-modified hierarchical nanoarray consisting of a heterojunction with a well-aligned cobalt phosphide nanowire core and nickel phosphide nanosheet shell on flexible carbon cloth (denoted as CoP@Ni2P-CC) is engineered. The phosphate-modulated heterogeneous phosphide with a tuned electronic structure, additional heterojunction interfaces, and high degree of covalency in the chemical bonds accelerates the reaction kinetics and enhances the energy storage performance. Due to these reasons, the as-obtained phosphide-based heterostructured CoP@Ni2P-CC electrode delivers a capacity of 475.9 C g-1 at 0.5 A g-1 with a satisfying rate capability, which is greatly superior to that of its transition metal counterparts (sulfide, selenide, and oxide). After being assembled into a flexible hybrid supercapacitor (FHSC), a wide operating voltage (1.8 V), high energy/power densities (49.8 W h kg-1/8.6 kW kg-1), and long-term stability (85.1% capacity retention after 10 000 cycles) were achieved. This work may provide a general method from multiple strategies for designing reliable pseudocapacitive materials for flexible electronics.