Maximizing Magnesiation Capacity of Nanowire Cluster Oxides by Conductive Macromolecule Pillaring and Multication Intercalation.

Magnesium metal batteries (MMBs) have obtained the reputation owing to the high volumetric capacity, low reduction potential, and dendrite-free deposition behavior of the Mg metal anode. However, the bivalent nature of the Mg2+ causes its strong coulombic interaction with the cathode host, which limits the reaction kinetics and reversibility of MMBs, especially based on oxide cathodes. Herein, a synergetic modulation of host pillaring and electrolyte formulation is proposed to activate the layered V2 O5 cathode with expanded interlayers via sequential intercalations of poly(3,4-ethylenedioxythiophene) (PEDOT) and cetyltrimethylammonium bromide (CTAB). The preservation of bundled nanowire texture, copillaring behavior of PEDOT and CTA+ , dual-insertion mode of Mg2+ and MgCl+ at cathode side enable the better charge transfers in both the bulk and interface paths as well as the interaction mitigation effect between Mg-species cations and host lattices. The introduction of CTA+ as electrolyte additive can also lower the interface resistance and smoothen the Mg anode morphology. These modifications endow the full cells coupled with metallic Mg anode with the maximized reversible capacity (288.7 mAh g-1 ) and superior cyclability (over 500 cycles at 500 mA g-1 ), superior to most already reported Mg-ion shuttle batteries even based on passivation-resistant non-Mg anodes or operated at higher temperatures.

Consecutive Nucleation and Confinement Modulation towards Li Plating in Seeded Capsules for Durable Li-Metal Batteries.

A dual modulation strategy of consecutive nucleation and confined growth of Li metal is proposed by using the metal-organic framework (MOF) derivative hollow capsule with inbuilt lithiophilic Au or Co-O nanoparticle (NP) seeds as heterogeneous host. The seeding-induced nucleation enables the negligible overpotential and promotes the inward injection of Li mass into the abundant cavities in host, followed by the conformal plating of Li on the outer surface of host during discharging. This modulation alleviates the dendrite growth and volume expansion of Li plating. The interconnected porous host network enables enhancement of cycling and rate performances of Li metal (a lifespan over 1200 h for Au-seeding symmetric cells, and an endurance of 220 cycles under an ultrahigh current density of 10 mA cm-2 for corresponding asymmetric cells). The hollow capsules integrated with lithiophilic seeds solve the deformation problem of Li metal for durable and long-life Li-metal batteries.

1-(3-Carboxyl-atophen-yl)-4,4'-bipyridin-1-ium dihydrate.

In the crystal structure of the title compound, C17H12N2O2·2H2O, the carboxyl-ate group is linked via O-H⋯O hydrogen bonds to two water mol-ecules. The crystal packing is best described as parallel layers (viewed along the a axis) of viologen and water mol-ecules associated via O-H⋯O hydrogen bonds and π-π inter-actions, with a centroid-centroid separation of 3.8276 (9) Å.

Unlocking solid-state conversion batteries reinforced by hierarchical microsphere stacked polymer electrolyte.

Pursuing all-solid-state lithium metal batteries with dual upgrading of safety and energy density is of great significance. However, searching compatible solid electrolyte and reversible conversion cathode is still a big challenge. The phase transformation at cathode and Li deformation at anode would usually deactivate the electrode-electrolyte interfaces. Herein, we propose an all-solid-state Li-FeF3 conversion battery reinforced by hierarchical microsphere stacked polymer electrolyte for the first time. This g-C3N4 stuffed polyethylene oxide (PEO)-based electrolyte is lightweight due to the absence of metal element doping, and it enables the spatial confinement and dissolution suppression of conversion products at soft cathode-polymer interface, as well as Li dendrite inhibition at filler-reinforced anode-polymer interface. Two-dimensional (2D)-nanosheet-built porous g-C3N4 as three-dimensional (3D) textured filler can strongly cross-link with PEO matrix and LiTFSI (TFSI: bistrifluoromethanesulfonimide) anion, leading to a more conductive and salt-dissociated interface and therefore improved conductivity (2.5 × 10-4 S/cm at 60 °C) and Li+ transference number (0.69). The compact stacking of highly regular robust microspheres in polymer electrolyte enables a successful stabilization and smoothening of Li metal with ultra-long plating/striping cycling for at least 10,000 h. The corresponding Li/LiFePO4 solid cells can endure an extremely high rate of 12 C. All-solid-state Li/FeF3 cells show highly stabilized capacity as high as 300 mAh/g even after 200 cycles and of ~200 mAh/g at extremely high rate of 5 C, as well as ultra-long cycling for at least 1200 cycles at 1 C. High pseudocapacitance contribution (>55%) and diffusion coefficient (as high as 10-12 cm2/s) are responsible for this high-rate fluoride conversion. This result provides a promising solution to conversion-type Li metal batteries of high energy and safety beyond Li-S batteries, which are difficult to realize true "all-solid-state" due to the indispensable step of polysulfide solid-liquid conversion.

Construction of solid-liquid fluorine transport channel to enable highly reversible conversion cathodes.

Conversion-type iron fluoride is a promising alternative cathode to intercalation oxides because of its higher energy density. However, its intrinsic solid-solid conversion is sluggish during repeated splitting and rebonding of metal-fluorine moieties. Here, we propose a solid-liquid conversion mechanism to activate the fluorine transport kinetics of iron oxyfluorides enabled by fluoride anion receptor of tris(pentafluorophenyl)borane (TPFPB). TPFPB promotes the dissociation of inert lithium fluoride and provides a facile fluorine transport channel at multiphase interfaces via the formation of solvated F− intermediate therein. The construction of solid-liquid channel with fluorinated cathode electrolyte interface is the key for the achievement of FeO0.3F1.7 and FeO0.7F1.3 in terms of sustaining conversion reaction (with an energy efficiency approaching 80%) and high-rate performance (with reversible capacity of 320 mAh/g at 2 A/g). The cathode energy densities can reach 1100 Wh/kg for FeO0.3F1.7 and 700 Wh/kg for FeO0.7F1.3 under the power densities of 220 and 4300 W/kg, respectively.

Robustness-Heterogeneity-Induced Ultrathin 2D Structure in Li Plating for Highly Reversible Li-Metal Batteries.

Anode interface modification is crucial for the stabilization of Li-metal batteries (LMBs), which have been considered as the most promising system for the electric vehicle market owing to their high energy density (500 W h kg-1). However, the biggest challenge for LMBs lies in the preservation of anode reversibility, including plated Li morphology control and dendritic Li inhibition during cycling. Here, we propose a nanostructure modulation strategy of Li grains and plating to activate the anode kinetics of LMBs without the compromise of anode stability. This modulation is triggered by the rapid deposition of ultrathin polydopamine coating on the Cu foil (PDA@Cu), which results in an unusual interlaced growth of vertical or lie-down two-dimensional Li nanoflakes on PDA. The high binding energy (>3 eV) between Li atoms and rich imino/carbonyl groups enables a superior lithiophilicity of PDA to homogenize the Li-ion flowing and Li-mass electroplating with negligible nucleation overpotential. The high Coulombic efficiency (98%) and low voltage hysteresis (∼20 mV) are stabilized for at least 300 cycles in the Li-PDA@Cu cell architecture. This PDA@Cu electrode can even tolerate much higher current densities of 5 and 10 mA cm-2 for 170 and 100 cycles, respectively. The interlaced network of Li nanosheets reinforces the electric contact and therefore charge transfer at the anode-electrolyte interface characterized by small interfacial resistance (<3 Ω cm2) and activation energy (0.28 eV). A viewpoint of robustness loss or mechanical heterogeneity in Li plating is discussed to disclose the evolution from column-like Li grains to porous Li sponges and then to compactly stacked Li nanoflakes with porosity shrinkage.

Built-In Catalysis in Confined Nanoreactors for High-Loading Li-S Batteries.

A cathode host with strong sulfur/polysulfide confinement and fast redox kinetics is a challenging demand for high-loading lithium-sulfur batteries. Recently, porous carbon hosts derived from metal-organic frameworks (MOFs) have attracted wide attention due to their unique spatial structure and customizable reaction sites. However, the loading and rate performance of Li-S cells are still restricted by the disordered pore distribution and surface catalysis in these hosts. Here, we propose a concept of built-in catalysis to accelerate lithium polysulfide (LiPSs) conversion in confined nanoreactors, i.e., laterally stacked ordered crevice pores encompassed by MoS2-decorated carbon thin layers. The functions of S-fixability and LiPS catalysis in these mesoporous cavity reactors benefit from the 2D interface contact between ultrathin catalytic MoS2 and conductive C pyrolyzed from Al-MOF. The integrated function of adsorption-catalysis-conversion endows the sulfur-infused C@MoS2 electrode with a high initial capacity of 1240 mAh g-1 at 0.2 C, long life cycle stability of at least 1000 cycles at 2 C, and high rate endurance up to 20 C. This electrode also exhibits commercial potential in view of considerable capacity release and reversibility under high sulfur loading (6 mg cm-2 and ∼80 wt %) and lean electrolyte (E/S ratio of 5 µL mg-1). This study provides a promising design solution of a catalysis-conduction 2D interface in a 3D skeleton for high-loading Li-S batteries.

Highly Reversible Conversion Anodes Composed of Ultralarge Monolithic Grains with Seamless Intragranular Binder and Wiring Network.

Conversion anodes enable a high capacity for lithium-ion batteries due to more than one electron transfer. However, the collapse of the host structure during cycling would cause huge volume expansion and phase separation, leading to the degradation and disconnection of the mixed conductive network of the electrode. The initial nanostructuring and loose spatial distribution of active species are often resorted to in order to alleviate the evolution of the electrode morphology, but at the cost of the decrease of grain packing density. The utilization of ultralarge microsized grains of high density as the conversion anode is still highly challenging. Here, a proof-of-concept grain architecture characterized by endogenetic binder matrix and wiring network is proposed to guarantee the structural integrity of monolithic grains as large as 50-100 µm during deep conversion reaction. Such big grains were fabricated by self-assembly and pyrolysis of a Keggin-type polyoxometalate-based complex with protonated tris[2-(2-methoxyethoxy)-ethyl]amine (TDA-1-H+). The metal-organic precursor can guarantee the firm adherence of numerous Mo-O clusters and nuclei into a highly elastic monolithic structure without evident grain boundaries and intergranular voids. The pyrolyzed TDA-1-H+ not only serves as in situ binder and conductive wire to glue adjacent Mo-O moieties but also acts as a Li-ion pathway to promote sufficient lithiation on surrounding Mo-O. Such a monolithic electrode design leads to an unusual high-conversion-capacity performance (1000 mAh/g) with satisfactory reversibility (reaching at least 750 cycles at 1 A/g). These cycled grains are not disassembled even after undergoing long-term cycling. The conception of the intragranular binder is further confirmed by consolidating the MoO2 porous network after in situ stuffing of MoS2 nanobinders.

Metal-Organic Frameworks as Electrolyte Additives To Enable Ultrastable Plating/Stripping of Li Anode with Dendrite Inhibition.

Suppressing the extrusion of Li dendrites and alleviating the volume expansion of Li anode during long-term cycling are of great significance to achieve highly reversible Li metal batteries of high energy density potential. However, the exploration of facile and effective solutions to smoothen anode surface is still a big challenge. Here, we propose a solid additive strategy by blending tailored metal-organic framework (MOF) grains with typical carbonate electrolyte to enable an ultrastable plating/stripping cycling of Li anode for at least 1400 h with evident inhibition of anode roughening and voltage polarization. Zr-based MOF (UiO-66) additive enables the smallest nucleation and plateau overpotentials (∼80 mV) during Li plating especially under high current density (2 mA/cm2) and large areal capacity (4 mAh/cm2). The kinetic and cyclic advantages of Li anode modulated by UiO-66 not only benefit from its intrinsic features (high surface area/porosity and thermal/electrochemical stability) but also from the reinforced solid electrolyte interface with low resistance, which consists of concentrated LiF and robust Zr-O-C moieties. Li-Li4Ti5O12 cell based on MOF additive can achieve a high reversibility for at least 900 cycles.

Stacking of Tailored Chalcogenide Nanosheets around MoO2-C Conductive Stakes Modulated by a Hybrid POM⊂MOF Precursor Template: Composite Conversion-Insertion Cathodes for Rechargeable Mg-Li Dual-Salt Batteries.

Mg anode has pronounced advantages in terms of high volumetric capacity, resource abundance, and dendrite-free electrochemical plating, which make rechargeable Mg-based batteries stand out as a representative next-generation energy storage system utilized in the field of large-scale stationary electric grid. However, sluggish Mg2+ diffusion in cathode lattices and facile passivation on the Mg anode hinder the commercialization of Mg batteries. Exploring a highly electroactive cathode prototype with hierarchical nanostructure and compatible electrolyte system with the capability of activating both an anode and a cathode is still a challenge. Here, we propose a POM⊂MOF (NENU-5) core-shell architecture as a hybrid precursor template to achieve the stacking of tailored chalcogenide nanosheets around MoO2-C conductive stakes, which can be employed as conversion-insertion cathodes (Cu1.96S-MoS2-MoO2 and Cu2Se-MoO2) for Mg-Li dual-salt batteries. Li-salt modulation further activates the capacity and rate performance at the cathode side by preferential Li-driven displacement reaction in Cu+ extrusible lattices. The heterogeneous conductive network and conformal dual-doped carbon coating enable a reversible capacity as high as 200 mAh/g with a coulombic efficiency close to 100%. The composite cathode can endure a long-term cycling up to 400 cycles and a high current density up to 2 A/g. The diversity of MOF-based materials infused by functional molecules or clusters would enrich the nanoengineering of electrodes to meet the performance demand for future multivalent batteries.