Reviving Cost-Effective Organic Cathodes in Halide-Based All-Solid-State Lithium Batteries.

The evolution of inorganic solid electrolytes has revolutionized the field of sustainable organic cathode materials, particularly addressing the dissolution problems in traditional liquid electrolytes. However, current sulfide-based all-solid-state lithium-organic batteries still face challenges such as high working temperatures, high costs, and low voltage. Here, we design an all-solid-state lithium battery based on a cost-effective organic cathode material phenanthrenequinone (PQ) and a halide solid electrolyte Li2ZrCl6. Thanks to the good compatibility between PQ and Li2ZrCl6, the PQ cathode achieved a high specific capacity of 248 mAh g-1 (96% of the theoretical capacity), a high average discharge voltage of 2.74 V (vs. Li+/Li), and a good capacity retention of 95% after 100 cycles at room temperature (25 °C). Furthermore, the interaction between the high-voltage carbonyl PQ cathode and both sulfide and halide solid electrolytes, as well as the redox mechanism of PQ cathode in all-solid-state batteries,  were carefully studied by a variety of advanced characterizations. We believe such a design and the corresponding investigations for the underlying chemistry give insights into the further development of practical all-solid-state lithium-organic batteries.

Design principles for sodium superionic conductors.

Motivated by the high-performance solid-state lithium batteries enabled by lithium superionic conductors, sodium superionic conductor materials have great potential to empower sodium batteries with high energy, low cost, and sustainability. A critical challenge lies in designing and discovering sodium superionic conductors with high ionic conductivities to enable the development of solid-state sodium batteries. Here, by studying the structures and diffusion mechanisms of Li-ion versus Na-ion conducting solids, we reveal the structural feature of face-sharing high-coordination sites for fast sodium-ion conductors. By applying this feature as a design principle, we discover a number of Na-ion conductors in oxides, sulfides, and halides. Notably, we discover a chloride-based family of Na-ion conductors NaxMyCl6 (M = La-Sm) with UCl3-type structure and experimentally validate with the highest reported ionic conductivity. Our findings not only pave the way for the future development of sodium-ion conductors for sodium batteries, but also consolidate design principles of fast ion-conducting materials for a variety of energy applications.

Manipulating Li2S2/Li2S mixed discharge products of all-solid-state lithium sulfur batteries for improved cycle life.

All-solid-state lithium-sulfur batteries offer a compelling opportunity for next-generation energy storage, due to their high theoretical energy density, low cost, and improved safety. However, their widespread adoption is hindered by an inadequate understanding of their discharge products. Using X-ray absorption spectroscopy and time-of-flight secondary ion mass spectrometry, we reveal that the discharge product of all-solid-state lithium-sulfur batteries is not solely composed of Li2S, but rather consists of a mixture of Li2S and Li2S2. Employing this insight, we propose an integrated strategy that: (1) manipulates the lower cutoff potential to promote a Li2S2-dominant discharge product and (2) incorporates a trace amount of solid-state catalyst (LiI) into the S composite electrode. This approach leads to all-solid-state cells with a Li-In alloy negative electrode that deliver a reversible capacity of 979.6 mAh g-1 for 1500 cycles at 2.0 A g-1 at 25 °C. Our findings provide crucial insights into the discharge products of all-solid-state lithium-sulfur batteries and may offer a feasible approach to enhance their overall performance.

A gradient oxy-thiophosphate-coated Ni-rich layered oxide cathode for stable all-solid-state Li-ion batteries.

High-energy Ni-rich layered oxide cathode materials such as LiNi0.8Mn0.1Co0.1O2 (NMC811) suffer from detrimental side reactions and interfacial structural instability when coupled with sulfide solid-state electrolytes in all-solid-state lithium-based batteries. To circumvent this issue, here we propose a gradient coating of the NMC811 particles with lithium oxy-thiophosphate (Li3P1+xO4S4x). Via atomic layer deposition of Li3PO4 and subsequent in situ formation of a gradient Li3P1+xO4S4x coating, a precise and conformal covering for NMC811 particles is obtained. The tailored surface structure and chemistry of NMC811 hinder the structural degradation associated with the layered-to-spinel transformation in the grain boundaries and effectively stabilize the cathode|solid electrolyte interface during cycling. Indeed, when tested in combination with an indium metal negative electrode and a Li10GeP2S12 solid electrolyte, the gradient oxy-thiophosphate-coated NCM811-based positive electrode enables the delivery of a specific discharge capacity of 128 mAh/g after almost 250 cycles at 0.178 mA/cm2 and 25 °C.

Manipulating Charge-Transfer Kinetics of Lithium-Rich Layered Oxide Cathodes in Halide All-Solid-State Batteries.

Employing lithium-rich layered oxide (LLO) as the cathode of all-solid-state batteries (ASSBs) is highly desired for realizing high energy density. However, the poor kinetics of LLO, caused by its low electronic conductivity and significant oxygen-redox-induced structural degradation, has impeded its application in ASSBs. Here, the charge transfer kinetics of LLO is enhanced by constructing high-efficiency electron transport networks within solid-state electrodes, which considerably minimizes electron transfer resistance. In addition, an infusion-plus-coating strategy is introduced to stabilize the lattice oxygen of LLO, successfully suppressing the interfacial oxidation of solid electrolyte (Li3 InCl6 ) and structural degradation of LLO. As a result, LLO-based ASSBs exhibit a high discharge capacity of 230.7 mAh g-1 at 0.1 C and ultra-long cycle stability over 400 cycles. This work provides an in-depth understanding of the kinetics of LLO in solid-state electrodes, and affords a practically feasible strategy to obtain high-energy-density ASSBs.

Realizing High-Performance Li-S Batteries through Additive Manufactured and Chemically Enhanced Cathodes.

Numerous efforts are made to improve the reversible capacity and long-term cycling stability of Li-S cathodes. However, they are susceptible to irreversible capacity loss during cycling owing to shuttling effects and poor Li+ transport under high sulfur loading. Herein, a physically and chemically enhanced lithium sulfur cathode is proposed to address these challenges. Additive manufacturing is used to construct numerous microchannels within high sulfur loading cathodes, which enables desirable deposition mechanisms of lithium polysulfides and improves Li+ and e- transport. Concurrently, cobalt sulfide is incorporated into the cathode composition and demonstrates strong adsorption behavior toward lithium polysulfides during cycling. As a result, excellent electrochemical performance is obtained by the design of a physically and chemically enhanced lithium sulfur cathode. The reported electrode, with a sulfur loading of 8 mg cm-2 , delivers an initial capacity of 1118.8 mA h g-1 and a reversible capacity of 771.7 mA h g-1 after 150 cycles at a current density of 3 mA cm-2 . This work demonstrates that a chemically enhanced sulfur cathode, manufactured through additive manufacturing, is a viable pathway to achieve high-performance Li-S batteries.

Suppressing Corrosion of Aluminum Foils via Highly Conductive Graphene-like Carbon Coating in High-Performance Lithium-Based Batteries.

Aluminum foil is the predominant cathodic current collector in lithium-based batteries due to the high electronic conductivity, stable chemical/electrochemical properties, low density, and low cost. However, with the development of next-generation lithium batteries, Al current collectors face new challenges, such as the requirement of increased chemical stability at high voltage, long-cycle-life batteries with different electrolyte systems, as well as improved electronic conductivity and adhesion for new electrode materials. In this study, we demonstrate a novel graphene-like carbon (GLC) coating on the Al foil in lithium-based batteries. Various physical and electrochemical characterizations are conducted to reveal the electronic conductivity and electrochemical stability of the GLC-Al foil in both carbonate- and ether-based electrolytes. Full-cell tests, including Li-S batteries and high-voltage Li-ion batteries, are performed to demonstrate the significantly improved cycling and rate performance of batteries with the use of the GLC-Al foil as current collectors. The cell using the GLC-Al foil can greatly reduce the potential polarization in Li-S batteries and can obtain a reversible capacity of 750 mAh g-1 over 100 cycles at 0.5C. Even with high-sulfur-loading cathodes, the Li-S battery at 1C still maintains over 500 mAh g-1 after 100 cycles. In high-voltage Li-ion batteries, the GLC-Al foil significantly improves the high-rate performance, showing an increased retained capacity by over 100 mAh g-1 after 450 cycles at 1C compared to the bare foil. It is believed that the developed GLC-Al foil brings new opportunities to enhance the battery life of lithium-based batteries.

Design of a 3D-Porous Structure with Residual Carbon for High-Performance Ni-Rich Cathode Materials.

Recently, LiNi0.8Co0.1Mn0.1O2 has drawn much attention because of its high energy density. Here, 3D-porous LiNi0.8Co0.1Mn0.1O2 and the one with residual carbon have been synthesized using a resorcinol-formaldehyde-assisted sol-gel approach. Scanning electron microscopy images verify that the synthesized LiNi0.8Co0.1Mn0.1O2 possesses a 3D-porous morphology. X-ray photoelectron spectroscopy analysis and transmission electron microscopy-mapping images indicate the existence of residual carbon in the secondary particle of 3D-porous LiNi0.8Co0.1Mn0.1O2. Furthermore, 3D-porous LiNi0.8Co0.1Mn0.1O2 with residual carbon exhibits outstanding electrochemical properties. At a current density of 1900 mA g-1, the 3D-porous LiNi0.8Co0.1Mn0.1O2 with residual carbon can still deliver a reversible capacity of 113 . Moreover, after 150 cycles at 0.2 C, the capacity retention of 3D-porous LiNi0.8Co0.1Mn0.1O2 with residual carbon reaches to 95%. The excellent electrochemical properties can be ascribed to the unique 3D-porous morphology and residual carbon in the secondary particle.

Research Progress in Improving the Cycling Stability of High-Voltage LiNi0.5Mn1.5O4 Cathode in Lithium-Ion Battery.

High-voltage lithium-ion batteries (HVLIBs) are considered as promising devices of energy storage for electric vehicle, hybrid electric vehicle, and other high-power equipment. HVLIBs require their own platform voltages to be higher than 4.5 V on charge. Lithium nickel manganese spinel LiNi0.5Mn1.5O4 (LNMO) cathode is the most promising candidate among the 5 V cathode materials for HVLIBs due to its flat plateau at 4.7 V. However, the degradation of cyclic performance is very serious when LNMO cathode operates over 4.2 V. In this review, we summarize some methods for enhancing the cycling stability of LNMO cathodes in lithium-ion batteries, including doping, cathode surface coating, electrolyte modifying, and other methods. We also discuss the advantages and disadvantages of different methods.

Morphologically controlled synthesis of porous spherical and cubic LaMnO3 with high activity for the catalytic removal of toluene.

A morphology-controlled molten salt route was developed to synthesize porous spherical LaMnO3 and cubic LaMnO3 nanoparticles using the as-prepared porous Mn2O3 spheres as template. The porous LaMnO3 spheres with an average pore size of about 34.7 nm and the cubic LaMnO3 nanoparticles with a good dispersion were confirmed by scanning electron microscope, transmission electron microscope, and N2 adsorption-desorption measurements. The mechanism of morphological transformation from the porous spherical structure to the cubic particle in the molten salt was proposed. The porous spherical LaMnO3 and cubic LaMnO3 catalysts exhibited high catalytic performance for the combustion of toluene, and the latter performed better than the former. Under the conditions of toluene/oxygen molar ratio = 1/400 and space velocity = 20,000 h(-1), the temperature required for 10, 50, and 90% toluene conversion was 110, 170, and 220 °C over the cubic LaMnO3 catalyst, respectively. Based on the results of X-ray photoelectron spectroscopic and hydrogen temperature-programmed reduction characterization, we deduce that the higher surface Mn(4+)/Mn(3+) molar ratio and better low-temperature reducibility enhanced the catalytic performance of cubic LaMnO3. Taking the facile morphology-controlled synthesis and excellent catalytic performance into consideration, we believe that the well-defined morphological LaMnO3 samples are good candidate catalytic materials for the oxidative removal of toluene.

Preparation of novel three-dimensional NiO/ultrathin derived graphene hybrid for supercapacitor applications.

A new type of three-dimensional (3D) NiO/ultrathin derived graphene (UDG) hybrid on commercial Ni foam (NF) for a binder-free pseudocapacitor electrode is presented. NiO nanoflakes are in situ grown by a chemical bath deposition (CBD) technique on the free-standing 3D UDG/NF scaffold, which is first prepared by a simple nanocasting process consisting of hydrothermal reaction and subsequent thermal transformation. The 3D UDG/NF scaffold with interconnected network affords a high conductivity due to the high graphitization degree and efficiently facilitates the electron transport to NiO. Moreover, the 3D NiO/UDG/NF hybrid allows for a thinner 3D active material layer under the same loading density, which could shorten the diffusion paths of ions. The NiO/UDG/NF hybrid is directly used as a binder-free supercapacitor electrode, which exhibited significantly improved supercapacitor performance compared to the bare CBD prepared NiO/NF electrode.