Fe3O4-modified FeCl3/graphite intercalation compound confinement architecture for unleashing the high-performance anode potential of lithium-ion batteries.

The ferric trichloride (FeCl3)-intercalated graphite intercalation compound (GIC) has high reversible capacity and bulk density, making it a promising anode material for lithium ion batteries. However, its practical application has been limited by the poor cycle performance due to chloride dissolution and shuttling issues. Herein, FeCl3-GIC is used as the precursor material to synthesize a nano-Fe3O4-modified intercalation material by a solvothermal method. The Fe3O4 moiety at the edge of FeCl3-GIC provides a robust chemical anchoring effect on the chlorides. Together with the two-dimensional graphite layer, it forms a confinement space, which effectively immobilizes soluble chlorides. Attributed to the distinctive structural design, the Fe3O4-FeCl3/GIC 25% C electrode offers a high reversible capacity of 691.4 mA h g-1 at 1000 mA g-1 after 400 cycles. At 2000 and 5000 mA g-1, the reversible specific capacity of the Fe3O4-FeCl3/GIC 25% C electrode is 345.6 and 218.3 mA h g-1, respectively. This work presents an innovative method to improve the lifespan of GIC.

MoS2 Hollow Multishelled Nanospheres Doped Fe Single Atoms Capable of Fast Phase Transformation for Fast-charging Na-ion Batteries.

Low Na+ and electron diffusion kinetics severely restrain the rate capability of MoS2 as anode for sodium-ion batteries (SIBs). Slow phase transitions between 2H and 1T, and from NaxMoS2 to Mo and Na2S as well as the volume change during cycling, induce a poor cycling stability. Herein, an original Fe single atom doped MoS2 hollow multishelled structure (HoMS) is designed for the first time to address the above challenges. The Fe single atom in MoS2 promotes the electron transfer, companying with shortened charge diffusion path from unique HoMS, thereby achieving excellent rate capability. The strong adsorption with Na+ and self-catalysis of Fe single atom facilitates the reversible conversion between 2H and 1T, and from NaxMoS2 to Mo and Na2S. Moreover, the buffering effect of HoMS on volume change during cycling improves the cyclic stability. Consequently, the Fe single atom doped MoS2 quadruple-shelled sphere exhibits a high specific capacity of 213.3 mAh g-1 at an ultrahigh current density of 30 A g-1, which is superior to previously-reported results. Even at 5 A g-1, 259.4 mAh g-1 (83.68 %) was reserved after 500 cycles. Such elaborate catalytic site decorated HoMS is also promising to realize other "fast-charging" high-energy-density rechargeable batteries.

Alkali-Ion Batteries by Carbon Encapsulation of Liquid Metal Anode.

Gallium-based metallic liquids, exhibiting high theoretical capacity, are considered a promising anode material for room-temperature liquid metal alkali-ion batteries. However, electrochemical performances, especially the cyclic stability, of the liquid metal anode for alkali-ion batteries are strongly limited because of the volume expansion and unstable solid electrolyte interphase film of liquid metal. Here, the bottleneck problem is resolved by designing carbon encapsulation on gallium-indium liquid metal nanoparticles (EGaIn@C LMNPs). A superior cycling stability (644 mAh g-1 after 800 cycles at 1.0 A g-1 ) is demonstrated for lithium-ion batteries, and excellent cycle stability (87 mAh g-1 after 2500 cycles at 1.0 A g-1 ) is achieved for sodium-ion batteries by carbon encapsulation of the liquid metal anode. Morphological and phase changes of EGaIn@C LMNPs during the electrochemical reaction process are revealed by in situ transmission electron microscopy measurements in real-time. The origin for the excellent performance is uncovered, that is the EGaIn@C core-shell structure effectively suppresses the non-uniform volume expansion of LMNPs from ≈160% to 127%, improves the electrical conductivity of the LMNPs, and exhibits superior electrochemical kinetics and a self-healing phenomenon. This work paves the way for the applications of room-temperature liquid metal anodes for high-performance alkali-ion batteries.

Revealing the Electrochemistry of Solid-State Li-SeS2 Battery via In-Situ Transmission Electron Microscopy.

Sex Sy is considered as a promising cathode material as it can deliver higher energy density than selenium (Se) and offer improved conductivity and enhanced reaction kinetics compared with S. However, the electrochemistry of the Li-SeS2 all-solid-state battery (ASSB) has not been well understood to date. Herein the electrochemistry of Li-SeS2 battery was revealed by in-situ transmission electron microscopy. The charge products were phase-separated Se and S, rather than the widely believed SeS2 . Among the various Sex Sy cathodes, SeS2 achieved the best electrochemical performance. The Li-SeS2 ASSB delivered a high reversible capacity of 1052 mAh g-1 at 1 A g-1 over 350 cycles, and a high areal capacity of 4 mAh cm-2 was also achieved with a high cathode mass loading of 7.6 mg cm-2 . These results represent the best performance achieved to date in the Li-SeS2 ASSB and brings us one step closer toward its practical applications.

Cryo-EM Revealing the Origin of Excessive Capacity of the Se Cathode in Sulfide-Based All-Solid-State Li-Se Batteries.

Selenium (Se), whose electronic conductivity is nearly 25 orders higher than that of sulfur (S) and whose theoretical volumetric capacity is 3254 mAh cm-3, is considered as a potential alternative to S to overcome the poor electronic conductivity issue of the S cathode in the lithium (Li)-S battery. However, the study of the Li-Se battery, particularly a Li-Se all-solid-state battery (ASSB), is still in its infancy. Herein, we report the performance of Li-Se ASSBs at both room temperature (RT) and high temperature (HT, 50 °C), using a Li10Si0.3PS6.9Cl1.8 (LSPSCl) solid-state electrolyte and Li-In anode. With a Se loading of 7.6 mg cm-2, the Li-Se battery displayed a record high reversible capacity of 6.8 mAh cm-2 after 50 cycles at HT, which exceeds the theoretical areal capacity of 5.2 mAh cm-2 for Se. Moreover, the RT Li-Se ASSB delivered an initial areal capacity of about 2 mAh cm-2 at a current density of 1 A g-1 for 1200 cycles with a capacity retention of 67%. Cryo-electron microscopy revealed that the excessive capacity of Se at HT can be attributed to the formation of a previously unknown S5Se4 phase during charging, which participated reversibly in a subsequent redox reaction. The formation of the S5Se4 phase originated from the reaction of Se with S, which was generated by the decomposition of LSPSCl at HT. These results unlock the electrochemistry of a Li-Se ASSB, suggesting that a Li-Se ASSB is a viable alternative to a Li-S battery for energy storage applications.

Enabling Long Cycle Life and High Rate Iron Difluoride Based Lithium Batteries by In Situ Cathode Surface Modification.

Metals fluorides (MFs) are potential conversion cathodes to replace commercial intercalation cathodes. However, the application of MFs is impeded by their poor electronic/ionic conductivity and severe decomposition of electrolyte. Here, a composite cathode of FeF2 and polymer-derived carbon (FeF2 @PDC) with excellent cycling performance is reported. The composite cathode is composed of nanorod-shaped FeF2 embedded in PDC matrix with excellent mechanical strength and electronic/ionic conductivity. The FeF2 @PDC enables a reversible capacity of 500 mAh g-1 with a record long cycle lifetime of 1900 cycles. Remarkably, the FeF2 @PDC can be cycled at a record rate of 60 C with a reversible capacity of 107 mAh g-1 after 500 cycles. Advanced electron microscopy reveals that the in situ formation of stable Fe3 O4 layers on the surface of FeF2 prevents the electrolyte decomposition and leaching of iron (Fe), thus enhancing the cyclability. The results provide a new understanding to FeF2 electrochemistry, and a strategy to radically improve the electrochemical performance of FeF2 cathode for lithium-ion battery applications.

Lithium Deposition-Induced Fracture of Carbon Nanotubes and Its Implication to Solid-State Batteries.

The increasing demand for safe and dense energy storage has shifted research focus from liquid electrolyte-based Li-ion batteries toward solid-state batteries (SSBs). However, the application of SSBs is impeded by uncontrollable Li dendrite growth and short circuiting, the mechanism of which remains elusive. Herein, we conceptualize a scheme to visualize Li deposition in the confined space inside carbon nanotubes (CNTs) to mimic Li deposition dynamics inside solid electrolyte (SE) cracks, where the high-strength CNT walls mimic the mechanically strong SEs. We observed that the deposited Li propagates as a creeping solid in the CNTs, presenting an effective pathway for stress relaxation. When the stress-relaxation pathway is blocked, the Li deposition-induced stress reaches the gigapascal level and causes CNT fracture. Mechanics analysis suggests that interfacial lithiophilicity critically governs Li deposition dynamics and stress relaxation. Our study offers critical strategies for suppressing Li dendritic growth and constructing high-energy-density, electrochemically and mechanically robust SSBs.

In situ observation of cracking and self-healing of solid electrolyte interphases during lithium deposition.

The growth of lithium (Li) whiskers is detrimental to Li batteries. However, it remains a challenge to directly track Li whisker growth. Here we report in situ observations of electrochemically induced Li deposition under a CO2 atmosphere inside an environmental transmission electron microscope. We find that the morphology of individual Li deposits is strongly influenced by the competing processes of cracking and self-healing of the solid electrolyte interphase (SEI). When cracking overwhelms self-healing, the directional growth of Li whiskers predominates. In contrast, when self-healing dominates over cracking, the isotropic growth of round Li particles prevails. The Li deposition rate and SEI constituent can be tuned to control the Li morphologies. We reveal a new "weak-spot" mode of Li dendrite growth, which is attributed to the operation of the Bardeen-Herring growth mechanism in the whisker's cross section. This work has implications for the control of Li dendrite growth in Li batteries.

In situ imaging electrocatalytic CO2 reduction and evolution reactions in all-solid-state Li-CO2 nanobatteries.

Li-CO2 batteries are promising energy storage devices owing to their high energy density and possible applications for CO2 capture. However, still some critical issues, such as high charging overpotential and poor cycling stability caused by the sluggish decomposition of Li2CO3 discharge products, need to be addressed before the practical applications of Li-CO2 batteries. Exploring highly efficient catalysts and understanding their catalytic mechanisms for the CO2 reduction reaction (CORR) and evolution reaction (COER) are critical for the application of Li-CO2 batteries. However, the direct imaging of electrocatalysis during CORR and COER is still elusive. Herein, we report the in situ imaging of electrocatalysis during CORR and COER in a Li-CO2 nanobattery using a Ni-Ru-coated α-MnO2 nanowire (Ni-Ru/MnO2) cathode in an advanced aberration corrected environmental transmission electron microscope. During the CORR, a thick Li2CO3 and carbon mixture layer was formed on the surface of the Ni-Ru/MnO2 nanowires via 4Li+ + 3CO2 + 4e-→ 2Li2CO3 + C. During the COER, the as-formed Li2CO3 decomposed via 2Li2CO3→ 2CO2 + O2 + 4Li+ + 4e-, while the as-formed amorphous carbon remained. In contrast, the decomposition of Li2CO3 on bare MnO2 nanowires was difficult, underscoring the important Ni-Ru bimetal electrocatalytic role in facilitating the COER. Our results provide an important understanding of the CO2 chemistry in Li-CO2 batteries, possibly helping in the designing of Li-CO2 batteries for energy storage applications.

Hierarchical Cobalt Selenides as Highly Efficient Microwave Absorbers with Tunable Frequency Response.

Microwave absorbing materials have attracted much attention in solving electromagnetic interference and pollution problems. Hierarchical cobalt selenides have been obtained through a facile selenization annealing process. The as-prepared samples exhibit distinct reflection losses (RL) and frequency responses via tailoring their crystalline configurations, with excellent absorption in Ku, X, or C band. All of the samples show RL greater than or near -50 dB with effective bandwidths more than 4 GHz, indicating that they may serve as high-efficient and frequency-tunable microwave absorbers. Especially, the sample annealed at 400 °C shows a competitive RL of -62.04 dB at 9.92 GHz with a thickness of 2.25 mm; meanwhile, its effective absorption bandwidth reaches 5.36 GHz with a thickness as small as 1.56 mm. The cobalt selenides as microwave absorbers exhibit a promising prospect applied in complex electromagnetic environments.

In situ imaging of electrocatalysis in a K-O2 battery with a hollandite α-MnO2 nanowire air cathode.

Using α-manganese dioxide (α-MnO2) nanowires as the air electrode, a K-O2 nanobattery is assembled in an aberration corrected environmental transmission electron microscope. It is found that the α-MnO2 nanowires are reduced into Mn3O4 and MnO during discharge; meanwhile, KO2 is formed on the surface of the α-MnO2 nanowires.