Anion-immobilized solid composite electrolytes based on metal-organic frameworks and superacid ZrO_(2) fillers for high-performance all solid-state lithium metal batteries

Anion-immobilized solid composite electrolytes(SCEs)are important to restrain the propagation of lithium dendrites for all solid-state lithium metal batteries(ASSLMBs).Herein,a novel SCEs based on metal-organic frameworks(MOFs,UiO-66-NH_(2))and superacid ZrO_(2)(S-ZrO_(2))fillers are proposed,and the samples were characterized by X-ray diffraction(XRD),scanning electron microscope(SEM),energy dispersive X-ray spectroscopy(EDS),thermo-gravimetric analyzer(TGA)and some other electrochemical measurements.The-NH_(2) groups of UiO-66-NH_(2) combines with F atoms of poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP)chains by hydrogen bonds,leading to a high electrochemical stability window of 5 V.Owing to the incorporation of UiO-66-NH_(2) and S-ZrO_(2) in PVDF-HFP polymer,the open metal sites of MOFs and acid surfaces of S-ZrO_(2) can immobilize anions by strong Lewis acid-base interaction,which enhances the effect of immobilization anions,achieving a high Li-ion transference number(t_(+))of 0.72,and acquiring a high ionic conductivity of 1.05×10^(-4) S·cm^(-1) at 60℃.The symmetrical Li/Li cells with the anion-immobilized SCEs may steadily operate for over 600 h at 0.05 mA·cm^(-2) without the shortcircuit occurring.Besides,the solid composite Li/LiFePO_(4)(LFP)cell with the anion-immobilized SCEs shows a superior discharge specific capacity of 158 mAh·g^(-1) at 0.2 C.The results illustrate that the anion-immobilized SCEs are one of the most promising choices to optimize the performances of ASSLMBs.

Practical development and challenges of garnet-structured Li_(7)La_(3)Zr_(2)O_(12) electrolytes for all-solid-state lithium-ion batteries:A review

All-solid-state Li-ion batteries(ASSLIBs)have been widely studied to achieve Li-ion batteries(LIBs)with high safety and energy density.Recent reviews and experimental papers have focused on methods that improve the ionic conductivity,stabilize the electrochemical performance,and enhance the electrolyte/electrode interfacial compatibility of several solid-state electrolytes(SSEs),including oxides,sulfides,composite and gel electrolytes,and so on.Garnet-structured Li_(7)La_(3)Zr_(2)O_(12)(LLZO)is highly regarded an SSE with excellent application potential.However,this type of electrolyte also possesses a number of disadvantages,such as low ionic conductivity,unstable cubic phase,and poor interfacial compatibility with anodes/cathodes.The benefits of LLZO have urged many researchers to explore effective solutions to overcome its inherent limitations.Herein,we review recent developments on garnet-structured LLZO and provide comprehensive insights to guide the development of garnet-structured LLZO-type electrolytes.We not only systematically and comprehensively discuss the preparation,element doping,structure,stability,and interfacial improvement of LLZOs but also provide future perspectives for these materials.This review expands the current understanding on advanced solid garnet electrolytes and provides meaningful guidance for the commercialization of ASSLIBs.

Experimental observation of spontaneous symmetry breaking in a quantum phase transition

Spontaneous symmetry breaking(SSB)plays a central role in understanding a large variety of phenomena associated with phase transitions,such as superfluid and superconductivity.So far,the transition from a symmetric vacuum to a macroscopically ordered phase has been substantially explored.The process bridging these two distinct phases is critical to understanding how a classical world emerges from a quantum phase transition,but so far remains unexplored in experiment.We here report an experimental demonstration of such a process with a quantum Rabi model engineered with a superconducting circuit.We move the system from the normal phase to the superradiant phase featuring two symmetry-breaking field components,one of which is observed to emerge as the classical reality.The results demonstrate that the environment-induced decoherence plays a critical role in the SSB.