Strategies to suppress the shuttle effect of redox mediators in lithium-oxygen batteries

Rechargeable lithium-oxygen(Li-O_(2))batteries are the next generation energy storage devices due to their ultrahigh theoretical capacity.Redox mediators(RMs)are widely used as a homogenous electrocatalyst in non-aqueous Li-O_(2)batteries to enhance their discharge capacity and reduce charge overpotential.However,the shuttle effect of RMs in the electrolyte solution usually leads to corrosion of the Li metal anode and uneven Li deposition on the anode surface,resulting in unwanted consumption of electrocatalysts and deterioration of the cells.It is therefore necessary to take some measures to prevent the shuttle effect of RMs and fully utilize the soluble electrocatalysts.Herein,we summarize the strategies to suppress the RM shuttle effect reported in recent years,including electrolyte additives,protective separators and electrode modification.The mechanisms of these strategies are analyzed and their corresponding requirements are discussed.The electrochemical properties of Li-O_(2)batteries with different strategies are summarized and compared.The challenges and perspectives on preventing the shuttle effect of RMs are described for future study.This review provides guidance for achieving shuttle-free redox mediation and for designing Li-O_(2)cells with a long cycle life,high energy efficiency and highly reversible electrochemical reactions.

In-plane isotropic separator-induced highly efficient sodium plating for unlocking the fast-charging capability of anode-free sodium battery at practical conditions

Ether-based electrolytes with excellent reductive stability are compatible with sodium(Na)metal an-odes,which enables stable cycling for Na metal batteries even in an anode-free configuration.However,the practical applications of anode-free sodium batteries(AFSBs)with a high theoretical energy density are restricted by the low-rate capability and limited cycle life.Here we demonstrate that the mechanical properties of the separators,which have been overlooked in previous studies,can significantly affect the cycling stability of AFSBs due to the intrinsic softness of Na and the large volume variation of AFSBs during Na plating/stripping.By using various separators including polypropylene(PP),polyethylene(PE),PP/PE/PP tri-layer,and aluminum oxide-coated separators,we find that the balanced elastic moduli of the separator along the machine direction and transverse direction are crucial for enabling highly effi-cient Na plating and unlocking the 4 C fast-charging capability of the AFSBs at practical conditions including a high cathode active mass loading(13.5 mg/cm^(2)),lean electrolyte addition(8.8 mL/cm^(2)),and no pre-sodiation process.This study provides an important separator design principle for the develop-ment of high-rate and long-cycle-life AFSBs.

Modification of solid electrolyte interface layer between PVDF-based electrolyte and lithium anode

Poly(vinylidene fluoride)(PVDF)-based polymer electrolytes(PEs)with good electrochemical performance and processability as well as low-cost advantage,have great potential applications in solid-state lithium(Li)metal batteries(SSLMBs).PVDF-based PEs are generally produced by employing a solution-casting approach with N,N-dimethylformamide(DMF)as the solvent,accompanied by the formation of[DMF-Li^(+)]complex,which facilitates the Li-ion transport.However,the residual DMF can react continuously with lithium(Li)metal,thereby deteriorating the interface layer in the middle of the PVDF-based PEs and Li anodes.Herein,we introduce propylene carbonate(PC)into the PVDF-based PEs to regulate the solvation structure and stabilize the interface layer between the PEs and Li anodes.PC accelerates the dissociation of lithium oxalyldifluoroborate(LiODFB).Consequently,“lithium propylene dicarbonate(LPDC)‒B-O”oligomer forms as the interfacial layer with high tenacity,homogeneity,and densification,which improves the interfacial contact and suppresses the continuous reaction between the residual DMF and Li anode.We further demonstrate that the PVDF-based PE prepared with DMF-PC mix-solvents shows improved room-temperature ionic conductivity(1.18×10^(-3) S/cm),enhanced stability against electrodes,and superior cycling performance in LiCoO_(2)-based SSLMBs(maintaining 84% of the initial discharge capacity after 300 cycles).

A molecular sieve-containing protective separator to suppress the shuttle effect of redox mediators in lithium-oxygen batteries

Lithium-oxygen(Li-O_(2))batteries have a great potential in energy storage and conversion due to their ultra-high theoretical specific energy,but their applications are hindered by sluggish redox reaction kinetics in the charge/discharge processes.Redox mediators(RMs),as soluble catalysts,are widely used to facilitate the electrochemical processes in the Li-O_(2)batteries.A drawback of RMs is the shuttle effect due to their solubility and mobility,which leads to the corrosion of a Li metal anode and the degradation of the electrochemical performance of the batteries.Herein,we synthesize a polymer-based composite protective separator containing molecular sieves.The nanopores with a diameter of 4Åin the zeolite powder(4A zeolite)are able to physically block the migration of 2,2,6,6-tetramethylpiperidinyloxy(TEMPO)molecules with a larger size;therefore,the shuttle effect of TEMPO is restrained.With the assistance of the zeolite molecular sieves,the cycle life of the Li-O_(2)batteries is significantly extended from~20 to 170 cycles at a current density of 250 mA·g^(-1)and a limited capacity of 500 mAh·g^(-1).Our work provides a highly effective approach to suppress the shuttle effects of RMs and boost the electrochemical performance of Li-O_(2)batteries.

Widely tunable and high resolution mid‑infrared laser based on BaGa_(4)Se_(7)optical parametric oscillator

The widely tunable and high resolution mid-infrared laser based on a BaGa_(4)Se_(7)(BGSe)optical parametric oscillator(OPO)was demonstrated.A wavelength tuning range of 2.76–4.64μm and a wavelength tuning resolution of about 0.3 nm were obtained by a BGSe(56.3°,0°)OPO,which was pumped by a 1064 nm laser.It is the narrowest reported wavelength tuning resolution for BGSe OPO,and was obtained by simultaneously controlling the angle and temperature of BGSe.