A High Capacity and Working Voltage Potassium-Based Dual Ion Batteries

Potassium-based dual ion batteries(KDIBs)have attracted significant attention owing to high working voltage,high safety,low processing cost,and environmental friendliness.Nevertheless,one great challenge for practical KDIBs is to develop suitable anode materials with high specific capacity.Herein,we report an architecture of hierarchically porous antimony nanoparticles/carbon nanofibers(HPSb CNFs)as flexible,free-standing anode for high-performance KDIBs.The HPSb CNFs with hierarchically porous structure,and high-content nitrogen doping,not only offer sufficient free space to tolerate the repetitive volume expansion of Sb nanoparticles during long-term cycling,but also greatly facilitate the transport of electrons and ions within electrode,ensuring high material utilization ratio.Thus,the KDIBs,constituted by HPSb CNFs-700(calcined at 700°C)anode and graphite cathode,exhibited a high reversible capacity of 440 m Ah g^(-1)with high discharge medium voltage of 4.5 V at a specific current of 200 m A g^(-1)(the highest capacity for all KDIBs normalized by the mass of the anode),and excellent cyclic life.Outstanding electrochemical reversibility of the KDIBs was further demonstrated by ex situ XRD,ex situ Raman spectrum,and HRTEM.These results suggest the as-designed HPSb CNFs-700 with highcapacity and long-term cycling stability is a promising anode material for high-performance KDIBs.

Pre-constructed SEI on graphite-based interface enables long cycle stability for dual ion sodium batteries

Lithium batteries have been widely used in all over the world for its high energy density, long-term cycle stability. While the resources of lithium metal and transition metal are limited, which restrict their applications in the grid energy storage. Dual ion sodium batteries(DISBs) possess higher energy density,especially owning high power density for its higher operating voltage(> 4.5 V). Nevertheless, the poor oxidation tolerance of carbonate electrolyte and the co-intercalation of solvents accompanied with anions are main obstacles to make the DISBs commercialization. Herein, a physical barrier(artificial SEI film) is pre-constructed in the Na||graphite batteries to solve these thorny problems. With the CSMG(covered SEI on modified graphite), batteries deliver higher capacity 40 mAh/g even under the current density of 300 mA/g and the capacity retention maintains very well after 100 cycles at a high operating voltage.Moreover, the function mechanism was revealed by in-situ XRD, demonstrating that the pre-constructed SEI can effectively suppress the irreversible phase transition and exfoliation of graphite, resulting from the co-intercalation of anions. Additionally, the work voltage windows of carbonate electrolyte are significantly broadened by establishing electrode/electrolyte interphase. This method opens up an avenue for the practical application of DISBs on the grid energy storage and other fields.

Revealing the anion intercalation behavior and surface evolution of graphite in dual-ion batteries via in situ AFM

Graphite as a positive electrode material of dual ion batteries(DIBs)has attracted tremendous attentions for its advantages including low lost,high working voltage and high energy density.However,very few literatures regarding to the real-time observation of anion intercalation behavior and surface evolution of graphite in DIBs have been reported.Herein,we use in situ atomic force microscope(AFM)to directly observe the intercalation/de-intercalation processes of PF6^-in graphite in real time.First,by measuring the change in the distance between graphene layers during intercalation,we found that PF6^-intercalates in one of every three graphite layers and the intercalation speed is measured to be 2μm-min^-1.Second,graphite will wrinke and suffer structural damnages at high voltages,along with severe electrolyte decomposition on the surface.These findings provide useful information for further optimizing the capacity and the stability of graphite anode in DIBs.

Sodium-based dual-ion batteries via coupling high-capacity selenium/graphene anode with high-voltage graphite cathode

Dual ion batteries(DIBs) exhibit broad application prospects in the field of electrical energy storage(EES)devices with excellent properties,such as high voltage,high energy density,and low cost.In the graphitebased DIBs,high voltage is needed to store enough anions with the formation of anion intercalation compound XCn(X=AlCl4-,PF6-,TFSI-,etc.).Hence,it is difficult for graphite-based DIBs to match proper anodes and electrolytes.Here,an Se/graphene composite is prepared via a convenient method,and assembled into a dual-ion full battery(DIFB) as anode with graphite cathode and 1 mol/L NaPF6 in EC:EMC(1:1,v:v).This DIFB has achieved a high discharge capacity of 75.9 mAh/g and high medium output voltage of 3.5 V at 0.1 A/g.Actually,the suitable anode materials,such as the present Se/graphene composite,are extremely important for the development and application of graphite-based DIBs.This study is enlightening for the design of future low-cost EES devices including graphite-based DIBs.