An Electrically Conducting Li-Ion Metal-Organic Framework

Metal-organic frameworks (MOFs) have emerged as an important, yet highly challenging class of electrochemical energy storage materials. The chemical principles for electroactive MOFs remain, however, poorly explored because precise chemical and structural control is mandatory. For instance, no anionic MOF with a lithium cation reservoir and reversible redox (like a conventional Li-ion cathode) has been synthesized to date. Herein, we report on electrically conducting Li-ion MOF cathodes with the generic formula Li2-M-DOBDC (wherein M = Mg2+ or Mn2+; DOBDC4- = 2,5-dioxido-1,4-benzenedicarboxylate), by rational control of the ligand to transition metal stoichiometry and secondary building unit (SBU) topology in the archetypal CPO-27. The accurate chemical and structural changes not only enable reversible redox but also induce a million-fold electrical conductivity increase by virtue of efficient electronic self-exchange facilitated by mix-in redox: 10(-7) S/cm for Li-2-Mn-DOBDC vs 10(-13) S/cm for the isoreticular H-2-Mn-DOBDC and Li-2-Mg-DOBDC, or the Mn-CPO-27 compositional analogues. This particular SBU topology also considerably augments the redox potential of the DOBDC4- linker (from 2.4 V up to 3.2 V, vs Li+/Li-0), a highly practical feature for Li-ion battery assembly and energy evaluation. As a particular cathode material, Li-2-Mn-DOBDC displays an average discharge potential of 3.2 V vs Li+/Li-0, demonstrates excellent capacity retention over 100 cycles, while also handling fast cycling rates, inherent to the intrinsic electronic conductivity. The Li-2-MDOBDC material validates the concept of reversible redox activity and electronic conductivity in MOFs by accommodating the ligand's noncoordinating redox center through composition and SBU design.

Automated summary

In this study, electrically conducting Li-ion MOF cathodes were developed by rational control of the ligand to transition metal stoichiometry and SBU topology. The research not only enabled reversible redox but also significantly increased the electrical conductivity, demonstrating the concept of reversible redox activity and electronic conductivity in MOFs. Li-2-MDOBDC material showed excellent performance as a cathode material for lithium-ion batteries, with potential applications in energy storage and evaluation.