Tetrathiafulvalene-Based Metal–Organic Framework as a High-Performance Anode for Lithium-Ion Batteries

Abstract

Metal–organic frameworks (MOFs) have aroused great interest as lithium-ion battery (LIB) electrode materials. In this work, we first report that a pristine three-dimensional tetrathiafulvalene derivatives (TTFs)-based zinc MOF, formulated [Zn2(py-TTF-py)2(BDC)2]·2DMF·H2O (1) (py-TTF-py = 2,6-bis­(4′-pyridyl)­tetrathiafulvalene and H2BDC = terephthalic acid), can work as a high-performance electrode material for rechargeable LIBs. The TTFs-Zn-MOF 1 electrode displayed a high discharge specific capacity of 1117.4 mA h g–1 at a current density of 200 mA g–1 after 150 cycles along with good reversibility. After undergoing elevated discharging/charging rates, the electrode showed superior lithium storage performance in the extreme case of 20 A g–1 and could finally recover the capability when the current rate was back to 200 mA g–1. Particularly, specific capacities of 884.2, 513.8, and 327.8 mA h g–1 were reached at high current densities of 5, 10, and 20 A g–1 after 180, 175, and 300 cycles along with good reversibility, respectively. Such an excellent performance is first reported for the LIB anode materials. TTFs-Zn-MOF 2, namely, [Zn2(py-TTF-py) (BDC)2]·DMF·2H2O (2), was prepared as a contrast to explore the relationship between the structures of the electrode materials and the electrochemical properties. Based on the structural analysis of 1 and 2 and ex situ X-ray photoelectron spectroscopy, the TTF moiety and the twofold TTF pillar play a key role in the excellent electrochemical performance. The full cell of MOF 1 with NMC 622 delivered the capacity of 131.9 mA h g–1 at 100 mA g–1 with the Coulombic efficiency of 99.45% after 70 cycles and exhibited the tolerance to high-current operation.

Dual‐Ligand Zn‐Based Metal–Organic Framework as Reversible and Stable Anode Material for Next Generation Lithium‐Ion Batteries

“…In addition, the Zn 2p spectra (Figure S1b, Supporting Information) exhibits two main peaks of Zn 2p 1/2 and Zn 2p 3/2 at 1044.41 and 1021.29 eV, respectively, and the difference of ≈23.12 eV further indicates the existence of Zn 2+ . [ 22 ] Moreover, the deconvolution of Zn 2p 3/2 spectra (Figure S1c, Supporting Information) showed two main peaks at 1020.80 and 1021.50 eV for ZnN and ZnO, respectively. [ 23 ] These results manifest the successful formation of Zn‐MOF@180 where Zn metal center was bonded with the oxygen and nitrogen atoms on the DHTP and TTPA ligands, respectively.…”

Metal-Organic Frameworks for Metal-Ion Batteries: Towards Scalability

“…This makes it possible to increase the effective anode area without changing the dimensional characteristics of the device, which, in its turn, promises miniaturization of existing batteries. A number of papers [41][42][43][44][45][46][47][48], considering such an approach, demonstrate the achievement of significant results in current densities, charge capacity, and cyclic stability. The mechanism of insertion/extraction of ions is also described in details in [44] using the example of aluminumbased MOF (Fig.…”

Enhancing Capacity and Stability of Anionic MOFs as Electrode Material by Cation Exchange

“…In recent years, different types of MOFs have also been investigated as electrode materials for several energy storage devices, including LIBs and sodium-ion batteries (SIBs), showing promising performance while delivering high capacities (Maiti et al, 2015;Hu et al, 2016;Weng et al, 2020;Baskoro et al, 2021;Feng and Wen, 2021). Many of these compounds incorporate transition metal ions such as Mn(II), Co(II), Ni(II), and Cu(II) (Zhang et al, 2014;Calbo et al, 2019;Wang et al, 2020).…”