Reversible anion intercalation in a layered aromatic amine: a high-voltage host structure for organic batteries

Abstract

International audienceCation insertion reactions in inorganic host frameworks are well-established phenomena. Over the last 40 years, a myriad of examples have been documented, which have given rise to key applications such as for electrochemical storage devices. By contrast, materials able to reversibly insert anions into their host lattice are rare, and consist essentially of graphite intercalation compounds (GICs), thus limiting their potential use. Organic materials, conversely, if properly designed, could pave the way for future developments in anionic insertion electrochemistry, by virtue of the rational incorporation of p-type redox-active organic moieties. Here, we report the discovery of a p-type organic host lattice based on a simple crystallized aromatic diamine. The reversible anion insertion process relies on the electrochemical activity of neutral secondary amino groups incorporated into a robust terephthalate backbone. XRD, TEM and EELS studies reveal the attainment of a unique lamellar structure conducive to the oxidative insertion of anions (including the bulky TFSI-). In a dual-ion cell configuration using lithium as the negative electrode, this organic structure can react reversibly at high operating potential (hEi z 3.22 V vs. Li+/Li) with good cycling performance even without carbon addition, hence generating further avenues for the development of organic batteries and more generally, the field of intercalation chemistry.

Sustainable Energy Storage: Recent Trends and Developments toward Fully Organic Batteries

“…Most of them revealed significant capacity drops or showed no stable voltage at all . Nevertheless, a 2,5‐dimethyl‐terephthalate enabled a stable discharge voltage of 0.8 V against lithium and a stable specific capacity of 160 mAh g −1 over at least 50 cycles, whereas the application of a 2,5‐bis(phenylamine) terephthalate led to a voltage of 3.2 V but only a moderate capacity of 70 mAh g −1 …”

Core–Shell Aluminum@Carbon Nanospheres for Dual‐Ion Batteries with Excellent Cycling Performance under High Rates

“…Researchers have continued to make progress in DIBs, including studies on the intercalation of different anions into graphite, different cathode materials (e.g., graphitic carbon, [6] metalorganic frameworks, [7] aromatic amines, [8] etc. Thus, both Li + cations and anions such as PF 6 − and BF 4 − can intercalate/deintercalate into/from the graphite layers during the charging and discharging processes.…”

Anodic oxidation of p-phenylenediamines in battery grade electrolytes

“…In addition, PC/LiClO 4 1 M electrolyte was first employed in order to be aligned with our former battery cycling tests performed on crystallized p-phenylenediamines derivatives [12,13]. Basically, the oxidation of PD in such an electrolyte shows two anodic peaks (I, II) located at 3.58 and 4.07 V vs. ) at peak II.…”

“…that crystallized conjugated diamines can accommodate anions at E > 3 V vs. Li + /Li 0 in the solid state with an overall reversible two-electron reaction making them interesting for positive electrode applications [12][13][14].…”