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. 2018 Apr 17;8(26):14193-14200.
doi: 10.1039/c8ra00129d.

Ferrocene-functionalized polyheteroacenes for the use as cathode active material in rechargeable batteries

Pierre-Olivier Schwartz  1 , Sebastian Förtsch  1 , Elena Mena-Osteritz  1 , Dagmar Weirather-Köstner  2 , Mario Wachtler  2 , Peter Bäuerle  1
Affiliations

Ferrocene-functionalized polyheteroacenes for the use as cathode active material in rechargeable batteries

Pierre-Olivier Schwartz et al. RSC Adv. .

Abstract

Herein we report the synthesis and characterization of new conjugated polymers bearing redox-active pendant groups for applications as cathode active materials in secondary batteries. The polymers comprise a ferrocene moiety immobilized at a poly(cyclopenta[2,1-b:3,4-b']dithiophene) (pCPDT, P1) or a poly(dithieno[3,2-b:2',3'-d]pyrrole) (pDTP, P2) backbone via an ester or an amide linker. Electrochemical and oxidative chemical polymerizations were performed in order to investigate the redox behaviour of the obtained polymers P1 and P2 and to synthesize materials on gram-scale for battery tests, respectively. During galvanostatic cycling in a typical battery environment, both polymers showed high reversible capacities of 90% and 87% of their theoretical capacity and excellent capacity retentions of 84% and 97% over 50 cycles.

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Conflict of interest statement

There are no conflicts to declare.

Figures

Scheme 1
Scheme 1. Syntheses of CPDT–Fc M1, DTP–Fc M2, and corresponding polymers pCPDT–Fc P1 and pDTP–Fc P2.
Fig. 1
Fig. 1. Crystal structure of CPDT–Fc M1: (a) molecular structure, (b) unit cell, and (c) intermolecular contacts: π–π interactions (red dotted lines) and H–π herringbone interactions (cyan dotted lines). Displacement ellipsoids are drawn in (a) and (b) at the 50% probability level. The ferrocene units in (c) are shown in light grey for clarity.
Fig. 2
Fig. 2. Electropolymerization of M1 (a) at a scan rate of 200 mV s−1 and M2 (c) at a scan rate of 100 mV s−1 in 0.1 M TBAPF6 in CH2Cl2 (monomer concentration 10−3 M). Cyclic voltammograms of pCPDT–Fc P1 (b) and pDTP–Fc P2 (d) in 0.1 M TBAPF6 in CH2Cl2 applying different scan rates.
Fig. 3
Fig. 3. UV-vis-NIR spectra obtained from spectroelectrochemical measurements on polymer P1 (a) and P2 (b). Applied voltages are referenced vs. Ag/AgCl. Arrows show the spectral changes upon increasing the applied voltage. Artefacts are marked with * in the spectra.
Fig. 4
Fig. 4. Cyclic voltammograms of (a) pCPDT–Fc P1 and (b) pDTP–Fc P2 in 1 M LiPF6/EC : DMC (1 : 1 by weight) at a scan rate of 0.1 mV s−1 and with a stepwise increase of the upper vertex potential.
Fig. 5
Fig. 5. Galvanostatic cycling performance of pCPDT–Fc P1 (a and c) and pDTP–Fc P2 (b and c) in 1 M LiPF6/EC : DMC (1 : 1 by wt.), at a current rate of 0.1C. In (c) the open symbols denote the charge capacities and the closed symbols denote the discharge capacities relative to the theoretical capacities.
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