Modification of Layered Cathodes of Sodium-Ion Batteries with Conducting Polymers

Layered oxides exhibit interesting performance as positive electrodes for commercial sodium-ion batteries. Nevertheless, the replacement of low-sustainable nickel with more abundant iron would be desirable. Although it can be achieved in P2-Na2/3Ni2/9Fe2/9Mn5/9O2, its performance still requires further improvement. Many imaginative strategies such as surface modification have been proposed to minimize undesirable interactions at the cathode-electrolyte interface while facilitating sodium insertion in different materials. Here, we examine four different approaches based on the use of the electron-conductive polymer poly(3,4-ethylene dioxythiophene) (PEDOT) as an additive: (i) electrochemical in situ polymerization of the monomer, (ii) manual mixing with the active material, (iii) coating the current collector, and (iv) a combination of the latter two methods. As compared with pristine layered oxide, the electrochemical performance shows a particularly effective way of increasing cycling stability by using electropolymerization. Contrarily, the mixtures show less improvement, probably due to the heterogeneous distribution of oxide and polymer in the samples. In contrast with less conductive polyanionic cathode materials such as phosphates, the beneficial effects of PEDOT on oxide cathodes are not as much in rate performance as in inhibiting cycling degradation, due to the compactness of the electrodes without loss of electrical contact between active particles.