Our entry into the Fourth industrial revolution since the turn of the century is set to revolutionize our daily life notably with the blooming of digital technologies such as communications, artificial intelligence, technologies related to the Internet of Things (IoT), 3-D printing or nano/bio-technologies. It is however hoped this new paradigm shift will integrate sustainable development goals and actions to address the critical damage caused by the previous industrial revolutions especially the threat of global warming. We have to be particularly aware there remains the urgent need for cleaner energy technologies which calls for a radical change in the energy mix to favour renewable energy and environmentally responsible energy storage solutions. To date, commercial batteries exclusively include inorganic electrode materials notably 3d transition-metals which are scarce, expensive and energy-greedy. In contrast, organic materials enable access to low cost and possibly greener compounds because composed of naturally abundant elements (i.e., C, H, O, N or S) moreover they are easier to recycle. In addition, they offer high structural designability through the well-established principles of organic chemistry and notably access to both n- and p-type electrochemical storage mechanisms making various cell or electrode configurations possible (Figure 1).

In 10 years, tremendous progress has been made to promote organic compounds in various rechargeable storage devices giving rise to nearly 15 published review articles especially for applications in non-aqueous (metallic) Li or Na-based batteries. However, several improvements are needed to further promote insertion organic electrode materials. For instance, only few studies have been reported in the literature regarding the assembly of full Li-ion organic cells while the literature is quite abundant in terms of Li metal-organic batteries; the main difficulty being to successfully synthesize robust lithiated cathode materials.

This contribution aims at reporting recent electrochemical data obtained with crystallized organic materials and explaining how it is possible to tune the electrochemical activity towards higher voltages depending on the molecular assembly and its electrostatic environment in Li enolate-based organic cathodes. In addition, a specific electrochemical study using soluble redox-active organic species will be reported providing to the Li battery community a supplementary proof concerning the high reactivity of the most popular supporting salt (i.e., LiPF₆) versus any labile proton potentially present in a battery electrolyte.