RESUMO
Aqueous organic redox flow batteries offer a safe and potentially inexpensive solution to the problem of storing massive amounts of electricity produced from intermittent renewables. However, molecular decomposition represents a major barrier to commercialization-and although structural modifications can improve stability, it comes at the expense of synthetic cost and molecular weight. Now, utilizing 2,6-dihydroxy-anthraquinone (DHAQ) without further structural modification, we demonstrate that the regeneration of the original molecule after decomposition represents a viable route to achieve low-cost, long-lifetime aqueous organic redox flow batteries. We used in situ (online) NMR and electron paramagnetic resonance, and complementary electrochemical analyses to show that the decomposition compound 2,6-dihydroxy-anthrone (DHA) and its tautomer, 2,6-dihydroxy-anthranol (DHAL) can be recomposed to DHAQ electrochemically through two steps: oxidation of DHA(L)2- to the dimer (DHA)24- by one-electron transfer followed by oxidation of (DHA)24- to DHAQ2- by three-electron transfer per DHAQ molecule. This electrochemical regeneration process also rejuvenates the positive electrolyte-rebalancing the states of charge of both electrolytes without introducing extra ions.
Assuntos
Antralina , Mitoxantrona , Eletrólitos/química , Íons , OxirreduçãoRESUMO
Ferrocene (Fc) is one of the very limited organic catholyte options for aqueous organic flow batteries (AOFBs), a potential electrochemical energy storage solution to the intermittency of renewable electricity. Commercially available Fc derivatives are barely soluble in water, while existing methods for making water-soluble Fc derivatives by appending hydrophilic or charged moieties are tedious and time-consuming, with low yields. Here, a strategy was developed based on host-guest inclusion to acquire water-soluble Fc-based catholytes by simply mixing Fc derivatives with ß-cyclodextrins (ß-CDs) in water. Factors determining the stability and the electrochemical behavior of the inclusion complexes were identified. When adopted in a neutral pH AOFB, the origin of capacity loss was identified to be a chemical degradation caused by the nucleophilic attack on the center FeIII atom of the oxidized Fc derivatives. By limiting the state of charge, a low capacity fade rate of 0.0073 % h-1 (or 0.0020 % per cycle) was achieved. The proposed strategy may be extended to other families of electrochemically active water-insoluble organic compounds, bringing more electrolyte options for practical AOFB applications.
RESUMO
Miller's Grizzled Langur (Presbytis hosei canicrus) is one of the least known and rarest primates in Borneo. With a limited geographic range along the central coast of East Kalimantan and the highly degraded Kutai National Park, its former stronghold, this subspecies is now extremely rare and has been listed as one of the world's 25 most endangered primates. From June 6 to August 2, 2011, we carried out both direct observation and camera trap surveys at two mineral springs (sepans) in the Wehea Forest, East Kutai district, East Kalimantan. Presbytis hosei canicrus was observed at the large sepan on 3 of 6 observation days and at the small sepan on 2 of 3 observation days with up to 11 individuals observed in a single day at a single site. Camera traps recorded a per day capture rate of 0.72 at the small sepan and 0.25 at the large sepan and a per photo capture rate of 0.50 and 0.005, respectively. These data suggest relatively frequent occurrence of P. h. canicrus at the sepans, but the langurs are rarely encountered elsewhere in the Wehea Forest. The discovery of P. h. canicrus in the Wehea Forest confirms the continued existence of this endangered primate and is the first solid evidence demonstrating that its geographic range extends further inland than previously thought. It is not known whether the population of P. h. canicrus within Wehea Forest is large and stable enough to be considered viable, but it is likely part of a larger population that may possibly occur across surrounding protected forests and logging concessions. Surveying this potentially large population, and securing its protection, should be a priority measure for ensuring the continued existence of P. h. canicrus.
