Nanotechnology and Functional Materials, Department of Engineering Sciences, The Ångström Laboratory, Uppsala University , Box 534, SE-751 21 Uppsala, Sweden.
J Am Chem Soc. 2017 Apr 5;139(13):4828-4834. doi: 10.1021/jacs.7b00159. Epub 2017 Mar 28.
Rechargeable batteries that use organic matter as the capacity-carrying material have previously been considered a technology for the future. Earlier batteries in which both the anode and cathode consisted of organic material required significant amounts of conductive additives and were often based on metal-ion electrolytes containing Li or Na. However, we have used conducting poly(3,4-ethylenedioxythiophene) (PEDOT), functionalized with anthraquinone (PEDOT-AQ) or benzonquinone (PEDOT-BQ) pendant groups as the negative and positive electrode materials, respectively, to make an all-organic proton battery devoid of metals. The electrolyte consists of a proton donor and acceptor slurry containing substituted pyridinium triflates and the corresponding pyridine base. This slurry allows the 2e/2H quinone/hydroquinone redox reactions while suppressing proton reduction in the battery cell. By using strong (acidic) proton donors, the formal potential of the quinone redox reactions is tuned into the potential region in which the PEDOT backbone is conductive, thus eliminating the need for conducting additives. In this all-organic proton battery cell, PEDOT-AQ and PEDOT-BQ deliver 103 and 120 mAh g, which correspond to 78% and 75%, respectively, of the theoretical specific capacity of the materials at an average cell potential of 0.5 V. We show that PEDOT-BQ determines the cycling stability of the device while PEDOT-AQ provides excellent reversibility for at least 1000 cycles. This proof-of-concept shows the feasibility of assembling all-organic proton batteries which require no conductive additives and also reveals where the challenges and opportunities lie on the path to producing plastic batteries.
先前，使用有机物作为储能材料的可充电电池被认为是未来的技术。在此之前，其正负极均由有机物组成的早期电池需要添加大量的导电添加剂，且通常基于含有 Li 或 Na 的金属离子电解质。然而，我们使用了经过蒽醌（PEDOT-AQ）或苯醌（PEDOT-BQ）官能化的导电聚（3,4-亚乙基二氧噻吩）（PEDOT）分别作为负、正极材料，制造了一种不含金属的全有机质子电池。电解质由质子供体和受体浆料组成，其中包含取代的吡啶三氟甲磺酸酯和相应的吡啶碱。这种浆料允许醌/氢醌 2e/2H 氧化还原反应发生，同时抑制电池中质子的还原。通过使用强（酸性）质子供体，醌氧化还原反应的形式电位被调整到 PEDOT 主链具有导电性的电位区域，从而无需使用导电添加剂。在这种全有机质子电池中，PEDOT-AQ 和 PEDOT-BQ 分别提供了 103 和 120 mAh g 的容量，这分别对应于材料理论比容量的 78%和 75%，平均电池电位为 0.5 V。我们表明，PEDOT-BQ 决定了器件的循环稳定性，而 PEDOT-AQ 则提供了至少 1000 次循环的优异可逆性。这一概念验证表明，组装无需导电添加剂的全有机质子电池是可行的，同时也揭示了在生产塑料电池的道路上，挑战和机遇所在。
