Lithium-sulfur (Li-S) batteries suffer from shuttle reactions during electrochemical cycling, which cause the loss of active material sulfur from sulfur-carbon cathodes, and simultaneously incur the corrosion and degradation of the lithium metal anode by forming passivation layers on its surface. These unwanted reactions therefore lead to the fast failure of batteries. The preservation of the highly reactive lithium metal anode in sulfur-containing electrolytes has been one of the main challenges for Li-S batteries. In this study, we systematically controlled and optimized the formation of a smooth and uniform solid electrolyte interphase (SEI) layer through electrochemical pretreatment of the Li metal anode under controlled current densities. A distinct improvement of battery performance in terms of specific capacity and power capability was achieved in charge-discharge cycling for Li-S cells with pretreated Li anodes compared to pristine untreated ones. Importantly, at a higher power density (1 C rate, 3 mA cm), the Li-S cells with pretreated Li anodes protected by a controlled elastomer (Li-Protected-by-Elastomer, LPE)) show the suppression of the Li dendrite growth and exhibit 3-4 times higher specific capacity than the untreated ones after 100 electrochemical cycles. The formation of such a controlled uniform SEI was confirmed, and its surface chemistry, morphology, and electrochemical properties were characterized by X-ray photoelectron spectroscopy, focused-ion beam cross sectioning, and scanning electron microscopy. Adequate pretreatment current density and time are critical in order to form a continuous and uniform SEI, along with good Li-ion transport property.
Animal experiments with biogalvanic cells have demonstrated that an average power of 80 muW can be derived continously for at least 2 years. There is a further scope to stabilize the power at 100 muW for considerable longer periods so that the chances of cardiac pacing with biogalvanic power have become bright. However, large scale efforts are necessary in in establishing the statistical reliability and the secured performance which are expensive and time consuming. Animal experiments with biofuel cells are still in preliminary stages. We derived a continous power of 40 muW (4MUW/cm2) at 575 mV over 150 days so far. This is the longest recorded period with such a high power density. The main problem in deriving higher power over longer period is to properly encapsulate the cell with materials which are hydrophilic and essentially biocompatible.
Body fluids contain a large number of amino acids along with glucose. Therefore, the electrochemical behavior of amino acids should be considered in studying the anodic oxidation reaction of glucose for biological applications. Potential-sweep and steady-state measurements with different platinum electrodes under neutral conditions have shown that the oxidation of amino acids is basically possible. However, their presence, especially as a mixture, has a remarkable influence on the glucose oxidation and the anodic reaction is strongly inhibited. With respect to the degree of inhibition, they can be classified into two groups. The inhibiting effect is particularly drastic in the case of basic and unsaturated amino acids as well as the ones containing sulphur because of their strong absorption at the electrode surface. The glucose currents are inhibited by about 90% under steady-state. In addition to the direct electrochemical inhibition, the following bacterial decomposition of amino acids is probably also responsible for the drastic effect. However, about 10% of the glucose currents still remain measurable indicating that glucose is detectable at physiological concentrations even under extremly unfavorable conditions. This result is of basic importance in operating a biofuel cell or in measuring glucose concentrations.
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