Rechargeability and economic aspects of alkaline zinc–manganese dioxide cells for electrical storage and load leveling

Abstract

h i g h l i g h t sZneMnO 2 battery was cycled at shallow DOD for more than 3000 cycles. Relatively low delivered cost of less than $150 per kWh. Mathematical model developed to understand the capacity fade mechanisms. Resistive film formation on the surface of MnO 2 particle during cycling. Change in SOC during cycling was used to measure capacity loss. Keywords:Rechargeable zincemanganese dioxide battery Cycle life ZneMnO 2 battery model Capacity fade model Film resistance a b s t r a c t Batteries based on manganese dioxide (MnO 2 ) cathodes are good candidates for grid-scale electrical energy storage, as MnO 2 is low-cost, relatively energy dense, safe, water-compatible, and non-toxic. Alkaline ZneMnO 2 cells, if cycled at reduced depth of discharge (DOD), have been found to achieve substantial cycle life with battery costs projected to be in the range of $100 to 150 per kWh (delivered). Commercialization of rechargeable ZneMnO 2 batteries has in the past been hampered due to poor cycle life. In view of this, the work reported here focuses on the long-term rechargeability of prismatic MnO 2 cathodes at reduced DOD when exposed to the effects of Zn anodes and with no additives or specialty materials. Over 3000 cycles is shown to be obtainable at 10% DOD with energy efficiency >80%. The causes of capacity fade during long-term cycling are also investigated and appear to be mainly due to the formation of irreversible manganese oxides in the cathode. Analysis of the data indicates that capacity loss is rapid in the first 250 cycles, followed by a regime of stability that can last for thousands of cycles. A model has been developed that captures the behavior of the cells investigated using measured state of charge (SOC) data as input. An approximate economic analysis is also presented to evaluate the economic viability of ZneMnO 2 batteries based on the experiments reported here.

Electrochemical Behavior of Electrolytic Manganese Dioxide in Aqueous KOH and LiOH Solutions: A Comparative Study

“…Major criteria for reversible cycling are to limit the depth of discharge to minimize the solubility of manganese in lower oxidation states, and to avoid the formation of soluble high oxidation state species during charging (i.e. MnO 4 2− ). 4,5,6,7 It has also been reported that the use of LiOH instead of KOH as the electrolyte can improve the cycle life of γ-MnO 2 .…”

“…MnO 4 2− ). 4,5,6,7 It has also been reported that the use of LiOH instead of KOH as the electrolyte can improve the cycle life of γ-MnO 2 . 8 The structure of γ-MnO 2 is highly defective both in terms of type and concentration of defects.…”

“…Jouanneau et al did make a comparative study of numerous MnO 2 samples with a range of defect contents in aqueous KOH solutions and non-aqueous LiOH solutions, with only a mild heat-treatment. 15 Minakshi et al compared MnO 2 in KOH and LiOH solutions, but only in the presence of zincate (Zn(OH) 4 2− ), which can affect the behavior of the material by reacting with the reduced form. 16 In light of reports of improved capacity retention in LiOH solutions (in comparison to KOH solutions), and in the interest of comparing proton and lithium ion uptake by non-heat treated material, we carried out a comparative study of γ-MnO 2 in aqueous LiOH and KOH solutions.…”

Impact of Triethanolamine as an Additive for Rechargeable Alkaline Zn/MnO2Batteries under Limited Depth of Discharge Conditions

“…> 4000 cycles at 5% DOD, 0.05 C rate; ∼3000 cycles at 10% DOD, 0.05 C rate; ∼2250 at 10% DOD, 0.1 C rate; ∼800 cycles at 10% DOD, 0.15 C; and ∼500 cycles at 20% DOD, 0.05 C rate). 19 It should be noted that the C-rates reported by Ingale et al were based on the cycled capacity of MnO 2 ; however, here they are reported based on the full 1 e − capacity of MnO 2 . For example, at 10% DOD cycling, a 0.2 C rate in this paper would be reported as 2 C in their work.…”

“…In a full cell, TEA increases the discharge end voltage, rate performance, and energy efficiency as well as significantly increases the lifetime of the battery by 297%. Electrode preparation.-Electrodes were prepared with slight modification to the procedure described by Ingale et al 19 Battery cathodes were prepared by combining 65 wt% EMD, 30 wt% graphite, and 5 wt% PTFE solids with a mortar and pestle. EMD and graphite powders were mixed thoroughly, and then the PTFE dispersion was added and mixed until uniform.…”