Influence of synthesis conditions on the electrochemical properties of nanostructured amorphous manganese oxide cryogels

Amorphous manganese oxides have received increasing attention in recent years as intercalation cathodes for rechargeable lithium batteries. The sol–gel method is a versatile method for achieving nanostructured amorphous oxides. In this paper, two different sol–gel routes are investigated, where nanostructured amorphous manganese oxide cryogels are obtained via freeze drying Mn(IV) oxide hydrogels formed in situ. In one route the hydrogels are formed by reaction between a solution of sodium permanganate and a solution of disodium fumarate, and in the other route by reaction between a solution of sodium permanganate and solid fumaric acid. Highly homogeneous monolithic manganese oxide hydrogels are obtained from both synthesis routes with precursor concentrations between 0.1 and 0.2 M. The freeze drying method proves to be an efficient method for obtaining nanostructured amorphous manganese oxide cryogels out of the hydrogels. Depending on the synthesis conditions of the hydrogels, the resultant cryogels can yield very high specific capacities for lithium intercalation and excellent rate performance. The cryogel with the best performance exhibits 289 mAh/g at a C/100 rate and 174 mAh/g at a 2C rate. Strong dependence of electrochemical properties of the cryogels on the synthesis conditions of the parent hydrogels has been observed. The different electrochemical properties are believed to be due to different surface areas and local structures of the cryogels derived from hydrogels synthesized under different conditions. This strong dependence gives rise to the possibility of achieving promising intercalation materials through tailoring the surface area and the local structure of amorphous manganese oxides by adjusting sol–gel synthesis conditions.