A promising group of inorganic salts recently emerged for the negative electrode of advanced lithium-ion batteries. Manganese carbonate combines low weight and significant lithium storage properties. Electron paramagnetic resonance (EPR) and magnetic measurements are used to study the environment of manganese ions during cycling in lithium test cells. To observe reversible lithium storage into manganese carbonate, preparation by a reverse micelles method is used. The resulting nanostructuration favors a capacitive lithium storage mechanism in manganese carbonate with good rate performance. Partial substitution of cobalt by manganese improves cycling efficiency at high rates.

Mesoporous FeC 2O 4 was prepared by dehydration of bulk monoclinic- and micellar orthorhombic FeC 2O 4.2H 2O precursors at 200 degrees C. The micellar material shows nanoribbon shaped particles, which are preserved after dehydration. These solids are used as high-capacity lithium storage materials with improved rate performance. The mesoporous nanoribbons exhibit higher capacities close to 700 mA h/g after 50 cycles at 2C (C = 1 Li h (-1) mol (-1)) rate between 0 and 2 V.

Orthorhombic cobalt oxalate dihydrate has been prepared in the form of nanoribbons by a reverse micelles method. The crystallographic structure of the resulting solid differs from the monoclinic massive product. A careful dehydration of the nanocrystals leads to anhydrous cobalt oxalate in which the nanoribbon-shaped particles are preserved and Co2+ ions are located in a centrosymmetric environment. CoC2O4 is used for the first time as high-capacity lithium storage materials with improved rate performance. The anhydrous solids react with lithium, leading to metallic cobalt and lithium oxalate, as shown by XAS and FTIR measurements. The new electrode material displays reversible capacities close to 900 mA·h·g−1 between 0 and 2 V versus lithium by a novel reaction mechanism which involves cobalt reduction−reoxidation.

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Different solid solutions in the Fe x Co 1Àx C 2 O 4 $2H 2 O system have been prepared in the form of nanoribbons by a reverse micelles method. The orthorhombic crystallographic structure differs from the monoclinic massive products FeC 2 O 4 $2H 2 O and CoC 2 O 4 $2H 2 O. The dehydration process is studied by thermal analysis to prepare the anhydrous solid solution oxysalts, in which the nanoribbonshaped particles are preserved and a porous system is developed. Anhydrous mixed oxalates are used for the first time as high-capacity lithium storage materials with improved rate performance, and display synergistic effects as compared with the end members. Fe 0.75 Co 0.25 C 2 O 4 displays a reversible capacity ca. 600 mA h g À1 at 5C rate with a very good capacity retention after 75 cycles by a hybrid mechanism. The solids display faradaic capacities due to a novel conversion reaction that produces nanodispersed transition metals, which is responsible for the high energy density, and a capacitive response that leads to high power densities in Li-ion batteries. The low temperature synthesis of these materials makes them an inexpensive option for this purpose.