Lithium Storage Mechanisms and Effect of Partial Cobalt Substitution in Manganese Carbonate Electrodes

Abstract

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.

Cobalt carbonate dumbbells for high-capacity lithium storage: A slight doping of ascorbic acid and an enhancement in electrochemical performances

“…In the previous studies about CoCO 3 , the extra-capacity contribution has been assigned to the reversible redox reaction between C 4þ in CO 2À 3 and its low valence states (e.g., C 0 ) under the catalysis of in-situ generated transition metal nanocrystals [9,10,18,21e25]. To analyze the galvanostatic discharge-charge behaviors of MnCO 3 electrodes, both Faradaic and non-Faradaic (capacitance) contributions were briefly summarized to reveal the ambiguous reaction mechanism of MCO 3 towards metallic lithium [11,16,17]. In view of the extremely high lithium storage capability of micro-rhombohedral FeCO 3 (e.g., the 120th reversible capacity~1018 mAh g À1 , 200 mA g À1 ), the unexpectedly detected ferric derivatives coming from the further oxidation of ferrous origins were mentioned, which could partly explain the excellent electrochemical properties of FeCO 3 micro-rhombohedra [7].…”

Preparation and characterization of basic carbonates as novel anode materials for lithium-ion batteries

“…In the most recent years, several metal carbonates, such as manganese carbonate [13], cobalt carbonate [14,15], Mn 1 À x Co x CO 3 [16], (BiO) 2 CO 3 and CdCO 3 [17], have been considered as potential candidates for anode materials in lithium-ion batteries due to high reversible capacity, good capacity retention and excellent cycle calendar life. Nevertheless, no literatures about basic carbonates as anode materials for lithium-ion batteries were ever reported.…”

Submicron peanut-like MnCO3 as an anode material for lithium ion batteries

“…Compared with square MnCO 3 synthesized in water/ethanol system, the SPs exhibit a high specific capacity of 55 17 (Cd1/3Co1/3Zn1/3)CO3 nano-flowers ~720 at 60 mA g -1 60 ~220 at 680 mA g - 1 22 MnCO3 microstructures ~450 at 233 mA g -1 25 ~400 at 932 mA g - 1 18 MnCO3 submicron ~500 at 466 mA g -1 80 16 CoCO3 urchin -like microspheres ~361 at 100 mA g -1 100 ~187 at 2000 mA g -1 23…”