Carbonophosphates: A New Family of Cathode Materials for Li-Ion Batteries Identified Computationally

Abstract

Identified Computationally. -A new class of materials which can intercalate lithium reversibly is discovered by a novel high-throughput ab initio computational approach. Na3FeCO3PO4 and Na3MnCO3PO4 are hydrothermally synthesized from aqueous solutions of FeSO4 or MnNO3, (NH4)2HPO4, and Na2CO3 (autoclave, 120°C, 70 h). Li-Na ion exchange produces Li 3 FeCO 3 PO 4 and Li 3 MnCO 3 PO 4 . The Mn carbonophosphate Li3MnCO3PO4 could potentially display a specific energy 45% greater than that of LiFePO4 and might be a promising cathode material for Li ion batteries. -(CEDER*, G.; et al.; Chem. Mater.

Roles of Processing, Structural Defects and Ionic Conductivity in the Electrochemical Performance of Na3MnCO3PO4Cathode Material

“…The aforementioned theoretical prediction and experimental investigations 13,[28][29][30] reveal clearly that Na 3 MnCO 3 PO 4 has a potential to be a high capacity cathode material for NIBs. Therefore, in this study, we have investigated factors, other than the electronic conductivity, that can affect the electrochemical properties of Na 3 MnCO 3 PO 4 as the cathode material for NIBs.…”

“…13 Recently, our group has shown that high specific capacities, reaching as high as 92% of the theoretical, can be achieved when aided by the addition of 53 wt% (60 vol%) carbon black (CB) which provides a continuous CB network interacting with almost all Na 3 MnCO 3 PO 4 particles in the cathode and allow them to participate in electrochemical reactions. 30 The aforementioned theoretical prediction and experimental investigations 13,[28][29][30] reveal clearly that Na 3 MnCO 3 PO 4 has a potential to be a high capacity cathode material for NIBs. Therefore, in this study, we have investigated factors, other than the electronic conductivity, that can affect the electrochemical properties of Na 3 MnCO 3 PO 4 as the cathode material for NIBs.…”

“…In this context, Na 3 MnCO 3 PO 4 has been predicted via ab initio calculations 28,29 to be capable of delivering two electron transfer redox reactions per formula and thus has a high theoretical capacity (i.e., 191 mAh/g of Na 3 MnCO 3 PO 4 ). The earlier experiments, however, were only able to obtain a low specific capacity of 125 mAh/g, i.e., ∼65% of the theoretical.13 Recently, our group has shown that high specific capacities, reaching as high as 92% of the theoretical, can be achieved when aided by the addition of 53 wt% (60 vol%) carbon black (CB) which provides a continuous CB network interacting with almost all Na 3 MnCO 3 PO 4 particles in the cathode and allow them to participate in electrochemical reactions. …”

“…15 One way to mitigate these intrinsic deficiencies is to search for high capacity anodes and cathodes. In this context, Na 3 MnCO 3 PO 4 has been predicted via ab initio calculations 28,29 to be capable of delivering two electron transfer redox reactions per formula and thus has a high theoretical capacity (i.e., 191 mAh/g of Na 3 MnCO 3 PO 4 ). The earlier experiments, however, were only able to obtain a low specific capacity of 125 mAh/g, i.e., ∼65% of the theoretical.…”

An intuitive and efficient method for cell voltage prediction of lithium and sodium-ion batteries

“…Although this may appear much easier to conduct than experiments, the procedure still requires a significant amount of work: both the alkali-rich and the alkali-poor compositions have to be computed within a reasonable numerical accuracy for their energy difference to be meaningful, and sometimes with functionals that go beyond the usual local density approximation 8 or generalized gradient approximation 9,10 . While this is certainly tractable for a quite large set of compounds 5,11 , it becomes limited or prohibitive when realistic materials including defects, disorder or dopants must be studied 12,13 . Above all, first-principles calculations are not straightforwardly utilizable by non informed users.…”