Phase diagram and electrochemical properties of mixed olivines from first-principles calculations

Malik, Rahul; Zhou, Fei; Ceder, Gerbrand

doi:10.1103/physrevb.79.214201

Cited by 79 publications

(85 citation statements)

References 37 publications

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“…On the other side, a slight overlap of Fe anodic and cathodic peaks can be associated with a single-phase transition. The single-phase behavior has been attributed to the effect of Mn 2+ , which dilutes the interactions responsible for the phase separation [42]. This is consistent with the findings published by Roberts et al [43].…”

Section: Resultssupporting

confidence: 72%

Enhanced kinetic behaviors of LiMn0.5Fe0.5PO4/C cathode material by Fe substitution and carbon coating

Yan

Wang

et al. 2015

J Solid State Electrochem

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The LiMn 0.5 Fe 0.5 PO 4 /C nanocrystallites with a uniform size (∼50 nm) are successfully prepared by employing a facile solvothermal method at 180°C. Amphiphilic carbonaceous material (ACM) is chosen as the carbon precursor and forms a homogeneous carbon layer covering the LiMn 0.5 Fe 0.5 PO 4 particles. The asprepared LiMn 0. 5 Fe 0. 5 PO 4 /C sample, with a high Brunauer-Emmett-Teller (BET) surface area of 69.3 m 2 g −1 , is used as the cathode material for lithiumion batteries (LIBs) and delivers a reversible capacity of 158 mAh g −1 at 0.05 C. It shows remarkable rate capability with discharge capacities of 130 mAh g −1 at 1 C, 105 mAh g − 1 at 10 C and 99 mAh g − 1 at 30 C. Meanwhile, the material maintains 121 mAh g −1 at 1 C after 150 cycles with 93 % capacity retention. The kinetic behaviors of LiMn 0.5 Fe 0.5 PO 4 /C sample are investigated by high throughout cyclic voltammetry. The small particle size, partial Fe substitution, and homogeneous carbon coating make a synergetic effect on enhancing the sample's electrochemical properties.

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Section: Resultssupporting

confidence: 72%

Enhanced kinetic behaviors of LiMn0.5Fe0.5PO4/C cathode material by Fe substitution and carbon coating

Yan

Wang

et al. 2015

J Solid State Electrochem

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“…The proposed two-electron activity leads to a high theoretical capacity of 231 mAh/g. 14 and similar behavior could be present in this system. The second set of peaks around 4.0 V corresponds to the predicted Mn 3+ /Mn 4+ activity in the active material.…”

Section: Discussionmentioning

confidence: 69%

Electrochemical Properties of Li3Fe0.2Mn0.8CO3PO4 as a Li-Ion Battery Cathode

Matts

Chen

Ceder

2013

ECS Electrochemistry Letters

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Previously conducted high-throughput ab initio calculations have identified carbonophosphates as a new class of polyanion cathode materials. Li 3 MnCO 3 PO 4 is the most promising candidate due to its high theoretical capacity and ideal voltage range. However, a major limitation of this material is its poor cyclability and experimentally observed capacity. In this work we synthesize Li 3 The need for lithium-ion batteries with higher energy density than existing materials has led to significant efforts to discover new cathode materials.1-3 High-throughput ab initio computation is an effective approach employed to accelerate the process of materials discovery. 4 This has led to the identification of several novel lithium intercalation materials. 3,5,6 One class of novel materials that has been predicted to function as intercalation cathodes for Li-ion batteries is the lithium transition metal carbonophosphates. 5 The Li 3 FeCO 3 PO 4 and Li 3 MnCO 3 PO 4 compounds are of particular interest, as shown in Table I, which shows data first reported by Chen et al. 3 Both are predicted to have accessible 2 + to 3 + redox couples, but the 3 + to 4 + couple in the manganese-containing compound is also expected to be active at a voltage compatible with existing electrolytes. As a result, Li 3 MnCO 3 PO 4 is of the greatest interest because it has a high theoretical capacity of 231 mAh/g and average voltage of 3.7 V. As polyanionic cathodes, lithium metal carbonophosphates could also be preferred over oxide cathode materials since they are generally less likely to release oxygen at high voltages. 4 The synthesis and characterization of both Li 3 FeCO 3 PO 4 and Li 3 MnCO 3 PO 4 have been previously reported.3 The lithiumcontaining carbonophosphates are not thermodynamic ground states, so the compounds are synthesized using ion-exchange techniques from the thermodynamically stable sodium carbonophosphates. As reported previously by Chen et al., Li 3 FeCO 3 PO 4 has a theoretical capacity of 115 mAh/g and can be easily synthesized using ion exchange methods. This compound cycles reversibly, close to its theoretical limit at a rate of C/5. In contrast, Li 3 MnCO 3 PO 4 shows a discharge capacity of 135 mAh/g on its first discharge at a rate of C/100, which is only ∼58% of its theoretical capacity. In addition, the capacity of Li 3 MnCO 3 PO 4 degrades in subsequent cycles. The poor performance in Li 3 MnCO 3 PO 4 could be due to many factors. However, we believe one major cause is the residual sodium (∼17%) ions sitting on Li sites as a result of an incomplete ion exchange during synthesis. The better-performing Li 3 FeCO 3 PO 4 shows no residual sodium after synthesis. 3Our approach is to substitute manganese in the Li 3 MnCO 3 PO 4 with iron to improve its performance by imparting the ion-exchangeability and cycling performance of the Li 3 FeCO 3 PO 4 on to Li 3 MnCO 3 PO 4 . Similar mixing techniques have been used in previous attempts to improve the performance of α-LiMnPO 4 . [7][8][9] In this paper we focus specifically...

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“…15(b)), for V-C system with a completely disordered vacancy configuration [69]. [56]. The phase diagram consists of two miscibility gaps at low temperature, the first between Fe 1Ày Mn y PO 4 (denoted by a) and Li y Fe 1Ày Mn y PO 4 (denoted by SS) and the second between Li y Fe 1Ày Mn y PO 4 (SS) and LiFe 1Ày Mn y PO 4 (denoted by b), where 0 6 y 6 1.…”

Section: Application Of Cluster Expansion In Other Calculationsmentioning

confidence: 98%

“…13, by applying FP-MC-combination calculation [56]. The phase diagram of Li x (Fe 1Ày Mn y )PO 4 shows two low temperature miscibility gaps separated by a solid solution phase centered at Li composition x % y, which correspond respectively to two states in which most Fe ions are oxidized and most Mn are not.…”

Section: Brief Overview On Applicationmentioning

confidence: 99%

Cluster expansion method and its application in computational materials science

Song

et al. 2016

Computational Materials Science

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Phase diagram and electrochemical properties of mixed olivines from first-principles calculations

Cited by 79 publications

References 37 publications

Enhanced kinetic behaviors of LiMn0.5Fe0.5PO4/C cathode material by Fe substitution and carbon coating

Enhanced kinetic behaviors of LiMn0.5Fe0.5PO4/C cathode material by Fe substitution and carbon coating

Electrochemical Properties of Li3Fe0.2Mn0.8CO3PO4 as a Li-Ion Battery Cathode

Cluster expansion method and its application in computational materials science

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