Improving the electrochemical kinetics of lithium manganese phosphate via co-substitution with iron and cobalt

Xiang, Wei; Zhong, Yanjun; Tang, Yan; Shen, Huihui; Wang, Enhui; Liu, Heng; Zhong, Benhe; Guo, Xiaodong

doi:10.1016/j.jallcom.2015.02.049

Cited by 26 publications

(10 citation statements)

References 33 publications

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“…The results are usually an improvement with respect to single doping. Such is the case, in particular, for co-doping Fe 2+ and Mg 2+ of LMP [187][188][189][190][191][192][193][194][195][196][197][198], co-doping Fe and Co [199], and co-doping Fe and Ti [200]. In the latter case, Li(Mn 0.85 Fe 0.15 ) 0.92 Ti 0.08 PO 4 /C delivered a capacity of 144 mAh g −1 with a capacity retention close to 100% over 50 cycles at 1 C. Note, however, that a systematic approach for a multi-element doping design in electrode materials for rechargeable batteries by an elitism-improved nondominated sorting genetic algorithm (NSGA-II) optimization led to the conclusion that the best electrochemical performance is expected for multi-doping LMP with optimum compositions LiMn 0.938 Mg 0.024 Co 0.016 Ni 0.022 PO 4 /C and LiMn 0.962 Co 0.012 Ni 0.026 PO 4 /C [201].…”

Section: Dopingmentioning

confidence: 99%

Olivine Positive Electrodes for Li-Ion Batteries: Status and Perspectives

Mauger

Julien

2018

Batteries

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Among the compounds of the olivine family, LiMPO 4 with M = Fe, Mn, Ni, or Co, only LiFePO 4 is currently used as the active element of positive electrodes in lithium-ion batteries. However, intensive research devoted to other elements of the family has recently been successful in significantly improving their electrochemical performance, so that some of them are now promising for application in the battery industry and outperform LiFePO 4 in terms of energy density, a key parameter for use in electric vehicles in particular. The purpose of this review is to acknowledge the current state of the art and the progress that has been made recently on all the elements of the family and their solid solutions. We also discuss the results from the perspective of their potential application in the industry of Li-ion batteries.The main disadvantage of olivines with respect to other cathode chemistries for lithium batteries is the lower energy density. This is evidenced in Table 1 where we have reported the gravimetric and volumetric energy densities of LFP and two other cathode materials which have also found a market place in commercial batteries for electric vehicles: the manganese spinel LiMn 2 O 4 , and "LiNiCoAl" (NCA). In terms of energy density, the winner is clearly NCA, the cathode material used by Panasonic to manufacture the batteries of Tesla cars. However, the low energy density of LFP was not an obstacle for its success for EV applications. The top-selling EV manufacturer in the world today is BYD, which makes its own batteries. Its success comes from its choice of the LFP cathode chemistry. As an example, BYD's LFP battery used by e6 taxis in Shenzen has a driving range of 200 km and can be charged to 80% in just 20 min, or 100% in only 40 min using a BYD DC fast charger. The town has 12,000 taxis which will be electric by the end of this year, and all of the 7,000,000 buses are already electric buses, 80% being BYD buses.

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Section: Dopingmentioning

confidence: 99%

Olivine Positive Electrodes for Li-Ion Batteries: Status and Perspectives

Mauger

Julien

2018

Batteries

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“…By decreasing the characteristic size of particles to the nanoscale level, coating particles with electrically or ionically conductive layers and supervalent cation doping, the low electrochemical performance of LFP caused by poor electronic/ionic conductivity has been extensively studied and successfully overcome as evident in the recent commercialization of LFP as the cathode for Li-ion batteries. [9][10][11][12] Compared with LFP, LMP has been much less explored due to its extremely poor electronic conductivity (o10 À10 S cm À1 ), Jahn-Teller distortion caused by unstable Mn(III) [d 4 :t 2g 3 e g 1 ] of MnPO 4 when delithiated and a huge volumetric change between LiMnPO 4 and MnPO 4 during intercalation/de-intercalation (ca. 8 To further increase the energy density, the iso-structural LiMnPO 4 (LMP) is a more exciting cathode material due to its superior redox potential with flat plateau at 4.1 V versus Li/Li + .…”

Section: Introductionmentioning

confidence: 99%

“…The theoretical energy density of LMP (701 W h kg À1 ) is 1.2 times greater than that of LFP (586.5 W h kg À1 ). [9][10][11][12] Compared with LFP, LMP has been much less explored due to its extremely poor electronic conductivity (o10 À10 S cm À1 ), Jahn-Teller distortion caused by unstable Mn(III) [d 4 :t 2g 3 e g 1 ] of MnPO 4 when delithiated and a huge volumetric change between LiMnPO 4 and MnPO 4 during intercalation/de-intercalation (ca. 10%).…”

Section: Introductionmentioning

confidence: 99%

Hydrothermal synthesis, evolution, and electrochemical performance of LiMn_0.5Fe_0.5PO₄ nanostructures

Xiang

Zhong

et al. 2015

Phys. Chem. Chem. Phys.

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LiMn0.5Fe0.5PO4 (LMFP) materials are synthesized by the hydrothermal approach in an organic-free and surfactant-free aqueous solution. The phase and morphological evolution of the material intermediates at different reaction temperatures and times are characterized by XRD, SEM and TEM, respectively. The results show that during temperature increase, the solubility product (Ksp) of the precursors (Li3PO4, Fe3(PO4)2 and (Mn,Fe)3(PO4)2) is the decisive parameter for the precipitation processes. Once the temperature locates at the range of 100-110 °C, the unstable precursors dissolve quickly and then LMFP nuclei are formed, followed by a dissolution-reprecipitation process. As the reaction progresses, the primary particles self-aggregate to form rod or plate particles to reduce the overall surface energy through oriented attachment (OA) and the Ostwald ripening (OR) mechanism. Moreover, the resultant concentration of the precursor significantly affects the crystal size of LMFP by altering the supersaturation degree of solution at the nucleation stage. The carbon coated LMFP nanostructure synthesized at 0.6 mol L(-1) (resultant concentration of PO4(3-)) delivers discharge capacities of 155, 100 and 81 mA h g(-1) at 0.1, 5 and 20 C rate, respectively. The understanding of nanostructural evolution and its influence on the electrochemical performance will pave a way for a high-performance LMFP cathode.

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“…∼150 mAh·g –1 . Due to the presence of uniform carbon coating (sucrose) and interspersed carbon particles (Super P) as well as small primary nanocrystals (∼50 nm), the electron transfer resistance is significantly reduced, and also, wettability of the cathode material increased due to unhindered electrolyte percolation . Fe substitution also played an important role to reduce the Jahn–Teller distortion of Mn 3+ and improved the electron and Li + ion transport properties of the nanocrystals .…”

Section: Processing–property Correlation In Polyanion Phosphatesmentioning

confidence: 99%

Phosphate Polyanion Materials as High-Voltage Lithium-Ion Battery Cathode: A Review

et al. 2021

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Followed by decades of successful efforts in developing cathode materials for high specific capacity lithium-ion batteries, currently the attention is on developing a high-voltage battery (>5 V vs Li/Li+) with an aim to increase the energy density for their many fold advantages over conventional <4 V batteries. Among the various cathode materials, phosphate polyanion materials (LiMPO4, where M is a single metal or a combination of metals) showed promising candidacy given their high electrochemical potential (4.8–5 V vs Li/Li+), long cycle stability, low cost, and achieved specific capacity (∼165 mAh·g–1) near to its theoretical limit (170 mAh·g–1). In this review, factors affecting the electrochemical potential of the cathode materials are reviewed and discussed. Techniques to improve the electrical and ionic conductivities of phosphate polyanion cathodes, namely, surface coating, particle size reduction, doping, and morphology engineering, are also discussed. A processing–property correlation in phosphate polyanion materials is also undertaken to understand relative merits and drawbacks of diverse processing techniques to deliver a material with targeted functionality. Strategies required for high-voltage phosphate polyanion cathode materials are envisioned, which are expected to deliver lithium-ion battery cathodes with higher working potential and gravimetric specific capacity.

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Improving the electrochemical kinetics of lithium manganese phosphate via co-substitution with iron and cobalt

Cited by 26 publications

References 33 publications

Olivine Positive Electrodes for Li-Ion Batteries: Status and Perspectives

Olivine Positive Electrodes for Li-Ion Batteries: Status and Perspectives

Hydrothermal synthesis, evolution, and electrochemical performance of LiMn_0.5Fe_0.5PO₄ nanostructures

Phosphate Polyanion Materials as High-Voltage Lithium-Ion Battery Cathode: A Review

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Improving the electrochemical kinetics of lithium manganese phosphate via co-substitution with iron and cobalt

Cited by 26 publications

References 33 publications

Olivine Positive Electrodes for Li-Ion Batteries: Status and Perspectives

Olivine Positive Electrodes for Li-Ion Batteries: Status and Perspectives

Hydrothermal synthesis, evolution, and electrochemical performance of LiMn0.5Fe0.5PO4 nanostructures

Phosphate Polyanion Materials as High-Voltage Lithium-Ion Battery Cathode: A Review

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Hydrothermal synthesis, evolution, and electrochemical performance of LiMn_0.5Fe_0.5PO₄ nanostructures