Precursor-based synthesis and electrochemical performance of LiMnPO4

Bramnik, Natalia N.; Ehrenberg, Helmut

doi:10.1016/j.jallcom.2007.09.118

Cited by 90 publications

(85 citation statements)

References 17 publications

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“…Although there are tremendous efforts to develop a practical LiMnPO 4 cathode, only limited literature data on this cathode material for LIBs are available [17,[20][21][22][23][24][25][26]. There are several synthetic techniques applied to prepare LiMnPO 4 /C composites.…”

Section: Studies On High-performance Limnpo 4 Olivine Cathodementioning

confidence: 99%

“…The Mn 2+ disorder on Li + sites was depressed by increasing the synthesis temperature, and the highest discharge capacity achieved is 68 mAh g 1 at a current density of 1.5 mA g 1 . The increase in carbon content up to 50% during the ballmilling of the solid-state reaction prepared LiMnPO 4 improves the conductivity of material as well as destroys big agglomerates and allowed about 30% of the theoretical capacity at C/5 [24]. Wang et al [25] reported a polyol synthesis of the platelet morphology of 30 nm thick LiMnPO 4 .…”

Section: Studies On High-performance Limnpo 4 Olivine Cathodementioning

confidence: 99%

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LiMnPO4 Olivine as a Cathode for Lithium Batteries

Bakenov¹,

Taniguchi

2011

TOMSJ

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The olivine structured mixed lithium-transition metal phosphates LiMPO 4 (M = Fe, Mn, Co) have attracted tremendous attention of many research teams worldwide as a promising cathode materials for lithium batteries. Among them, lithium manganese phosphate LiMnPO 4 is the most promising considering its high theoretical capacity and operating voltage, low cost and environmental safety. Various techniques were applied to prepare this perspective cathode for lithium batteries. The solution based synthetic routes such as spray pyrolysis, precipitation, sol-gel, hydrothermal and polyol synthesis allow preparing nanostructured powders of LiMnPO 4 with enhanced electrochemical properties, which is mostly attributed to the higher chemical homogeneity and narrow particle size distribution of the material. Up-to-date, the LiMnPO 4 /C composites prepared by the spray pyrolysis route have the best electrochemical performance among the reported in the literature.

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Section: Studies On High-performance Limnpo 4 Olivine Cathodementioning

confidence: 99%

Section: Studies On High-performance Limnpo 4 Olivine Cathodementioning

confidence: 99%

LiMnPO4 Olivine as a Cathode for Lithium Batteries

Bakenov¹,

Taniguchi

2011

TOMSJ

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“…Recently, LiMnPO 4 powder prepared by the polyol method by Kim et al 23 showed a reversible capacity of about 115 mAh g −1 . Reports by Dominko et al 24 and Bramnik and Ehrenberg 25 demonstrated the poor electrochemical performance of LiMnPO 4 as a cathode material for rechargeable lithium-ion batteries. Yamada et al [3][4][5][6] and Okada et al, 26 who extensively studied olivine cathodes, also could not achieve a good electrochemical performance for LiMnPO 4 cathodes.…”

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confidence: 99%

LiMnPO[sub 4] as an Advanced Cathode Material for Rechargeable Lithium Batteries

Martha

Markovsky

Grinblat

et al. 2009

J. Electrochem. Soc.

299

239

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LiMnPO 4 nanoparticles synthesized by the polyol method were examined as a cathode material for advanced Li-ion batteries. The structure, surface morphology, and performance were characterized by X-ray diffraction, high resolution scanning electron microscopy, high resolution transmission electron microscopy, Raman, Fourier transform IR, and photoelectron spectroscopies, and standard electrochemical techniques. A stable reversible capacity up to 145 mAh g −1 could be measured at discharge potentials Ͼ4 V vs Li/Li + , with a reasonable capacity retention during prolonged charge/discharge cycling. The rate capability of the LiMnPO 4 electrodes studied herein was higher than that of LiNi 0.5 Mn 0.5 O 2 and LiNi 0.8 Co 0.15 Al 0.05 O 2 ͑NCA͒ in similar experiments and measurements. The active mass studied herein seems to be the least surface reactive in alkyl carbonate/LiPF 6 solutions. We attribute the low surface activity of this material, compared to the lithiated transition-metal oxides that are examined and used as cathode materials for Li-ion batteries, to the relatively low basicity and nucleophilicity of the oxygen atoms in the olivine compounds. The thermal stability of the LiMnPO 4 material in solutions ͑measured by differential scanning calorimetry͒ is much higher compared to that of transition-metal oxide cathodes. This is demonstrated herein by a comparison with NCA electrodes. 2 Among them, LiMnPO 4 is of particular interest as it offers the advantages of a flat discharge voltage profile at 4.1 V vs Li/Li + , the expected safety features, and an abundance of the relevant elements in the earth's crust.1-6 Hence, LiMnPO 4 can be an ideal substitute for the commonly used cathode material, LiCoO 2 , which is expensive, toxic, and demonstrates problematic safety features. The three-dimensional framework of the olivine structure is stabilized by the strong covalent bonds between the oxygen and the P 5+ ions, resulting in PO 4 3− tetrahedral polyanions. As a result, lithium metal phosphate materials do not undergo a structural rearrangement during lithiation and delithiation. This indicates that LiMPO 4 electrodes may demonstrate better stability and capacity retention during prolonged cycling as compared to lithiated transition-metal oxide cathode materials such as LiCoO 2 , LiNiO 2 , LiMnO 2 , and LiMn 2 O 4 . However, LiMPO 4 compounds and LiMnPO 4 , in particular, suffer from poor electronic and ionic ͑Li + ͒ conductivity, which means a limited rate capability ͑especially at low temperatures͒.

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“…The increase in carbon content up to 50% during the ballmilling of the solid-state reaction prepared LiMnPO 4 improves the conductivity of material as well as destroys big agglomerates and allowed about 30% of the theoretical capacity at C/5 in Ref. 18. Wang et al 4 reported a polyol synthesis of the platelet morphology of ϳ30 nm thick LiMnPO 4 .…”

mentioning

confidence: 99%

LiMg[sub x]Mn[sub 1−x]PO[sub 4]/C Cathodes for Lithium Batteries Prepared by a Combination of Spray Pyrolysis with Wet Ballmilling

Bakenov

Taniguchi

2010

J. Electrochem. Soc.

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The LiMg x Mn 1−x PO 4 /C ͑x = 0, 0.02, 0.04, 0.12͒ composite cathode was successfully prepared by a combination of spray pyrolysis and wet ballmilling with heat-treatment. The composite cathode had narrow particle size distribution with an average particle size of 99 nm. The Mg doping on the Mn site led to the electrochemical performance enhancement of the composite cathode, which was confirmed by cyclic voltammetry, ac impedance spectroscopy, and charge-discharge tests. The Mg-doped composite cathode exhibited a high discharge capacity in lithium cell, which remarkably increased with an increase in the charge cutoff voltage under galvanostatic charge-discharge. The LiMg 0.04 Mn 0.96 PO 4 /C cathode exhibited a discharge capacity of 154 mAh g −1 ͑above 93% of the theoretical value͒ at 0.1C when charge-discharged galvanostatically to 4.9 V. Along with enhanced discharge capacity, the cell exhibited a good rate capability under the galvanostatic charge-discharge. Under the trickle mode conditions, the cell exhibited discharge capacities of 154, 136, 106, and 74 mAh g −1 at 0.05, 0.1, 1, and 5C, respectively. © 2010 The Electrochemical Society. ͓DOI: 10.1149/1.3294698͔ All rights reserved. Lithium-ion batteries ͑LIBs͒ are leading the rapidly growing market of portable power sources for various applications starting from the miniature devices, such as peacemakers and chipsets, to electricity powered automobiles and energy storage facilities. Rechargeable LIBs with liquid electrolytes were developed and introduced into the market by Sony Corporation 1 in 1991. Despite its outstanding properties compared with other types of batteries such as nickel-cadmium and metal hydride batteries, LIBs suffer from the application of high cost and toxic materials, mainly as positive electrodes. Therefore, the main demand in the field of LIBs is to develop low cost and environment-friendly materials to substitute commercial cathodes such as expensive and toxic cobalt-containing cathodes. Among other candidates to replace the high cost and toxic cobalt-based cathodes for LIBs, the olivine structured phosphates LiMPO 4 ͑M = Fe, Mn, Ni͒ are the most promising ones due to the reliable combination of theoretical capacity and cost, nontoxicity, and high electrochemical and thermal stabilities.2-5 However, high ionic and electronic resistance of these materials restricts achieving high electrochemical activity. This disadvantage has been successfully overcome for the LiFePO 4 cathodes via the synthesis of nanosized powders, the conductive layer coating of the compound particles surface and doping with cations. [3][4][5][6][7][8][9] It was shown that in the presence of carbon in the cation-doped olivine LiFePO 4 , the carbothermal reduction of iron phosphate at high temperatures leads to the formation of phosphides at the grain boundaries, and this nanonetwork could be responsible for the grain-boundary transport enhancement.9,10 The same process could be readily extendable to other olivines such as LiMnPO 4 .9 Chung et al. 11 showed tha...

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Precursor-based synthesis and electrochemical performance of LiMnPO4

Cited by 90 publications

References 17 publications

LiMnPO4 Olivine as a Cathode for Lithium Batteries

LiMnPO4 Olivine as a Cathode for Lithium Batteries

LiMnPO[sub 4] as an Advanced Cathode Material for Rechargeable Lithium Batteries

LiMg[sub x]Mn[sub 1−x]PO[sub 4]/C Cathodes for Lithium Batteries Prepared by a Combination of Spray Pyrolysis with Wet Ballmilling

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