Developments in nanostructured LiMPO4 (M = Fe, Co, Ni, Mn) composites based on three dimensional carbon architecture

Dimesso, Lucangelo; Förster, Christoph; Jaegermann, Wolfram; Khanderi, Jayaprakash; Tempel, Hermann; Popp, Alexander; Engstler, Jörg; Schneider, Jörg J.; Sarapulova, Angelina; Mikhailova, Daria; Schmitt, Ljubomira Ana; Oswald, Steffen; Ehrenberg, Helmut

doi:10.1039/c2cs15320c

Cited by 137 publications

(70 citation statements)

References 67 publications

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“…Other lithium transition metal phosphates including LiMPO 4 (M = Mn, Co, Ni) [3,4], Li 3 V 2 (PO 4 ) 3 [5,6], LiVOPO 4 [7,8], Li 9 M 3 (PO 4 ) 2 (P 2 O 7 ) 3 (M = V, Cr, Al, Ga) [9,10], Li 2 MP 2 O 7 (M = Mn, Co, Fe) [11,12] and their derivatives [13][14][15], have also received a lot of attention due to their great thermal stability and competitive energy density. For one particular, Li 3 V 2 (PO 4 ) 3 shows higher theoretical capacity (~ 197 mAh g -1 vs. ~ 166 mAh g -1 for LiFePO 4 ) and higher average operation voltage plateau (~ 4.0 V vs. ~ 3.5 V for LiFePO 4 ), leading to its higher energy density (~ 800 Wh g -1 vs. ~ 560 Wh g -1 for LiFePO 4 ) [1,5].…”

Section: Introductionmentioning

confidence: 99%

Three-dimensional-network Li3V2(PO4)3/C composite as high rate lithium ion battery cathode material and its compatibility with ionic liquid electrolytes

Chou

Zhou

et al. 2014

Journal of Power Sources

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Section: Introductionmentioning

confidence: 99%

Three-dimensional-network Li3V2(PO4)3/C composite as high rate lithium ion battery cathode material and its compatibility with ionic liquid electrolytes

Chou

Zhou

et al. 2014

Journal of Power Sources

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“…Olivine-structured metal phosphates LiMPO 4 (M = Fe, Mn, Co, Ni) are an interesting material family to replace the layered metal oxides LiMO 2 as the positive electrode. [1][2][3][4] Their safety owing to their intrinsic structural stability is very tempting for large-scale batteries. The orthorhombic olivine structure (space group Pnma) is composed of LiO 6 and MO 6 octahedra and PO 4 tetrahedra, such that Li + -ion diffusion during lithiation/delithiation takes place only in one dimension, along the b axis.…”

mentioning

confidence: 99%

Electrochemical Performance and Delithiation/Lithiation Characteristics of Mixed LiFe_1-_yM_yPO₄(M= Co, Ni) Electrode Materials

Jalkanen

Karppinen

2015

J. Electrochem. Soc.

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Solid solutions of LiFe 1-y M y PO 4 /C (M = Co, Ni) within the whole substitution range (0 ≤ y ≤ 1) are systematically investigated as safe high-voltage positive electrode materials for Li-ion battery. Especially the similarities and differences between the Co-and Ni-substitution schemes are highlighted. With increasing substitution level y, the orthorhombic unit cell shrinks and the Li + -ion diffusion channel area decreases, more rapidly for the smaller-sized Ni substituent. While the Co 2+ /Co 3+ redox couple shows reversible electrochemical activity, only an initial, partial delithiation is achieved for the Ni 2+ /Ni 3+ couple at all y. However, both substitution schemes similarly affect the Fe 2+ /Fe 3+ redox couple by increasing its potential and enhancing the kinetics. Particularly, a mutual influence of Fe and Co/Ni on the delithation/lithiation characteristics is proposed: ex situ XRD analysis shows signs of a phase-composition change in the Fe 2+ /Fe 3+ region for higher y, and correspondingly, a changed Co 2+ /Co 3+ redox mechanism for lower y is indicated by cyclic voltammetry. We suggest that this behavior is related to a substitution-induced decrease in the volume change between the lithiated and delithiated phases. For the Co-substitution scheme, a composition around y ≈ 0.5 seems optimal for combining a high energy density and a kinetically beneficial, diffusional single-phase delithiation/lithiation mechanism. Li-ion batteries have been traditionally used for small, portable consumer electronics, but their utilization in large-scale applications is rapidly growing. As the size of the battery packs is increasing, the matters of safety, cost, and cycle-life become more crucial. In addition, for applications in transportation, high energy and power densities are demanded. Olivine-structured metal phosphates LiMPO 4 (M = Fe, Mn, Co, Ni) are an interesting material family to replace the layered metal oxides LiMO 2 as the positive electrode.1-4 Their safety owing to their intrinsic structural stability is very tempting for large-scale batteries. The orthorhombic olivine structure (space group Pnma) is composed of LiO 6 and MO 6 octahedra and PO 4 tetrahedra, such that Li + -ion diffusion during lithiation/delithiation takes place only in one dimension, along the b axis. 3,5The iron-based olivine LiFePO 4 is already commercially used in Li-ion batteries; it shows a theoretical capacity of 170 mAh g −1 , high safety and cycle stability, and is in addition cheap and environmentally friendly.1 The delithiation/lithiation (charge/discharge) reaction proceeds as a two-phase reaction with a varying LiFePO 4 /FePO 4 ratio, which brings about a kinetic limitation due to the single Fe valence (Fe 2+ or Fe 3+ ) in the two end-phases, resulting in low carrier density. 1,6 Additionally, the two-phase reaction pathway is restricted by nucleation and growth, when compared to a diffusional single-phase solidsolution mechanism. 7 However, narrow single-phase solid-solution regions are suggested to exist at room-tem...

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“…The experimental procedures for the preparation and characterizations of the samples have been previously reported [3][4][5]. The samples in the LiMPO 4 system (M = Fe, Co, Ni) have been prepared by dissolving in water lithium acetate, iron sulfate (cobalt acetate, nickel acetate) as precursors (molar ratio 1:1) with citric acid (2 x mol [Fe, Co, Ni]), then adding phosphoric acid in the equimolar ratio with Li ions.…”

Section: Methodsmentioning

confidence: 99%

Nanostructured LiMPO₄(M = Fe, Mn, Co, Ni) – carbon composites as cathode materials for Li-ion battery

Dimesso

Spanheimer

Nguyen

et al. 2012

EPJ Web of Conferences

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Abstract. Nanostructured materials are considered to be strong candidates for fundamental advances in efficient storage and/or conversion. In nanostructured materials transport kinetics and surface processes play determining roles. This work describes recent developments in the synthesis and characterization of composites which consist of lithium metal phosphates (LiMPO 4 , M = Fe, Mn, Co, Ni) coated on nanostructured carbon supports (unordered nanofibers, foams). The composites have been prepared by coating the carbon structures in aqueous (or polyols) solutions containing lithium, metal ions and phosphates. After drying out, the composites have been thermally treated at different temperatures (between 600-780°C) for 5-12 hours under nitrogen. The formation of the olivine structured phase was confirmed by the X-ray diffraction analysis on powders prepared under very similar conditions. The surface investigation revealed the formation of an homogeneous coating of the olivine phase on the carbon structures. The electrochemical performance on the composites showed a dramatic improvement of the discharge specific capacity (measured at a discharge rate of C/25 and room temperature) compared to the prepared powders. The delivered values were 105 mAhg -1 for M = Fe, 100 mAhg -1 for M = Co, 70 mAhg -1 for M = Mn and 30 mAhg -1 for M = Ni respectively.

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Developments in nanostructured LiMPO4 (M = Fe, Co, Ni, Mn) composites based on three dimensional carbon architecture

Cited by 137 publications

References 67 publications

Three-dimensional-network Li3V2(PO4)3/C composite as high rate lithium ion battery cathode material and its compatibility with ionic liquid electrolytes

Three-dimensional-network Li3V2(PO4)3/C composite as high rate lithium ion battery cathode material and its compatibility with ionic liquid electrolytes

Electrochemical Performance and Delithiation/Lithiation Characteristics of Mixed LiFe_1-_yM_yPO₄(M= Co, Ni) Electrode Materials

Nanostructured LiMPO₄(M = Fe, Mn, Co, Ni) – carbon composites as cathode materials for Li-ion battery

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Developments in nanostructured LiMPO4 (M = Fe, Co, Ni, Mn) composites based on three dimensional carbon architecture

Cited by 137 publications

References 67 publications

Three-dimensional-network Li3V2(PO4)3/C composite as high rate lithium ion battery cathode material and its compatibility with ionic liquid electrolytes

Three-dimensional-network Li3V2(PO4)3/C composite as high rate lithium ion battery cathode material and its compatibility with ionic liquid electrolytes

Electrochemical Performance and Delithiation/Lithiation Characteristics of Mixed LiFe1-yMyPO4(M= Co, Ni) Electrode Materials

Nanostructured LiMPO4(M = Fe, Mn, Co, Ni) – carbon composites as cathode materials for Li-ion battery

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Electrochemical Performance and Delithiation/Lithiation Characteristics of Mixed LiFe_1-_yM_yPO₄(M= Co, Ni) Electrode Materials

Nanostructured LiMPO₄(M = Fe, Mn, Co, Ni) – carbon composites as cathode materials for Li-ion battery