Challenges in the synthesis of high voltage electrode materials for lithium-ion batteries: a review on LiNiPO4

Rommel, Stefan Michael; Schall, N.; Brünig, Christian; Weihrich, Richard

doi:10.1007/s00706-013-1134-0

Cited by 47 publications

(29 citation statements)

References 102 publications

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“…When aiming at high energy density applications, increasing the cell voltage by replacing Fe by Co or Ni could be beneficial. However, although the theoretical energy densities of LiCoPO 4 and LiNiPO 4 are very high, the experimentally achieved, practical values are lower than those measured for LiFePO 4 , due to low specific discharge capacities/lack of electrochemical activity, high polarization and possible irreversible structural changes [8][9][10][11][12][13]. A possible solution for improving the electrochemical performance is to use mixed compositions of LiFe 1-y M y PO 4 (M = Co, Ni) at high substitution levels (y = 0.2-0.8), where the M 2+ /M 3+ redox couple reacts at its own plateau increasing the average electrode potential and thus further the cell voltage and energy density.…”

Section: Introductionmentioning

confidence: 64%

Local structures in mixed Li Fe1−M PO4 (M=Co, Ni) electrode materials

Jalkanen

Lindén

Karppinen

2015

Journal of Solid State Chemistry

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Section: Introductionmentioning

confidence: 64%

Local structures in mixed Li Fe1−M PO4 (M=Co, Ni) electrode materials

Jalkanen

Lindén

Karppinen

2015

Journal of Solid State Chemistry

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“…[10][11][12] Among the four types of LiMPO 4 , according to previous computational results, LiNiPO 4 possesses the highest operation voltage of 5.1 V vs. Li/Li + , the highest energy density as well as the smallest volume change. 16,17 However, the major drawback of the sluggish kinetics of the electronic and lithium ion transport for LiNiPO 4 cathodes restricts the development of LiNiPO 4 . 16,17 However, the major drawback of the sluggish kinetics of the electronic and lithium ion transport for LiNiPO 4 cathodes restricts the development of LiNiPO 4 .…”

Section: Introductionmentioning

confidence: 99%

Designed synthesis of a unique single-crystal Fe-doped LiNiPO₄ nanomesh as an enhanced cathode for lithium ion batteries

et al. 2015

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In this report, a novel and unique single-crystal hierarchical Fe-doped LiNiPO 4 nanomesh is first devised and fabricated by a new strategy of super-low crystal mismatch between the precursor and the final sample through in situ doping at room temperature. The unique architecture obtained possesses numerous outstanding properties. Its special two-dimensional (2D) morphology can effectively help to shorten pathways for fast lithium ion diffusion and enlarge the exposed surface for more lithium-exchange channels. Furthermore, the hierarchical porous structure can be beneficial to the electrolyte's rapid diffusion and the Li ions' fast exchange as well as buffer the volume expansion. Importantly, Fe doping into LiNiPO 4 can significantly improve the electrical conductivity and the structural stability, so as to enhance Li storage performance. In this work, the systematic electrochemical performance of the LiNiPO 4 -based cathode is thoroughly presented for the first time, which represents a great breakthrough in high-voltage cathodes for LIBs.

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“…17,28,41,42 Nevertheless, graphitic carbon foam/LiNiPO 4 composites (with 90 wt-% carbon) prepared by Dimesso et al 43 have shown reversible electrochemical activity (oxidation at 5. 45 As a result, the Li + diffusion channels would be blocked by the immobile Ni 2+ . Although the theoretical energy densities of LiCoPO 4 and LiNiPO 4 materials are very high, the experimentally achieved, practical values are worse than those measured for LiFePO 4 due to low specific discharge capacities/lack of electrochemical activity and high polarization.…”

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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Challenges in the synthesis of high voltage electrode materials for lithium-ion batteries: a review on LiNiPO4

Cited by 47 publications

References 102 publications

Local structures in mixed Li Fe1−M PO4 (M=Co, Ni) electrode materials

Local structures in mixed Li Fe1−M PO4 (M=Co, Ni) electrode materials

Designed synthesis of a unique single-crystal Fe-doped LiNiPO₄ nanomesh as an enhanced cathode for lithium ion batteries

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

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Challenges in the synthesis of high voltage electrode materials for lithium-ion batteries: a review on LiNiPO4

Cited by 47 publications

References 102 publications

Local structures in mixed Li Fe1−M PO4 (M=Co, Ni) electrode materials

Local structures in mixed Li Fe1−M PO4 (M=Co, Ni) electrode materials

Designed synthesis of a unique single-crystal Fe-doped LiNiPO4 nanomesh as an enhanced cathode for lithium ion batteries

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

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Designed synthesis of a unique single-crystal Fe-doped LiNiPO₄ nanomesh as an enhanced cathode for lithium ion batteries

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