Topochemical Synthesis of Sodium Metal Phosphate Olivines for Sodium-Ion Batteries

Lee, Kyu‐Tae; Ramesh, T. N.; Nan, Feihong; Botton, Gianluigi A.; Nazar, Linda F.

doi:10.1021/cm200450y

Cited by 299 publications

(246 citation statements)

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“…5 (ref. 6), which are performed as state-ofthe-art high-performance cathodes for Na-ion batteries, and are much higher than for other intercalation compounds such as fluorophosphates 12,13 , NASICONs 14 and olivines 15 . By combing state-of-the-arts anodes 27,56,57 , and electrolytes, such as ionic liquids 58 or NaPF 6 in EC:PC (ref.…”

Section: Discussionmentioning

confidence: 99%

“…There is an urgent need for alternative energy storage devices with a performance comparable to, or better than rechargeable lithium batteries. One possible approach is to use sodium as an alternative charge carrier [3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18] to lithium, as the cost of sodium carbonate (Na 2 CO 3 ), for example, is only 3% of Li 2 CO 3 (ref. 5).…”

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Aromatic porous-honeycomb electrodes for a sodium-organic energy storage device

et al. 2013

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Rechargeable batteries using organic electrodes and sodium as a charge carrier can be highperformance, affordable energy storage devices due to the abundance of both sodium and organic materials. However, only few organic materials have been found to be active in sodium battery systems. Here we report a high-performance sodium-based energy storage device using a bipolar porous organic electrode constituted of aromatic rings in a porous-honeycomb structure. Unlike typical organic electrodes in sodium battery systems, the bipolar porous organic electrode has a high specific power of 10 kW kg À 1 , specific energy of 500 Wh kg À 1 , and over 7,000 cycle life retaining 80% of its initial capacity in half-cells. The use of bipolar porous organic electrode in a sodium-organic energy storage device would significantly enhance cost-effectiveness, and reduce the dependency on limited natural resources. The present findings suggest that bipolar porous organic electrode provides a new material platform for the development of a rechargeable energy storage technology.

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Section: Discussionmentioning

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Aromatic porous-honeycomb electrodes for a sodium-organic energy storage device

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“…19 Unlike LiMPO 4 , the NaMPO 4 thermodynamically stable phase obtained under the conventional synthesis conditions is the maricite phase that is known to be electrochemically inactive with respect to the olivine phase. 20,21 Among the polyanionic frameworks, pyrophosphate compounds offer a stable three-dimensional (P 2 O 7 ) 4 − framework with multiple sites for Na ions. Fe-based pyrophosphates have been reported to exhibit enhanced rate capability performance most likely because of the presence of open diffusion pathways for Na ions.…”

Section: Introductionmentioning

confidence: 99%

Exploring the Ni redox activity in polyanionic compounds as conceivable high potential cathodes for Na rechargeable batteries

et al. 2017

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Although nickel-based polyanionic compounds are expected to exhibit a high operating voltage for batteries based on the Ni 2+/3+ redox couple activity, some rare experimental studies on the electrochemical performance of these materials are reported, resulting from the poor kinetics of the bulk materials in both Li and Na nonaqueous systems. Herein, the electrochemical activity of the Ni 2+/3+ redox couple in the mixed-polyanionic framework Na 4 Ni 3 (PO 4 ) 2 (P 2 O 7 ) is reported for the first time. This novel material exhibits a remarkably high operating voltage when cycled in sodium cells in both carbonate-and ionic liquid-based electrolytes. The application of a carbon coating and the use of an ionic liquid-based electrolyte enable the reversible sodium ion (de-)insertion in the host structure accompanied by the redox activity of Ni 2+/3+ at operating voltages as high as 4.8 V vs Na/Na + . These results present the realization of Ni-based mixed polyanionic compounds with improved electrochemical activity and pave the way for the discovery of new Na-based high potential cathode materials. NPG Asia Materials (2017) 9, e370; doi:10.1038/am.2017.41; published online 31 March 2017 INTRODUCTION Lithium-ion batteries have been largely recognized as the most efficient electrochemical energy storage devices for both portable electronics and electric vehicle applications. 1,2 However, the growth and diversification of the energy storage market trigger interest in low-cost and environmentally friendly alternative systems. In addition, recent concerns over the cost and future availability of lithium highlight the urgent need to exploit alternative energy storage systems. 3 In these terms, sodium (Na)-ion batteries are attractive candidates because of the electrochemistry that is similar to the well-established lithium-ion technology. 4 To date, the LiFePO 4 olivine with (PO 4 ) 3 − polyanionic framework, owing to its superior thermal stability and low cost, is considered to be one of the best electrode materials for lithium-ion batteries, mostly in view of its stable operating voltage and satisfactory specific capacity. However, the intrinsic tunability of the operating voltage of polyanionic compounds because of the presence of different transition metals such as Mn, Co and Ni 5-7 has triggered interest in alternative frameworks exhibiting higher cell voltages. According to theoretical prediction, lithium nickel phosphate has a remarkably high working potential (~5.1 V vs Li + /Li) because of the Ni 2+/3+ redox activity. 8 Unfortunately, several studies have demonstrated that the implementation of this material is restricted by several drawbacks such as the intrinsic sluggish kinetics attributable to the low electronic conductivity, the poor lithium transport in commonly used electrolyte systems and the structural

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“…However, they suffer from a substantial capacity decay with cycling, owing to crystal structure collapse and/or unstable electrode-electrolyte interfaces (10). For more stable host frameworks, various polyanion structures have also been studied as SIB cathodes as a natural extension of the success shown in the LIB materials of the same classes, including TM fluorophosphates (11)(12)(13)(14)(15), pyrophosphates (16)(17)(18) and phosphates (19)(20)(21)(22). However, most of these materials still exhibited insufficient cycle lifetimes and large voltage steps that limit their practical capacity.…”

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Role of intermediate phase for stable cycling of Na ₇ V ₄ (P ₂ O ₇ ) ₄ PO ₄ in sodium ion battery

Lim

Kim

Chung

et al. 2013

Proc. Natl. Acad. Sci. U.S.A.

140

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Sodium ion batteries offer promising opportunities in emerging utility grid applications because of the low cost of raw materials, yet low energy density and limited cycle life remain critical drawbacks in their electrochemical operations. Herein, we report a vanadium-based ortho-diphosphate, Na 7 V 4 (P 2 O 7 ) 4 PO 4 , or VODP, that significantly reduces all these drawbacks. Indeed, VODP exhibits single-valued voltage plateaus at 3.88 V vs. Na/Na + while retaining substantial capacity (>78%) over 1,000 cycles. Electronic structure calculations reveal that the remarkable single plateau and cycle life originate from an intermediate phase (a very shallow voltage step) that is similar both in the energy level and lattice parameters to those of fully intercalated and deintercalated states. We propose a theoretical scheme in which the reaction barrier that arises from lattice mismatches can be evaluated by using a simple energetic consideration, suggesting that the presence of intermediate phases is beneficial for cell kinetics by buffering the differences in lattice parameters between initial and final phases. We expect these insights into the role of intermediate phases found for VODP hold in general and thus provide a helpful guideline in the further understanding and design of battery materials.cathode | single voltage | atomic reorganization | ab initio calculation S odium ion batteries (SIBs) provide advantages of unlimited resource, low material cost, and easy worldwide accessibility that could make them the material of choice for grid-scale energy storage systems (1, 2). Unfortunately, the electrochemical performance of current SIBs remains inferior to that of lithium ion batteries (LIBs). In particular, we require SIB cathode materials that give a long cycle life with large capacities and high voltages under fast operating conditions, comparable to the Li counterparts.Numerous layered Na x MO 2 [M = Co, Mn, Fe, Ni, Cr, and multicomponent transition metals (TMs)] have been intensively studied as candidate SIB cathodes because such layer-structured materials typically exhibit higher capacities than other classes of materials (3-10). However, they suffer from a substantial capacity decay with cycling, owing to crystal structure collapse and/or unstable electrode-electrolyte interfaces (10). For more stable host frameworks, various polyanion structures have also been studied as SIB cathodes as a natural extension of the success shown in the LIB materials of the same classes, including TM fluorophosphates (11-15), pyrophosphates (16-18) and phosphates (19)(20)(21)(22). However, most of these materials still exhibited insufficient cycle lifetimes and large voltage steps that limit their practical capacity. The Prussian blue family has also been extensively investigated for both organic (23, 24) and aqueous electrolytes (25) owing to its unique advantages related to low material cost, low temperature synthesis, and decent electrochemical performance from well-developed ionic channel structures. However, the as-syn...

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Topochemical Synthesis of Sodium Metal Phosphate Olivines for Sodium-Ion Batteries

Cited by 299 publications

References 30 publications

Aromatic porous-honeycomb electrodes for a sodium-organic energy storage device

Aromatic porous-honeycomb electrodes for a sodium-organic energy storage device

Exploring the Ni redox activity in polyanionic compounds as conceivable high potential cathodes for Na rechargeable batteries

Role of intermediate phase for stable cycling of Na ₇ V ₄ (P ₂ O ₇ ) ₄ PO ₄ in sodium ion battery

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Topochemical Synthesis of Sodium Metal Phosphate Olivines for Sodium-Ion Batteries

Cited by 299 publications

References 30 publications

Aromatic porous-honeycomb electrodes for a sodium-organic energy storage device

Aromatic porous-honeycomb electrodes for a sodium-organic energy storage device

Exploring the Ni redox activity in polyanionic compounds as conceivable high potential cathodes for Na rechargeable batteries

Role of intermediate phase for stable cycling of Na 7 V 4 (P 2 O 7 ) 4 PO 4 in sodium ion battery

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Role of intermediate phase for stable cycling of Na ₇ V ₄ (P ₂ O ₇ ) ₄ PO ₄ in sodium ion battery