High‐Voltage Pyrophosphate Cathodes

Barpanda, Prabeer; Nishimura, Shin Ichi; Yamada, Atsuo

doi:10.1002/aenm.201100772

Cited by 223 publications

(154 citation statements)

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“…[11][12][13][14][15][16] The polyanionic frameworks offer considerable variety to the host structures, redox couples, and ionic diffusion of the positive electrode materials. [17][18][19] In particular, NASICON-type Na 3 V 2 (PO 4 ) 3 is promising because of the high redox potential at 3.37 V and the high theoretical capacity of 118 mAh/g for V 4+ /V 3+ in Na 1+2x V 2 (PO 4 ) 3 (0¯x¯1). [20][21][22][23][24][25][26][27] Na 3 V 2 (PO 4 ) 3 consists of [V 2 (PO 4 ) 3 ] units interconnected by PO 4 , wherein three-dimensional open channel is formed for Na-ion diffusion.…”

Section: Introductionmentioning

confidence: 99%

Potentiometric Study to Reveal Reaction Entropy Behavior of Biphasic Na1+2xV2(PO4)3 Electrodes

et al. 2016

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Sodium-ion batteries potentially provide the opportunities to realize the energy storage system beyond the stateof-the-art lithium-ion batteries, though at present their performance is limited partly due to lack of suitable positive electrode materials. NASICON-type Na 3 V 2 (PO 4 ) 3 is a promising candidate for the positive electrode materials because of its high capacity and high operating potential, however, the electrode reaction of Na 1+2x V 2 (PO 4 ) 3 (0 : x : 1) including a biphasic region is not yet fully understood. Here, in order to clarify the microscopic mechanism of the biphasic reaction, the reaction entropy of the electrochemical cell including the Na 1+2x V 2 (PO 4 ) 3 positive electrode was measured using the potentiometric method. The temperature-dependent open-circuitvoltage reveals that the reaction entropy is almost constant for 0.1 : x : 0.9. The constant reaction entropy of the electrochemical cell suggests that the electrode reaction proceeds through the boundary migration between the Na-rich and -poor phases without substantial change in the configurational entropy.

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Section: Introductionmentioning

confidence: 99%

Potentiometric Study to Reveal Reaction Entropy Behavior of Biphasic Na1+2xV2(PO4)3 Electrodes

et al. 2016

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“…LiMPO 4 cathode materials for lithium-ion batteries [5][6][7][8][9][10][11][12][13][14][15][16][17][18].…”

Section: Introductionunclassified

“…So far, Li 2 FeP 2 O 7 as cathode for LIBs suffers from the low rate capability or poor cycling stability because of its low electronic and ionic conductivity [5][6][7][8][9][10][11][12][13][14][15][16][17][18]. As the counterpart of Li 2 FeP 2 O 7 , LiFePO 4 also showed the low electronic and ionic conductivity [3,6,7].…”

Section: Introductionmentioning

confidence: 99%

Study on Vanadium Substitution to Iron in Li2FeP2O7 as Cathode Material for Lithium-ion Batteries

Xu¹,

Chou²,

Gu³

et al. 2014

Electrochimica Acta

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Dou, S. (2014). Study on vanadium substitution to iron in Li2FeP 2O7 as cathode material for lithium-ion batteries. Electrochimica Acta, Study on vanadium substitution to iron in Li2FeP 2O7 as cathode material for lithium-ion batteries AbstractA series of Li2Fe1-3x/2VxP 2O7 (x = 0, 0.025, 0.05, 0.075, and 0.1) cathode materials for LIBs were prepared by the sol-gel method. Structural characterization of Li2Fe1-3x/2VxP2O7 (x = 0, 0.025, 0.05, 0.075, and 0.1) samples was conducted by synchrotron X-ray diffraction. The morphology and oxidation states of Fe2+ and V 3+ in the Li2Fe1-3x/2VxP 2O7 samples were confirmed by scanning electron microscopy and magnetic susceptibility measurements, respectively. The electrochemical measurements indicated that Li2Fe1-3x/2VxP 2O7 (x = 0.025) delivered the higher reversible capacity of 79.9 mAh g-1 at 1 C in the voltage range of 2.0 -4.5 V with higher 77.9% capacity retention after 300 cycles than those of Li 2FeP2O7 (48.9 mAh g-1 and 72.6%). Moreover, the rate capability of Li2Fe1-3x/2V xP2O7 (x = 0.025) were also significantly enhanced through vanadium substitution to iron of Li2Fe 1-3x/2VxP2O7. The vanadium substituted to Fe2 site of Li2FeP2O7 decreases Li occupying the Li5 position in the FeO5 unit, leading to a low degree exchange between Li and Fe in the MO5 (M = Li and Fe). The low degree cation disorder was beneficial to lithium-ion extraction/insertion during the charge-discharge process and hence enhances the capacity and rate capability. The low degree cation disorder was beneficial to lithium-ion extraction/insertion during the charge-discharge process and hence enhances the capacity and rate capability.1

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“…[64][65][66][67][68] In general, both atomistic simulations and first-principles studies find these materials to be fast 3D conductors with low activation barriers for Li and Na migration. 67,68 Another class of phosphate cathodes that has enjoyed considerable interest is the tavorite family, with a structure similar to that of LiFe (PO 4 )(OH).…”

Section: Polyanion Oxidesmentioning

confidence: 99%

Computational studies of solid-state alkali conduction in rechargeable alkali-ion batteries

Deng

Ong

2016

NPG Asia Mater

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The facile conduction of alkali ions in a crystal host is of crucial importance in rechargeable alkali-ion batteries, the dominant form of energy storage today. In this review, we provide a comprehensive survey of computational approaches to study solid-state alkali diffusion. We demonstrate how these methods have provided useful insights into the design of materials that form the main components of a rechargeable alkali-ion battery, namely the electrodes, superionic conductor solid electrolytes and interfaces. We will also provide a perspective on future challenges and directions. The scope of this review includes the monovalent lithium-and sodium-ion chemistries that are currently of the most commercial interest. NPG Asia Materials (2016) 8, e254; doi:10.1038/am.2016.7; published online 25 March 2016 INTRODUCTIONThe facile conduction of alkali ions in a crystal is of critical importance in energy storage. Today, the dominant form of energy storage in consumer electronics is the rechargeable lithium-ion (Li-ion) battery, 1-5 a device that functions entirely on the basis of the reversible transport of Li + ions. With one of the highest energy densities of known energy storage technologies, Li-ion batteries are finding increasingly large-scale applications in electrified transportation and grid storage. In recent years, there has also been a resurgence of interest in rechargeable sodium-ion (Na-ion) batteries, 6-12 which function on the same basic principle but with Na + instead of Li + because of concerns regarding the abundance and cost of lithium. Figure 1 shows a representation of a rechargeable alkali-ion battery. The typical electrode in an alkali-ion battery is an intercalation compound, which, as the name implies, stores alkali ions by inserting them into its crystal structure in a topotactic manner. During discharge, A + ions are transported from the anode, through the electrolyte and into the cathode. The reverse happens during charge. Throughout this review, we will adopt the customary terminology of defining the 'cathode' as the positive electrode during discharge, even though the formal definition of the cathode changes depending on whether the charging or discharging process is being referred to. Current cathodes are typically transition metal oxides, and the insertion/removal of each A + in the cathode is accompanied by the concomitant reduction/oxidation of a transition metal ion to accommodate the compensating insertion/removal of an electron. Graphitic carbon is the most common anode.The performance of a rechargeable alkali-ion battery depends crucially on the ease with which alkali ions move in the host crystal of the cathode and anode, in the electrolyte, and in the electrodeelectrolyte interface. Poor alkali transport in any part of the battery

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High‐Voltage Pyrophosphate Cathodes

Cited by 223 publications

References 64 publications

Potentiometric Study to Reveal Reaction Entropy Behavior of Biphasic Na<sub>1+2</sub><i><sub>x</sub></i>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub> Electrodes

Potentiometric Study to Reveal Reaction Entropy Behavior of Biphasic Na<sub>1+2</sub><i><sub>x</sub></i>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub> Electrodes

Study on Vanadium Substitution to Iron in Li2FeP2O7 as Cathode Material for Lithium-ion Batteries

Computational studies of solid-state alkali conduction in rechargeable alkali-ion batteries

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