An Unnoticed Inorganic Solid Electrolyte: Dilithium Sodium Phosphate with the Nalipoite Structure

López, Marı́a C.; Ortiz, Gregório F.; Dompablo, M. Elena Arroyo-de

doi:10.1021/ic4030537

Cited by 23 publications

(23 citation statements)

References 39 publications

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“…The temperature dependence of conductivity for Li 2 NaPO 4 sample showed an Arrheniustype behavior [6]. A significant improvement from the value observed at R.T. 6.5 10 -6 S cm -1 is observed at 70 ºC, reaching a total conductivity of ca.…”

Section: Methodsmentioning

confidence: 75%

“…Nalipoite Li 2 NaPO 4 was synthesized and characterized as previously described [6]. Electrochemical impedance spectroscopy measurements (EIS) were performed with an AUTOLAB PGSTAT12 system by applying an AC signal with 5 mV amplitude over the frequency range from 1 MHz -100 mHz.…”

Section: Methodsmentioning

confidence: 99%

“…To calculate the energy at the saddle point, cubic splines were fit through the images along each hop. More details about the computational method can be found in [6].…”

Section: Methodsmentioning

confidence: 99%

“…In this structure chains of LiO 4 tetrahedra run parallel to the a axis; these chains are connected by vertex along the c axis. We have recently reported [6] that the nalipoite-Li 2 NaPO 4 displays high ionic conductivities of 6.5 x10 -6 and 1.5 x10 -5 S cm -1 at 25 and 70ºC, respectively, which has been ascribed to the motion of Li ions.…”

Section: Introductionmentioning

confidence: 99%

“…In this sense, other cations could replace Na ions in the octahedral sites of the Nalipoite structure. Following our previous study [6], in this work we combine computations and experiments to investigate the lithium motion in Nalipote-Li 2 NaPO 4 and in the virtual Li 2 KPO 4 phase.…”

Section: Introductionmentioning

confidence: 99%

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Computational and Experimental investigation of Nalipoite-Li₂APO₄ (A = Na, K) electrolytes for Li-ion batteries

2015

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The potential ionic conductors Li 2 APO 4 (A = Na, K) are investigated combining experiments and first principles calculations at the Density Functional Theory level. A high ionic conductivity of 6.5 x10 -6 and 1.5 x10 -5 S cm -1 at 25 and 70ºC, respectively, is found in Nalipoite-Li 2 NaPO 4 . For this mixed phosphate the energy barriers to Li motion are calculated. The lower energy barrier (0.7 eV) implies the inter-chain diffusion of Li in the b-c plane. We predict that ionic mobility is enhanced in the isostructural Li 2 KPO 4 , with the lowest calculated energy barrier being 0.4 eV.

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Section: Methodsmentioning

confidence: 75%

Section: Methodsmentioning

confidence: 99%

“…To calculate the energy at the saddle point, cubic splines were fit through the images along each hop. More details about the computational method can be found in [6].…”

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Computational and Experimental investigation of Nalipoite-Li₂APO₄ (A = Na, K) electrolytes for Li-ion batteries

2015

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Aqueous Solution‐Processable Small Molecular Metal‐Chelate Complex Electrolyte for Flexible All‐Solid State Energy Storage Devices

Lee

Jeong

Kim

et al. 2015

Advanced Energy Materials

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solar cells (OSCs), organic thin fi lm transistors (OTFTs), organic memory devices (OMDs), etc. [4][5][6][7][8] Interestingly, liquid or gel-type electrolytes have been still used for sophisticated energy storage devices including batteries and capacitors, [9][10][11][12][13][14] even though a couple of inorganic solid-state electrolytes such as thio-LISICON (Li 3.25 Ge 0.25 P 0.75 S 4 ), Li 2 NaPO 4 (nalipoite structure), and a-60Li 2 S·40SiS 2 have been developed. [15][16][17] Here we note that such inorganic electrolytes cannot be used for fl exible devices because of their intrinsic brittleness. In the case of liquid electrolytes such as aqueous solutions, [ 18,19 ] organic solutions, [ 20,21 ] and ionic liquids, [ 22,23 ] there are essential limitations for miniaturizing devices because of tricky sealing processes to avoid leakage of electrolyte solutions that are normally toxic and corrosive.Compared to the liquid electrolytes, gel-type electrolytes deliver improved processability but they do still contain liquid components so that they bear potential disadvantages as liquid electrolytes do. To date, most reports claiming "solid-state electrolytes" have employed gel-type electrolytes such as proton conducting polymer gel electrolytes, [24][25][26] lithium ion gel polymer electrolytes, [27][28][29] and alkaline gel polymer electrolytes. [30][31][32] Hence a perfect solid-state electrolyte without including any liquid components should be developed to achieve real ultrathin/ fl exible devices in the coming fl exible electronics era. In addition, the perfect solid-state electrolyte is required to have solution processability using water as a solvent in consideration of environmental issue for using toxic solvents in the conventional fabrication processes. In particular, a well-defi ned small molecular electrolyte, which is of course highly reproducible in the large scale synthesis, is practically desirable for device miniaturization toward a nanoscale energy storage device that needs only few molecules in the thickness direction of the electrolyte nanolayers.In this work, we attempted to design a small molecular metal-chelate complex that has three sulfonic acid groups per molecule in order to maximize solubility in water and secure proton ions for energy storage. Taking into account easy synthesis for possible mass production, one-step synthesis protocol was adopted on the basis of condensation reaction between aluminum triisopropoxide (AltiP) and 8-hydroxyquinoline-5-sulfonic acid (HQSA). The resulting metal-chelate A small molecular metal-chelate complex, tris(8-hydroxyquinoline-5-sulfonic acid) aluminum (AlQSA 3 ), that has three sulfonic acid groups per molecule leading to an excellent solubility in water is reported as a liquid-free perfect solid-state electrolyte for fl exible fi lm-type all-solid-state energy storage devices. The AlQSA 3 material is synthesized by one-step reaction of aluminum triisopropoxide and 8-hydroxyquinoline-5-sulfonic acid. The aqueous solutions of AlQSA 3 are applied to fabric...

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Self‐Organised TiO₂ Nanotubes for 2D or 3D Li‐Ion Microbatteries

Kyeremateng

2014

ChemElectroChem

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This paper presents a Review on the development of thin‐film (all‐solid‐state) Li‐ion microbatteries. The need to move from 2D to 3D configurations, the ever‐increasing necessity to adopt Li‐ion or rocking‐chair technology in microbatteries, and the development of new processing techniques and materials are discussed. Materials based on TiO2 are very promising as negative electrodes for Li‐ion microbatteries. Strong emphasis is placed on the possibility of utilising TiO2, especially self‐supported nanotubular TiO2, as an anode material for commercial 2D or 3D Li‐ion microbatteries. The use of TiO2 is ecologically and economically competitive and provides cells with low self‐discharge while eliminating the risk of overcharging due to its relatively high operating voltage. The high operating voltage of TiO2 also presents the advantage of negligible electrolyte decomposition. Each polymorphic form of TiO2 (anatase, rutile, TiO2(B), or brookite) has an attractive lithium storage behaviour, especially, when nanostructured. Owing to their remarkable nanoarchitecture, TiO2 nanotubes grown by potentiostatic anodization, and their derivatives (cation‐ or anion‐doped and hierarchical composites with nanostructured metals or metal oxides), deserve attention for the fabrication of 2D or 3D Li‐ion microbatteries.

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An Unnoticed Inorganic Solid Electrolyte: Dilithium Sodium Phosphate with the Nalipoite Structure

Cited by 23 publications

References 39 publications

Computational and Experimental investigation of Nalipoite-Li₂APO₄ (A = Na, K) electrolytes for Li-ion batteries

Computational and Experimental investigation of Nalipoite-Li₂APO₄ (A = Na, K) electrolytes for Li-ion batteries

Aqueous Solution‐Processable Small Molecular Metal‐Chelate Complex Electrolyte for Flexible All‐Solid State Energy Storage Devices

Self‐Organised TiO₂ Nanotubes for 2D or 3D Li‐Ion Microbatteries

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An Unnoticed Inorganic Solid Electrolyte: Dilithium Sodium Phosphate with the Nalipoite Structure

Cited by 23 publications

References 39 publications

Computational and Experimental investigation of Nalipoite-Li2APO4 (A = Na, K) electrolytes for Li-ion batteries

Computational and Experimental investigation of Nalipoite-Li2APO4 (A = Na, K) electrolytes for Li-ion batteries

Aqueous Solution‐Processable Small Molecular Metal‐Chelate Complex Electrolyte for Flexible All‐Solid State Energy Storage Devices

Self‐Organised TiO2 Nanotubes for 2D or 3D Li‐Ion Microbatteries

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Computational and Experimental investigation of Nalipoite-Li₂APO₄ (A = Na, K) electrolytes for Li-ion batteries

Computational and Experimental investigation of Nalipoite-Li₂APO₄ (A = Na, K) electrolytes for Li-ion batteries

Self‐Organised TiO₂ Nanotubes for 2D or 3D Li‐Ion Microbatteries