Crystalline LiPON as a Bulk-Type Solid Electrolyte

López-Aranguren, Pedro; Reynaud, Marine; Głuchowski, Paweł; Bustinza, Ainhoa; Galcerán, Montserrat; Amo, Juan Miguel López del; Armand, Michel; Casas‐Cabañas, Montse

doi:10.1021/acsenergylett.0c02336

Cited by 55 publications

(90 citation statements)

References 37 publications

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“…The bulk ionic conductivity of Li 3 P 5 O 14 at 303 K is comparable to sputtered LiPON glass thin film electrolytes ((1−3) × 10 −6 S cm −1 at 298 K), 51,52,100,101 which are routinely used in the production of thin film batteries, and the bulk-type electrolyte Li 3.6 PO 3.4 N 0.6 (3.0 × 10 −7 S cm −1 at 298 K), 102 a crystalline polymorph of LiPON SSE with the highest ionic conductivity among all reported crystalline LiPON SSEs. The room temperature ionic conductivity of Li 3 P 5 O 14 is higher than that of conventional crystalline metal oxide coatings, such as Li 4 Ti 5 O 12 (5.8 × 10 −8 S cm −1 ), 103 LiTaO 3 (2.1 × 10 −10 S cm −1 ), 104 LiNbO 3 (∼10 −26 S cm −1 ), 105 and LiAlO 2 (below 10 −15 S cm −1 ), 27−29 and is comparable to some of their amorphous/glass state, such as LiNbO 3 glass (10 −5 −10 −6 S cm −1 ).…”

Section: Synthesis and Phase Puritymentioning

confidence: 90%

Extended Condensed Ultraphosphate Frameworks with Monovalent Ions Combine Lithium Mobility with High Computed Electrochemical Stability

et al. 2021

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Extended anionic frameworks based on condensation of polyhedral main group non-metal anions offer a wide range of structure types. Despite the widespread chemistry and earth abundance of phosphates and silicates, there are no reports of extended ultraphosphate anions with lithium. We describe the lithium ultraphosphates Li3P5O14 and Li4P6O17 based on extended layers and chains of phosphate, respectively. Li3P5O14 presents a complex structure containing infinite ultraphosphate layers with 12-membered rings that are stacked alternately with lithium polyhedral layers. Two distinct vacant tetrahedral sites were identified at the end of two distinct finite Li6O16 26– chains. Li4P6O17 features a new type of loop-branched chain defined by six PO4 3– tetrahedra. The ionic conductivities and electrochemical properties of Li3P5O14 were examined by impedance spectroscopy combined with DC polarization, NMR spectroscopy, and galvanostatic plating/stripping measurements. The structure of Li3P5O14 enables three-dimensional lithium migration that affords the highest ionic conductivity (8.5(5) × 10–7 S cm–1 at room temperature for bulk), comparable to that of commercialized LiPON glass thin film electrolytes, and lowest activation energy (0.43(7) eV) among all reported ternary Li–P–O phases. Both new lithium ultraphosphates are predicted to have high thermodynamic stability against oxidation, especially Li3P5O14, which is predicted to be stable to 4.8 V, significantly higher than that of LiPON and other solid electrolytes. The condensed phosphate units defining these ultraphosphate structures offer a new route to optimize the interplay of conductivity and electrochemical stability required, for example, in cathode coatings for lithium ion batteries.

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Section: Synthesis and Phase Puritymentioning

confidence: 90%

Extended Condensed Ultraphosphate Frameworks with Monovalent Ions Combine Lithium Mobility with High Computed Electrochemical Stability

et al. 2021

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“…[1][2][3][4][5] As one of the critical components of SSLMBs, many types of SSEs have been developed, including sulfide-type, [6] garnet-type, [7] sodium superionic conductor type, [8] polymer-type, [9] halide-type, [10] and lithium phosphorus oxynitride. [11] Among them, garnet structured ceramic electrolyte Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO) with high ionic conductivity, good chemical stability against Li, and wide electrochemical window is the most promising to realize the high energy density and high safety SSLMBs. [12][13][14][15][16][17] Unfortunately, LLZTO matching with Li metal electrode commonly suffers from poor interface contact, Li dendrite penetration, and dramatic volume variations during the Li striping/plating process, which results in an inferior electrochemical performance in SSLMBs.…”

Section: Doi: 101002/smll202202911mentioning

confidence: 99%

High‐Performance Composite Lithium Anodes Enabled by Electronic/Ionic Dual‐Conductive Paths for Solid‐State Li Metal Batteries

Yang

et al. 2022

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Solid‐state lithium metal batteries (SSLMBs) promise high energy density and high safety by employing high‐capacity Li metal anode and solid‐state electrolytes. However, the construction of the composite Li metal electrode is a neglected but important subject when the extensive research focuses on the interface between the solid electrolyte Li6.4La3Zr1.4Ta0.6O12 and Li metal anode. Here, an electronic–ionic conducting composite Li metal anode consisting of Li–Al alloy and LiF is constructed to achieve the stable electronic–ionic transport channel and the intimate interface contact, which can realize the uniform Li deposition and the efficiency utilization of lithium in composite Li metal electrode. Therefore, the symmetric battery with composite Li metal electrode exhibits the high critical current density with 1.2 mA cm−2 and stable cycle for 1500 h at 0.3 mA cm−2, 25 °C. Moreover, the SSLMBs matched with LiFePO4 and LiNi0.8Co0.1Mn0.1O2 achieve the outstanding electrochemical performance, verifying the feasibility of composite Li metal electrode in various SSLMBs systems.

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“…Phosphates are also applied as artificial SEI for alloy anode. Lithium phosphorus oxynitride (LiPON) has shown promising application on solid batteries with high energy and power densities attributed to its high ionic conductivity and mechanical modulus 89,90 . Benefit from the above advantages, LiPON can be adopted as artificial SEI on alloyed anode to alleviate volume changes during cycling and improve conductivity of active ions.…”

Section: Interface Engineering Strategies Toward Improved Performancementioning

confidence: 99%

Interface engineering towardhigh‐efficiencyalloy anode for next‐generation energy storage device

Wang

Tang

2021

EcoMat

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Alloy materials are considered as the promising anodes for next‐generation energy storage devices attributed to their high theoretical capacities and suitable working voltage. However, further commercialization is hindered by their remarkable volume change during cycling. The interface engineering has been proposed as an effective strategy to alleviate the volume expansion and improve the electrochemical performance of alloy anode. In this review, we discuss the failure mechanisms for alloy anode during charging/discharging processes. Then the mechanisms of interface engineering for alloy anode were proposed. Next, the interface engineering strategies for alloy anode such as artificial solid electrolyte interphase (SEI), structure control, and electrolyte composition design toward improved performance were summarized. Finally, the challenge and perspective of interface engineering of alloy anodes was discussed. This review may promote the development of alloy anode with improved electrochemical performance for practical renewable energy applications.image

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Crystalline LiPON as a Bulk-Type Solid Electrolyte

Cited by 55 publications

References 37 publications

Extended Condensed Ultraphosphate Frameworks with Monovalent Ions Combine Lithium Mobility with High Computed Electrochemical Stability

Extended Condensed Ultraphosphate Frameworks with Monovalent Ions Combine Lithium Mobility with High Computed Electrochemical Stability

High‐Performance Composite Lithium Anodes Enabled by Electronic/Ionic Dual‐Conductive Paths for Solid‐State Li Metal Batteries

Interface engineering towardhigh‐efficiencyalloy anode for next‐generation energy storage device

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