Analysis of Li distribution in ultrathin all-solid-state Li-ion battery (ASSLiB) by neutron depth profiling (NDP)

Tomandl, I.; Vacı́k, J.; Kobayashi, T.; Sierra, Y. Mora; Hnatowicz, V.; Lavreniev, V.; Horák, P.; Ceccio, G.; Cannavó, Antonino; Baba, Mamoru; Ye, Rongbin

doi:10.1080/10420150.2019.1701471

Cited by 20 publications

(10 citation statements)

References 17 publications

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“…There have been numerous studies over the last several years, where NDP has been applied to the study of Li-ion battery materials. [54,[57][58][59][60] In this study, NDP was utilized to examine the Li concentration profile of a pristine LNMO/LiPON sample to investigate the possibility of LNMO overlithiation.…”

Section: Concentration Gradient Across Lnmo/lipon Interfacementioning

confidence: 99%

Unraveling the Stable Cathode Electrolyte Interface in all Solid‐State Thin‐Film Battery Operating at 5 V

Shimizu

Cheng

Weaver

et al. 2022

Advanced Energy Materials

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Spinel‐type LiNi0.5Mn1.5O4 (LNMO) is one of the most promising 5 V‐class cathode materials for Li‐ion batteries that can achieve high energy density and low production costs. However, in liquid electrolyte cells, the high voltage causes continuous cell degradation through the oxidative decomposition of carbonate‐based liquid electrolytes. In contrast, some solid‐state electrolytes have a wide electrochemical stability range and can withstand the required oxidative potential. In this work, a thin‐film battery consisting of an LNMO cathode with a solid lithium phosphorus oxynitride (LiPON) electrolyte is tested and their interface before and after cycling is characterized. With Li metal as the anode, this system can deliver stable performance for 600 cycles with an average Coulombic efficiency >99%. Neutron depth profiling indicates a slight overlithiated layer at the interface prior to cycling, a result that is consistent with the excess charge capacity measured during the first cycle. Cryogenic electron microscopy further reveals intimate contact between LNMO and LiPON without noticeable structure and chemical composition evolution after extended cycling, demonstrating the superior stability of LiPON against a high voltage cathode. Consequently, design guidelines are proposed for interface engineering that can accelerate the commercialization of a high voltage cell with solid or liquid electrolytes.

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Section: Concentration Gradient Across Lnmo/lipon Interfacementioning

confidence: 99%

Unraveling the Stable Cathode Electrolyte Interface in all Solid‐State Thin‐Film Battery Operating at 5 V

Shimizu

Cheng

Weaver

et al. 2022

Advanced Energy Materials

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“…In conclusion, it can also be said that the nondestructive NDP method proved to be suitable for the study of diffusion parameters of Li in solids (particularly in metals). This method can also be used for in situ and operando analyses of Li behavior in functional systems, such as lithium batteries or their components. − The present data should, however, be considered as only preliminary ones. To obtain more precise and more reliable information on Li diffusion in copper (or other relevant solids), further experiments using the two-dimensional (2D) NDP method (with spectroscopic multipixel detectors) on better-defined samples and structures are planned.…”

Section: Discussionmentioning

confidence: 99%

“…There are only a few experimental techniques that are able to determine Li diffusion coefficients in solids (most of them, however, indirectly), e.g., cyclic voltammetry, electrochemical impedance spectroscopy, galvanostatic intermittent titration technique, capacity intermittent titration technique, or galvanostatic and potentiostatic intermittent titration techniques . In addition, also neutron depth profiling (NDP), a nondestructive nuclear analytical method using an intense thermal neutron beam ( E n = 0.025 eV), represents a technique for investigating the behavior of Li (atoms/ions) in solid materials. − Using NDP, it is possible (with an advantage) to directly reconstruct the spatial distribution of Li atoms in thin films, as well as the change in Li distribution caused by external factors such as electrostatic potential or elevated ambient temperature. In this work, we applied the noninvasive NDP method to determine the diffusion coefficients of Li in thin “copper/lithium/copper” multilayer systems for several annealing temperatures.…”

Section: Introductionmentioning

confidence: 99%

Diffusion of Lithium in Thin Copper Measured by Neutron Depth Profiling

et al. 2020

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The diffusion of lithium in copper was measured in thin Cu/ Li/Cu multilayer systems with a narrow Li slab sandwiched between two copper coating layers. The measurement was performed using a nondestructive neutron depth profiling (NDP) technique installed at the LWR-15 research reactor in R ̌ez. The diffusion coefficients have been obtained for different annealing temperatures between 100 and 500 °C: 4.6 × 10 −17 cm 2 /s for 100 °C, 4.2 × 10 −17 cm 2 /s for 200 °C, 8.9 × 10 −17 cm 2 /s for 300 °C, and 2.06 × 10 −15 cm 2 /s for 500 °C. The NDP technique makes it possible to advantageously determine the diffusion parameters directly on the basis of measuring the Li depth profiles. The measurement of Li diffusion is important not only for a better understanding of the diffusion mechanism of Li in solids but also for relevant technological applications, such as the efficient generation of Li ions for radioactive ion beams (RIB) in isotope separation online (ISOL) facilities, or for monitoring of Li-ion migration in active lithium-ion batteries (LIBs).

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“…Prior results obtained in experiments using a thermal neutron flux intensity of 5 × 10 6 n cm −2 s −1 , required around 10 h simply to obtain one spectrum with satisfactory statistics. [ 12 ] The much higher neutron flux intensity at JRR‐3 was therefore estimated to enable the measurement of a comparable spectrum in only 17 min. Moreover, by enriching the isotope ratio of lithium‐6 of the raw materials (e.g., LiCoO 2 and Li 3 PO 4 ) used for all‐solid‐state batteries, the concentration of lithium‐6 in the batteries could be increased greater than 12 times.…”

Section: Introductionmentioning

confidence: 99%

“…Against that background, ion beam analysis [4][5][6][7][8][9][10][11] and 6 Li(n,α) 3 H thermal neutron-induced nuclear reactions [12][13][14][15][16][17] have been used to quantitatively track the transport of lithium ions in all-solid-state battery-related materials to date. However, due to fundamental limitations of these approaches, both methods have only succeeded in analyzing the depth distribution of lithium ions in the battery in specific charged and discharged states, [4][5][6][7][8][9][10][11][12][13][14]17] or in tracking their transport with very poor statistics.…”

Section: Introductionmentioning

confidence: 99%

In‐Operando Lithium‐Ion Transport Tracking in an All‐Solid‐State Battery

Kobayashi

Ohnishi

Osawa

et al. 2022

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An all‐solid‐state battery is a secondary battery that is charged and discharged by the transport of lithium ions between positive and negative electrodes. To fully realize the significant benefits of this battery technology, for example, higher energy densities, faster charging times, and safer operation, it is essential to understand how lithium ions are transported and distributed in the battery during operation. However, as the third lightest element, methods for quantitatively analyzing lithium during operation of an all‐solid‐state device are limited such that real‐time tracking of lithium transport has not yet been demonstrated. Here, the authors report that the transport of lithium ions in an all‐solid‐state battery is quantitatively tracked in near real time by utilizing a high‐intensity thermal neutron source and lithium‐6 as a tracer in a thermal neutron‐induced nuclear reaction. Furthermore, the authors show that the lithium‐ion migration mechanism and pathway through the solid electrolyte can be determined by in‐operando tracking. From these results, the authors suggest that the development of all‐solid‐state batteries has entered a phase where further advances can be carried out while understanding the transport of lithium ions in the batteries.

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Analysis of Li distribution in ultrathin all-solid-state Li-ion battery (ASSLiB) by neutron depth profiling (NDP)

Cited by 20 publications

References 17 publications

Unraveling the Stable Cathode Electrolyte Interface in all Solid‐State Thin‐Film Battery Operating at 5 V

Unraveling the Stable Cathode Electrolyte Interface in all Solid‐State Thin‐Film Battery Operating at 5 V

Diffusion of Lithium in Thin Copper Measured by Neutron Depth Profiling

In‐Operando Lithium‐Ion Transport Tracking in an All‐Solid‐State Battery

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