Real-time observation of lithium fibers growth inside a nanoscale lithium-ion battery

Ghassemi, Hessam; Au, Ming; Chen, Ning; Heiden, Patricia A.; Yassar, Reza S.

doi:10.1063/1.3643035

Cited by 72 publications

(47 citation statements)

References 18 publications

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“…Bulk magnetic susceptibility effects lead to orientation dependent frequency shifts 24,29 . It is assumed that mossy Li grows parallel to the electrode surface and more densely then dendritic Li, which is assumed to grow more or less perpendicularly to the surface, thus parallel to the direction of the applied electric field 53 . In the following a gas tight NMR cell container design is described, which enables long-time investigations.…”

Section: Introductionmentioning

confidence: 99%

Long-run in operando NMR to investigate the evolution and degradation of battery cells

Kayser

Mester

Mertens

et al. 2018

Phys. Chem. Chem. Phys.

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To improve the lifetime of lithium-ion batteries, a detailed understanding of the degradation mechanisms is essential. Nuclear magnetic resonance (NMR) is able to unravel the reversible as well as irreversible transient changes of composition, shape and morphology in a battery cell. Using a newly developed cylindrical battery container free of metallic components in combination with a numerically optimized saddle coil, in operando NMR investigations of battery cells over hundreds of charge/discharge cycles are presented. Alternating with NMR data acquisition, electrochemical impedance spectra (EIS) can be recorded, which enables correlative analysis of the two techniques. Long-run in operando NMR measurements on a Li metal vs. graphite cell reveal the formation and evolution of mossy and dendritic Li microstructures over a period of 1000 h, which illustrates the capabilities of NMR to identify dendrite mitigation strategies in cells operated under realistic conditions.

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Section: Introductionmentioning

confidence: 99%

Long-run in operando NMR to investigate the evolution and degradation of battery cells

Kayser

Mester

Mertens

et al. 2018

Phys. Chem. Chem. Phys.

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“…14,15 Numerous experimental studies have addressed the issue of dendrite growth in lithium batteries. 8,[16][17][18][19][20][21][22][23][24][25] While the increase in current density in the vicinity of a dendrite or globule is, perhaps, the most important driving force in the process, this increase has thus far escaped experimental scrutiny. To our knowledge, only the average current density has been reported in previous studies on cells containing lithium metal electrodes.…”

mentioning

confidence: 99%

Influence of Electrolyte Modulus on the Local Current Density at a Dendrite Tip on a Lithium Metal Electrode

Harry

Higa

Srinivasan

et al. 2016

J. Electrochem. Soc.

108

115

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Understanding and controlling the electrochemical deposition of lithium is imperative for the safe use of rechargeable batteries with a lithium metal anode. Solid block copolymer electrolyte membranes are known to enhance the stability of lithium metal anodes by mechanically suppressing the formation of lithium protrusions during battery charging. Time-resolved hard X-ray microtomography was used to monitor the internal structure of a symmetric lithium-polymer cell during galvanostatic polarization. The microtomography images were used to determine the local rate of lithium deposition, i.e. local current density, in the vicinity of a lithium globule growing through the electrolyte. Measurements of electrolyte displacement enabled estimation of local stresses in the electrolyte. At early times, the current density was maximized at the globule tip, as expected from simple current distribution arguments. At later times, the current density was maximized at the globule perimeter. We show that this phenomenon is related to the local stress fields that arise as the electrolyte is deformed. The local current density, normalized for the radius of curvature, decreases with increasing compressive stresses at the lithium-polymer interface. To our knowledge, our study provides the first direct measurement showing the influence of local mechanical stresses on the deposition kinetics at lithium metal electrodes. There is increasing interest in the transport of ions at lithium metal electrodes due to the current focus on increasing the energy density of rechargeable lithium batteries.1 In theory, replacing a graphite electrode with lithium metal in a lithium-ion battery will result in a 40% increase in gravimetric energy density.2 Battery chemistries with energy densities that are substantially larger than that of the lithium-ion chemistry, such as lithium-sulfur and lithium-air, rely on the availability of a rechargeable lithium metal anode. Electrodeposition of metallic films is also an integral step in the manufacture and use of a broad range of devices spanning consumer electronics to energy storage.3-5 Conventionally, in both batteries and electrochemical processing, metals are electrodeposited from liquid electrolytes. [6][7][8] However, recent advances in polymer and ceramic electrolytes have allowed for the deposition (and stripping) of metals from electrolytes with a high modulus.9-11 These stiff electrolyte materials influence the mechanism of metallic electrodeposition. Notably, stiff polymer electrolytes are known to suppress the growth of dendrites in batteries containing a lithium metal anode.12,13 Suppressing the growth of protruding metallic lithium structures, like dendrites and globules, is imperative for the safe and reliable use of high energy density, rechargeable batteries with metallic anodes. 14,15 Numerous experimental studies have addressed the issue of dendrite growth in lithium batteries. 8,[16][17][18][19][20][21][22][23][24][25] While the increase in current density in the vicinity of a dendrite o...

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“…Owing to the inherent instability of lithium metal deposition, research shifted to lithium-ion-based batteries during the 1980s (refs 1,2,4). Current commercial lithium-ion batteries using graphite as a negative electrode exhibit an approximately tenfold lower specific charge capacity but safer operation compared with lithium metal electrodes; however, despite this development, lithium dendrite formation has not been entirely inhibited in graphite anodes either, especially when cycled at high current densities, in overcharge conditions, or at low temperatures 8,[12][13][14][15] .…”

mentioning

confidence: 99%

Improving battery safety by early detection of internal shorting with a bifunctional separator

et al. 2014

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Lithium-based rechargeable batteries have been widely used in portable electronics and show great promise for emerging applications in transportation and wind-solar-grid energy storage, although their safety remains a practical concern. Failures in the form of fire and explosion can be initiated by internal short circuits associated with lithium dendrite formation during cycling. Here we report a new strategy for improving safety by designing a smart battery that allows internal battery health to be monitored in situ. Specifically, we achieve early detection of lithium dendrites inside batteries through a bifunctional separator, which offers a third sensing terminal in addition to the cathode and anode. The sensing terminal provides unique signals in the form of a pronounced voltage change, indicating imminent penetration of dendrites through the separator. This detection mechanism is highly sensitive, accurate and activated well in advance of shorting and can be applied to many types of batteries for improved safety.

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Real-time observation of lithium fibers growth inside a nanoscale lithium-ion battery

Cited by 72 publications

References 18 publications

Long-run in operando NMR to investigate the evolution and degradation of battery cells

Long-run in operando NMR to investigate the evolution and degradation of battery cells

Influence of Electrolyte Modulus on the Local Current Density at a Dendrite Tip on a Lithium Metal Electrode

Improving battery safety by early detection of internal shorting with a bifunctional separator

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