Direct observation of lithium dendrites inside garnet-type lithium-ion solid electrolyte

Ren, Yaoyu; Shen, Yang; Lin, Yuanhua; Nan, Ce‐Wen

doi:10.1016/j.elecom.2015.05.001

Cited by 521 publications

(372 citation statements)

References 15 publications

Supporting

Mentioning

350

Contrasting

Unclassified

Order By: Relevance

“…Some black spots and cracks were clearly confirmed on the pellet surface. Moreover, some of the cracks penetrated along a thickness direction and reached the opposing pellet surface, indicating that the short circuit locally occurred around these cracks due to the propagation of Li dendrite into SE [33,[47][48][49]. We also observed the microstructures of fractured cross sections of LLZT pellets using SEM and the results are shown in Figure 7.…”

Section: Stability Against LI Deposition and Dissolution Reaction At mentioning

confidence: 73%

“…Together with further examination of the propagation mechanism of Li dendrite into garnet-type SE, both the critical current density at which the short circuit occurs and the threshold in the capacity for Li deposition for stable cycling must be enhanced further to realize a solid-state battery with a garnet-type oxide SE and Li metal anode. We believe that this could be achieved by reducing the interfacial charge-transfer resistance further and by structural improvement of the garnet-type SE by decreasing the porosity [34,47,48], controlling grain size [41,44], and modifying the grain boundary [45,50].…”

Section: Stability Against LI Deposition and Dissolution Reaction At mentioning

confidence: 99%

See 1 more Smart Citation

Formation and Stability of Interface between Garnet-Type Ta-doped Li7La3Zr2O12 Solid Electrolyte and Lithium Metal Electrode

et al. 2018

View full text Add to dashboard Cite

Garnet-type Li 7-x La 3 Zr 2-x Ta x O 12 (LLZT) is considered a good candidate for the solid electrolyte in all-solid-state lithium batteries because of its reasonably high conductivity around 10 −3 S cm −1 at room temperature and stability against lithium (Li) metal with the lowest redox potential. In this study, we synthesized LLZT with a tantalum (Ta) content of 0.45 via a conventional solid-state reaction process and constructed a Li/LLZT/Li symmetric cell by attaching Li metal foils on the polished top and bottom surfaces of an LLZT pellet. We investigated the influence of heating temperatures and times on the interfacial charge-transfer resistance between LLZT and the Li metal electrode. In addition, the effect of the interface resistance on the stability for Li deposition and dissolution was examined using a galvanostatic cycling test. The lowest interfacial resistance of 25 Ω cm 2 at room temperature was obtained by heating at 175 • C (5 • C lower than the melting point of Li) for three to five hours. We confirmed that the current density at which the short circuit occurs in the Li/LLZT/Li cell via the propagation of Li dendrite into LLZT increases with decreasing interfacial charge transfer resistance.

show abstract

Section: Stability Against LI Deposition and Dissolution Reaction At mentioning

confidence: 73%

Section: Stability Against LI Deposition and Dissolution Reaction At mentioning

confidence: 99%

Formation and Stability of Interface between Garnet-Type Ta-doped Li7La3Zr2O12 Solid Electrolyte and Lithium Metal Electrode

et al. 2018

View full text Add to dashboard Cite

show abstract

“…For example, dendrites form and grow through the grain structure of Li garnet solid electrolytes even though their shear modulus is >50 GPa, a value predicted to be sufficiently high to suppress dendrite growth (8). Applying an external pressure above what is believed to be the yield strength of Li also does not fully eradicate dendrites, most likely because of the dearth of high-fidelity mechanical properties data for Li.…”

mentioning

confidence: 99%

“…com/Li-Foil-30000mmL-35mmW-0.17mmTh.aspx) Li anode would require a separator with a shear modulus of at least 17.5 GPa to suppress them, whereas a much lower value of 2.92 GPa is sufficient for the <111> orientation. This holds as long as no dendrite growth occurs through pores or grain boundaries, which can be achieved by using dense electrolyte preparation methods like pressure-assisted sintering (8).…”

mentioning

confidence: 99%

Enhanced strength and temperature dependence of mechanical properties of Li at small scales and its implications for Li metal anodes

Ahmad

Aryanfar

et al. 2016

Proc. Natl. Acad. Sci. U.S.A.

243

191

View full text Add to dashboard Cite

Most next-generation Li ion battery chemistries require a functioning lithium metal (Li) anode. However, its application in secondary batteries has been inhibited because of uncontrollable dendrite growth during cycling. Mechanical suppression of dendrite growth through solid polymer electrolytes (SPEs) or through robust separators has shown the most potential for alleviating this problem. Studies of the mechanical behavior of Li at any length scale and temperature are limited because of its extreme reactivity, which renders sample preparation, transfer, microstructure characterization, and mechanical testing extremely challenging. We conduct nanomechanical experiments in an in situ scanning electron microscope and show that micrometer-sized Li attains extremely high strengths of 105 MPa at room temperature and of 35 MPa at 90°C. We demonstrate that single-crystalline Li exhibits a power-law size effect at the micrometer and submicrometer length scales, with the strengthening exponent of −0.68 at room temperature and of −1.00 at 90°C. We also report the elastic and shear moduli as a function of crystallographic orientation gleaned from experiments and first-principles calculations, which show a high level of anisotropy up to the melting point, where the elastic and shear moduli vary by a factor of ∼4 between the stiffest and most compliant orientations. The emergence of such high strengths in small-scale Li and sensitivity of this metal's stiffness to crystallographic orientation help explain why the existing methods of dendrite suppression have been mainly unsuccessful and have significant implications for practical design of future-generation batteries.dendrite | size effect | elastic anisotropy | dislocation | elevated temperature I ncreased adoption of electric vehicles requires an improvement in the energy density of rechargeable Li ion batteries. Li metal anode is a common and necessary ingredient in commercialization pathways for next-generation Li ion batteries. In the near term, Li metal coupled with an advanced cathode could lead to a specific energy of 400 Wh/kg at the cell level, which represents 200% improvement over current state of the art (1). In the longer term, Li metal coupled with a S and O 2 cathode could lead to even higher specific energies of >500 Wh/kg. Despite over 40 y of research, overcoming the uncontrollable dendrite growth during cycling has remained an insurmountable obstacle for Li-based components (2). Among multiple attempted approaches to eliminate or even reduce the dendrite growth, mechanical suppression has emerged as one of the most promising routes. In their pioneering theoretical work, Monroe et al. (3) considered a solid polymer electrolyte (SPE) in contact with a Li metal electrode and performed a linear stability analysis of the deformation at the interface. They used linear elasticity to compute the stresses generated at the interface due to small deformations. They found that the dendrite growth decays with time if the shear modulus of the SPE is higher than about t...

show abstract

“…109 More recently, there have been efforts to investigate the interfacial behaviors between Li-ion conductors and cathode/anode in detail, with a growing number of in situ and ex situ analytical tools applied to studying the Li + transfer at interfaces. 110,111 All-solid-state Li-S batteries could be a highly promising alternative to the conventional liquid electrolyte Li-S batteries. In summary, the prospectus of Li-S batteries has been improved remarkably over the past years.…”

Section: Discussionmentioning

confidence: 99%

Review—From Nano Size Effect to In Situ Wrapping: Rational Design of Cathode Structure for High Performance Lithium−Sulfur Batteries

Chen

Shen

Wang

et al. 2017

J. Electrochem. Soc.

View full text Add to dashboard Cite

Rechargeable Li-S batteries have become attractive for next-generation energy storage technology due to their high specific energy, low cost, and materials earth abundance. However, the Li-S technology has not been successfully commercialized because of several outstanding challenges including fast capacity fading, low Coulombic efficiency, and limited rate capability. Over the past few years, considerable efforts have been devoted to solving the challenges associated with the sulfur cathode. In this mini review, we summarize our recent advances in Li-S cathodes, such as the understanding of the nano-size effect in sulfur materials, the design of polymer functional additives, and the realization of a novel in situ wrapping approach for Li-S cathodes. The current Li-S technology calls for a rational design of the Li-S cathode that can lead to excellent overall performance of Li-S batteries. Sulfur is a promising cathode material, which is highly earth abundant and with a theoretical specific capacity as high as 1672 mAh g −1 . When the sulfur cathode couples with a lithium metal anode to assemble rechargeable lithium-sulfur (Li-S) batteries, their theoretical specific energy density can reach 2600 Wh kg −1 , which is 3-5 folds higher than those of state-of-the-art Li-ion batteries.1-3 Because of the high energy density and low cost, rechargeable Li-S batteries are promising for applications not only in consumer electronics but also in energy storage and electric vehicles. [4][5][6] Although the research on Li-S batteries has been ongoing for over three decades, two major challenges still remain in this field: one is the low specific capacity due to high electrical resistivity of elementary S and the solid reduction products ((Li 2 S 2 and Li 2 S)) in the cathodes; the other is the fast capacity fading owing to the shuttle effect, i.e. polysulfide intermediates formed during discharge/charge cycles dissolve in the electrolyte, diffuse to the anode, react with Li metal, and form insoluble Li 2 S 2 and Li 2 S at the anodic region, leading to the loss of lithium metal and sulfur cathodic materials. 7,8 In the past few years, researches have mainly focused on designing nanostructured sulfur host materials to address challenges related to poor electrical conductivity of S/Li 2 S 2 /Li 2 S.9-19 A quantum leap for the nanostructure approach was the utilization of ordered mesoporous carbon CMK-3 to trap sulfur, as reported by Nazar et al. in 2009. 20 The conductive mesoporous carbon framework precisely constrains the growth of sulfur within its channels and thus enables fast electronic and ionic transport. Following this work, Cui et al. designed a series of sulfur nanostructures with complicated host materials demonstrating excellent electrochemical performances.9 Various nanostructured host materials, including but not limited to carbon/sulfur, 11,14,16,17,21 polymer/sulfur, [22][23][24] and metal oxide/sulfur composites 12,25,26 have been investigated. These nanostructures provide new merits and opportunities: (1)...

show abstract

Direct observation of lithium dendrites inside garnet-type lithium-ion solid electrolyte

Cited by 521 publications

References 15 publications

Formation and Stability of Interface between Garnet-Type Ta-doped Li7La3Zr2O12 Solid Electrolyte and Lithium Metal Electrode

Formation and Stability of Interface between Garnet-Type Ta-doped Li7La3Zr2O12 Solid Electrolyte and Lithium Metal Electrode

Enhanced strength and temperature dependence of mechanical properties of Li at small scales and its implications for Li metal anodes

Review—From Nano Size Effect to In Situ Wrapping: Rational Design of Cathode Structure for High Performance Lithium−Sulfur Batteries

Contact Info

Product

Resources

About