Lithium–Magnesium Alloy as a Stable Anode for Lithium–Sulfur Battery

Kong, Linglong; Wang, Lu; Ni, Zhu‐Chao; Liu, Sheng; Li, Guo‐Ran; Gao, Xueping

doi:10.1002/adfm.201808756

Cited by 184 publications

(135 citation statements)

References 56 publications

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“…Additionally, there are literature reports that suggest a very high lithium diffusion coefficient of the β-phase of up to D(Li) ≈ 10 −7 cm² s −1 , which is the key ingredient to the better transport kinetics inside the alloy anode. [48] In solid-state batteries, the retained structural rigidity and morphological stability will have an even greater influence, as morphologically unstable anodes (such as pure lithium anodes) can hardly operate without high external pressure. Even if the lithium in a remaining α-phase cannot be addressed during cycling, the values are as high as 1850 mAh g −1 and 1220 mAh cm −3 , which are still much higher compared to commonly used graphite anodes (350 mAh g −1 and 760 mAh cm − ³).…”

Section: Introductionmentioning

confidence: 99%

Diffusion Limitation of Lithium Metal and Li–Mg Alloy Anodes on LLZO Type Solid Electrolytes as a Function of Temperature and Pressure

Krauskopf

Mogwitz

Rosenbach

et al. 2019

Advanced Energy Materials

316

421

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enable the lithium metal anode with high rate capability. [1][2][3][4] While in LIBs with liquid electrolytes, lithium dendrite growth and low Coulombic efficiency prevent the use of lithium metal as an anode material, [3,[5][6][7][8][9][10][11] solid electrolytes (SEs) had been predicted to be able to block dendrite growth due to their high shear modulus. [12,13] In this context, Li 7 La 3 Zr 2 O 12 (LLZO) type garnet SEs [14] have attracted great attention as they combine high ionic conductivity with sufficient electrochemical stability against lithium metal, which prevents fast degradation and growth of a resistive interphase. [15,16] Nevertheless, certain issues at the lithium|solid electrolyte interface remain unsolved. [17,18] Lithium penetration through garnet-type SEs currently limits the possible charge rates. [19][20][21][22][23] In this context, it was found that good contact to a small reservoir of lithium metal is highly beneficial to prevent inhomogeneous lithium nucleation, which then reduces the lithium penetration susceptibility. [24] All previous results underline the need for sufficient and homogeneous contact between metal and SE during battery operation. Thus, it is of upmost importance for lithium metal solid-state battery development to prevent pore formation and growth at the anode interface during battery discharge. [24][25][26] Indeed, while the intrinsic charge transfer kinetics of the lithium|LLZO interface was found to be sufficiently fast for practical applications (R int < 2 Ωcm²), [26,27] recent work shows that the morphological instability of the (pure) lithium metal anode on solid electrolytes under anodic load is an inherent, fundamental problem that needs to be solved for battery designs that do not allow high operation pressures in the MPa range. [26,28] The morphological instability stems from the vacancy injection into lithium metal during anodic dissolution, which is a general phenomenon of parent metal electrodes. [29,30] It leads to contact loss and unwanted local current constriction during cell discharge. Therefore, transport of lithium in the lithium metal anode itself needs to be better understood and tuned to further increase the rate capability of cells with a lithium metal anode (i.e., to per-cycle areal capacities of 5 mAh cm −2 at current densities ranging to 10 mA cm −2 ). [31] However, the currently run, predominantly short-term lithium shuttling experiments onThe morphological instability of the lithium metal anode is the key factor restricting the rate capability of lithium metal solid state batteries. During lithium stripping, pore formation takes place at the interface due to the slow diffusion kinetics of vacancies in the lithium metal. The resulting current focusing increases the internal cell resistance and promotes fast lithium penetration. In this work, galvanostatic electrochemical impedance spectroscopy is used to investigate operando the morphological changes at the interface by analysis of the interface capacitances. Therewith, the effect of temper...

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Section: Introductionmentioning

confidence: 99%

Diffusion Limitation of Lithium Metal and Li–Mg Alloy Anodes on LLZO Type Solid Electrolytes as a Function of Temperature and Pressure

Krauskopf

Mogwitz

Rosenbach

et al. 2019

Advanced Energy Materials

316

421

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“…[185][186][187] Kong's research group suggested that a Li-rich lithium-magnesium (LiÀ Mg) alloy forms a MgO-containing passivation layer on a LiÀ Mg alloy surface during reaction with lithium in the cell. [188] The study was based on the difference in exchange current density between Mg (0.81 mA cm À 2 ) and Li Figure 6. a) Schematic illustration of the ability of a LiPON-coated lithium metal anode in the lithium-sulfur battery.…”

Section: Controlling the Lithium Metal Surface: Chemical Components Amentioning

confidence: 99%

“…> 500 (1600 mA g À 1 ) TMP-HFE [184] Electrolyte-additive in situ 1 350 S@pPAN composite (5.6 mg cm À 2 ) > 50 (0.483 mA cm À 2 ) LiPON [179] Nitrogen plasma-assisted deposition ex situ 3 600 CNT/S composite (7 mg cm À 2 ) 120 (0.79 mA cm À 2 ) MgO-containing layer [188] Reaction of LiÀ Mg alloy in situ --NBC/CNT/C (2 mg cm À 2 ) 200 (168 mA g À 1 ) N-doped porous carbon nanosheet [192] Attaching the Li surface ex situ 0.5 1600 N-CNT/S (0.7 mg cm À 2 ) 1400 (3.0 A g À 1 ) Metal fluoride complex [193] (MFC, Li 18-crown-6/PVDF [261] Spin coating ex situ 1 149 S 200 (335 mA g À 1 ) Sericin protein [262] Drop casting ex situ 10 160 N-doped carbon/S (1 mg cm À 2 ) 520 (1672 mA g À 1 ) Fluorinated ethers [170] Electrolyte-additive in situ --Bulk sulfur 200 (167 mA g À 1 ) Li 3 PS 4 [169] Immersing Li in P 4 S 16 / NMP ex situ 0.5 2000 S@C (0.8-1.3 mg cm À 2 ) 400 (5 A g À 1 ) Li metal PEO-UPy/THF [263] Drop casting ex situ 1 1000 NMC622 (8 mg cm À 2 ) 200 (180 mA g À 1 ) Toluene (TOL) [203] Electrolyte-additive in situ --NMC532 (9 mg cm À 2 )…”

mentioning

confidence: 99%

Lithium Metal Interface Modification for High‐Energy Batteries: Approaches and Characterization

Lee

Song

Cho

et al. 2020

Batteries & Supercaps

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Rechargeable batteries have been a profoundly greater part of our lives than we could have ever imagined. The rechargeable Li‐ion batteries (LIBs) that have been developed for transport systems even put fossil fuels in the corner. However, state‐of‐the‐art Li‐ion batteries with graphite anodes are now approaching their theoretical specific energy limits, so they cannot meet the increasing demands of a range of portable electronics and large‐scale energy storage systems. Li metal is one of the most promising anode materials that could break through the energy density bottleneck of Li‐ion batteries due to its ultrahigh specific capacity and very low potential compared to other anode materials. Nonetheless, the direct use of Li metal in commercial battery systems has been hindered due to significant obstacles associated with it such as safety issues, corrosion from chemical reactions that occur inside the battery, or poor cycling performance. The fundamental reason for these problems is the dendritic growth of Li‐ions on the Li metal anode during cycling, as a result of the interfacial phenomena of Li metal and electrolytes. Modification of the Li metal interface with an electrolyte presents an efficient solution to solve these problems. In this review, the current challenges facing the development of Li metal anodes are presented in detail. The most recent advances in Li metal anodes using a controlled interface between the Li metal surface and an electrolyte are highlighted and an introduction on the synthesis and production methods for the application of high‐energy‐density battery systems such as Li‐oxygen (Li−O2), Li‐sulfur (Li−S), and Li metal batteries with high‐energy density cathodes is presented. Furthermore, the recent developments in the in situ/operando analysis tools adopted for the investigation of Li metal anodes such as the structural and chemical changes, dynamic properties, and solid–electrolyte interface (SEI) layer properties are described and summarized. Finally, some suggestions are given in the direction of the development of Li metal with artificial surface layers for use in future high‐energy batteries.

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“…The Mg matrix provided host for the lithium to acquire an even deposition. Also, Mg element participated in the formation of a robust SEI (Kong et al, 2019). Other types of lithium alloys such as Li/Sn (Qiu et al, 2019) and Li/Al (Zhong et al, 2018) had also been proven effective though more studies are still needed.…”

Section: Providing Host Materials For Lithium Depositionmentioning

confidence: 99%

Methods to Improve Lithium Metal Anode for Li-S Batteries

et al. 2019

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The lithium-sulfur (Li-S) battery has received a lot of attention because it is characterized by high theoretical energy density (2,600 Wh/kg) and low cost. Though many works on the "shuttle effect" of polysulfide have been investigated, lithium metal anode is a more challenging problem, which leads to a short life, low coulombic efficiency, and safety issues related to dendrites. As a result, the amelioration of lithium metal anode is an important means to improve the performance of lithium sulfur battery. In this paper, improvement methods on lithium metal anode for lithium sulfur batteries, including adding electrolyte additives, using solid, and/or gel polymer electrolyte, modifying separators, applying a protective coating, and providing host materials for lithium deposition, are mainly reviewed. In addition, some challenging problems, and further promising directions are also pointed out for future research and development of lithium metal for Li-S batteries.

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Lithium–Magnesium Alloy as a Stable Anode for Lithium–Sulfur Battery

Cited by 184 publications

References 56 publications

Diffusion Limitation of Lithium Metal and Li–Mg Alloy Anodes on LLZO Type Solid Electrolytes as a Function of Temperature and Pressure

Diffusion Limitation of Lithium Metal and Li–Mg Alloy Anodes on LLZO Type Solid Electrolytes as a Function of Temperature and Pressure

Lithium Metal Interface Modification for High‐Energy Batteries: Approaches and Characterization

Methods to Improve Lithium Metal Anode for Li-S Batteries

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