Dendrite-Free Electrodeposition and Reoxidation of Lithium-Sodium Alloy for Metal-Anode Battery

Stark, Johanna; Ding, Yi; Kohl, Paul A.

doi:10.1149/1.3622348

Cited by 127 publications

(95 citation statements)

References 26 publications

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“…The sharp Li filaments can pierce through the separator with increasing cycle time, thus provoking internal short-circuiting (12). Most previous academic research to settle this bottleneck focuses on solid electrolyte interphase (SEI) stabilization/modification by introducing various additives (13)(14)(15)(16)(17). These electrolyte additives interact with Li quickly and create a protective layer on the Li metal surface, which helps reinforce the SEI (13)(14)(15)(16)(17).…”

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confidence: 99%

“…Most previous academic research to settle this bottleneck focuses on solid electrolyte interphase (SEI) stabilization/modification by introducing various additives (13)(14)(15)(16)(17). These electrolyte additives interact with Li quickly and create a protective layer on the Li metal surface, which helps reinforce the SEI (13)(14)(15)(16)(17). Furthermore, recent study in our group has also shown the employment of interconnected hollow carbon spheres (18) and hexagonal boron nitride (19) as mechanically and chemically stable artificial SEI which effectively block Li dendrite growth.…”

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confidence: 99%

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Composite lithium metal anode by melt infusion of lithium into a 3D conducting scaffold with lithiophilic coating

Liang

Lin

Zhao

et al. 2016

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

788

533

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Lithium metal-based battery is considered one of the best energy storage systems due to its high theoretical capacity and lowest anode potential of all. However, dendritic growth and virtually relative infinity volume change during long-term cycling often lead to severe safety hazards and catastrophic failure. Here, a stable lithium-scaffold composite electrode is developed by lithium melt infusion into a 3D porous carbon matrix with "lithiophilic" coating. Lithium is uniformly entrapped on the matrix surface and in the 3D structure. The resulting composite electrode possesses a high conductive surface area and excellent structural stability upon galvanostatic cycling. We showed stable cycling of this composite electrode with small Li plating/stripping overpotential (<90 mV) at a high current density of 3 mA/cm 2 over 80 cycles.Li composite | Li metal anode | melt infusion | 3D scaffold | lithiophilic N owadays the increasing demand for portable electronic devices as well as electric vehicles raises an urgent need for high energy density batteries. Lithium (Li) metal anode has long been regarded as the "Holy Grail" of battery technologies, due to its light weight (0.53 g/cm 3 ) (1), lowest anode potential (−3.04 V vs. the standard hydrogen electrode) (1), and high specific capacity (3,860 mAh/g vs. 372 mAh/g for conventional graphite anode) (1). It possesses an even higher theoretical capacity than the recently intensely researched anodes such as Ge, Sn, and Si (2-10). In addition, the demand for copper current collectors (9 g/cm 3 ) in conventional batteries with graphite anodes can be eliminated by employment of Li metal anodes, hence reducing the total cell weight dramatically. Therefore, Li metal could be a favorable candidate to be used in highly promising, next-generation energy storage systems such as Li−sulfur battery and Li−air battery.The safety hazard associated with Li metal batteries, originating from the uncontrolled dendrite formation, has become a hurdle against the practical realization of Li metal-based batteries (11,12). The sharp Li filaments can pierce through the separator with increasing cycle time, thus provoking internal short-circuiting (12). Most previous academic research to settle this bottleneck focuses on solid electrolyte interphase (SEI) stabilization/modification by introducing various additives (13-17). These electrolyte additives interact with Li quickly and create a protective layer on the Li metal surface, which helps reinforce the SEI (13-17). Furthermore, recent study in our group has also shown the employment of interconnected hollow carbon spheres (18) and hexagonal boron nitride (19) as mechanically and chemically stable artificial SEI which effectively block Li dendrite growth.In addition to the notorious Li dendrite formation, another significant factor that contributes considerably to the battery shortcircuiting is the volume change of Li metal during electrochemical cycling, which is usually overlooked (20,21). During battery cycling, Li metal is deposited/stripped ...

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confidence: 99%

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confidence: 99%

Composite lithium metal anode by melt infusion of lithium into a 3D conducting scaffold with lithiophilic coating

Liang

Lin

Zhao

et al. 2016

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

788

533

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“…z E-mail: aponrouch@icmab.es dendrite growth was prevented when a sodium salt was added to the electrolytes based either on conventional organic solvents 7 or ionic liquids. 8 Room temperature operation sodium-ion batteries (SIB) using liquid electrolytes while avoiding the use of metal anodes are intensively researched nowadays due to prospects of significantly lower cost, when compared to LIB, coupled to concerns of a future limited lithium supply derived from wide deployment of LIB in large scale applications (transportation and grid).…”

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confidence: 99%

On the Comparative Stability of Li and Na Metal Anode Interfaces in Conventional Alkyl Carbonate Electrolytes

Iermakova

Dugas

Palacín

et al. 2015

J. Electrochem. Soc.

268

275

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A comparative study of the electrode/electrolyte interface was carried out for lithium and sodium metal anodes in electrolytes consisting in 1 M LiPF 6 in EC 0.5 :DMC 0.5 (LP30) and 1 M NaPF 6 in both EC 0.5 :DMC 0.5 and EC 0.45 PC 0.45 DMC 0.1 . Symmetric Li/Li cells exhibited low polarization and smooth charge discharge curves with current densities of 0.1 and 1 mA/cm 2 . In contrast, large overpotentials were observed even at 0.1 mA/cm 2 for Na/Na cells. Such differences cannot be related to ionic conductivity of the electrolytes but are rather due to an enhanced interfacial resistance (R ct + R SEI ) as deduced from impedance measurements. The composition of the SEI layer was investigated by FTIR and found to be stable for Li electrodes but to evolve upon cycling for Na electrodes which is also in agreement with differences in surface morphology detected by SEM. A lower stability (partial solubility) of the SEI would also enable to understand the differences in the impedance of identical hard carbon (HC) electrodes in cells with either Li or Na counterelectrodes. These results cast some concerns on the reliability of the so termed half cell characterization and call for caution when interpreting the results of potential electrode materials for sodium ion batteries. The use of metallic anodes has attracted large attention in the battery field due to their high capacity and low operation potential. Nonetheless, almost all commercialized technologies are either primary cell (e.g. alkaline Zn/MnO 2 ), operating through chemical reaction mechanisms (e.g. Ni/Cd in which Cd oxidizes to Cd(OH) 2 , using liquid metal anodes (Na/S cells) or polymer 1 electrolytes, thus avoiding many of the problems of metal reversible plating/stripping in liquid electrolytes. Indeed, the formation of metal dendrites upon cycling was early identified as bottleneck for the development of safe Li metal anode batteries which lead to the commercialization of Li-ion batteries (LIB) to the expense of a severe penalty in energy density. Even so, lithium metal anodes are widely used as counter (or also reference) electrodes in the so termed half cell tests, performed mostly at laboratory scale within the battery research community. These are mostly intended to assess the electrochemical performance of a given compound as either positive or negative electrode material for LIB in a simple way, avoiding the assembly of full cells in which electrode balancing can severely affect performance. Their outcomes are typically the electrochemical capacity and operation potential values at different rates. The reliability of extrapolating such half cell testing results to potential performance in full cells relies on the stability of the Solid Electrolyte Interphase (SEI) typically formed on the surface of lithium metal anodes as a result of electrolyte degradation reactions. 2The development of a room temperature sodium (solid) metal anode battery technology, using conventional liquid electrolytes does not seem to have been seriously considered in the pa...

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“…From previous work, it has been shown that lithium and sodium can be co-deposited to form a non-dendritic deposit. 11,19 The lithium/sodium co-deposit consisted of many spheres with at least one indentation on the surface. This morphology is shown in Figure 5a where 1.3 C/cm 2 was passed over 5000 s. This co-deposit was studied in detail in a previous paper.…”

Section: Resultsmentioning

confidence: 99%

“…11,19 A non-dendritic, sphere-like lithium morphology was achieved through the co-deposition sodium with lithium. The remaining alkali TFSI salts have been synthesized and their reduction potentials characterized, opening the door for their study in conjunction with lithium.…”

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confidence: 99%

Effect of Alkali and Alkaline Earth Metal Salts on Suppression of Lithium Dendrites

Goodman

Kohl

2014

J. Electrochem. Soc.

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Lithium dendrites are needle-like structures that form during the electrodeposition of lithium metal. These whiskers complicate the use of lithium metal as an anode in lithium batteries because they can puncture the separator and short circuit the battery. In addition, the large surface area and poor adhesion of the deposit contributes to loss of coulombic efficiency. The effect of alkali and alkaline earth metal ions on the morphology of electrodeposited lithium metal has been studied. Varying concentrations of alkali and alkaline earth metal ions were added to a 1 M lithium bis(trifluoromethanesulfonyl)imide (Li-TFSI) trimethylbutylammonium bis(trifluoromethanesulfonyl)imide (N 1114 -TFSI) electrolyte. Lithium metal was electrodeposited from each electrolyte and examined ex-situ by scanning electron microscopy (SEM). Alkali metal ions, with the exception of sodium, had little or no effect on the deposited lithium morphology. However, alkaline earth metal ions at 0.05 M concentration significantly reduced the occurrence of dendrites. When the concentration of the alkaline earth metal ions was increased to 0.1 M, dendrites were completely eliminated and lithium was deposited in a sphere-like morphology. Energy dispersive X-ray spectroscopy (EDX) showed that no alkaline earth metals were found in the sphere-like deposits, suggesting that dendrite mitigation occurred through an adsorption mechanism. Lithium-ion batteries based on graphite anodes have been commercialized and used in mobile devices due to their high power and energy density. The graphite anode operates close to its theoretical capacity of 329 mAh/g. Thus, to increase the energy density of the overall battery, a new anode material must be developed. Reducing lithium ions on a substrate, rather than intercalating them into graphite, raises the specific capacity of the anode to 3861 mAh/g and is compatible with existing cathodes and future high-voltage cathodes.Lithium-metal anodes suffer from low cycling efficiency for several reasons. First, the solid electrolyte interface (SEI) that forms on graphite anodes to protect the electrode from further reaction with the electrolyte, does not form as well on a metallic lithium surface. Second, the lithium metal anode undergoes extreme volume changes when going between the charged and discharged states, which can significantly disrupt the SEI during each cycle. Finally, when lithium metal is deposited on a substrate, such as during battery charging, lithium does not deposit as a dense, cohesive, planar layer, but rather deposits as needle-like structures, sometimes called dendrites, as shown in Figure 1.Adding SEI forming additives and restricting the battery to shallow discharge cycles can mitigate some of these problems, however, these restrictions are not desirable. Vinylene carbonate (VC) has been shown to be a valuable additive for lithium metal batteries, yielding higher efficiencies and increased cycle life.1,2 VC and other cyclic carbonates have been shown to form an SEI via ring-opening reactions tha...

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Dendrite-Free Electrodeposition and Reoxidation of Lithium-Sodium Alloy for Metal-Anode Battery

Cited by 127 publications

References 26 publications

Composite lithium metal anode by melt infusion of lithium into a 3D conducting scaffold with lithiophilic coating

Composite lithium metal anode by melt infusion of lithium into a 3D conducting scaffold with lithiophilic coating

On the Comparative Stability of Li and Na Metal Anode Interfaces in Conventional Alkyl Carbonate Electrolytes

Effect of Alkali and Alkaline Earth Metal Salts on Suppression of Lithium Dendrites

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