Electrolyte additive enabled fast charging and stable cycling lithium metal batteries

Zheng, Jianming; Engelhard, Mark H.; Mei, Donghai; Jiao, Shuhong; Polzin, Bryant J.; Zhang, Ji‐Guang; Xu, Wu

doi:10.1038/nenergy.2017.12

Cited by 1,124 publications

(763 citation statements)

References 28 publications

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“…All the results confirm that the MHD can effectively suppress the dendrite formation and benefit to the uniform Li metal deposition. [4,53,61] But the concentration polarization is reduced greatly by MHD effect under magnetic field, which promotes the uniform nucleation of Li. At the 242th cycle, the CE is below 70%.…”

Section: Resultsmentioning

confidence: 99%

Magnetic Field–Suppressed Lithium Dendrite Growth for Stable Lithium‐Metal Batteries

Shen

Wang

et al. 2019

Advanced Energy Materials

210

134

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for the battery technologies. However, the main impediment for the practical application of lithium metal batteries is the lithium dendrite formation. [5] It not only penetrates the separator to induce the short circuit of the batteries, [6] but also generates high surface area in the anode to accelerate the unwanted side reactions between electrolytes and lithium metal, resulting in the electrolyte depletion and the subsequent battery failure. [7][8][9] Up to now, many strategies targeting lithium dendrites suppression rely on the "internal strategies," i.e., the modification or optimization of the components inside the cells. Those strategies include electrolyte optimization, artificial solid electrolyte interphase (SEI) design, and synthesis of 3D current collector. [1] Electrolyte additives such as LiF, [10] LiNO 3 , [11] and Li 2 S x [12] were chosen to form stable SEI on the surface of Li anode to suppress the dendrite growth. [13] For creating artificial SEI layer on the anode, gas treatment [14] (N 2 , O 2 , CO 2 , or SO 2 ), liquid treatment (Li 3 PO 4[15] and Cu 3 N/styrene−butadiene rubber [16] ), and physical deposition of nanofilm (Al 2 O 3 , [17] carbon, [18] and organic polymer [19] ) are the three typical methods by accessing the internal interface of the battery. The rational design of 3D current collectors also helps to inhibit dendritic growth. [20] One type of 3D current collectors is lithiophilic matrix such as lithiophilic-lithiophobic gradient interfacial layer, [21] N-doped graphene, [22] and metal−organic framework, [23] which redistributes Li-ions to the anode surface through chemical bonding interactions to achieve uniform lithium deposition. The other type is conductive matrix including porous carbon, [7] graphene matrix, [24] 3D-ordered macroporous Cu, [25] and fibrous metal felt [26] that reduces dendritic growth by reducing the current density with a large surface area. [27,28] Although these "internal strategies" could effectively suppress the dendrite formation, cell stability becomes a concern due to the change of the cell environment such as the use of additives and the modification of the electrode.Introducing an "external strategy," by using external magnetic field to rearrange the Li + concentration on the anode surface, could achieve a uniform lithium deposition. The latest study shows that the growth of Li dendrites stems from the nonuniform Li + concentration on the electrode surface. [29] Lithium metal is the most attractive anode material due to its extremely high specific capacity, minimum potential, and low density. However, uncontrollable growth of lithium dendrite results in severe safety and cycling stability concerns, which hinders the application in next generation secondary batteries. In this paper, a new and facile method imposing a magnetic field to lithium metal anodes is proposed. That is, the lithium ions suffering Lorentz force due to the electromagnetic fields are put into spiral motion causing magnetohydrodynamics (MHD) effect. This MHD effect can effecti...

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Section: Resultsmentioning

confidence: 99%

Magnetic Field–Suppressed Lithium Dendrite Growth for Stable Lithium‐Metal Batteries

Shen

Wang

et al. 2019

Advanced Energy Materials

210

134

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“…These additives include Cs + , 82 LiF, 83 ) unless CC License in place (see abstract 90 LiTFSI−lithium bis(fluorosulfonyl)imide (LiFSI) dual salt, 91 and 0.05 M LiPF 6 additive in LiTFSI−LiBOB dual-salt, 92 etc. However, it should be noted that due to the etching nature of LiPS-rich electrolyte in the Li−S battery, these electrolyte additives functioning well in other Li metal batteries are not always effective in the Li−S batteries.…”

Section: Metal Protection In Li−s Batteriesmentioning

confidence: 99%

Review—Li Metal Anode in Working Lithium-Sulfur Batteries

Cheng

Huang

Zhang

2017

J. Electrochem. Soc.

238

169

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Due to the high theoretical energy density of 2600 Wh kg −1 , lithium-sulfur batteries are strongly regarded as the promising nextgeneration energy storage devices. However, the practical applications of lithium-sulfur batteries are challenged by several obstacles, including the low sulfur utilization and poor lifespan, which are partly attributed to the shuttle of lithium polysulfides and lithium dendrite growth in working lithium-sulfur batteries. Suppressing lithium dendrite growth is a necessary step not only for a safe and efficient Li metal anode, but also for a high capacity cell with a high Coulombic efficiency. Herein we review the lithium metal anode protection in a polysulfide-rich environment, relative to most reviews on lithium metal anode without considering the effect of lithium polysulfides in lithium metal batteries. Firstly, the importance and dilemma of Li metal anode issues in lithium-sulfur batteries are underscored, aiming to arouse the attentions to Li metal anode protection. Specific attentions are paid to the surface chemistry of Li metal anode in a polysulfide-rich lithium-sulfur battery. Next, the proposed strategies to stabilize solid electrolyte interface and protect Li metal anode are included. Finally, a general conclusion and a perspective on the current limitations, as well as recommended future research directions of Li metal anode in lithium-sulfur batteries are presented. The ever-increasing requirement for efficient and economic energy storage technologies has triggered the continued research into advanced battery systems.1 Lithium ion batteries, based on the lithium intercalation chemistry, have dominated the battery market since their commercial application in the 1990s.2 However, conventional lithium ion batteries are very expensive and their energy densities (theoretically, 350 − 500 Wh kg −1 , practically, 100 − 250 Wh kg −1 ) seem insufficient for long-range electrical vehicles and high-end portable electronics. These emerging demands have energized the evolution of other alternative rechargeable batteries with higher energy density and longer lifespan.3 Lithium−sulfur (Li−S) battery, a 'beyond Li-ion' technology, has drawn extensive attentions due to its high specific capacity (1675 mAh g −1 ) and energy density (2600 Wh kg −1 ). 4-6The greater energy storage ability of Li−S batteries is realized through the phase-transformation electrochemistry based on elemental sulfur cathode and metallic lithium anode [S 8 + 16Li ↔ 8Li 2 S], 7,8 which is fundamentally different from current transition metal-based cathodes and graphite-based anodes in Li-ion batteries.The conversion chemistry in a Li−S cell offers not only significant advantages as mentioned above, but also some critical challenges, such as the low conductivity of sulfur and lithium sulfide, the huge volumetric change from sulfur (71 mol L −1 ) to lithium sulfide (36 mol L −1 ), and the shuttle of long-chain polysulfide intermediates during discharge/charge cycling.9-12 Therefore, a composite cathode with sulfur in ...

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“…Silicon and Li-metal have been proposed as promising anode materials for rechargeable LIB 3,4 because of their high theoretical capacity of 4212 mA h g À1 (ref. 5) (for Li 22 Si 5 ), 6 and 3860 mA h g À1 , 7,8 respectively.…”

Section: Introductionmentioning

confidence: 99%

Dendrite formation in silicon anodes of lithium-ion batteries

Selis

Seminario

2018

RSC Adv.

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Rechargeable lithium-ion batteries require a vigorous improvement if we want to use them massively for high energy applications. Silicon and metal lithium anodes are excellent alternatives because of their large theoretical capacity when compared to graphite used in practically all rechargeable Li-ion batteries.However, several problems need to be addressed satisfactorily before a major fabrication effort can be launched; for instance, the growth of lithium dendrites is one of the most important to take care due to safety issues. In this work we attempt to predict the mechanism of dendrite growth by simulating possible behaviors of charge distributions in the anode of an already cracked solid electrolyte interphase of a nanobattery, which is under the application of an external field representing the charging of the battery; thus, elucidating the conditions for dendrite growth. The extremely slow drift velocity of the Li-ions of $1 mm per hour in a typical commercial Li-ion battery, makes the growth of a dendrite take a few hours; however, once a Li-ion arrives at an active site of the anode, it takes an extremely short time of $1 ps to react. This large difference in time-scales allows us to perform the molecular dynamics simulation of the ions at much larger drift velocities, so we can have valuable results in reasonable computational times. The conditions before the growth are assumed and conditions that do not lead to the growth are ignored. We performed molecular dynamics simulations of a pre-lithiated silicon anode with a Li : Si ratio of 21 : 5, corresponding to a fully charged battery. We simulate the dendrite growth by testing a few charge distributions in a nanosized square representing a crack of the solid electrolyte interphase, which is where the electrolyte solution comes into direct contact with the LiSi alloy anode.Depending on the selected charge distributions for such an anode surface, the dendrites grow during the simulation when an external field is applied. We found that dendrites grow when strong deviations of charge distributions take place on the surface of the crack. Results from this work are important in finding ways to constrain lithium dendrite growth using tailored coatings or pre-coatings covering the LiSi alloy anode.

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Electrolyte additive enabled fast charging and stable cycling lithium metal batteries

Cited by 1,124 publications

References 28 publications

Magnetic Field–Suppressed Lithium Dendrite Growth for Stable Lithium‐Metal Batteries

Magnetic Field–Suppressed Lithium Dendrite Growth for Stable Lithium‐Metal Batteries

Review—Li Metal Anode in Working Lithium-Sulfur Batteries

Dendrite formation in silicon anodes of lithium-ion batteries

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