High‐Voltage Lithium‐Metal Batteries Enabled by Localized High‐Concentration Electrolytes

Chen, Shuru; Zheng, Jianming; Mei, Donghai; Han, Kee Sung; Engelhard, Mark H.; Zhao, Wengao; Xu, Wu; Li, Jun; Zhang, Ji‐Guang

doi:10.1002/adma.201706102

Cited by 823 publications

(813 citation statements)

References 41 publications

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“…[24] Recently, Komaba and Lu have reported the highly reversible graphite anode for PIBs at concentrated potassium bis(fluorosulfonyl)imide (KFSI)/ dimethoxyethane (DME) and KFSI/ethyl methyl carbonate electrolytes, respectively. [27] They also diluted concentrated LiFSI in sulfone with a fluorinated ether for high-voltage (4.9 V) lithium metal batteries. To overcome these disadvantages in using HCE, several groups have added a low-polarity cosolvent to dilute an HCE by forming a localized high-concentration electrolyte (LHCE).…”

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confidence: 99%

Localized High‐Concentration Electrolytes Boost Potassium Storage in High‐Loading Graphite

Qin

Xiao

Zheng

et al. 2019

Advanced Energy Materials

166

152

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graphite has a theoretical capacity of 279 mAh g −1 . [3,17] In 2015, Ji and Hu have separately demonstrated the electrochemical intercalation of K ions into graphite in potassium hexafluorophosphate (KPF 6 )/ ethylene carbonate (EC)-diethyl carbonate (DEC) electrolytes. [4,18] However, their works did not achieve a highly reversible K + insertion/extraction process in KPF 6 /EC-DEC electrolyte because the formed solid electrolyte interphase (SEI) becomes fragile and unstable due to the large volume variation (≈60%) during K + insertion/extraction. [19,20] Compared to the conventional lowconcentration electrolyte (LCE), adopting a high-concentration electrolyte (HCE, e.g., >3 m) is a promising strategy to solve the above problem because it possesses some unusual physicochemical and electrochemical properties due to the unique solvation structure of ions, which make it different from an LCE. [21][22][23][24] In 2007, Jeong adopted the concentrated lithium bisperfluoroethylsulfonyl imide LiN(SO 2 C 2 F 5 ) 2 / propylene carbonate (PC) to realize a reversible graphite anode for lithium-ion batteries. [24] Recently, Komaba and Lu have reported the highly reversible graphite anode for PIBs at concentrated potassium bis(fluorosulfonyl)imide (KFSI)/ dimethoxyethane (DME) and KFSI/ethyl methyl carbonate electrolytes, respectively. [25,26] Despite these progresses, the issues of high viscosity, low ionic conductivity, and the increased cost of the HCE still hinder its practical applications. To overcome these disadvantages in using HCE, several groups have added a low-polarity cosolvent to dilute an HCE by forming a localized high-concentration electrolyte (LHCE). It is believed that the introduced cosolvent does not participate in the solvation process. Zhang's group used the bis(2,2,2,-tri-fluoroethyl) ether to dilute the concentrated lithium bis(fluorosulfonyl) imide (LiFSI)/dimethyl carbonate and improve the coulombic efficiency (CE) of lithium metal anodes without dendrite formation. [27] They also diluted concentrated LiFSI in sulfone with a fluorinated ether for high-voltage (4.9 V) lithium metal batteries. [28] Wang's group used the same cosolvent in the concentrated LiFSI/DME to increase both coulombic efficiencies of S cathode and Li anode for Li-S batteries. [29] However, none of the LHCE reported to date has been applied in PIBs, its stability and compatibility with PIBs remain in question.Herein, our work reports for the first time that a highly reversible K + insertion/extraction into graphite interlayer can Reversible intercalation of potassium-ion (K + ) into graphite makes it a promising anode material for rechargeable potassium-ion batteries (PIBs). However, the current graphite anodes in PIBs often suffer from poor cyclic stability with low coulombic efficiency. A stable solid electrolyte interphase (SEI) is necessary for stabilizing the large interlayer expansion during K + insertion. Herein, a localized high-concentration electrolyte (LHCE) is designed by adding a highly fluorinated ether into the con...

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confidence: 99%

Localized High‐Concentration Electrolytes Boost Potassium Storage in High‐Loading Graphite

Qin

Xiao

Zheng

et al. 2019

Advanced Energy Materials

166

152

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“…[10][11][12][13] Ether-based electrolyte has been extensively used in lithium-air and lithiumsulfur batteries. [16,17] In SIBs, ether [16,17] In SIBs, ether…”

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confidence: 99%

Lithium‐Pretreated Hard Carbon as High‐Performance Sodium‐Ion Battery Anodes

Xiao

Soto

et al. 2018

Advanced Energy Materials

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107

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large size of sodium-ions, there are also uniqueness in the development of SIB materials and the tuning of electrodeelectrolyte interphases, etc. [3] One of the most representative examples is that the intercalation of sodium-ion in graphite is thermodynamically inhibited by the interlayer distance, whereas the lithium-ion intercalation is favorable. [1,3] Hard carbon (HC) with expanded interlayer distance was investigated as the-state-of-the-art anode that allows sodium-ion storage via pore absorption, defect binding, and intercalation into the turbostratic graphenic nanodomains. [4][5][6][7] HC structure and the unique ion storage mechanism inevitably induce more reduction decomposition of the electrolyte, solid electrolyte interphase (SEI) formation, ion trapping, and hence lead to worse Coulombic efficiency than graphite. [8] Delicate control of the HC defects and surface area is therefore particularly required. [5,9] It is known that the electrochemical reversibility and the rate and life performance of LIBs and SIBs are to a great extent dictated by the SEI formation and its chemical/electrochemical reactivity and stability. [5,10,11] Concerning this, attempts also have been made to tune the SEI coverage, thickness, stability, and ionic conductivity, etc., by developing novel electrolytes or electrolyte additives that decompose preferentially to form SEI or tailoring the surface area and physiochemical properties of the carbon materials. [10][11][12][13] Ether-based electrolyte has been extensively used in lithium-air and lithiumsulfur batteries. [14,15] The solvent-in-salt electrolyte design also has expanded the application of ether electrolyte to LIBs with graphite anodes and high-voltage cathodes. [16,17] In SIBs, ether Hard carbon (HC) is the state-of-the-art anode material for sodium-ion batteries (SIBs). However, its performance has been plagued by the limited initialCoulombic efficiency (ICE) and mediocre rate performance. Here, experimental and theoretical studies are combined to demonstrate the application of lithium-pretreated HC (LPHC) as high-performance anode materials for SIBs by manipulating the solid electrolyte interphase in tetraglyme (TEGDME)-based electrolyte. The LPHC in TEGDME can 1) deliver > 92% ICE and ≈220 mAh g −1 specific capacity, twice of the capacity (≈100 mAh g −1 ) in carbonate electrolyte; 2) achieve > 85% capacity retention over 1000 cycles at 1000 mA g −1 current density (4 C rate, 1 C = 250 mA g −1 ) with a specific capacity of ≈150 mAh g −1 , ≈15 times of the capacity (10 mAh g −1 ) in carbonate. The full cell of Na 3 V 2 (PO 4 ) 3 -LPHC in TEGDME demonstrated close to theoretical specific capacity of ≈98 mAh g −1 based on Na 3 V 2 (PO 4 ) 3 cathode, ≈2.5 times of the value (≈40 mAh g −1 ) with nontreated HC. This work provides new perception on the anode development for SIBs.

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“…[26] However, LIPON based systems are chemically reactive and sensitive to atmospheric exposure, also possessing a residual open circuit potential (OCP) which opposes continued potentiation and creates challenges for voltage-driven neural networks. Several approaches have been proposed to avoid the Li dendrite formation, such as employing electrolyte additives to slow down the dendrite formation rate, [33,34] utilizing highly concentrated electrolyte to avoid electrolyte depletion [35] and pattering nanoscale ion transport path to regulate Li-ion flux distribution. [27,28] Polymer-based solid-state electrolyte systems give better control over OCP and stability, but patterning of top gate architecture with PEO: LiClO 4 electrolyte is challenging since they are soluble in a commonly used lithographic solvent.…”

Section: Introductionmentioning

confidence: 99%

Controlled Ionic Tunneling in Lithium Nanoionic Synaptic Transistor through Atomically Thin Graphene Layer for Neuromorphic Computing

Nikam

Kwak

Lee

et al. 2019

Adv Elect Materials

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computers due to the dense neural network of synapses. [3,4] Developing a highspeed and a low-cost artificial synapse device to build an artificial neural network to simulate the human brain like functionalities is the dominant scientific goal of the twenty-first century. Colossal exertion has been committed to developing a synapse device that can trigger the synaptic plasticity and nonvolatility. The conventional neural prototype chip was fabricated based on traditional complementary metal-oxide-semiconductor (CMOS) circuits. [5] However, consumption of high power due to a large number of transistors in COMS circuit limits its further development. [6,7] Besides, a different type of two-terminal memristor such as oxidebased resistive random-access memory (RRAM), [8] ferroelectric memory, [9][10][11][12] and phase-change memory (PCM) [13][14][15] has been employed to mimic the synaptic activity due to reversible analog switching. However, reduced control over conductance change and asynchronous read/write operation limit the application of twoterminal devices as a synaptic element. [16] More recently, a nanoionics synaptic transistor (IST) has been extensively studied and proposed as a suitable candidate for artificial synapses. [17][18][19][20] An IST consists of ionically conducting gate electrolyte and insulating or semiconducting channel. An IST relies on field-driven ion migration from an electrolyte to channel, thereby changing its doping state and hence its conductivity. This device shows reversibility near analog switching, nonvolatility, and low switching energy because of a filamentforming free switching. Additionally, these devices give a high level of accuracy to emulate the synaptic functionalities because synaptic weight update modulated by the gate terminal while the read operation performed on a channel.Recently, several reports show the synaptic behavior by adding and extracting the oxygen (O 2− ) or proton (H + ) in a channel from the electrolyte layer. [17,19,21,22] Both oxygen and proton-based synaptic transistors show unstable behavior and non-linearity due to the structural deformation of a channel as well as the electrolyte layer by mobile H + and O 2− ion. The advantage of using Li + ion in IST is due to more excellent Lithium nanoionic transistors have recently emerged as promising artificial synaptic devices for neuromorphic hardware systems. However, mimicking the essential synaptic functionalities including nonvolatile conductance modulation with a near-linear analog weight update has been a crucial milestone in those synaptic devices and has a direct impact on pattern recognition accuracy. The volatile channel conductance change due to the instability of the solid electrolyte interface and lithium-ion nucleation at electrolyte-channel interface are two key phenomena responsible for the nonlinear switching in lithium nanoionics transistor. Graphene is proposed as an atomically thin ionic tunneling layer to establish nonvolatile analog multilevel conduction in lithium nanoionic transisto...

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High‐Voltage Lithium‐Metal Batteries Enabled by Localized High‐Concentration Electrolytes

Cited by 823 publications

References 41 publications

Localized High‐Concentration Electrolytes Boost Potassium Storage in High‐Loading Graphite

Localized High‐Concentration Electrolytes Boost Potassium Storage in High‐Loading Graphite

Lithium‐Pretreated Hard Carbon as High‐Performance Sodium‐Ion Battery Anodes

Controlled Ionic Tunneling in Lithium Nanoionic Synaptic Transistor through Atomically Thin Graphene Layer for Neuromorphic Computing

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