Transient Behavior of the Metal Interface in Lithium Metal–Garnet Batteries

Fu, Kun; Gong, Yunhui; Fu, Zhezhen; Hu, Liangbing; Yao, Yonggang; Liu, Boyang; Carter, Marcus; Wachsman, Eric D.; Hu, Liangbing

doi:10.1002/anie.201708637

Cited by 260 publications

(156 citation statements)

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“…Interestingly, the interfacial resistance decreases to 12 Ω cm 2 after 100 cycles at 200 µA cm −2 and 60 °C (Figure a), which is due to the improved contact between metallic Li and the SE (Figure S5b, Supporting Information). The interfacial resistance in our work is comparable to or even lower than those at the Li/oxide SE interfaces, although interfacial modifications with Al 2 O 3 (≈1 Ω cm 2 ), Al (≈75 Ω cm 2 ), Mg (≈70 Ω cm 2 ), Carbon (≈105 Ω cm 2 ), and polymer (≈220 Ω cm 2 ) were conducted in previous works.…”

Section: Resultssupporting

confidence: 59%

“…It is difficult for an individual polymer or oxide to achieve fast lithium ion transportation both in the SE and across the electrode/SE interface. Therefore, interfacial modifications, such as Al 2 O 3 , Mg, and carbon, which can alloy with metallic Li, were used to lower the interfacial resistance between metallic Li and oxide‐based SEs. Furthermore, Goodenough and co‐workers created a polymer/ceramic/polymer sandwich‐structured electrolyte to decrease the resistances at the Li/SE and cathode/SE interfaces .…”

Section: Introductionmentioning

confidence: 99%

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Nanostructured Metal–Organic Framework (MOF)‐Derived Solid Electrolytes Realizing Fast Lithium Ion Transportation Kinetics in Solid‐State Batteries

Guo

2019

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107

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Solid‐state batteries are hindered from practical applications, largely due to the retardant ionic transportation kinetics in solid electrolytes (SEs) and across electrode/electrolyte interfaces. Taking advantage of nanostructured UIO/Li‐IL SEs, fast lithium ion transportation is achieved in the bulk and across the electrode/electrolyte interfaces; in UIO/Li‐IL SEs, Li‐containing ionic liquid (Li‐IL) is absorbed in Uio‐66 metal–organic frameworks (MOFs). The ionic conductivity of the UIO/Li‐IL (15/16) SE reaches 3.2 × 10−4 S cm−1 at 25 °C. Owing to the high surface tension of nanostructured UIO/Li‐IL SEs, the contact between electrodes and the SE is excellent; consequently, the interfacial resistances of Li/SE and LiFePO4/SE at 60 °C are about 44 and 206 Ω cm2, respectively. Moreover, a stable solid conductive layer is formed at the Li/SE interface, making the Li plating/stripping stable. Solid‐state batteries from the UIO/Li‐IL SEs show high discharge capacities and excellent retentions (≈130 mA h g−1 with a retention of 100% after 100 cycles at 0.2 C; 119 mA h g−1 with a retention of 94% after 380 cycles at 1 C). This new type of nanostructured UIO/Li‐IL SEs is very promising for solid‐state batteries, and will open up an avenue toward safe and long lifespan energy storage systems.

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Section: Resultssupporting

confidence: 59%

Section: Introductionmentioning

confidence: 99%

Nanostructured Metal–Organic Framework (MOF)‐Derived Solid Electrolytes Realizing Fast Lithium Ion Transportation Kinetics in Solid‐State Batteries

Guo

2019

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107

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“…[26,32,33] Quite a number of studies reported on lithium alloying interlayers, such as Ge, Al, Sn, Au, Si, Mg, and Ag, aiming to improve the interface kinetics. [24,39,41,42] Thus one must assume that most of the interlayers mainly act as contact mediator during cell assembly and new solutions need to be found to address and circumvent the vacancy diffusion limitation of lithium metal anodes. [41,42] A closer look shows that the operating principle of alloys and alloy interlayers is still not well understood.…”

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

318

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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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“…On the other hand, the coating layer should be as thin as possible (nanometers) to decrease the migration distance of Li + ions. K. Fu et al [203] employed the vapor decomposition method to prepare an ultrathin Mg layer (5-100 nm) on the LLZO. Some metallic and nonmetallic elements can be employed to modify the SSEs.…”

Section: Interface Engineering To Minimize the Interfacial Resistancementioning

confidence: 99%

Section: Interface Engineering To Minimize the Interfacial Resistancementioning

confidence: 99%

Interfacial Incompatibility and Internal Stresses in All‐Solid‐State Lithium Ion Batteries

Liu

et al. 2019

Advanced Energy Materials

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The continuous depletion of fossil fuels, the increase of oil prices, and the need to decrease CO 2 emissions have stimulated intensive research on developing alternative renewable and clean energy sources. [1] Among these alternative energy sources, rechargeable Li-ion batteries (LIBs) are one of the promising candidates. To date, the LIBs basically consisting of a positive electrode (cathode), an electrolyte, and a negative electrode (anode) have widespread applications, such as portable electronic devices, pure electric vehicles (PEVs), and hybrid electric vehicles (HEVs). [2] The state-of-the-art electrolytes are usually the lithium salts (LiPF 6 , LiBF 4 , and LiCF 3 SO 3 ) dissolved in organic solvents, i.e., ethylene carbonate, propylene carbonate, polyethylene oxide, and dimethyl carbonate, [3] which exhibit excellent wetting of the electrodes and produce a fast transfer of Li + ions upon charging and discharging. However, they suffer from flammability, poor electrochemical stability, limited temperature range of operation, and low power density. [4] There is an ever-increasing demand for batteries with a higher energy and power density, although current LIBs offer volumetric and gravimetric energy densities up to 770 Wh L −1 and 260 Wh kg −1 , respectively. [5] To improve the energy/power density of LIBs, one way is to adopt high-potential cathode materials such as LiNi 0.5 Mn 1.5 O 4 (LNMO). The high-voltage plateau of LNMO (≈4.7 V vs Li/Li + ) makes its energy density 20-30% higher than the energy density of commercial LiCoO 2 and LiFePO 4 . [6] However, successful commercialization of the LNMO is restricted in high-energy LIBs due to electrolyte decomposition and side reaction of the cathodes and liquid electrolytes when operating at high voltages. [7,8] The other way to improve the energy/power density is to replace the conventional graphite anode with Li metal. The Li metal, with a low anode potential (−3.04 V vs standard hydrogen electrode) and high specific capacity (3862 mAh g −1 for the Li anode versus 372 mAh g −1 for the graphite anode), [9][10][11] has been considered as the "Holy Grail" of battery technologies. When paired with sulfur and oxygen, the theoretical energy density of Li-S (≈2567 Wh kg −1 ) and Li-O 2 (≈3505 Wh kg −1 ) batteries is far higher than the theoretical energy density of conventional LIBs (≈387 Wh kg −1 ). [12][13][14][15] When Li metal approaches the liquid electrolytes, however, unstable Li/electrolyte interface Rechargeable Li-ion batteries (LIBs) are electrochemical storage device widely applied in electric vehicles, mobile electronic devices, etc. However, traditional LIBs containing liquid electrolytes suffer from flammability, poor electrochemical stability, and limited operational temperature range. Replacement of the liquid electrolytes with inorganic solid-state electrolytes (SSEs) would solve this problem. However, several critical issues, such as poor interfacial compatibility, low ionic conductivity at ambient temperatures, etc., need to be surmounted befor...

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Transient Behavior of the Metal Interface in Lithium Metal–Garnet Batteries

Cited by 260 publications

References 46 publications

Nanostructured Metal–Organic Framework (MOF)‐Derived Solid Electrolytes Realizing Fast Lithium Ion Transportation Kinetics in Solid‐State Batteries

Nanostructured Metal–Organic Framework (MOF)‐Derived Solid Electrolytes Realizing Fast Lithium Ion Transportation Kinetics in Solid‐State Batteries

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

Interfacial Incompatibility and Internal Stresses in All‐Solid‐State Lithium Ion Batteries

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