Improving the Li-ion conductivity and air stability of cubic Li7La3Zr2O12 by the co-doping of Nb, Y on the Zr site

Gai, Jianli; Zhao, Erqing; Ma, Feifei; Sun, Dongping; Ma, Xiangyuan; Jin, Yongcheng; Wu, Qingliu; Cui, Yongjie

doi:10.1016/j.jeurceramsoc.2017.12.002

Cited by 117 publications

(44 citation statements)

References 32 publications

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“…After the Li + /H + ion exchange upon exposure to aqueous solutions was observed in lithium‐garnet‐type powders, the effect of air exposure (mainly moisture and CO 2 ) was investigated for dense Li 7 La 3 Zr 2 O 12 [ 231 ] and Al‐, [ 136,229,230,233 ] Ta‐, [ 232 ] Ga‐, [ 244 ] Nb‐, [ 245 ] and Nb/Y [ 246 ] ‐doped LLZO pellets. The garnet‐type LLZO structure is thermodynamically unstable when exposed to ambient (dry to humid) air, leading to the formation of a lithium carbonate (Li 2 CO 3 ) contamination layer and higher interfacial resistance at the Li/LLZO interface.…”

Section: Solid Electrolytes: Sulfides and Oxidesmentioning

confidence: 99%

Solid‐State Li–Metal Batteries: Challenges and Horizons of Oxide and Sulfide Solid Electrolytes and Their Interfaces

Kim

Balaish

Wadaguchi

et al. 2020

Advanced Energy Materials

447

355

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lightweight, and compact and allow for versatile device geometries. They must also be scalable and offer high energy density to provide improved packing efficiency and longer device operation. Although both Ni-MH batteries and LIBs have been commercialized since the 1990s, [1] LIBs possess twice the gravimetric/volumetric energy density (250 Wh kg −1 /700 Wh L −1 vs 170 Wh kg −1 /350 Wh L −1 ), [2] higher battery voltage (3.7 V vs 1.2 V), and longer cycle life with lower self-discharge, [3] contributing tremendously to the proliferation of portable electronic devices (e.g., mobile phones, laptops, cameras, tablets) as well as emerging new technologies such as wearable electronic devices (e.g., smart watches and sport-related tracking devices). Their high gravimetric/ volumetric energy density, [2] excellent cycle life (thousands of cycles), and lack of the memory effect have positioned LIBs as state-of-the-art power sources and one of the greatest successes of modern electrochemistry, revolutionizing the way we acquire, process, transmit, and share information globally. Nevertheless, advances in battery energy density, safety, costs, and flexibility in shape and size are still needed to keep up with the rapidly growing demand for devices with even longer runtime as well as real-time data collection and transmission capabilities in addition to increasingly energy-demanding applications such as electric vehicles (EVs) and electricity grid storage. Even though LIBs were first commercialized in all electric vehicles (EVs) in 2010 and also emerged for grid application in the same time frame, the low energy density (≈250 Wh kg −1 ) and high average cost (≈$156 kWh −1 in 2019) of conventional LIBs do not meet the requirements for advanced EVs and grid-scale energy storage. [4][5][6] Specifically, the driving range per charge (miles), which is related to the energy density of each cell, and the cost are important parameters for EVs. For example, one 85 kWh battery pack in a Tesla Model S requires 7104 LIB cells, with an energy density of 265 Wh kg −1 , providing an average range of 250 miles, which is ahead of the range of other EVs but still behind the target of 375 miles. [4] In grid-scale applications, LIBs can be used for various tasks: frequency regulation, peak shaving, load leveling, and large-scale integration of renewable energies, with specific properties generally required for each task. For frequency regulation, LIBs need to provide a fast response, high rate performance, and high-power capability,The introduction of new, safe, and reliable solid-electrolyte chemistries and technologies can potentially overcome the challenges facing their liquid counterparts while widening the breadth of possible applications. Through tech-historic evolution and rationally analyzing the transition from liquidbased Li-ion batteries (LIBs) to all-solid-state Li-metal batteries (ASSLBs), a roadmap for the development of a successful oxide and sulfide-based ASSLB focusing on interfacial challenges is introduced, while accounting ...

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Section: Solid Electrolytes: Sulfides and Oxidesmentioning

confidence: 99%

Solid‐State Li–Metal Batteries: Challenges and Horizons of Oxide and Sulfide Solid Electrolytes and Their Interfaces

Kim

Balaish

Wadaguchi

et al. 2020

Advanced Energy Materials

447

355

View full text Add to dashboard Cite

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“…The Li + conductivity ( σ ) equals to the concentration of removable Li + ( n c ) multiply by elementary charge ( e ), and multiply by mobility of Li + ( μ ) (

σ = n_{normalc} \cdot e \cdot μ false)

. Therefore, Li + concentration and the mobility have great effect on Li + conductivity.…”

Section: Introductionmentioning

confidence: 99%

“…The Li + conductivity (σ) equals to the concentration of removable Li + (n c ) multiply by elementary charge (e), and multiply by mobility of Li + (μ) ( = n c ⋅ e ⋅ ). 20 Therefore, Li + concentration and the mobility have great effect on Li + conductivity. A lot of research have found that when Li + concentration is approximate 6.4 moles, the LLZO exhibits the highest Li + conductivity.…”

mentioning

confidence: 99%

Dual regulation of Li⁺ migration of Li_6.4La₃Zr_1.4M_0.6O₁₂ (M = Sb, Ta, Nb) by bottleneck size and bond length of M−O

et al. 2019

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Bottleneck size is the minimum Li+ migration channel of Li7La3Zr2O12 (LLZO) and it greatly influences the Li+ conductivity. Doping different elements on the Zr site of LLZO can adjust the bottleneck size and improve the Li+ conductivity. However, the regulation mechanism is not clear. In this work, Li6.4La3Zr1.4M0.6O12 (M = Sb, Ta, Nb) has been prepared and the bottleneck size has been adjusted by doping different pentavalent ions. The results manifest that the cell parameter and bottleneck size decrease with the rise of the radius of doped pentavalent ions. This is because larger pentavalent ion leads to larger bond length of M–O, and weaker covalent component between M5+ and O2‐, corresponding, the formal charge on the M5+ become larger, and the bond length of La–O slightly decreases due to the coulomb repulsion between La3+ and M5+ increase. While, the activation energy drop firstly and then rise with the rise of bottleneck size because of the migration of Li+ not only relate to the size of the migration channel but also to the strength of M–O covalent bonding. The bottleneck size and bond length of M–O synergistically affect the migration of Li+.

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“…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. [70] …”

mentioning

confidence: 99%

“…[67,68] When paired with Li metal, a high resistance (Figure 2f) usually takes place at the LLZO/Li interface due to these reaction products. [70] [70] …”

mentioning

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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Improving the Li-ion conductivity and air stability of cubic Li7La3Zr2O12 by the co-doping of Nb, Y on the Zr site

Cited by 117 publications

References 32 publications

Solid‐State Li–Metal Batteries: Challenges and Horizons of Oxide and Sulfide Solid Electrolytes and Their Interfaces

Solid‐State Li–Metal Batteries: Challenges and Horizons of Oxide and Sulfide Solid Electrolytes and Their Interfaces

Dual regulation of Li⁺ migration of Li_6.4La₃Zr_1.4M_0.6O₁₂ (M = Sb, Ta, Nb) by bottleneck size and bond length of M−O

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

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Improving the Li-ion conductivity and air stability of cubic Li7La3Zr2O12 by the co-doping of Nb, Y on the Zr site

Cited by 117 publications

References 32 publications

Solid‐State Li–Metal Batteries: Challenges and Horizons of Oxide and Sulfide Solid Electrolytes and Their Interfaces

Solid‐State Li–Metal Batteries: Challenges and Horizons of Oxide and Sulfide Solid Electrolytes and Their Interfaces

Dual regulation of Li+ migration of Li6.4La3Zr1.4M0.6O12 (M = Sb, Ta, Nb) by bottleneck size and bond length of M−O

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

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Dual regulation of Li⁺ migration of Li_6.4La₃Zr_1.4M_0.6O₁₂ (M = Sb, Ta, Nb) by bottleneck size and bond length of M−O