Antiperovskite Li<sub>3</sub>OCl Superionic Conductor Films for Solid‐State Li‐Ion Batteries

Lu, Xiaofeng; Howard, John W; Chen, Aiping; Zhu, Jinlong; Li, Shuai; Wu, Gang; Dowden, P. C.; Xu, Hongwu; Zhao, Yusheng; Jia, Q. X.

doi:10.1002/advs.201500359

Cited by 177 publications

(94 citation statements)

References 25 publications

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“…The determined composition of the lithium hydroxyl chloride synthesized by our reaction protocol was nearly Li 2 OHCl (see the Experimental Section and Figure S1 of the Supporting Information), which shows virtually no deviation from stoichiometry. The overlay of 1 H − , 16 O − , 37 Cl − , and 7 Li + clearly indicates uniform lateral distribution. In addition to NMR, we used TOF-SIMS imaging to reveal the lateral distribution of four elements of interest on the surface of the SSEs, such as H, O, Cl, and Li in case of Li 2 OHCl ( Figure 1C).…”

Section: Elemental Compositionmentioning

confidence: 92%

“…The overlay of 1 H − , 16 O − , 37 Cl − , and 7 Li + clearly indicates uniform lateral distribution. In the positive mode m/z spectrum ( Figure 1E) the intensity of 7 Li + ions is three orders of magnitude higher than other positive species, indicating that there is no detectable contamination by other metals. The existence of high intensity OH − proves the presence of hydroxyl ions in Li 2 OHCl.…”

Section: Elemental Compositionmentioning

confidence: 92%

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Protons Enhance Conductivities in Lithium Halide Hydroxide/Lithium Oxyhalide Solid Electrolytes by Forming Rotating Hydroxy Groups

Song

Xiao

Turcheniuk

et al. 2017

Advanced Energy Materials

119

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Li‐halide hydroxides (Li2OHX) and Li‐oxyhalides (Li3OX) have emerged as new classes of low‐cost, lightweight solid state electrolytes (SSE) showing promising Li‐ion conductivities. The similarity in the lattice parameters between them, careless synthesis, and insufficient rigor in characterization often lead to erroneous interpretations of their compositions. Finally, moisture remaining in the synthesis or cell assembling environment and variability in the equivalent circuit models additionally contribute to significant errors in their properties. Thus, there remains a controversy about the real values of Li‐ion conductivities in such SSEs. Here an ultra‐fast synthesis and comprehensive material characterization is utilized to report on the ionic conductivities of contaminant‐free Li2+xOH1−xCl (x=0‐0.7), and Li2OHBr not exceeding 10‐4 S cm‐1 at 110 °C. Using powerful combination of experimental and numerical approaches, it is demonstrated that the presence of H in these SSEs yields significantly higher Li+ ‐ionic conductivity. Born‐Oppenheimer molecular dynamics simulations show excellent agreement with experimental results and reveal an unexpected mechanism for faster Li+ transport. It involves rotation of a short OH‐group in SSEs, which opens lower‐energy pathways for the formation of Frenkel defects and highly‐correlated Li+ jumps. These findings will reduce the existing confusions and show new avenues for tuning SSE compositions for further improved Li‐ion conductivities.

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Section: Elemental Compositionmentioning

confidence: 92%

Section: Elemental Compositionmentioning

confidence: 92%

Protons Enhance Conductivities in Lithium Halide Hydroxide/Lithium Oxyhalide Solid Electrolytes by Forming Rotating Hydroxy Groups

Song

Xiao

Turcheniuk

et al. 2017

Advanced Energy Materials

119

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“…[1][2][3][4][5][6] Titanium dioxide (TiO 2 ) emerges as a promising anode material for LIBs owing to its low-cost, nontoxicity, excellent chemical stability, superior safety, high rate performance and good cycling performance. [1][2][3][4][5][6] Titanium dioxide (TiO 2 ) emerges as a promising anode material for LIBs owing to its low-cost, nontoxicity, excellent chemical stability, superior safety, high rate performance and good cycling performance.…”

Section: Introductionmentioning

confidence: 99%

Titanium dioxide nanotrees for high-capacity lithium-ion microbatteries

Wen

Jiang

et al. 2016

J. Mater. Chem. A

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Li-ion microbatteries find wide applications in microdevices. It is of importance to develop electrode materials with high areal capacity, excellent rate capability and superior safety for microbatteries. TiO 2 nanowire arrays satisfy the requirements of high areal capacity, short transport lengths and superior safety for microbatteries, but their areal/volumetric capacity is hindered by the insufficient surface area. TiO 2 nanotrees can effectively eliminate these disadvantages of TiO 2 nanowires; however, the electrochemical performances of TiO 2 nanotrees for Li-ion microbatteries remain unexplored. It is highly desired yet challenging to construct two-dimensional TiO 2 nanobranches with ultrathin thickness and large length on nanoarrays, to maximize the surface area and structural hierarchy of electrodes. Herein, we developed a novel synthetic strategy to fabricate TiO 2 nanotrees by depositing anatase/TiO 2 (B) mixed phase ultrathin nanobelts onto single-crystalline anatase nanowire arrays. The nanobelt branches were several nanometers in thickness and 200-260 nm in length. The growth process and the electrochemical mechanism were investigated. The unique nanoarchitecture and optimal phase structure endow the electrode with high areal capacity and rate capability, which is the best performance for TiO 2 nanowire arrays ever documented. The 2nd discharge capacity of the TiO 2 nanotrees at 0.1 mA cm -2 is ca. 267 μAh cm -2 , corresponding to a volumetric capacity of 330 mAh cm -3 . The TiO 2 nanotrees have an areal capacity of 205, 141, 97 and 69 μAh cm -2 at the current density of 0.5, 2.0, 5.0 and 10.0 mA cm -2 , respectively. The capacity can maintain stable for 400 charge-discharge cycles at 1.0 mA cm -2. The present strategy may give hints to elegant electrode designs for energy applications.This journal is

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“…Deiseroth et al in 2008, [157] also is also a fast lithium conductor. [161] However, purified phases and large-scale manufacturing are hard to be achieved during their preparation. [158,159] The lithium argyrodites have a very wide electrochemical window (0-7 V vs Li/Li + ), [159] suggesting their encouraging application in the ASSLIBs.…”

Section: Othersmentioning

confidence: 99%

“…The in situ TEM technique for battery research, first reported by J.Y. 2019, 9,1901810 (3-(4)) × 10 −4 [165] 2.17-4.21 [163] >2.4 [166] P, LiTiPO 5 , AlPO 4 ,Li 3 PO 4 [163] O 2 , LiTi 2 (PO 4 ) 3 , Li 4 P 2 O 7 , AlPO 4 [163] LAGP Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 1.8 × 10 −4 [167] 2.70-4.27 [163] 0.85-6.2 [168] Ge, GeO 2 , Li 4 1.71-2.01 [163] 7 [159] P, Li 2 S, LiCl [163] Li 3 PS 4 , LiCl, S [163] Li 7 P 2 S 8 I 6.3 × 10 −4 [172] 1.71-2.31 [163] 10 [172] P, Li 2 S, LiI [163] LiI, S, P 2 S 5 [163] Antiperovskite Li 3 OCl 8.5 × 10 −4 [173] ->5 [161] -- (Figure 7a-c), preventing the c-LLZO from being further reduced while maintaining a facile Li + transport. C. Ma et al [175] introduced in situ TEM to find that the cubic-Li 7−3x Al x La 3 Zr 2 O 12 (c-LLZO) was unstable against Li.…”

Section: Dynamic Characterization Of the Sse/electrode Interfacesmentioning

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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Antiperovskite Li₃OCl Superionic Conductor Films for Solid‐State Li‐Ion Batteries

Cited by 177 publications

References 25 publications

Protons Enhance Conductivities in Lithium Halide Hydroxide/Lithium Oxyhalide Solid Electrolytes by Forming Rotating Hydroxy Groups

Protons Enhance Conductivities in Lithium Halide Hydroxide/Lithium Oxyhalide Solid Electrolytes by Forming Rotating Hydroxy Groups

Titanium dioxide nanotrees for high-capacity lithium-ion microbatteries

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

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Antiperovskite Li3OCl Superionic Conductor Films for Solid‐State Li‐Ion Batteries

Cited by 177 publications

References 25 publications

Protons Enhance Conductivities in Lithium Halide Hydroxide/Lithium Oxyhalide Solid Electrolytes by Forming Rotating Hydroxy Groups

Protons Enhance Conductivities in Lithium Halide Hydroxide/Lithium Oxyhalide Solid Electrolytes by Forming Rotating Hydroxy Groups

Titanium dioxide nanotrees for high-capacity lithium-ion microbatteries

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

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Antiperovskite Li₃OCl Superionic Conductor Films for Solid‐State Li‐Ion Batteries