Li+/Na+ Ion Exchange in Layered Na2/3(Ni0.25Mn0.75)O2: A Simple and Fast Way to Synthesize O3/O2-Type Layered Oxides

Hua, Weibo; Wang, Shuaiwei; Wang, K.; Missyul, Alexander; Fu, Qiang; Darma, Mariyam Susana Dewi; Li, H.; Baran, Volodymyr; Liu, Laijun; Kübel, Christian; Binder, Joachim R.; Knapp, Michael; Ehrenberg, Helmut; Indris, Sylvio

doi:10.1021/acs.chemmater.1c00962

Cited by 18 publications

(23 citation statements)

References 57 publications

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“…NNO is typically produced from NiO and Na 2 O 2 or Na 2 O at elevated temperatures under oxidizing conditions − for studying its magnetic and electrochemical properties. − Because of the large size difference between Na + ( r = 1.02 Å) and Ni 2+ /Ni 3+ [ r (Ni 2+ ) = 0.69 Å, r (Ni 3+ ) = 0.56 Å], they separate readily into different layers, without formation of interlayer occupancy defects. Overall, NNO represents an attractive parent compound for topotactic ion exchange (Na + vs Li + ), which has already been demonstrated for other layered materials. − …”

Section: Introductionmentioning

confidence: 78%

Low-Temperature Ion Exchange Synthesis of Layered LiNiO₂ Single Crystals with High Ordering

et al. 2023

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Layered Ni-rich oxide cathode materials are being explored in an effort to boost the energy density of lithium-ion batteries, especially for automotive applications. Among them, the ternary-phase LiNiO2 (LNO) is a promising candidate but brings along various issues, such as poor structural stability. The material is prone to disordering (Li off-stoichiometry) when prepared by conventional solid-state synthesis, leading to the presence of Ni2+ in the Li layer. These point defects negatively affect the utilization of the Li inventory, thereby limiting the practical specific capacity. In this work, we report on a two-step synthesis approach that avoids the formation of nickel substitutional defects. First, NaNiO2 (NNO) is prepared, showing no such defects due to larger differences in ionic radii between Ni2+/Ni3+ and Na+. NNO is then subjected to Na+/Li+ exchange under mild conditions. In so doing, monolithic LNO particles free of NiLi • defects can be produced at relatively low temperatures. Notably, this route allows for tailoring of the grain size, a strategy that may be used to gain insights into the structure–size–property relations in single-crystalline LNO.

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Section: Introductionmentioning

confidence: 78%

Low-Temperature Ion Exchange Synthesis of Layered LiNiO₂ Single Crystals with High Ordering

et al. 2023

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“…[ 39,40 ] The Li + /Na + ion‐exchange reaction is a type of chemical reaction in which Na‐containing substances react with Li salt solutions to selectively remove Na‐ions and replace them with Li‐ions from the solution. [ 41 ] As a consequence, the obtained Li‐containing materials possess a crystallographic structure, particle morphology, and size similar to their Na analogues. Inspired by the motives described above, this work uses single‐crystalline layered Na 2/3 [Ni 0.25 Mn 0.75 ]O 2 as a starting material to controllably synthesize Co‐free Li‐rich layered Li[Li 0.2 Ni 0.2 Mn 0.6 ]O 2 single crystals (LLNMO‐SC).…”

Section: Introductionmentioning

confidence: 99%

Structural Origin of Suppressed Voltage Decay in Single‐Crystalline Li‐Rich Layered Li[Li_0.2Ni_0.2Mn_0.6]O₂ Cathodes

Yang

Wang

Han

et al. 2022

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electric vehicles (HEVs), next-generation lithium-ion batteries (LIBs) that utilize high-energy cathode materials are crucially needed. [1][2][3] Among various types of cathode materials, Li-and Mn-rich layered oxides (LMLOs) are regarded as one of the most promising cathode candidates owing to their high capacity (≥250 mAh g −1 ) and low cost. [4][5][6][7] The high capacity of LMLOs is widely believed to originate predominantly from the reversible cationic and anionic redox activities, [8][9][10] which remarkably overcome the capacity limitations of conventional cathode materials (<200 mAh g −1 ) like olivine LiFePO 4 (space group: Pnma), [11,12] spinel LiMn 2 O 4 (Fd3m), [13,14] and layered Li[Ni,Co,Mn]O 2 (NCM, square brackets represent transition metal ions located on octahedral positions, R3m) [15][16][17][18] because of the sole transition metal (TM) redox activity in these cathodes. Nevertheless, LMLOs always undergo a severe voltage decay upon cycling, [19,20] which seriously hinders the practical application of LMLOs. Over the last two decades, a series of attempts have been made to reveal the underlying structural degradation mechanism and mitigate the voltage decay during extended cycling.Lithium-and manganese-rich layered oxides (LMLOs, ≥ 250 mAh g −1 ) with polycrystalline morphology always suffer from severe voltage decay upon cycling because of the anisotropic lattice strain and oxygen release induced chemo-mechanical breakdown. Herein, a Co-free single-crystalline LMLO, that is, Li[Li 0.2 Ni 0.2 Mn 0.6 ]O 2 (LLNMO-SC), is prepared via a Li + /Na + ionexchange reaction. In situ synchrotron-based X-ray diffraction (sXRD) results demonstrate that relatively small changes in lattice parameters and reduced average micro-strain are observed in LLNMO-SC compared to its polycrystalline counterpart (LLNMO-PC) during the charge-discharge process. Specifically, the as-synthesized LLNMO-SC exhibits a unit cell volume change as low as 1.1% during electrochemical cycling. Such low strain characteristics ensure a stable framework for Li-ion insertion/extraction, which considerably enhances the structural stability of LLNMO during long-term cycling. Due to these peculiar benefits, the average discharge voltage of LLNMO-SC decreases by only ≈0.2 V after 100 cycles at 28 mA g −1 between 2.0 and 4.8 V, which is much lower than that of LLNMO-PC (≈0.5 V). Such a single-crystalline strategy offers a promising solution to constructing stable high-energy lithium-ion batteries (LIBs).

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“…Since MMT is in the form of two-dimensional nanosheets, the movement of Li + on the MMT interlayer might change its layer spacing. However, the XRD of ordinary light sources cannot distinguish these kinds of small changes [41,42]. Thus, we used the high-resolution SRD of the CMP/ VAMMT to measure the interlayer space of MMT before and after cycling 5 times of charge and discharge at 0.1 mA cm −2 in the symmetrical Li||Li cells.…”

Section: Understanding LI + Transport Machnism In Cmp/ Vammtmentioning

confidence: 99%

Quasi-Solid-State Ion-Conducting Arrays Composite Electrolytes with Fast Ion Transport Vertical-Aligned Interfaces for All-Weather Practical Lithium-Metal Batteries

Wang

et al. 2022

Nano-Micro Lett.

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The rapid improvement in the gel polymer electrolytes (GPEs) with high ionic conductivity brought it closer to practical applications in solid-state Li-metal batteries. The combination of solvent and polymer enables quasi-liquid fast ion transport in the GPEs. However, different ion transport capacity between solvent and polymer will cause local nonuniform Li+ distribution, leading to severe dendrite growth. In addition, the poor thermal stability of the solvent also limits the operating-temperature window of the electrolytes. Optimizing the ion transport environment and enhancing the thermal stability are two major challenges that hinder the application of GPEs. Here, a strategy by introducing ion-conducting arrays (ICA) is created by vertical-aligned montmorillonite into GPE. Rapid ion transport on the ICA was demonstrated by 6Li solid-state nuclear magnetic resonance and synchrotron X-ray diffraction, combined with computer simulations to visualize the transport process. Compared with conventional randomly dispersed fillers, ICA provides continuous interfaces to regulate the ion transport environment and enhances the tolerance of GPEs to extreme temperatures. Therefore, GPE/ICA exhibits high room-temperature ionic conductivity (1.08 mS cm−1) and long-term stable Li deposition/stripping cycles (> 1000 h). As a final proof, Li||GPE/ICA||LiFePO4 cells exhibit excellent cycle performance at wide temperature range (from 0 to 60 °C), which shows a promising path toward all-weather practical solid-state batteries.

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Li⁺/Na⁺ Ion Exchange in Layered Na_2/3(Ni_0.25Mn_0.75)O₂: A Simple and Fast Way to Synthesize O3/O2-Type Layered Oxides

Cited by 18 publications

References 57 publications

Low-Temperature Ion Exchange Synthesis of Layered LiNiO₂ Single Crystals with High Ordering

Low-Temperature Ion Exchange Synthesis of Layered LiNiO₂ Single Crystals with High Ordering

Structural Origin of Suppressed Voltage Decay in Single‐Crystalline Li‐Rich Layered Li[Li_0.2Ni_0.2Mn_0.6]O₂ Cathodes

Quasi-Solid-State Ion-Conducting Arrays Composite Electrolytes with Fast Ion Transport Vertical-Aligned Interfaces for All-Weather Practical Lithium-Metal Batteries

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Li+/Na+ Ion Exchange in Layered Na2/3(Ni0.25Mn0.75)O2: A Simple and Fast Way to Synthesize O3/O2-Type Layered Oxides

Cited by 18 publications

References 57 publications

Low-Temperature Ion Exchange Synthesis of Layered LiNiO2 Single Crystals with High Ordering

Low-Temperature Ion Exchange Synthesis of Layered LiNiO2 Single Crystals with High Ordering

Structural Origin of Suppressed Voltage Decay in Single‐Crystalline Li‐Rich Layered Li[Li0.2Ni0.2Mn0.6]O2 Cathodes

Quasi-Solid-State Ion-Conducting Arrays Composite Electrolytes with Fast Ion Transport Vertical-Aligned Interfaces for All-Weather Practical Lithium-Metal Batteries

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Li⁺/Na⁺ Ion Exchange in Layered Na_2/3(Ni_0.25Mn_0.75)O₂: A Simple and Fast Way to Synthesize O3/O2-Type Layered Oxides

Low-Temperature Ion Exchange Synthesis of Layered LiNiO₂ Single Crystals with High Ordering

Low-Temperature Ion Exchange Synthesis of Layered LiNiO₂ Single Crystals with High Ordering

Structural Origin of Suppressed Voltage Decay in Single‐Crystalline Li‐Rich Layered Li[Li_0.2Ni_0.2Mn_0.6]O₂ Cathodes