Cr3+ and Nb5+ co-doped Ti2Nb10O29 materials for high-performance lithium-ion storage

Yang, Changchun; Yu, Sun; Ma, Yu; Lin, Chunfu; Xu, Zhihao; Zhao, Hua; Wu, Shunqing; Zheng, Peng; Zhu, Zhaowu; Li, Jianbao; Wang, Ning

doi:10.1016/j.jpowsour.2017.06.026

Cited by 90 publications

(64 citation statements)

References 34 publications

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“…The unpaired electrons in the Cr 3+ 3d orbitals easily transported in the γ‐LCSVO lattice, thus effectively increasing its electronic conductivity. [ 8 ] A galvanostatic intermittent titration technique (GITT) was employed to study Li + diffusivity. The GITT curves of γ‐LCSVO‐MP, γ‐LSVO, and β‐LVO are showed in Figure 2g and Figure S8a,c in the Supporting Information, respectively, and their corresponding Li + diffusion coefficients ( D Li ) calculated using the Fick's second law are illustrated in Figure 2h and Figure S8b,d in the Supporting Information.…”

Section: Resultsmentioning

confidence: 99%

Conductive Li_3.08Cr_0.02Si_0.09V_0.9O₄ Anode Material: Novel “Zero‐Strain” Characteristic and Superior Electrochemical Li⁺ Storage

Liang

Yang

Han

et al. 2020

Advanced Energy Materials

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some issues, such as insufficient battery longevity, safety risks, and limited driving ranges/speeds. [1] Thus, high-performance LIBs with long-term cycle life, good safety, and high energy/power densities are pursued. Particularly, the cycle life is essential in actual applications. Capacity decay of LIBs primarily derives from the fact that electrode materials generally suffer mechanical stresses since the strains associated with phase transitions or lattice-parameter variations during Li + insertion-extraction are generally obvious. Mismatched lattice parameters between dominated and coexisting phases in two-phase reactions or large unitcell volume variations in solid-solution reactions can lead to the fracture phase interfaces, thus significantly contributing to the capacity decay. These issues can be completely avoided in "zero-strain" electrode materials whose unit-cell volume variations are negligible (<1%) during discharging-charging. Spinel Li 4 Ti 5 O 12 , a typical "zero-strain" anode material, has been demonstrated for thousands cycles in LIBs. This excellent cycling stability stems from its tiny volume variation (≈0.2%) upon cycling. [2] Other "zero-strain" anode materials, such as LiCrTiO 4 and LiY(MoO 4 ) 2 , also present decent cycling stability. [3] Clearly, "zero-strain" materials are ideal for a long operational energy storage. To the best of our knowledge, however, the very limited "zero-strain" anode materials explored for LIBs so far commonly present small reversible capacities "Zero-strain" compounds are ideal energy-storage materials for long-term cycling because they present negligible volume change and significantly reduce the mechanically induced deterioration during charging-discharging. However, the explored "zero-strain" compounds are very limited, and their energy densities are low. Here, γ phase Li 3.08 Cr 0.02 Si 0.09 V 0.9 O 4 (γ-LCSVO) is explored as an anode compound for lithium-ion batteries, and surprisingly its "zero-strain" Li + storage during Li + insertion-extraction is found through using various state-of-the-art characterization techniques. Li + sequentially inserts into the 4c(1) and 8d sites of γ-LCSVO, but its maximum unitcell volume variation is only ≈0.18%, the smallest among the explored "zero-strain" compounds. Its mean strain originating from Li + insertion is only 0.07%. Consequently, both γ-LCSVO nanowires (γ-LCSVO-NW) and micrometer-sized particles (γ-LCSVO-MP) exhibit excellent cycling stability with 90.1% and 95.5% capacity retention after as long as 2000 cycles at 10C, respectively. Moreover, γ-LCSVO-NW and γ-LCSVO-MP respectively deliver large reversible capacities of 445.7 and 305.8 mAh g −1 at 0.1C, and retain 251.2 and 78.4 mAh g −1 at 10C. Additionally, γ-LCSVO shows a suitably safe operating potential of ≈1.0 V, significantly lower than that of the famous "zero-strain" Li 4 Ti 5 O 12 (≈1.6 V). These merits demonstrate that γ-LCSVO can be a practical anode compound for stable, high-energy, fast-charging, and safe Li + storage.The ORCID identificati...

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Section: Resultsmentioning

confidence: 99%

Conductive Li_3.08Cr_0.02Si_0.09V_0.9O₄ Anode Material: Novel “Zero‐Strain” Characteristic and Superior Electrochemical Li⁺ Storage

Liang

Yang

Han

et al. 2020

Advanced Energy Materials

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“…For calibration of measurement data, small amount of AB powders were mixed into both TNO‐A and TNO‐V in the analysis. As shown in Figure A, two peaks of Ti 2P 1/2 and Ti 2P 3/2 spectra in TNO‐A are observed at binding energy around 465.3 and 459.7 eV, suggesting that the existence and occupying of Ti 4+ in an octahedral environment . These peaks are confirmed in TNO‐V, but Ti 2P 3/2 spectrum in TNO‐V slightly shifts toward lower binding energy compared to TNO‐A, indicating that small amounts of Ti 4+ in TNO‐V are reduced to Ti 3+ caused by introduction of oxygen vacancy .…”

Section: Resultsmentioning

confidence: 82%

“…These peaks are confirmed in TNO‐V, but Ti 2P 3/2 spectrum in TNO‐V slightly shifts toward lower binding energy compared to TNO‐A, indicating that small amounts of Ti 4+ in TNO‐V are reduced to Ti 3+ caused by introduction of oxygen vacancy . In Figure B for Nb 3d spectra, two peaks located at 208.1 eV for Nb 3d 5/2 and 210.9 eV for Nb 3d 3/2 are confirmed in TNO‐A indicating the presence of Nb 5+ . These two peaks are also detected in TNO‐V, but the peak shift toward lower binding energy due to the presence of Nb 4+ caused by introduction of oxygen vacancy are quite small, so the presence of Nb 4+ in V‐TNO could not be characterized enough.…”

Section: Resultsmentioning

confidence: 94%

“…Moreover, these oxides are nontoxic and more importantly, their redox potential should avoid possible lithium plating. To date, the electrochemical properties for various niobium‐based oxides have been reported . Among them, mixed titanium‐niobium oxides TiNb 2 O 7 , Ti 2 Nb 10 O 29 , and TiNb 24 O 62 have high theoretical capacity around 390‐400 mAh g −1 due to Ti 4+/3+ , Nb 5+/4+ , and Nb 4+/3+ redox couples .…”

Section: Introductionmentioning

confidence: 99%

“…Cu 2+ , Ru 4+ , and Mo 6+ doping is confirmed to be effective to improve electrochemical performance for TiNb 2 O 7 . Cr 3+ and Nb 5+ co‐doped Ti 2 Nb 10 O 29 shows mush superior electrochemical performance to non‐doped one . In addition, electrochemical properties of Ti 2 Nb 10 O 29 can be improved greatly by introducing oxygen vacancy in the crystal structure .…”

Section: Introductionmentioning

confidence: 99%

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Characterization of vacuum‐annealed TiNb₂O₇ as high potential anode material for lithium‐ion battery

Inada

Mori

Kumasaka

et al. 2018

Int J Applied Ceramic Tech

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Electrochemical properties of mixed titanium‐niobium oxide TiNb2O7 (TNO) synthesized via vacuum annealing as high potential anode material for lithium‐ion batteries were investigated. Crystal structure, size, and morphology are nearly independent of the annealing atmosphere for starting materials but the color of vacuum‐annealed TNO (TNO‐V) is dark blue while white for the air‐annealed one (TNO‐A). X‐ray photoelectron spectroscopy analysis also indicated that Ti4+ and Nb5+ in TNO are partially reduced into Ti3+ and Nb4+ due to the introduction of oxygen vacancy. Electronic conductivity for TNO‐V was around 10−3 S cm−1 at room temperature and much higher than that for TNO‐A (=10−11 S cm−1). In electrochemical testing, both TNO‐A and TNO‐V electrodes showed reversible capacity of 260‐270 mAh g−1 at low current density of 0.5 mA cm−2, while at higher current density of 5.0 mA cm−2, TNO‐V electrode retained higher reversible capacity of 140 mAh g−1 than that for TNO‐A electrode (=80 mAh g−1). The enhancement of intrinsic electronic conductivity greatly contributes to improve the rate performance of TNO.

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Synergy of Ion Doping and Spiral Array Architecture on Ti₂Nb₁₀O₂₉: A New Way to Achieve High‐Power Electrodes

Deng

Zhu

Liu

et al. 2020

Adv Funct Materials

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Ameliorating electronic/ionic transport and structural stability of electrode materials is important to the development of power‐intensive lithium ion batteries. Despite its great potential as a high‐power anode, titanium niobium oxide (Ti2Nb10O29, TNO) still underperforms due to its unsatisfactory electronic/ionic conductivity. In this work, a powerful synergistic strategy by combining ion doping and spiral array architecture to boost high‐rate performance of TNO is reported. Cr3+ doped TNO nanoparticles (Cr‐TNO) of 5–10 nm intimately grow on a conductive vertical graphene@TiC‐C (VGTC) skeleton, forming novel Cr‐TNO@VGTC spiral arrays. The unique spiral growth of TNO is achieved due to the confinement effect of VGTC skeleton. Meanwhile, a more open TNO crystal structure with faster ion transfer paths and enhanced structural stability is realized by Cr3+ doping, demonstrated via density functional theory calculation and in situ synchrotron X‐ray diffraction technique. Benefiting from the superior conductive network, enhanced intrinsic electronic/ionic conductivity of Cr‐TNO and reinforced structural stability, the Cr‐TNO@VTC arrays show prominent high‐power performance with a large capacity of 220 mAh g−1 at 40 C (power density of ≈11 kW kg−1) and superior durability (91% retention after 500 cycles). This work provides a new path for the construction of widespread high‐power electrodes for fast energy storage.

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Cr3+ and Nb5+ co-doped Ti2Nb10O29 materials for high-performance lithium-ion storage

Cited by 90 publications

References 34 publications

Conductive Li_3.08Cr_0.02Si_0.09V_0.9O₄ Anode Material: Novel “Zero‐Strain” Characteristic and Superior Electrochemical Li⁺ Storage

Conductive Li_3.08Cr_0.02Si_0.09V_0.9O₄ Anode Material: Novel “Zero‐Strain” Characteristic and Superior Electrochemical Li⁺ Storage

Characterization of vacuum‐annealed TiNb₂O₇ as high potential anode material for lithium‐ion battery

Synergy of Ion Doping and Spiral Array Architecture on Ti₂Nb₁₀O₂₉: A New Way to Achieve High‐Power Electrodes

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Cr3+ and Nb5+ co-doped Ti2Nb10O29 materials for high-performance lithium-ion storage

Cited by 90 publications

References 34 publications

Conductive Li3.08Cr0.02Si0.09V0.9O4 Anode Material: Novel “Zero‐Strain” Characteristic and Superior Electrochemical Li+ Storage

Conductive Li3.08Cr0.02Si0.09V0.9O4 Anode Material: Novel “Zero‐Strain” Characteristic and Superior Electrochemical Li+ Storage

Characterization of vacuum‐annealed TiNb2O7 as high potential anode material for lithium‐ion battery

Synergy of Ion Doping and Spiral Array Architecture on Ti2Nb10O29: A New Way to Achieve High‐Power Electrodes

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Product

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Conductive Li_3.08Cr_0.02Si_0.09V_0.9O₄ Anode Material: Novel “Zero‐Strain” Characteristic and Superior Electrochemical Li⁺ Storage

Conductive Li_3.08Cr_0.02Si_0.09V_0.9O₄ Anode Material: Novel “Zero‐Strain” Characteristic and Superior Electrochemical Li⁺ Storage

Characterization of vacuum‐annealed TiNb₂O₇ as high potential anode material for lithium‐ion battery

Synergy of Ion Doping and Spiral Array Architecture on Ti₂Nb₁₀O₂₉: A New Way to Achieve High‐Power Electrodes