Crystallographic Engineering Enables Fast Low‑Temperature Ion Transport of TiNb2O7 for Cold‑Region Lithium‑Ion Batteries

Crystallographic Engineering Enables Fast Low‑Temperature Ion Transport of TiNb2O7 for Cold‑Region Lithium‑Ion Batteries
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Crystallographic Engineering Enables Fast Low-Temperature Ion Transport of TiNb2O7 for Cold-Region Lithium-Ion Batteries - Nano-Micro Letters

TiNb2O7 represents an up-and-coming anode material for fast-charging lithium-ion batteries, but its practicalities are severely impeded by slow transfer rates of ionic and electronic especially at the low-temperature conditions. Herein, we introduce crystallographic engineering to enhance structure stability and promote Li+ diffusion kinetics of TiNb2O7 (TNO). The density functional theory computation reveals that Ti4+ is replaced by Sb5+ and Nb5+ in crystal lattices, which can reduce the Li+ diffusion impediment and improve electronic conductivity. Synchrotron radiation X-ray 3D nano-computed tomography and in situ X-ray diffraction measurement confirm the introduction of Sb/Nb alleviates volume expansion during lithiation and delithiation processes, contributing to enhancing structure stability. Extended X-ray absorption fine structure spectra results verify that crystallographic engineering also increases short Nb-O bond length in TNO-Sb/Nb. Accordingly, the TNO-Sb/Nb anode delivers an outstanding capacity retention rate of 89.8% at 10 C after 700 cycles and excellent rate performance (140.4 mAh g−1 at 20 C). Even at −30 °C, TNO-Sb/Nb anode delivers a capacity of 102.6 mAh g−1 with little capacity degeneration for 500 cycles. This work provides guidance for the design of fast-charging batteries at low-temperature condition.

As fast-charging lithium-ion batteries race toward sub-zero markets, the anode bottleneck—graphite plating risk and Li4Ti5O12 capacity ceiling—intensifies. Now, researchers from Harbin Institute of Technology, led by Prof. Yan Zhang and Prof. Shuaifeng Lou, unveil an Sb/Nb co-doped TiNb2O7 (TNO) anode that unlocks 140 mAh g-1 at 20 C and 500 stable cycles at −30 °C. Published in Nano-Micro Letters, the work delivers a practical pouch cell delivering 1.14 Ah at 17 C with 93.8 % retention after 700 cycles.

Why Crystallographic Engineering Matters

  • Band-Gap Narrowing: Sb5+substitution lowers the gap from 1.83 → 1.64 eV, doubling intrinsic electronic conductivity.
  • Li⁺ Highway Expansion: Nb5+ enlarges lattice parameters a & c, cutting diffusion barrier from 0.96 → 0.74 eV along the b-axis.
  • Low-T Robustness: Stronger Sb–O bonds (6.51 vs 6.13 eV ICOHP) suppress lattice distortion, holding volume swing to 9 % versus 9.5 % in pristine TNO.

Innovative Design & Features

  • Single-Step Solid-State Route: Commercial Sb2O3+ Nb2O5 co-dope at 1100 °C yields 500 nm–2 µm rod crystals without secondary phases.
  • Multi-Scale Verification: In-situ XRD tracks solid-solution → two-phase → solid-solution pathway; synchrotron 3D nano-CT shows crack-free grains after 500 cycles at −30 °C.
  • Pseudocapacitive Boost: 92 % capacitive contribution at 1 mV s-1 enables 102 mAh g-1 at −30 °C with 99.96 % CE.

Applications & Future Outlook

  • Pouch-Cell Validation: TNO-Sb/Nb || NCM (N/P 1.05) delivers 94 Wh kg-1, 243 Wh L-1and 0.0089 % fade per cycle at 3 C.
  • Extreme Climate Suitability: Stable from −40 °C (101 mAh g-1, 0.2 C) to high-rate 20 C, outperforming 14 reported TNO variants.
  • Scalable Pathway: Earth-abundant dopants and ambient-air synthesis position the material for gigafactory adoption in cold-region EVs and aviation.

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Batteries
Physical Sciences > Materials Science > Materials for Energy and Catalysis > Batteries
Electrochemistry
Physical Sciences > Chemistry > Physical Chemistry > Electrochemistry
Nanoengineering
Technology and Engineering > Biological and Physical Engineering > Nanoengineering
Nanoscale Design, Synthesis and Processing
Physical Sciences > Materials Science > Nanotechnology > Nanoscale Design, Synthesis and Processing
Density Functional Theory
Physical Sciences > Chemistry > Theoretical Chemistry > Density Functional Theory
  • Nano-Micro Letters Nano-Micro Letters

    Nano-Micro Letters is a peer-reviewed, international, interdisciplinary and open-access journal that focus on science, experiments, engineering, technologies and applications of nano- or microscale structure and system in physics, chemistry, biology, material science, and pharmacy.