分子滴定策略:利用内置电场检测 LiFePO4 中的锂扩散系数

IF 2.9 3区 化学 Q3 CHEMISTRY, PHYSICAL
Zexin Lin, Zhihao Deng, Xianrun Cao, Lu Guo, Feifei Zhang, Sheng Liu, Juezhi Yu and Gangfeng Ouyang
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引用次数: 0

摘要

电滴定技术一直被用于检测电极材料的Li+扩散系数。然而,受电极添加剂、电池组装方法的影响,特别是对反应区域的不准确评估往往导致不可靠的结果。在这里,我们提出了一种分子滴定技术(MTT)来检测LiFePO4中的锂扩散系数(DLi)。该方法减轻了繁琐的电极制备过程,避免了添加剂的影响,修正了实际反应面积误差,缩短了测试时间,使测试比传统的滴定技术更加精确和高效。将[Fe(CN)6]3-溶液滴入LiFePO4固体中,记录溶液的电位变化率(rp)。在此基础上,建立了内置电场(BIEF)电子传递模型,并利用Huggins-Weppner方程建立了DLi与rp之间的关系。最后,根据记录的数据和建立的公式,测试了Li1-xFePO4(1≤x≤0)的去锂化扩散系数为1~8×10-15 cm2/s。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

A molecular titration strategy: utilizing a built-in electric field to measure the lithium diffusion coefficient in LiFePO4†

A molecular titration strategy: utilizing a built-in electric field to measure the lithium diffusion coefficient in LiFePO4†

Electrometric titration techniques have long been used to measure the Li+ diffusion coefficients of electrode materials. However, the influence of electrode additives, cell assembly methods, and in particular, inaccurate assessments of the reaction area often lead to unreliable results. Here, we propose a molecular titration technique (MTT) to measure the lithium diffusion coefficient (DLi) in LiFePO4. This MTT alleviates the tedious electrode preparation procedure, circumvents the influence of additives, reduces the real reaction area errors, and shortens the testing time, making the testing more precise and efficient than the traditional titration techniques. In detail, [Fe(CN)6]3− solution is used to oxidize LiFePO4 to Li+ and FePO4, while the potential change rate (rp) of the solution is recorded. Then, a built-in electric field (BIEF) electron transferring model is established, and the relationship between DLi and rp is formulated using the Huggins–Weppner equation. Eventually, the de-lithiation diffusion coefficient of Li1−xFePO4 (1 ≤ x ≤ 0) is measured to be 1–8 × 10−15 cm2 s−1 based on the recorded data and established formulae.

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来源期刊
Physical Chemistry Chemical Physics
Physical Chemistry Chemical Physics 化学-物理:原子、分子和化学物理
CiteScore
5.50
自引率
9.10%
发文量
2675
审稿时长
2.0 months
期刊介绍: Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.
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