The safety monitoring of lithium-ion batteries (LIBs) is of great significance for realizing all-climate and full-lifespan battery management. In-situ measurement of anode potential with implanted reference electrodes (REs) has proven to be effective to monitor and avoid the occurrence of severe side reactions like Li plating to ensure the safe and fast charging. However, the intrinsic measurement errors caused by local blocking effects, which also can be referred to as potential artefacts, are seldom taken into consideration in existing studies, yet they highly dominate the correctness of conclusions inferred from REs. In this study, aiming at exploring the physical origin of the measurement errors and ensure reliable potential monitoring, electrochemical and post-mortem tests are conducted using commercial pouch cells with implanted REs. Corresponding electrochemical model which describes the blocking effects, is established to validate the abnormal absence of lithium plating that predicted by measured anode potentials under various charging rates. Theoretical derivation is further presented to explain the error sources, which can be attributed to increased local liquid potential of the RE position. Most importantly, with the guidance of error analysis, a novel parameter-independent error correction method for RE measurements is proposed for the first time, which is proven to be adequate to estimate the real anode potentials and deduce the critical C-rate of Li plating with extra safety margin. After error correction, the resulting critical C-rates are all within the range of 0.55 ± 0.03C, which is close to the C-rate of 0.6–0.7C obtained from experiments. In addition, this error correction method can be performed conveniently with only some simple RE measurements of polarization voltages, totally independent of battery electrochemical and geometric parameters. This study provides highly practical error correction method for RE measurements in real LIBs, substantially facilitating the fast diagnosis and safety evaluation of Li plating during charging of LIBs.

锂离子电池（LIBs）的安全监测对于实现全气候、全寿命电池管理具有重要意义。使用植入式参比电极 (RE) 原位测量阳极电位已被证明可有效监控和避免锂电镀等严重副反应的发生，以确保安全快速充电。然而，由局部阻塞效应引起的固有测量误差，也可以称为潜在的人工制品，在现有研究中很少考虑，但它们在很大程度上决定了从 RE 推断出的结论的正确性。在这项研究中，为了探索测量误差的物理起源并确保可靠的电位监测，电化学和验尸测试使用带有植入 RE 的商用软包电池进行。建立了描述阻塞效应的相应电化学模型，以验证通过在各种充电速率下测量的阳极电位预测的锂镀层的异常缺失。进一步提出了理论推导来解释误差源，这可归因于 RE 位置的局部液体势增加。最重要的是，在误差分析的指导下，首次提出了一种新的与参数无关的稀土测量误差校正方法，该方法被证明足以估计实际阳极电位并推导出锂电镀的临界 C 速率具有额外的安全裕度。纠错后，得到的临界 C-rate 均在 0.55±0.03C 范围内，接近实验获得的 C-rate 0.6-0.7C。此外，这种误差校正方法可以方便地执行，只需对极化电压进行一些简单的 RE 测量，完全独立于电池电化学和几何参数。该研究为实际LIBs中RE测量提供了高度实用的误差校正方法，大大促进了LIBs充电过程中锂电镀的快速诊断和安全评估。