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Research Papers

In Situ Imaging of Lithium-Ion Batteries Via the Secondary Ion Mass Spectrometry

[+] Author and Article Information
Cheng-Kai ChiuHuang

Mechanical and Aerospace
Engineering Department,
North Carolina State University,
R3311 Engineering Building 3,
Campus Box 7910, 911 Oval Drive,
Raleigh, NC 27695
e-mail: cchiuhu@ncsu.edu

Chuanzhen Zhou

Analytical Instrumentation Facility,
North Carolina State University,
Raleigh, NC 27695

Hsiao-Ying Shadow Huang

Mechanical and Aerospace
Engineering Department,
North Carolina State University,
R3311 Engineering Building 3,
Campus Box 7910, 911 Oval Drive,
Raleigh, NC 27695

1Corresponding author.

Manuscript received April 1, 2014; final manuscript received July 10, 2014; published online August 19, 2014. Assoc. Editor: Arunkumar Subramanian.

J. Nanotechnol. Eng. Med 5(2), 021002 (Aug 19, 2014) (5 pages) Paper No: NANO-14-1027; doi: 10.1115/1.4028010 History: Received April 01, 2014; Revised July 10, 2014

To develop lithium-ion batteries with a high rate-capability and low cost, the prevention of capacity loss is one of major challenges, which needs to be tackled in the lithium-ion battery industry. During electrochemical processes, lithium ions diffuse from and insert into battery electrodes accompanied with the phase transformation, whereas ionic diffusivity and concentration are keys to the resultant battery capacity. In the current study, we compare voltage versus capacity of lithium-ion batteries at different current-rates (C-rates) discharging. Larger hysteresis and voltage fluctuations are observed in higher C-rate samples. We investigate origins of voltage fluctuations by quantifying lithium-ion intensity and distribution via a time-of-flight secondary ion mass spectrometry (ToF-SIMS). The result shows that for fully discharged samples, lithium-ion intensity and distribution are not C-rate dependent, suggesting different lithium-ion insertion mechanisms at a higher C-rate discharging might be solely responsible for the observed low frequency voltage fluctuation.

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Figures

Grahic Jump Location
Fig. 2

Images of the sample surface (a) before and (b) after the sputtering process. The crater size is 80 × 80 μm2, and the analysis area is 10 × 10 μm2 in the middle of the sample to avoid the crater effects.

Grahic Jump Location
Fig. 1

Schematic of the ToF-SIMS technique for imaging lithium-ion intensity and distribution. The time required for atoms/molecules to hit the mass detector is calculated and the spectra of mass to charge ratio is obtained (inset).

Grahic Jump Location
Fig. 3

Voltage versus capacity curves at different C-rates (1 C, 2 C, 6 C, and 10 C) for commercial 26650 cylindrical LiFePO4 lithium-ion batteries. The voltage gap increases with increasing C-rate. Inset: linear trend lines between the capacities of 0.005 and 0.025 (A h/g). An increase in downward slope is observed from 1 C to 6 C. In addition, what appeared to be a low frequency (approx. 0.02 Hz) voltage fluctuation is observed in the 10 C sample. Note: The capacity is calculated based on the cell weight rather than pure electrode materials.

Grahic Jump Location
Fig. 4

Normalized intensity/counts depth-profiles of two positive ions (i.e., Fe+ and 6Li+) at different C-rates for each tested sample

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Fig. 5

Ratios of Li+/Fe+ measured at different C-rates and it is observed that the depth-profile is not entirely C-rate dependent. It is also observed that a 6Li+ deficiency exists on the material surface (between the depth of 500 and 1000 nm), and it could be due to the removal of over-potential upon finishing discharging.

Grahic Jump Location
Fig. 6

ToF-SIMS images (128 μm × 128 μm) showing the intensity distribution of two positive ions (i.e., 6Li+ and Fe+) at different C-rates. (a) 6Li+ and (b) Fe+ intensity distributions of 1 C sample # 3. (c) 6Li+ and (d) Fe+ intensity distributions of 6 C sample # 3. (e) 6Li+ and (f) Fe+ intensity distributions of 10 C sample # 3. For different C-rate samples, similar maximum intensities of 6Li+ (ca 250) and Fe+ (ca 76) are observed, suggesting the intensity distribution is C-rate independent for fully discharged samples.

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