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A study on heat generation characteristics of Na3V2(PO4)3 cathode and hard carbon anode-based sodium-ion cells

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Abstract

We report here the heat generation and impedance characteristics of prototype 18650-sized sodium-ion cells using pristine Na3V2(PO4)3 (P-NVP) and modified Na3.2V1.8Zn0.2(PO4)3 (M-NVP) cathodes, hard carbon (HC) anode and an ether-based non-flammable electrolyte, 1 M NaBF4 in tetraglyme. Comparison of calorimetric studies performed on 18650-sized cells reveals lower heat generation in M-NVP versus HC compared to P-NVP versus HC owing to low internal resistance achieved as a result of Zn2+ doping in M-NVP. Both irreversible heat generation arose due to internal resistance and reversible heat generation caused by entropic changes in the electrode materials are elucidated. Furthermore, variation in subcomponents of internal resistance in both 18650-sized full cells and CR2016-sized half-cells is analysed by fitting electrochemical impedance spectra into equivalent circuit models. Individual contributions of anode and cathode to the impedance characteristics of the cells are determined by analysing impedance data of the half-cells using the distribution of relaxation times method. The results reveal lower diffusion resistance, as well as charge transfer resistance in M-NVP cells compared to P-NVP counterpart, accounting for the observed lower total internal resistance in M-NVP versus HC and thus lower heat generation in M-NVP versus HC cell than P-NVP versus HC cell.

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The raw/processed data required to reproduce these findings cannot be shared at this time as the data also form part of an ongoing study.

Abbreviations

∂U/∂T :

Entropic coefficient/V K−1

C :

Capacitance/F

C p :

Specific heat capacity/kJ kg−1 K−1

\(\frac{{{\text{d}}T}}{{{\text{d}}t}}\) :

Temperature gradient/K s−1

Est. :

Estimated

I :

Current/A

I p :

Pulse current/A

Im:

Imaginary

m :

Mass/kg

Q 1, Q 2 :

Constant phase elements

Q irr :

Irreversible heat generation/J

Q rev :

Reversible heat generation/J

Q total :

Total heat generation/J

R :

Resistance/Ω

R CEI :

Cathode–electrolyte interphase resistance/Ω

R ct :

Charge-transfer resistance/Ω

R d :

Diffusion resistance/Ω

Re:

Real

R i :

Internal resistance/Ω

R s :

Series resistance/Ω

R SEI :

Solid–electrolyte interphase resistance/Ω

R total :

Total resistance/Ω

T :

Instantaneous temperature/K

τ :

Time constant/s

V :

Cell voltage/V

Z :

Impedance/Ω

Δt :

Time step/s

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Acknowledgements

The authors thank the National Research Foundation (under the Energy Programme and administrated by Energy Market Authority), the Ministry of Education in Singapore and the National University of Singapore for funding. LUS thanks the Ministry of Education (MoE) in Singapore for research scholarship and extends his gratitude to Kang Du and Abhinav Tripathi for the support and guidance given.

Funding

This research is supported by National Research Foundation, under the Energy Programme and administrated by Energy Market Authority (EP Award No. NRF2015EWT-EIRP002-017/WBS No. R-265-000-568-279), Ministry of Education in Singapore (WBS No. R-265-000-510-112) and National University of Singapore (WBS No. R-261-510-001-646).

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Authors and Affiliations

  1. Department of Mechanical Engineering, National University of Singapore, Singapore, 117575, Singapore

    Lihil Uthpala Subasinghe, Chen Wang, Satyanarayana Reddy Gajjela, Markas Law, Balasundaram Manikandan & Palani Balaya

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  1. Lihil Uthpala Subasinghe
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Contributions

LUS performed conceptualization, methodology, formal analysis, investigation, visualization, and writing—original draft. CW was involved in methodology, investigation, validation, and supplying 18,650 cells for the study. SRG contributed to methodology, investigation, validation, and resources related to 18,650 cell fabrication, funding acquisition—project schedule and budget planning, and writing—review and editing. ML done conceptualization, methodology, and investigation related to cathode material, and writing—review and editing. BM performed conceptualization, methodology, and resources related to thermal characterization, and writing—review and editing. PB contributed to conceptualization, resources, supervision, project administration, funding acquisition, and writing—review and editing.

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Correspondence to Palani Balaya.

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Subasinghe, L.U., Wang, C., Gajjela, S.R. et al. A study on heat generation characteristics of Na3V2(PO4)3 cathode and hard carbon anode-based sodium-ion cells. J Therm Anal Calorim 147, 8631–8649 (2022). https://doi.org/10.1007/s10973-021-11151-0

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