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Macroporous Thick Tin Foil Negative Electrode via Chemical Etching for Lithium-ion Batteries

화학적 식각을 통해 제조한 리튬이온 이차전지용 고용량 다공성 주석후막 음극

  • Kim, Hae Been (Graduate School of Knowledge-Based Technology and Energy, Korea Polytechnic University) ;
  • Lee, Pyung Woo (Department of Chemical Engineering and Biotechnology, Korea Polytechnic University) ;
  • Lee, Dong Geun (Department of Chemical Engineering and Biotechnology, Korea Polytechnic University) ;
  • Oh, Ji Seon (Department of Chemical Engineering and Biotechnology, Korea Polytechnic University) ;
  • Ryu, Ji Heon (Graduate School of Knowledge-Based Technology and Energy, Korea Polytechnic University)
  • 김해빈 (한국산업기술대학교지식기반기술.에너지대학원) ;
  • 이평우 (한국산업기술대학교생명화학공학과) ;
  • 이동근 (한국산업기술대학교생명화학공학과) ;
  • 오지선 (한국산업기술대학교생명화학공학과) ;
  • 류지헌 (한국산업기술대학교지식기반기술.에너지대학원)
  • Received : 2019.02.04
  • Accepted : 2019.02.15
  • Published : 2019.02.28

Abstract

A macroporous Sn thick film as a high capacity negative electrode for a lithium ion secondary battery was prepared by using a chemical etching method using nitric acid for a Sn film having a thickness of $52{\mu}m$. The porous Sn thick film greatly reduced the over-voltage for the alloying reaction with lithium by the increased reaction area. At the same time. The porous structure of active Sn film plays a part in the buffer and reduces the damage by the volume change during cycles. Since the porous Sn thick film electrode does not require the use of the binder and the conductive carbon black, it has substantially larger energy density. As the concentration of nitric acid in etching solution increased, the degree of the etching increased. The etching of the Sn film effectively proceeded with nitric acid of 3 M concentration or more. The porous Sn film could not be recovered because the most of Sn was eluted within 60 seconds by the rapid etching rate in the 5 M nitric acid. In the case of etching with 4 M nitric acid for 60 seconds, the appropriate porous Sn film was formed with 48.9% of weight loss and 40.3% of thickness change during chemical acid etching process. As the degree of etching of Sn film increased, the electrochemical activity and the reversible capacity for the lithium storage of the Sn film electrode were increased. The highest reversible specific capacity of 650 mAh/g was achieved at the etching condition with 4 M nitric acid. The porous Sn film electrode showed better cycle performance than the conventional electrode using a Sn powder.

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Fig. 1. (a) The weight loss ratio and (b) thickness change of thick Sn film after chemical etching according to the concentration of nitric acid.

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Fig. 3. FE-SEM images of the chemically-etched Sn foils for 60 seconds: (a) pristine, (b) 2 M HNO3, (c) 3 M HNO3, and (d) 4 M HNO3.

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Fig. 4. 3D-profiles from optical microscope of the chemically-etched Sn foils for 60 seconds: (a) 2 M HNO3, (b) 3 M HNO3, and (c) 4 M HNO3.

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Fig. 5. (a) The galvanostatic charge/discharge voltage profiles and (b) the differential discharge capacity plots at first cycle obtained from Li/Sn-film half-cells.

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Fig. 2. Optical microscope images of the chemicallyetched Sn foils for 60 seconds: (a) pristine, (b) 2 M HNO3, (c) 3 M HNO3, and (d) 4 M HNO3.

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Fig. 6. The dealloying (discharge) capacity delivered by Li/Sn-film and Li/Sn-powder half-cells.

Acknowledgement

Supported by : 한국연구재단

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