열전지용 리튬음극의 전기화학적 특성

임채남; 윤현기; 안태영; 여재성; 하상현; 유혜련; 백승수; 조장현; Chae-Nam Im; Hyun Ki Yoon; Tae-Young Ahn; Jae Seong Yeo; Sang Hyeon Ha; Hye-Ryeon Yu; Seungsu Baek; Jang Hyeon Cho

Applied Chemistry for Engineering, Vol.29, No.6, 696-702, December, 2018

DOI10.14478/ace.2018.1048 Export Citation

열전지용 리튬음극의 전기화학적 특성

Electrochemical Properties of Lithium Anode for Thermal Batteries

임채남, 윤현기, 안태영, 여재성, 하상현, 유혜련, 백승수, 조장현^†

국방과학연구소 제4기술연구본부 4부

Chae-Nam Im, Hyun Ki Yoon, Tae-Young Ahn, Jae Seong Yeo, Sang Hyeon Ha, Hye-Ryeon Yu, Seungsu Baek, and Jang Hyeon Cho^†

The 4th R&D Institute, 4, Agency for Defense Development, Yuseong P.O.Box 35, Daejeon 34060, Korea

E-mail:

초록

최근 열전지는 우주 및 국방분야에서 활용하기 위하여 고출력 및 고에너지 밀도의 새로운 전극재료가 요구되는 실정이다. 본 논문에서는 성형성과 용량의 한계를 가지는 펠릿 타입의 리튬-실리콘 합금(Li(Si)) 음극을 대체하기 위하여 고밀도를 가지는 리튬음극을 제조하고, 단위전지 및 열전지의 전기화학적 성능에 미치는 영향을 고찰하였다. 리튬음극은 500 ℃에서 안정적인 작동을 위하여 철 분말을 바인더로 사용하였고 리튬 중량별(17, 15, 13 wt%) 단위전지 성능평가를 통해 리튬 13 wt%에서 안정적인 성능을 확인하였다. 또한 리튬음극을 사용한 단위전지의 개회로전압이 2.06V로 Li(Si) 음극 개회로전압 1.93 V에 비해 약 0.1 V 이상 높게 나타났고, first phase에서 리튬음극의 비용량은 1,632As.g-1로 Li(Si) 음극의 비용량 1,181 As.g-1에 비해 약 1.4배 정도 성능이 향상됨을 확인하였다. 리튬음극을 적용한 열전지를 상온 및 고온 성능시험 결과를 통하여 Li(Si) 음극 열전지에 비해 전압 및 작동시간 등이 탁월하며, 출력특성 및 에너지밀도가 획기적으로 향상됨을 확인하였다.

Recently, the current thermal battery technology needs new materials for electrodes in the power and energy density to meet various space and defense requirements. In this paper, to replace the pellet type Li(Si) anode having limitations of the formability and capacity, electrochemical properties of the lithium anode with high density for thermal batteries were investigated. The lithium anode (Li 17, 15, 13 wt%) was fabricated by mixing the molten lithium and iron powder used as a binder to hold the molten lithium at 500 ℃. The single cell with 13 wt% lithium showed a stable performance. The 2.06 V (OCV) of the lithium anode was significantly improved compared to 1.93 V (OCV) of the Li(Si) anode. Specific capacities during the first phase of the lithium anode and Li(Si) were 1,632 and 1,181 As.g-1, respectively. As a result of the thermal battery performance test at both room and high temperatures, the voltage and operating time of lithium anode thermal batteries were superior to those of using Li(Si) anode thermal batteries. The power and energy densities of Li anode thermal batteries were also remarkably improved.

Keywords:thermal battery;electrochemical properties;Li anode;Li(Si) anode

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[1] Guidotti RA, Masset P, J. Power Sources, 161(2), 1443 (2006)

[2] Choi Y, Cho S, Lee YS, J. Ind. Eng. Chem., 20(5), 3584 (2014)

[3] Choi Y, Yu HR, Cheong H, Cho S, Lee YS, Appl. Chem. Eng., 25(2), 161 (2014)

[4] Reisner DE, Xiao TD, Ye H, Dai J, Guidotti RA, Reinhardt FW, J. New Mater. Electrochem. Syst., 2, 279 (1999)

[5] Gevorkyan AG, Cohen R, Raz O, 47th Power Sources Conference, 390-392, Orlando, FL, USA (2016).

[6] Harney D, Thin film thermal batteries, 44th Power Sources Conference, 669-671, Las Vegas, NV, USA (2010).

[7] Guidotti RA, Masset PJ, J. Power Sources, 183(1), 388 (2008)

[8] Bowser GC, Moser JR, Molten metal anode, US Patent 3,930,888 (1976).

[9] Machodo D, Golan S, Londner I, Jacobsohn E, Fe-Li-Al anode composite and termal battery containing the same, US Patent 7,354,678 (2008).

[10] Briscoe JD, Durliat E, Salver-Disma F, Stewart I, 42nd Power Sources Conference, 117-120, Philadelphia, PA, USA (2006).

[11] Clark AJ, Thaler C, Stewart I, Reid J, 39th Power Sources Conference, June, Cherry Hill, USA (2000).

[12] Sweeney JR, Mckirdy I, Comrie R, Stewart I, Aerospace Energetic Equipment Conference, Avignon, France (2004).

[13] Choi YS, Yu HR, Cheong HW, J. Power Sources, 276, 102 (2015)

[14] Klasons V, Lamb CM, Thermal batteries, in: Handbook of Batteries, 21.1-21.22, McGraw-Hill, USA (2002).

[15] Masset P, Guidotti RA, J. Power Sources, 177, 509 (2008)

[16] Fujiwara S, Inaba M, Tasaka A, J. Power Sources, 196(8), 4012 (2011)

[17] Masset P, Schoeffert S, Poinso JY, Poignet JC, J. Electrochem. Soc., 152(2), A405 (2005)

[18] Fujiwara S, Inaba M, Tasaka A, J. Power Sources, 195(22), 7691 (2010)