Feasibility of Using Active Batteries for Munitions Applications

Transcription

1 Feasibility of Using Active Batteries for Munitions Applications Dr. Jeffrey Read 7-Dec-2016

2 Outline Background ARL Active battery systems Long term storage data Li/CF x batteries Li/SOCl 2 Liquid cathode batteries Possible Research Areas Active Cathode Studies Electrolyte additives for Li passivation Cathode collector / corrosion protection

3 Electrochemistry ARL Energy Storage Technology Team (5PIs, 2 PD) High voltage and high capacity materials for increased energy density in Li-ion batteries Multiscale modeling of electrode/electrolyte interactions Dielectric materials for high energy and high power storage Advanced Battery Chemistry Team (4 PIs, 1 PD) Single ion conducting ceramic materials that enable new battery chemistries Li/S and Li/Air. Electrolytes and electrolyte additives for high voltage systems Grid storage chemistries (dual intercalation, molten Li/S) Hybrid Li-ion systems Aqueous Battery Team (2 PI s 3 PD) Aqueous Li-ion systems Nanostructured conversion electrodes for Li-ion batteries Rechargeable chemistries focusing on Li and Mg metal systems Fuel Cell Team (6 PIs, 1 PD) Development of non-noble electrocatalysts for acid-alkaline fuel cell. Modeling and simulation methods to understand transport phenomena in hybrid membrane fuel cell. Alkaline membrane electrolyte assembly (MEA) performance Alternate Routes to Fuel (1PI, 1PD) H 2 production from Photosystem I, wide bandgap semiconductors Effects of plasmonics on catalysis

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5 Battery Systems Conversion cathode New Systems Primary Li/SOCl 2 Br 2 -Cl 2 Primary Li/SOCl 2 (Li/S, Li/MnO 2 )

6 Conventional Thinking Shelf life of active batteries Linden, Handbook of Batteries, sec. 6.11, 7.20

7 Storage Studies Li/FeS 2 Energizer L91 crimp sealed cell Storage at 43C, 53C, and 63C 6 months Discharge at 23C, -40C, and 60C (0.5 A) voltage (V) C discharge time (min) 60 C discharge initial, pre-shock (SN 257) 0.9 initial, post-shock (SN 089) Discharged 43C for 6 mo (SN 158) } at ambient 53C for 6 mo (SN 090) 63C for 6 mo (SN 128) C for 6 mo (SN 220) Discharged 53C for 6 mo (SN 250) } at 60 C 63C for 6 mo (SN 139) Ambient temperature and 60 C discharges of L91 batteries stored at 43 C, 53 C, and 63 C for 6 months. Initial discharges at ambient temperature before and after thermal shock are also shown voltage (V) C storage R. Lennen, B. Poese, J. Swank, A. Goldberg, 42 nd Power Sources Conference, Paper C storage time (min) 43 C storage 43C storage (SN 029) 43C storage (SN 077) 43 storage (SN 167) 53C storage (SN 293) 53C storage (SN 328) 53C storage (SN 061) 63C storage (SN 251) 63C storage (SN 125) -40 C discharges of L91 batteries stored at 43 C, 53 C, and 63 C for 6 months.

8 Li/FeS y = x R 2 = E a = kj/mol (activation energy of diffusion) ln(mass loss (g)) /T(K) Complex plots of impedance to 0.1 Hz minimum frequency for thermally shocked batteries stored at 63 C for 6 months. Arrhenius dependence of mass losses in batteries stored at different temperatures for 6 months Storage ambient humidity 95% rel. humidity temperature m (g) m (g) 23 C ± C ± ± C ± ± C ± ± Average 6 month weight losses (errors are 95% confidence intervals about the mean) R. Lennen, B. Poese, J. Swank, A. Goldberg, 42 nd Power Sources Conference, Paper 5.2 Electrolyte is diffusing out and water in though the crimp seal Difficult to characterize Li/FeS 2 chemistry with these cells Need to be hermetically sealed cells

9 Storage Studies Li/MnO 2, Li/CF x, Li/SOCl 2 Estimated RT shelf life vs. 20 year goal Store at 75C Reliability test: RT, 400Ω, 5 s Discharge through 5000 Ω Li/MnO 2 (6 models, crimp) 5-15 year shelf life Li/CF x (crimp) 22 year shelf life Li/CF x (crimp and encapsulated) 40+ year shelf life Li/SOCl 2 (crimp) 1 year shelf life Li/SOCl 2 (hermetic) 20+ year shelf life Air Gun tests 30,000g set-back Li/CF x (crimp and encapsulated) No change in CCV Li/SOCl 2 (hermetic) Battery type M5 C2 T V change in CCV Position Before air gun firing Open Circuit Voltage Closed Circuit Voltage Ri (Ω) After air gun firing Open Circuit Voltag Closed Circuit Voltage Ri (Ω) Horizontal Vertical Vertical Horizontal Horizontal Vertical Vertical Horizontal Horizontal Vertical Vertical M. Templeman, J. Swank, 37 th Power Sources Conference, p T3 Horizontal Vertical

10 Storage Studies Li/CF x Store from RT to 90C, 2-15 years Discharge testing post storage Titanium collectors, graphite coated Glass-metal seals Discharge capacity better under 80C discharge.

11 Li/CF x Noble metals coated on titanium current collectors for use in nonaqueous Li/CF x cells, TAKEUCHI E.S., Patent EP (A2), US (A1) Ir and Pt sputtered Titanium collectors reduce impedance, even after 100C storage. Large Impedance growth between Titanium collector and graphite coating Capacity loss is due to Titanium oxidation and subsequent deposition on the Li anode Fateev, Russian Journal of Electrochemistry, 36 (7) 2000

12 Li/SOCl 2 Discharge reaction (moderate rate) 4 Li + 2SOCl 2 4 LiCl + S + SO 2 Li Passivation Direct reaction / passivation by SOCl 2 (LiCl film) LiCl film can be easily disturbed High temperature storage thickens the film and increases voltage delay Electrolyte purity has a strong effect on voltage delay/capacity loss Li alloys improve voltage recovery post storage PCl 5 and CaCl 2 reduce Li anode passivation during storage at 71C. Ca metal plates on the Li and provides excellent passivation Driscoll, Brummer, Gudrais, Holleck, Toland, ECOM F, DAAB07-74-C-0030

13 Requirements / Reserve Batteries Requirements 20 year shelf 70C -40C / +70C operation Fast Rise Time (10 s 100 s ms) Typical Liquid Reserve Battery Limited size Low Energy Density ( 5 Wh/l ) Moderate Power Density Active Primary batteries rated 5-20 year shelf 20C -40C / +70C operation 1% 20C: Li-MnO 2 1% 20C: SOCl 2 0.5% 20C: Li-CF x Typical Primary Battery Small Size Single cell High Energy Density Low Power Density

14 Possible Battery Research Inherent stability of specific cathode materials: CF x, MnO 2, and SOCl 2 Corrosion of collectors in presence of cathodes Collector passivation, collector coating Lithium anode passivation, electrolyte additives Wide operating temperature range electrolytes Can Active batteries be useful for reserve type applications? Focus on solid cathode systems first (CF x, MnO 2 ) Look at low rate discharge as possible fix for Li passivation in solid cathode batteries Hybrid Power design Low rate Lithium + Supercapacitor Li/I 2, Li/CF x

15 Thank You Jeff Read, (301)