Feasibility of Using Active Batteries for Munitions ......Dr. Jeffrey Read 7-Dec-2016. UNCLASSIFIED UNCLASSIFIED The Nation’s Premier Laboratory for Land Forces Background ... 12/8/2016

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UNCLASSIFIED The Nation’s Premier Laboratory for Land ForcesUNCLASSIFIED The Nation’s Premier Laboratory for Land Forces

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Feasibility of Using Active Batteries for Munitions Applications

Dr. Jeffrey Read7-Dec-2016

UNCLASSIFIED

UNCLASSIFIED The Nation’s Premier Laboratory for Land Forces

Background• Electrochemistry @ ARL• Active battery systems• Long term storage data• Li/CFx batteries• Li/SOCl2 Liquid cathode batteries

Possible Research Areas• Active Cathode Studies• Electrolyte additives for Li passivation• Cathode collector / corrosion protection

Outline

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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)• H2 production from Photosystem I, wide bandgap semiconductors• Effects of plasmonics on catalysis

Electrochemistry Research @ ARL

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(Li/S, Li/MnO2)

Primary Li/SOCl2

Primary Li/SOCl2 Br2-Cl2

Battery Systems

Conversion cathode New Systems

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Shelf life of active batteries

Linden, Handbook of Batteries, sec. 6.11, 7.20

Conventional Thinking

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Li/FeS2 • Energizer L91 crimp sealed cell • Storage at 43C, 53C, and 63C 6 months• Discharge at 23C, -40C, and 60C (0.5 A)

0.5

0.7

0.9

1.1

1.3

1.5

0 20 40 60 80 100 120 140

time (min)

volta

ge (V

)

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)

43˚C storage

53˚C storage

63˚C storage

-40˚C discharges of L91 batteries stored at 43˚C, 53˚C, and 63˚C for 6 months.

0.5

0.7

0.9

1.1

1.3

1.5

1.7

0 50 100 150 200 250 300 350 400

time (min)

volta

ge (V

)

initial, pre-shock (SN 257)initial, post-shock (SN 089)43C for 6 mo (SN 158)53C for 6 mo (SN 090)63C for 6 mo (SN 128)43C for 6 mo (SN 220)53C for 6 mo (SN 250)63C for 6 mo (SN 139)

Discharged at ambient

Discharged at 60˚C

23˚Cdischarge

60˚Cdischarge

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

R. Lennen, B. Poese, J. Swank, A. Goldberg, 42nd Power Sources Conference, Paper 5.2

Storage Studies

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Li/FeS2

Complex plots of impedance to 0.1 Hz minimum frequency for thermally shocked batteries stored at 63˚C for 6 months.

ambient humidity 95% rel. humidity∆m (g) ∆m (g)

23˚C 0.0025 ± 0.000143˚C 0.0129 ± 0.0013 0.0182 ± 0.002153˚C 0.0373 ± 0.0030 0.0177 ± 0.001863˚C 0.1178 ± 0.0056 0.0491 ± 0.0114

Storage temperature

Average 6 month weight losses (errors are 95% confidence intervals about the mean)

y = -9425.9x + 25.704

R2 = 0.9847

-7

-6

-5

-4

-3

-2

-1

0

0.00295 0.003 0.00305 0.0031 0.00315 0.0032 0.00325 0.0033 0.00335 0.0034

1/T(K)

ln(m

ass

loss

(g))

Ea = 78.371 kJ/mol(activation energy of diffusion)

Arrhenius dependence of mass losses in batteriesstored at different temperatures for 6 months

• Electrolyte is diffusing out and water in though the crimp seal

• Difficult to characterize Li/FeS2chemistry with these cells

• Need to be hermetically sealed cells

R. Lennen, B. Poese, J. Swank, A. Goldberg, 42ndPower Sources Conference, Paper 5.2

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Li/MnO2, Li/CFx, Li/SOCl2Estimated RT shelf life vs. 20 year goal Store at 75C Reliability test: RT, 400Ω, 5 s Discharge through 5000 Ω

• Li/MnO2 (6 models, crimp)• 5-15 year shelf life

• Li/CFx (crimp)• 22 year shelf life

• Li/CFx (crimp and encapsulated)• 40+ year shelf life

• Li/SOCl2 (crimp)• 1 year shelf life

• Li/SOCl2 (hermetic)• 20+ year shelf life

Air Gun tests 30,000g set-back• Li/CFx (crimp and encapsulated)

• No change in CCV

• Li/SOCl2 (hermetic)• 0.5 – 2.0V change in CCV

Before air gun firing After air gun firing

Battery type

Position Open Circuit

Voltage

Closed Circuit Voltage

Ri (Ω)

Open Circuit Voltag

Closed Circuit

Voltage

Ri (Ω)

M5

Horizontal - - - 3.282 2.25 126

Vertical - - - 3.219 3.08 17

Vertical - - - 3.266 3.12 18

C2

Horizontal 3.428 2.90 62 3.395 2.91 57

Horizontal 3.439 2.91 62 3.398 2.90 59

Vertical 3.425 2.90 61 3.399 2.89 60

Vertical 3.452 2.95 58 3.405 2.94 55

T1

Horizontal 3.704 1.52 236 3.688 3.53 18

Horizontal 3.694 1.76 209 3.688 3.54 16

Vertical 3.712 2.96 81 3.686 3.54 16

Vertical 3.713 3.18 57 3.689 3.53 17

T3 Horizontal 3.680 2.68 109 3.651 3.45 22

Vertical 3.681 2.68 109 3.672 3.35 35 M. Templeman, J. Swank, 37th Power Sources Conference, p 346-349

Storage Studies

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Li/CFx 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.

Storage Studies

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Li/CFx

• Large Impedance growth between Titanium collector and graphite coating

• Capacity loss is due to Titanium oxidation and subsequent deposition on the Li anode

Noble metals coated on titanium current collectors for use in nonaqueous Li/CFx cells, TAKEUCHI E.S., Patent EP1309023 (A2), US2006141340 (A1) • Ir and Pt sputtered Titanium collectors reduce

impedance, even after 100C storage.

Fateev, Russian Journal of Electrochemistry, 36 (7) 2000

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Li/SOCl2Discharge reaction (moderate rate)4 Li + 2SOCl2 4 LiCl + S + SO2

Li Passivation• Direct reaction / passivation by

SOCl2 (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

• PCl5 and CaCl2 reduce Li anode passivation during storage at 71C.

• Ca metal plates on the Li and provides excellent passivation

Driscoll, Brummer, Gudrais, Holleck, Toland, ECOM-74-0030-F, DAAB07-74-C-0030

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Requirements / Reserve Batteries

Requirements• 20 year shelf life @ 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 life @ 20C• -40C / +70C operation • 1% loss/year @ 20C: Li-MnO2• 1% loss/year @ 20C: SOCl2• 0.5% loss/year @ 20C: Li-CFx

Typical Primary Battery• Small Size• Single cell• High Energy Density• Low Power Density

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Possible Battery Research• Inherent stability of specific cathode materials: CFx, MnO2, and SOCl2• 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 (CFx, MnO2)• Look at low rate discharge as possible fix for Li passivation in solid

cathode batteries• Hybrid Power design

• Low rate Lithium + Supercapacitor• Li/I2, Li/CFx

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Thank You

• Jeff Read, [email protected], (301) 394-0313

mailto:[email protected]

Documents

Feasibility of Using Active Batteries for Munitions ......Dr. Jeffrey Read 7-Dec-2016. UNCLASSIFIED UNCLASSIFIED The Nation’s Premier Laboratory for Land Forces Background ... 12/8/2016