1

USG and Quallion STTR Test Packs

Demonstration Packs in Support of MDA and USG Li-Ion LEOModeling and Cell Performance Programs

Harlan Lewis and Bruce Moore, NAVSEA Crane, INScott Verzwyvelt, USG, Washington, DC

Hisashi Tsukamoto, Quallion, Sylmar, CAEmail: harlan.lewis@navy.mil

2009 NASA Battery WorkshopHuntsville, AL

17-19 November 2009

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STTR Battery Packs

Outline:

•

STTR Battery Test–

Test Purpose and Plan

–

Hardware Setup–

Data Collection

–

Test Data–

Conclusions

3

STTR Batteries

Purpose:

●

NAVSEA Crane Code GXSR has built and is testing two Li- ion batteries of 10 Ah USG and 15 Ah Quallion prismatic cells

in 3P8S configurations with eight “virtual”

cells of three, in support of an MDA Phase III contract. The MDA Phase III seeks to develop a physics-based first principles model for LEO cycling of Li-Ion batteries, and this testing is to provide performance data against which the model can be evaluated. The model is being developed by Dr. Ralph White (Univ. of South Carolina), in conjunction with the USG and Quallion LLC.

●

This test is not intended to be a life test, but a performance characterization of flight like battery configurations.

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STTR Batteries

Pack Description:Cells are USG Gen 1.0 design with LiCoO2

positive, and Quallion Gen 1.0 design with LiNiCoAlO2

, true prismatics. Both have MCMB negatives. The USG Gen 1.0 design has been subsequently modified to increase the anode/cathode ratio.

Design criteria are for 10 or 15 Ah; actual capacities are 14.35 Ah for the USG cells, 16.42 Ah for the Quallion cells, and we derate 5/6ths to 11.96 Ah and 13.68 name plate capacity, respectively.

Test Plan:Packs are being cycled for 500 LEO cycles at each of nine matrix conditions, with operational and standard capacity, impedance, and DC resistance measurements at the conclusion of each condition.

5

Condition Number

Temperature (°C)

DoD (%/Ah) Peak Charge Rate@ Amps

Discharge Rate*

Amps1

15

30/10.76 11.91 ~C/3 18.45 ~C/2

2 40/14.35 15.88 ~C/2.25 24.60 ~C/1.5

3 50/17.94 19.85 ~C/1.8 30.75 ~C/1.2

4

25

30/10.76 11.91 18.45

5 40/14.35 15.88 24.60

6 50/17.94 19.85 30.75

7

35

30/10.76 11.91 18.45

8 40/14.35 15.88 24.60

9 50/17.94 19.85 30.75

@

At peak charge rate (CC) to 4.0 V max and hold (CV) at 4.0 V for a total charge timeof 61 min

*

At discharge rate for a total discharge time of 35 min

Matrix Test Plan – USG Pack

STTR Batteries

6

Condition Number

Temperature (°C)

DoD (%/Ah) Peak Charge Rate@ Amps

Discharge Rate*

Amps1

15

30/12.31 13.68 ~C/3 20.52 ~C/2

2 40/16.42 18.24 ~C/2.25 27.36~C/1.5

3 50/20.52 22.80 ~C/1.8 34.20 ~C/1.2

4

25

30/12.31 13.68 20.52

5 40/16.42 18.24 27.36

6 50/20.52 22.80 34.20

7

35

30/12.31 13.68 20.52

8 40/16.42 18.24 27.36

9 50/20.52 22.80 34.20

@

At peak charge rate (CC) to 4.0 V max and hold (CV) at 4.0 V for a total charge timeof 61 min

*

At discharge rate for a total discharge time of 35 min

Matrix Test Plan – Quallion pack

STTR Batteries

7

Thermal Grease

Top view(looking down on cold plate)

10 Ah OGA cell or15 Ah Quallion cell

Cold Plate

Restraining rod stockFasteners not shown

(at least 4 )

Side View (without rod stock)

Insulating Plate

Al plateL-Brackets

Kapton & thermal grease

+

- - -

+ + +

- - -

+ + +

- - -

+ + +

- - -

+ +

Total Length of Pack is 21.315”

V1

V2

V3

V4

V8

V7

V6

V5

Top and Side Views of Pack Assembly

STTR Batteries

All virtual cells are in thermal contact andwithin each virtual pack, as well.

8

V1

V2

V3

V4

V8

V6

V7

V5

A

B

C

A

A

A

A

A

A

A

B

B

B

B

B

B

B

C

C

C

C

C

C

C

TemTemperature Monitoring Locations –

Top View

STTR Batteries

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STTR Batteries

Location of Temperature Probes

STTR USG Battery

Assembled USG Pack Illustrating Virtual Cell Configuration with Wiring 10

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STTR Quallion Battery

Assembled Quallion Pack Illustrating Virtual Cell Configuration with Wiring11

12

Data Collection:Twenty thermistors for temperature sensingVirtual cell and pack voltages as well as individual cell voltages in two virtual cells

Charge Control:Charge control and cell removal hardware for each virtual cellVoltage adjustable 2.80<V<4.60Voltage regulation ±0.002 VMaximum current capability 30 A

Shunt Bypass:One circuit per virtual cell (resistor + relay)Bypasses excessive current during taper chargeBalance rate C/20Voltage window specifies variable activate and release values, e.g. Activate 4.005, Release 3.995

STTR Batteries

13

STTR USG Battery

13

14

STTR USG Battery

Wider Spread at lower EoDV.

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15

STTR USG Battery

The separation of virtual cell capacity increased at the 15 Celsius 50% DoDmeasurement. The 50% DoD also saw the highest charge rate (C/1.8) for its matrix value of ~500 cycles.

Slight separationon recharge.

Increased spreadat lower EoDV.

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STTR USG Battery

Narrower spread andslightly higher EoDVthan at 15°C.

16

17

STTR USG BatteryVoltage / Current Plot Cycle 2300 (25°C - 40% DOD)

3.7

3.7

3.8

3.8

3.9

3.9

4.0

4.0

4.1

0 20 40 60 80 100 120

Cycle Time (min))

Volta

ge

-30

-25

-20

-15

-10

-5

0

5

10

15

20

Cur

rent

(Am

ps)

Cell 01 VoltsCell 02 Volts

Cell 03 VoltsCell 04 Volts

Cell 05 VoltsCell 06 VoltsCell 07 Volts

Cell 08 VoltsCell 03a Volts

Cell 03b VoltsCell 03c VoltsCell 08a Volts

Cell 08b VoltsCell 08c Volts

Pack Current

Narrower spread andslightly higher EoDVthan at 15°C.

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Voltage / Current Plot Cycle 2825 (25°C - 50% DOD)

3.4

3.5

3.6

3.7

3.8

3.9

4.0

4.1

0 20 40 60 80 100 120

Cycle Time (min)

Volta

ge

-35

-25

-15

-5

5

15

25

Cur

rent

(Am

ps)

Cell 01 VoltsCell 02 Volts

Cell 03 VoltsCell 04 VoltsCell 05 VoltsCell 06 Volts

Cell 07 VoltsCell 08 VoltsCell 03a VoltsCell 03b Volts

Cell 03c VoltsCell 08a VoltsCell 08b VoltsCell 08c Volts

Pack Current

STTR USG Battery

Greater spread andlower EoDV thanprevious plots.

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STTR USG Battery

Note steep drop inCell #5 on discharge.

2.5

2.7

2.9

3.1

3.3

3.5

3.7

3.9

4.1

0 10 20 30 40 50 60 70 80 90 100

Cycle Time

Volts

-40

-20

0

20

40

60

80

100

120

140

Am

ps

Cell 01 Volts

Cell 02 Volts

Cell 03 Volts

Cell 04 Volts

Cell 05 Volts

Cell 06 Volts

Cell 07 Volts

Cell 08 Volts

Pack Current

Cycle 2927 Voltage/Current Plot - 25°C and 50% DoD

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STTR USG Battery

Voltage 25C 50% DOD

3.0

3.2

3.4

3.6

3.8

4.0

4.2

2650 2700 2750 2800 2850 2900 2950

Cycle Number

Volta

ge

Cell 01 Volts

Cell 02 Volts

Cell 03 Volts

Cell 04 Volts

Cell 05 Volts

Cell 06 Volts

Cell 07 Volts

Cell 08 Volts

All virtual cells show significant capacityloss, and especially #5, at 25°C, 50% DoD.

Discharge Voltage Cycle Plot, 2650-2927, at 25°C and 50% DoD

Cycle Number

21

STTR USG BatteryVC5 Voltage Current at end of C2 discharge

3.70000

3.75000

3.80000

3.85000

3.90000

3.95000

4.00000

4.05000

3/11/09 6:28 3/11/09 6:43 3/11/09 6:57 3/11/09 7:12 3/11/09 7:26 3/11/09 7:40 3/11/09 7:55

Voltage

Tim

e

-20.00

0.00

20.00

40.00

60.00

80.00

100.00

Cell 01 Volts

Cell 02 VoltsCell 03 Volts

Cell 04 Volts

Cell 05 VoltsCell 06 Volts

Cell 07 Volts

Cell 08 VoltsPack Current

End of VC5 CC charge earlier,due to higher impedance.

Unsure sure if it is only impedance related; could have lithium plated out such that the cathode is shifted to greater voltages also.

Charge Voltage Cycle 2927, at 25°C and 50% DoD

Vol

tage

Time

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STTR USG Battery

STTR Cell Voltage- Capacity Cycles- Cell 5

2.9

3.0

3.1

3.2

3.3

3.4

3.5

3.6

3.7

3.8

3.9

4.0

4.1

0 100 200 300 400 500 600 700 800 900

Cycle Time (min)

Volta

ge

Cell Impedance measured at C Rate Pulse 5a (SN53) = .0118 5b (SN86) = .0150 5c (SN88) = .0106

Cell Capacities (AmpHr)

Cell 5A Const Curr Chg 7.436 Taper Chg 11.642 Hi Rate Dis 10.050 Lo Rate Dis 11.564 Cell 5B Const Curr Chg 4.897 Taper Chg 9.803 Hi Rate Dis 6.824 Lo Rate Dis 9.490 Cell 5C Const Curr Chg 6.673 Taper Chg 10.833 Hi Rate Dis 8.568 Lo Rate Dis 10.636

Middle cell reached highcurrent discharge of 3.0 Vfirst. So more residual capacity at C/30.

Note that the middle cell tapers earliest on charge, and completes discharge last, at C/30.

Individual Cell Voltages on Charge, Virtual Cell #5

Vol

tage

Cycle Time

23

STTR USG BatteryEnd of Charge/Discharge Cycling Voltage Trend

STTR - AH Trend Plot

-20

-15

-10

-5

0

5

10

15

20

0 500 1000 1500 2000 2500 3000 3500 4000

Cycle

Ahr

Cell 01 AmpHrCell 02 AmpHrCell 03 AmpHrCell 04 AmpHrCell 05 AmpHrCell 06 AmpHrCell 07 AmpHrCell 08 AmpHr

30% DOD15°C

40% DOD15°C

50% DOD15°C

30% DOD25°C

40% DOD25°C

50% DOD25°C

30% DOD35°C

End of Charge Voltage

End of CC Charge Voltage

End of Discharge Voltage

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End of Charge/Discharge Voltage Trend

3

3.2

3.4

3.6

3.8

4

0 500 1000 1500 2000 2500 3000 3500 4000

Cycle

Volts

BTSV_01

BTSV_02

BTSV_03

BTSV_04

BTSV_05

BTSV_06

BTSV_07

BTSV_08

30% DOD15°C

40% DOD15°C 50% DOD

15°C

30% DOD25°C 40% DOD

25°C

50% DOD25°C

30% DOD35°C

End of Discharge Voltage

End of Charge Voltage

STTR USG BatteryEnd of Charge/Discharge Cycling Voltage Trend

Resumption ofcycling with onlysix of eight virtualcells.

Cell #4&5removed.

At 35°C and40% DoD, allthe cells failed.

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V1

V2

V3

V4

V8

V6

V7

V5

A

B

C

A

A

A

A

A

A

A

B

B

B

B

B

B

B

C

C

C

C

C

C

C

TemTemperature Monitoring Locations –

Top View

STTR Batteries

Two end cellsremoved.

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STTR USG BatterySTTR Cycles 3484 to 3490

2.5

2.7

2.9

3.1

3.3

3.5

3.7

3.9

4.1

4.3

6/23/09 14:24 6/23/09 16:48 6/23/09 19:12 6/23/09 21:36 6/24/09 0:00 6/24/09 2:24 6/24/09 4:48

Time/Date

Volts

-80

20

120

220

320

420

Am

ps

Cell 01 VoltsCell 02 VoltsCell 03 VoltsCell 06 VoltsCell 07 VoltsCell 08 VoltsPack Current

Last Seven Cycles of USG STTR Pack at 35°C and 40% DoD

STTR Cycles 3484 to 3490

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STTR USG Battery

STTR Cycle 3490

2.5

2.7

2.9

3.1

3.3

3.5

3.7

3.9

4.1

4.3

6/24/09 0:57 6/24/09 1:26 6/24/09 1:55 6/24/09 2:24 6/24/09 2:52 6/24/09 3:21Time/Date

Volts

-80

20

120

220

320

420

Am

psCell 01 VoltsCell 02 VoltsCell 03 VoltsCell 06 VoltsCell 07 VoltsCell 08 VoltsPack Current

Last Cycle of USG STTR Pack at 35°C and 40% DoD

STTR Cycle 3490

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Pack Capacity Cycles

-45.0

-40.0

-35.0

-30.0

-25.0

-20.0

-15.0

-10.0

-5.0

0.0

0 500 1000 1500 2000 2500 3000 3500 4000

Cycle Number

Am

p H

rs

Cell 01 AmpHr

Cell 02 AmpHr

Cell 03 AmpHr

Cell 04 AmpHr

Cell 05 AmpHr

Cell 06 AmpHr

Cell 07 AmpHr

Cell 08 AmpHr

25°C35°C

15°C

25°C

15°C

25°C

15°C25°C15°C15°C15°C

Post50% DOD / 25°C

RegimeCapacity Results

Post30% DOD / 35°C

RegimeCapacity Results

STTR USG BatteryPost Matrix Value Capacities

The chart shows decreasing capacity after each matrix interval. Capacities wereremeasured at 15°C after each measurement at the higher matrix temperatures.

ConclusionsThis program of matrix cycling to provide cycle life data at three temperatures and

three DoD’s at each temperature completed the 15°C matrix DoD’s and two of the 25°C DoD’s. At those matrix values, there did not appear to be significant cell voltage divergence.

At the third 25°C matrix value of 50% DoD, problems with cell #5 caused us to discontinue that matrix value. The cycling was then resumed at 35°C at 30% DoD, when cell #5 immediately lost capacity and fell below the cutoff voltage, so it and a companion cell were removed, to balance the pack at six cells. Cycling continued at that matrix value to the completion of the 500 cycle interval. This was followed by the regular capacity evaluations. Then the next matrix value of 40% DoD was begun, at which time all the cells failed.

A review of the capacity data at 15°C and 50% DoD showed an indication of capacity divergence in the measurements, although subsequent open circuit

stand measurements did not indicate higher or divergent self discharge issues among

the virtual cells.We now believe that the 15°C, 50% DoD cycling with its higher charge rates caused

lithium plating during recharge, which became evident in the performance at 25°C and 50% DoD. Although the entire pack had been reconditioned with a C/2

charge followed by a C/100 discharge at cycle 2927, in an attempt to remove the Li plate on the anode, the subsequent cycling showed no recovery.

STTR USG Battery

29

30

STTR Quallion Battery

Virtual Cell 3P8S Voltage/Current Plot - Cycle 300 (25°C, 30%DOD)

3.4

3.5

3.6

3.7

3.8

3.9

4

0 10 20 30 40 50 60 70 80 90 100

Cycle Time (Min)

Cel

l Vol

tage

-30

-20

-10

0

10

20

Pack

Cur

rent

(Am

ps)

Cell 01 Volts

Cell 02 Volts

Cell 03 Volts

Cell 04 Volts

Cell 05 Volts

Cell 06 Volts

Cell 07 Volts

Cell 08 Volts

Cell 03a Volts

Cell 03b Volts

Cell 03c Volts

Cell 08a Volts

Cell 08b Volts

Cell 08c Volts

Pack Current

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STTR Quallion BatteryVirtual Cell 3P8S Temperature Plot - Cycle 300 (25°C, 30%DOD)

20

21

22

23

24

25

26

27

28

29

30

0 10 20 30 40 50 60 70 80 90 100

Cycle Time (Min)

Tem

pera

ture

(°C

)

Amb Temp

Temp Cell 01b T-Mid

Temp Cell 02b T-Mid

Temp Cooloing Sleeve

Temp Cell 03b T-Mid

Temp Cell 03a B-Bot

Temp Cell 03c T-Mid

Temp Cell 03b B-Mid

Temp Cell 03c B-Top

Temp Cell 03b T-Term

Temp Cell 04b T-Mid

Temp Cell 05b T-Mid

Temp Cell 06b T-Mid

Temp Cell 07b T-Mid

Temp Cell 08b T-Mid

Temp Cell 08a B-Bot

Temp Cell 08c T-Mid

Temp Cell 08b B-Mid

Temp Cell 08b T-Term

Temp Cell 08c B-Top

Temp Cold Plate

Discharge Charge

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STTR Quallion BatteryVirtual Cell 3P8S Voltage/Current Plot - Cycle 800 (25°C, 40%DOD)

3.4

3.5

3.6

3.7

3.8

3.9

4

0 10 20 30 40 50 60 70 80 90 100

Cycle Time (Min)

Cel

l Vol

tage

-35

-25

-15

-5

5

15

25

Pack

Cur

rent

(Am

ps)

Cell 01 Volts

Cell 02 Volts

Cell 03 Volts

Cell 04 Volts

Cell 05 Volts

Cell 06 Volts

Cell 07 Volts

Cell 08 Volts

Cell 03a Volts

Cell 03b Volts

Cell 03c Volts

Cell 08a Volts

Cell 08b Volts

Cell 08c Volts

Pack Current

33

STTR Quallion Battery

33

Virtual Cell 3P8S Temperature Plot - Cycle 800 (25°C, 40%DOD)

20

21

22

23

24

25

26

27

28

29

30

0 10 20 30 40 50 60 70 80 90 100

Cycle Time (Min)

Tem

pera

ture

(°C

)

Amb TempCell 03a VoltsCell 03b VoltsCell 03c VoltsCell 08a VoltsCell 08b VoltsCell 08c VoltsTemp Cell 01b T-MidTemp Cell 02b T-MidTemp Cooloing SleeveTemp Cell 03b T-MidTemp Cell 03a B-BotTemp Cell 03c T-MidTemp Cell 03b B-MidTemp Cell 03c B-TopTemp Cell 03b T-TermTemp Cell 04b T-MidTemp Cell 05b T-MidTemp Cell 06b T-MidTemp Cell 07b T-MidTemp Cell 08b T-MidTemp Cell 08a B-BotTemp Cell 08c T-MidTemp Cell 08b B-MidTemp Cell 08b T-TermTemp Cell 08c B-TopTemp Cold Plate

34

STTR Quallion Battery

X1GL1 Voltage Trend Plot

35

STTR Quallion Battery

Virtual Cell Amp hr Trend

36

STTR Quallion Battery

Conclusions

For the 3P8S pack built with the Quallion 15 Ah cells, it was decided to begin the cycling at 25°C for the three DoD values, then proceed to 35°C

for the next three DoD values, and finally, to complete the matrix at 15°C. This is intended to hold off any low temperature and high recharge rate effects on the virtual cell pack performance until completion of the higher temperature matrix values, in order to accumulate a complete data set for the matrix.

To date, we have completed the first two matrix values of 30% and 40% DoD at 25°C, and the data do not show any untoward trends thus far.

37

AcknowledgementsThe STTR work is being performed with the support of the Missile Defense Agency under a Phase III Contract HQ0006-06-C-7381, between Quallion LLC and the Univ. of South Carolina, with supplementary MDA funding for the battery pack testing at NAVSEA Crane.

The authors gratefully acknowledge the work of William Sylvester and James Wood in constructing the packs and performing the electrical wiring, and Evan Hand and Jason Leonard for the Charge Control and Cell Removal hardware design and construction, as well as the software/hardware interface.

STTR Battery Packs