Quallion Technology - NASA · 28/09/2004 · Quallion Technology 1. ... 12744 San FernanQuallion...

Quallion Technology 1. Zero Volt Storage Capability 2. SaFE-LYTE Technology3. Matrix Battery Pack

H. TsukamotoCEO and CTO

Quallion LLC, 12744 San Fernando Road, Sylmar, CA 91342

Quallion Technology 1. Zero Volt Storage Capability 2. SaFE-LYTE Technology3. Matrix Battery Pack

H. TsukamotoH. TsukamotoCEO and CTOCEO and CTO

Quallion LLC, 12744 San Fernando Road, Sylmar, CA 91342Quallion LLC, 12744 San Fernando Road, Sylmar, CA 91342

NASA Aerospace Battery WorkshopNASA Aerospace Battery WorkshopDecember, 2005December, 2005

www.quallion.com©2005 Quallion LLC

1.1. Zero Volt Storage CapabilityZero Volt Storage Capability

LiC6 C6 + Li+ + e-

Time

Pot

entia

l vs.

Li/L

i+

LiC6 C6 + Li+ + e-

Li1-xCoO2 + xLi+ + xe- LiCoO2

Cu Cu2+ + 2e- (~ 2.8-3.2 V)

Conventional Battery

Zero-Volt Crossing Potential (ZCP)

Substrate Dissolution Potential (SDP)

Time

Pot

entia

l vs.

Li/L

i+


Zero-Volt TM Battery



Battery Voltage

Negative Potential

Positive Potential

Negative Potential

Positive Potential

United States Patent 6,596,439 and 6,553,263


Metal Polarization TestMetal Polarization TestCounter Electrode

DisassembledCounter Electrode

AssembledReference Electrode

Polarization Test CellWorking Electrode

38 mm x 38 mm square

Polished with SiCsandpaper

Ultrasonically Cleaned

Vacuum dried overnight

Test Conditions

LiPF6 EC:DEC

37° C

Scan Rate: 0.167mV/s

Testing inside a Glove box

Working Area 1.98 cm2


Polarization CurvesPolarization Curves

Cu: 2.8 V

Ti: 3.8 V

Al

Comparison of Metal PolarizationPo

tent

ial [

V vs

Li/L

i+]

SDPLiPF6 EC:DEC at 37° C, Scan Rate: 0.167mV/s


Titanium Foil for Negative Substrate14 days at 0 Volts Room Temp

LiCoO2 Cu Foil Substrate

LiCoO2 Ti Foil Substrate

14 days at 0 Volts Room Temp

Titanium Foil for Negative Substrate

Capacity Retention:

79.9%

CC Charge: C/10 to 4.0VCV Charge: 4.0V to C/100 cutoffDischarge: C/10 to 3.0VTemperature: Room TempStorage: 0V, at RT for 14 days

Capacity Retention:

98.6%


Titanium Foil for Negative SubstrateTitanium Foil for Negative Substrate

Did not have zeroDid not have zero--volt storage capability at volt storage capability at 37C storage

14 days at 0 Volts at 37 deg C

LiCoO2 Ti Foil Substrate

37C storage

CC Charge: C/10 to 4.0VCV Charge: 4.0V to C/100 cutoffDischarge: C/10 to 3.0VStorage: 0V, at 37 deg C for

14 days

Capacity Retention:

73.5%


AC Impedance / Cyclic AC Impedance / Cyclic VoltammetryVoltammetry TestingTesting

CE

WE

RE

Test Sample 15x20mm Cu

mesh wrapped with 250um Li foil

5x7.5mm Cu mesh wrapped with 250um Li foil

Polypropylene Jar

Insulin Syringe

Ni wire (tab end)

15mm protrusion

to weld sample

Apply UV epoxy to hold wire

Test Conditions

LiPF6 EC:DEC

RT or 37° C

Testing inside a Glove box


Negative Electrode Cyclic Negative Electrode Cyclic VoltammetryVoltammetry ScanScan

SEI formation

Li insertion

Li de-insertionSEI film decomposition

Negative Half Cell; LiPF6 EC:DEC at 25° C; Scan Rate: 0.2 mV/s

I (A

/cm

2 )

E (V vs Li/Li+)

Graphite electrode on platinum pin


SEI DecompositionSEI Decomposition

After the storage time at 37oC, impedance decreased indicating that the SEI Film has decomposed.

Fresh Cell

After SEI formation

Storage at 37oC 3.8 V for 7 hours

Storage at 23oC 3.8 V for 7 hours

Negative Half Cell; LiPF6 EC:DEC at 25° C;100kHz – 0.05 Hz


Three Key PotentialsThree Key Potentials

Time

Pot

entia

l vs.

Li/L

i+

Zero Volt Battery



Film Dissolution Potential (FDP)


Li1-xNiCoO2 + xLi+ + xe- LiNiCoO2

ZCP < FDP and ZCP < SDP


Zero-VoltTM Storage CapabilityZeroZero--VoltVoltTMTM StorageStorage CapabilityCapability

Conventional Cell LiCoO2Copper Foil

Zero-VoltTM Cell LiNiCoO2Titanium Foil

Capacity Check CycleCC Charge: C/2 to 4.1VCV Charge: 4.1V to C/20 cutoffDischarge: C/2 to 2.7VStorage: 0V, at 37 deg C

100mAh Cells

Zero-VoltTM Storage Testing

1. Initial cycle

2. Connect 68 Ohm resistor and store at 37°C

3. Cycle after storage

4. Compare discharge capacities before and after storage

United States Patent 6,596,439 and 6,553,263


SONY hard carbon cell vs. Quallion zero-volt 18650 cells

SONY hard carbon cell vs. Quallion zero-volt 18650 cells

Quallion 18650SONY

20mOhm


SONY hard carbon cell vs. Quallion zero-volt cells-Before and After 3 days Storage at Zero Volt-

SONY hard carbon cell vs. Quallion zero-volt cells-Before and After 3 days Storage at Zero Volt-

40C storageRoom temperature storage

SONY Hard Carbon 18650

Quallion zero-volt 18650


2. What is SaFE-LYTE™ ?Electrolyte immiscible additive2. What is SaFE-LYTE™ ?Electrolyte immiscible additive

Issued on 9/28/04 Patent No. 6,797,437

Claim 1“substantially immiscible in the non-aqueous electrolyte solution”


What is SaFE-LYTE™?Self-extinguishing additive


Flammability Test

A: EC/DEC Soaking

B: SaFE-LYTETM Soaking

Ignite the unsoaked paper at the bottom of the stripPaper





18650 + SaFE-LYTETM18650 + SaFE-LYTETM

Sanyo 18650WOvercharge test conditions

2C to 12V

2.0

2.5

3.0

3.5

4.0

4.5

5.0

5.5

6.0

0 10 20 30 40 50 60 70 80Time (min)

Volta

ge (V

)

20

40

60

80

100

120

140

160

180

200

Tem

pera

ture

(°C

)

Control

0.4g additive

1.4g additive

18650 at 2C rate to 12V

SaFE-LYTE H : >220CCathode thermal reaction temperature: 170-190CSaFE-LYTE M : 160C


3. Matrix Battery Pack3. Matrix Battery Pack

No parallelconnections

Parallelconnections

Conventional Battery Pack Matrix Battery Pack


Survivability ComparisonSurvivability ComparisonSurvivability Comparison

self-discharge high internalimpedance

decreasedcapacity

F1 F2 F3

3P7S test pack


Conventional pack test results F1, F2, F3 failures

Conventional pack test results F1, F2, F3 failures

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

0 1 2 3 4 5

Cycle Number

Volta

ge (V

) Parallel 1KOhm resistor

Control-1

Serial 100mOhm resistor Exclude R

Serial 100mOhm resistor include R

Un-Matched Capacity Cell (1.8Ah)

Control-2

100% DODRoom temperature29.4 V18.9 V

The conventional pack cannot survive more than one cycle with three failure modes present.The conventional pack cannot survive more than one cycle with three failure modes present.


Conventional battery packConventional battery pack--11stst cyclecycle--

7S-3P non-Matrix Individual Cell Voltage Profile

0

0.5

1

1.5

2

2.5

3

3.5

4

4.5

5

0 2000 4000 6000 8000 10000 12000 14000 16000 18000 20000

Time (S)

Volta

ge (V

)

Self Discharge- F1

Control

Serial connect 100mOhm exclude resistor(F2)Serial connect 100mOhm include resistor(F2)

Low Capacity- F3

F3

F2

F1

F3


Conventional pack results, F1 and F2Conventional pack results, F1 and F2

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

0 1 2 3 4 5

Cycle Number

Volta

ge (V

)

Parallel 1KOhm Resistor

Control-1

Serial 100mOhm resistor Exclude R

Serial 100mOhm resistor include R

Un-Matched Capacity Cell (2.45Ah)

Control-2

100% DODRoom temperature29.4 V18.9 V

• Even after replacement of the unmatched capacity cell with a correct capacity cell, the voltages still drop.

• Even after replacement of the unmatched capacity cell with a correct capacity cell, the voltages still drop.


Matrix Battery Pack-1st cycle-

Matrix Battery Pack-1st cycle-

0.000

0.500

1.000

1.500

2.000

2.500

3.000

3.500

4.000

4.500

5.000

0 2000 4000 6000 8000 10000 12000 14000 16000 18000 20000

Time (S)

Volta

ge (V

)

ControlSerial 100mOhm Resistor Exclude R (F2)Serial 100mOhm Resistor Include R (F2)Self-Discharge (F1)Low Capacity (F3)

F2


Quallion Matrix Pack Test Results F1, F2, F3Quallion Matrix Pack Test Results F1, F2, F3

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

0 2 4 6 8 10 12 14 16 18 20

Cycle Number

Volta

ge (V

)

Control

Serial 100mOhm Exclude R

Serial 100mOhm include R

Parallel 1KOhm resistor

Un-Matched Capacity (1.8Ah)

F1

• Voltages of individual batteries under failure conditions are able to maintain operational voltage levels.

• Only one cell under the self-discharge condition loses its voltage, but only when nearing 20 cycles.

• Voltages of individual batteries under failure conditions are able to maintain operational voltage levels.

• Only one cell under the self-discharge condition loses its voltage, but only when nearing 20 cycles.


Hybrid Matrix Battery PackMatrix Battery Pack Can Accommodate

Different Capacity and Impedance Cells if Needed

Hybrid Matrix Battery PackMatrix Battery Pack Can Accommodate

Different Capacity and Impedance Cells if Needed

200W/kg1000W/kgPower density

200Wh/kg120Wh/kgEnergy density

HE CellsHP Cells

HP Matrix HE Matrix


HP+HE: Flexible Performance-15C pulse test-

HP+HE: Flexible PerformanceHP+HE: Flexible Performance--15C pulse test15C pulse test--

0

1

2

3

4

5

6

2 2.5 3 3.5 4

Test_Time(h)

Volta

ge(V

)

4HP configuration3HP+1HE configuration

• 4HP: configuration has a smaller voltage drop

• 3HP+1HE: slightly larger voltage drop but more capacity

• 4HP: configuration has a smaller voltage drop

• 3HP+1HE: slightly larger voltage drop but more capacity

15C x 10 sec. pulse discharge, 2 min. rest, 15Cx 10sec. pulse charge

It is possible to vary the battery pack performance characteristics without changing the footprint of the battery pack.It is possible to vary the battery pack performance characteristics without changing the footprint of the battery pack.


Modular Approach with Matrix Battery PackModular Approach with Matrix Battery Pack

• Modular pack– Reduces the complexity

of many cells– Interchangeable and

reconfigurable– HE module pack and HP

module Hybrid pack

• Modular pack– Reduces the complexity

of many cells– Interchangeable and

reconfigurable– HE module pack and HP

module Hybrid pack

HEV module

10P of 3Ah cell30Ah Modular Pack

Habitation Modul


Re-configurable on earth and in spaceRe-Matrix + Modular-

Re--configurable on earth and in spaceconfigurable on earth and in space--Matrix + ModularMatrix + Modular--

• Easily changed• Simple connections• Configurable on the fly

• Easily changed• Simple connections• Configurable on the fly


Quallion TechnologyQuallion TechnologyQuallion Technology1. Zero-volt capability

• Range safety (battery assembly at discharge state)• In space storage without maintenance charge

2. SaFE-LYTETM

• Significant safety improvement in combination with Current Interrupting Device

3. Matrix Battery Pack• Improve reliability and survivability• HP + HE hybrid pack• Modular approach

1. Zero-volt capability• Range safety (battery assembly at discharge state)• In space storage without maintenance charge

2. SaFE-LYTETM

• Significant safety improvement in combination with Current Interrupting Device

3. Matrix Battery Pack• Improve reliability and survivability• HP + HE hybrid pack• Modular approach

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