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Transcript of 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+
Li1-xCoO2 + xLi+ + xe- LiCoO2
Zero-Volt TM Battery
Substrate Dissolution Potential (SDP)
Zero-Volt Crossing Potential (ZCP)
Battery Voltage
Negative Potential
Positive Potential
Negative Potential
Positive Potential
United States Patent 6,596,439 and 6,553,263
www.quallion.com©2005 Quallion LLC
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
www.quallion.com©2005 Quallion LLC
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
www.quallion.com©2005 Quallion LLC
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%
www.quallion.com©2005 Quallion LLC
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%
www.quallion.com©2005 Quallion LLC
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
www.quallion.com©2005 Quallion LLC
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
www.quallion.com©2005 Quallion LLC
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
www.quallion.com©2005 Quallion LLC
Three Key PotentialsThree Key Potentials
Time
Pot
entia
l vs.
Li/L
i+
Zero Volt Battery
Substrate Dissolution Potential (SDP)
Zero-Volt Crossing Potential (ZCP)
Film Dissolution Potential (FDP)
Li1-xCoO2 + xLi+ + xe- LiCoO2
Li1-xNiCoO2 + xLi+ + xe- LiNiCoO2
ZCP < FDP and ZCP < SDP
www.quallion.com©2005 Quallion LLC
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
www.quallion.com©2005 Quallion LLC
SONY hard carbon cell vs. Quallion zero-volt 18650 cells
SONY hard carbon cell vs. Quallion zero-volt 18650 cells
Quallion 18650SONY
20mOhm
www.quallion.com©2005 Quallion LLC
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
www.quallion.com©2005 Quallion LLC
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”
www.quallion.com©2005 Quallion LLC
What is SaFE-LYTE™?Self-extinguishing additive
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
www.quallion.com©2005 Quallion LLC
What is SaFE-LYTE™?Self-extinguishing additive
What is SaFE-LYTE™?Self-extinguishing additive
www.quallion.com©2005 Quallion LLC
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
www.quallion.com©2005 Quallion LLC
3. Matrix Battery Pack3. Matrix Battery Pack
No parallelconnections
Parallelconnections
Conventional Battery Pack Matrix Battery Pack
www.quallion.com©2005 Quallion LLC
Survivability ComparisonSurvivability ComparisonSurvivability Comparison
self-discharge high internalimpedance
decreasedcapacity
F1 F2 F3
3P7S test pack
www.quallion.com©2005 Quallion LLC
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.
www.quallion.com©2005 Quallion LLC
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
www.quallion.com©2005 Quallion LLC
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.
www.quallion.com©2005 Quallion LLC
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
www.quallion.com©2005 Quallion LLC
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.
www.quallion.com©2005 Quallion LLC
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
www.quallion.com©2005 Quallion LLC
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.
www.quallion.com©2005 Quallion LLC
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
www.quallion.com©2005 Quallion LLC
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
www.quallion.com©2005 Quallion LLC
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