BATTERIES
CEA TECHNOLOGIES & FACILITIES
Customized Battery Developments to
stand drastic conditions
R&D and Prototyping
Manufacturing & Testing
Pilot Platforms
ENERGY & POWER BATTERIES
High Energy Batteries
Under Development Technologies
(>250Wh/Kg)
High Power Batteries
LFP-Based Technologies and beyond
X-trem Conditions Batteries (Beacons,
Sensors…)
Low T°, High T°, Corrosive environment…
PROOF OF CONCEPT
Florence FUSALBA
Scale 1 Demonstration; Vehicle
integration…
e-Bus with its high power fast charging
station system
| PAGE 1
Presentation of CEA & LITEN
French Atomic and Renewable Energy Commission
CEA : 10 R&D Centers in France
4 main research priorities
•Defense & Global Security
•Energy
•Health and Information Technology
•Fundamental Research
Key figures (2011-12)
•Staff : 15 982
•Budget : 4,2 b€
•613 priority patents applications field
« Laboratory for Innovation in New Energy Technologies and Nanomaterials »
R&D
⇒ Solar energy & smart building
⇒ Transport technologies
⇒ Energy sources for portable electronics
⇒ Nanomaterials
⇒ Biomass & Hydrogen Technologies
•Staff : 1200
•Budget : 170 M€ (140M€ turnover)
• 840patents
•>250 p on batteries
http://www.cea.fr/
http://www-liten.cea.fr
| PAGE 2
Embedded Energy : Specific Batteries
Customized battery development to stand drastic conditions
Applications
CEA Tech Competences
integrated approach from
system dedicated to battery
CEA LITEN has an
materials
to
developments :
Electrodes
Materials
Cells
Prototyping (TRL 3-6) have been realized in several
application fields :
Module
Battery Pack
Safety tests
CEA LITEN develops customized Li-ion
technologies and designs depending on
technical specifications, for example :
Military application
Security (beacons)
Spatial Sensor
Si-C Technology
3.4V - 1.25Ah 260Wh/kg cells
Reduced cyclability
For 70Wh 13.6V Si Battery pack
Higher autonomy at 20°C (+60%)
& -20°C (+180%) versus
commercial
For Energy Efficient Soldier…
NMC/Si-C Technology
3.4V – 1.2Ah, 250-270Wh/kg
Operating from -20°C to 55°C
In a power mode
Cospas-Sarsat approval
UL1642-qualified
NCA/G Technology
3.6V - 450mAh
Cell mechanical design
to sustain extreme
environment (vibration,
acceleration, vacuum…)
- Safe & Stable energy or Power batteries integrating LiFePO4
- High Energy Li-ion cells integrating high capacity electrodes
- Costs care
Aerospace Battery characteristics aimed :
- Long life time: at least 10 years
- Resistant to hard environmental conditions
- Operational between -50°C to 100°C
- Large pressure range : 50 to 1100mbars or for vacuum
Aeronautic Large
Capacity/High
Energy Li-ion cells
Si-C Technology
3.4V – 40Ah
300Wh/kg (C/10 @45°C)
Micro Hybrid –
Start & Stop
EVs, Buses, other large
vehicles, stationary
High Power
Fast charge
24V – 15Wh
Bipolar Architecture
Various P/E ratio
3.3V – 10Ah LiFePO4 Technology
1.9V – 11Ah Li4Ti5O12 Technology
Designed electrolytes,3
components…
Contact : florence.fusalba@cea.fr
PILOT : PRODUCTION REPRESENTATIVE ENVIRONMENT
Semi Industrial Line: Dry room ~ 1000m² (Dew points: -20°C & -40°C)
All materials &
components
electronically tracked
during the process
thanks to bar codes
-
A stabilized design to investigate chemistries with capability to produce prototypes in a production
relevant environment
Prototypes Performances stable, Manufacturing process definition established, Process flow
validated… Manufacturing yield compatible with an industrial transfer…
| PAGE 4
CEA PROPRIETARY
CELLS PILOT MANUFACTURING
PILOT LINE BATTERIES
-
A fully devoted Industrialization Methods Team
A Platform Quality Group to follow MRL-TRL of CEA Technologies
All materials & components are electronically tracked during process
On Line process control (electrode loading, adhesion…)
A Life Cycle Analysis Group (On Line Defectivity & Cost Analysis)
Manufacturing
Readiness
Level
MRL6: RELIABLE PROTOTYPE
Simulated Operating
Environment
MRL7: PRE-PRODUCT
Operating Environment
TRL5: RELIABLE PROTOTYPE
Stabilized performances in
Simulated Operating
Environment
TRL6:PROTOTYPE becomes a
PRODUCT…
Indus. Pilot Line
Indus. Representative
equipments
TRL5
MRL7
TRL6
MRL6
prototyping
Indus. Relevant
equipments
laboratory
Basic
Principle
CEA PROPRIETARY
Technology
Readiness
Level
Demonstrator
‘high fidelity’
Proof of concept
‘low fidelity’
Product
ELECTRICAL POWER SYSTEM PLATFORM
Modules
From…
TRL6-8
Prototype or Commercial Cells
… To
Power System
Packs
With…
Power System Testing & Simulation
TARGETS :
With innovative sensors, electronics,
electric architectures, …
1 - SAFETY
2 - HIGH ENERGY
3 - HIGH POWER
4 - COST REDUCTION
| PAGE 6
BATTERY SYSTEM FROM TRL3 TO TRL6-8
Electrical test benches:
High power ~300 channels
Low power (Includes
formation) 480 channels
Battery Modules & pack
assembly with emanagement
Semi automatic assembly with
full components tracking
Battery Modules & Packs Assembly ~500m²
ca. 20 to 40 battery packs (EVs sizes)/month
CEA PROPRIETARY
| PAGE 7
EXAMPLE 1- AUTOMOTIVE ENERGY BATTERY PACK - 30 KWH
2012
Raw material
Assembly
585 cells
13 modules in series
90kW discharge
40 kW charge
150 km estimated
CEA Cell
Pack
Module
Conditionning
30 KWh
83 Wh/kg
| PAGE 8
A COMPLETE OFFER FROM TRL3 TO TRL6-8
Development of innovative solutions
Electrochemistry
Electronics: power line communication bus, electric arc detection,
intelligence measuring and balancing systems, non dissipative balancing…
Power electronics: battery pack parallelization systems, switchable
modules, high reliability auxiliaries supply without 12V battery…
Mechanics and thermal management: battery pack architecture,
contribution of the battery pack to the mechanical stiffness of the system,
cooling…
Connectics: high current rate rack modules, PCB and power busbar,
specific connectors…
| PAGE 9
ELECTRICAL SYSTEM SUMMARY
Sensors…
Communication…
Cells balancing:
Dissipative/Non Dissipative
Electromechanical Conception/Protection Devices:
Contactors
Fuses
State indicators:
SOC
SOH
SOE…
Reversible switched modules
Arc fault detection
CEA PROPRIETARY
| PAGE 10
BMS & Battery Systems
Ensure safety
Improve performances: Life Cycle Cost (€/kWh, €/km) Wh/kg
Improve service, maintenance, diagnosis
Improve information for end user
HMI Diagnostic
ECUs (EMS, charger, inverter, …)
Communication
Sensors
U, I, Temp
…, X
Pack
Architecture
CPU
Actuators
Data fusion
Control algorithms
State indicators
Safety, thermal, …
Cells Balancing
Connection
SOE-SOH-SOS
BMS
Casing
Battery Pack
Thermal Design
Algorithms
Modeling
Tests – Characterization
| PAGE 11
CEA skills
LITEN
LETI
Cells design
Cells characterization
Modeling & Algorithms
E/E Architecture .
System design
Innovative sensors
Power electronic
components
Hardware, Firmware,
- component integration
.
- Embedded software
Battery pack integration
Power train test bench
Vehicle monitoring
Operating systems
Vehicle communication
AUTOSAR
Data fusion
LITEN
LIST
INES Facilities dedicated to all Storage
• The STORE Platform: an outstanding test facility in Europe
♦ More than 200 cycling channels (up to 700 V, 1000 A, 250kW)
♦ Thermo regulated baths, climatic chambers (-40°C, +120°C)
♦ Two laboratories for physical-chemical analyses, safety tests
♦ For all storage systems investigation (simulation, emulation, profile of use testing,
ageing…)
-Zebra Sodium-beta (High T°)
-Supercapacitors
-Li-ion, Lead-acid, Ni-MH, Ni-Cd
-Redox Flow…
Redox Flow Battery
Investire Thematic Network : 2001-2004
REX DER-LAB : 2005-2011
Infrastructure DERRI
BATTMARK PROGRAM
Batteries Benchmark Program
All technologies / All applications
Club Membership to Access CEA Data Base
Customers :
•
Batteries end-users (support for supplier, model
selection)
•
Manufacturers to position itself
50 references from 40 manufacturers
CEA DATA BASE:
• Performances & Ageing (cycling & calendaring)
Confidential Membership:
• Through a R&D program or
• Through a Subscription
• Data remain CEA Property/No members diffusion
| PAGE 14
OUTLINE
Introducing High Energy >250Wh/kg
Perspectives
High Specific Energy Lithium
Batteries
High Specific
Energy Li-ion
Cells Aluminum
cylindrical hard
casing
C ~ 35Ah, E >
250Wh/kg BOL
Especially for
those applications
where embedded
energy remains a
challenge
| PAGE 15
Cell Energy
CEA Li-ion Cell Technologies for High Energy
Technology
Gravimetric Energy
Density / Wh.kg-1
Status
LFP/Graphite
120 to 155
Pilot Line
NCA-NMC/Graph.
180 to 220
State of the art
5V Spinel/Graphite
200 to 240
Ready but R&D
on electrolyte
HE-LMO/Graphite
220 to 280
Under
development
LFP/Si-C
155 to 180
Not a target
NCA-NMC/Si-C
250 to 300
Niche markets
HE-LMO/Si-C
280 to 350
Under
development
18Ah – 130Wh/kg
35Ah – 150Wh/kg
40Ah – 300Wh/kg
| PAGE 16
The technology selected for Energy >250Wh/kg
• NMC (180mAh/g) or NCA (200mAh/g)
xLi2MnO3●(1-x)LiMO2 with
M=Mn,Co,Ni,… 3.5V vs Li
• With Si-C composite
500
450
400
350
250
1.5
LiMn2O4
LiCoO2 NCA, NMC
Market
Li3V2(PO4)3
3.5
Li(Li,Ni,Co,Mn,…)O2
LiFePO4
‘LiMnO2’
Li2FeSiO4
0
50
100
150
200
250
300
-1
Specific Capacity / mAh.g
In soft packaging
500Wh/L ; 200Wh/kg
• NMC / SiSi-C
300Wh/L ; 100-120Wh/kg
150
50
100
150
200
er
rgy
Ene
Market
Materials for High Energy
applications
licon
Carbon-Si
300 Wh/Kg
Wh/Kg
A
250
Wh/kg
• HEHE-LMO /Si/Si-C
s
composite
400Wh/Kg
B
In rigid casing
Carbon
0
(graphite negative electrode)
Li2CoSiO4 ?
+ vs. Carbon
+ vs.
Titanium
oxides
200
Li4Ti5O12
0.5
Energy Density
above 250 Wh.kg-1
‘LiMn1.5Ni0.5O4’
LiMnPO4
700Wh/L ; 300Wh/kg
300
TiO2-B
1
of the
electrolyte
above 4.3V
vs. Li
550
Wh/L
2
Materials for High Power,
Safety and Long Life
applications
4.5
2.5
+ vs. Si/C composites
w
Po
Potential / V vs. Li+/Li
2.5
/ V vs. Li+/Li
Li-rich Mn-based layered oxides
Discharge Potential
• HE-Lamellar Oxide (250mAh/g):
LiNiPO4
Li2CoPO4F
LiCoPO4
Instability
Li-metal
100 200 300 400
3400
3600
-1
• HEHE-LMO/SiLMO/Si-C
> 250 Wh/Kg
B
Specific Capacity / mAh.g Source: Saft
| PAGE 17
CEA SILICON-BASED TECHNOLOGY SUCCESS STORY
53734 ELEMENTS (1.2AH) OF 250WH/KG OPERATION AT LOW T°
IN POWER MODE
A World Premiere
It is the first battery manufactured in series from
an accumulator of more than 250Wh/kg. This
specific energy is reached thanks to an Siliconbased electrochemistry allowing to offer an
BREITLING EMERGENCY II
exceptional autonomy, power-rate and safety
2008-2010
2008
Project Kick Off
2013
2009
2010
Proof of Concept in
Representative
CEA PROPRIETARY Environment
R&D
At -20°C, high performances up to
2C rate
70% of the capacity recovered at 20°C
UL1642 standard compatibility
Cospas-Sarsat : 121 & 406MHz (24h
at AT & 20-22h EOL (2 years) at -20°C
121MHz off)
2013
Commercialization
| PAGE 18
High Energy Li-ion Battery for Energy Efficient
Military/Soldier (2010)
Battery
Acknowledgements to
Table legends:
Italic= Calculated value
Bold = Corrected value due to additional interface
resistance at electrical test bench (Pressure
connection for the commercial battery not for HE
battery)
*only between 80-50% SoC
HE
(4S)
Capacity @C/5 20°C
5
(Ah)
371
Weight (g)
Nominal voltage
13.6
@C/5 20°C (V)
Energy @C/5 20°C
68
(Wh)
Gravimetric energy
183
@C/5 20°C (Wh/kg)
Volumetric energy
285
@C/5 20°C (Wh/L)
Internal resistance
220
(mΩ)
Specific Autonomy
20°C (h)
8h30
(µ
µcycles 4,5A (6s) –
0,1A (54s))
Specific Autonomy
20°C (h)
12
(µ
µcycles of 45W
(6s) – 1W (54s))
Specific Autonomy
-20°C (h)
7h15
(µ
µcycles 4,5A (6s) –
0,1A (54s))
Specific Autonomy
-20°C (h)
10
(µ
µcycles of 45W
(6s) – 1W (54s))
Specific Energy
163
density 20°C
(Wh/kg)
Specific Energy
136
density -20°C
(Wh/kg)
Competitor
(3S)
∆
4.2
+20%
370
+0.3%
10.8
+25%
45
+50%
120
+50%
225
+25%
330
-33%
7h20
+15%
8
+50%
3h50*
+85%
3h30*
+185%
103
+60%
48*
+180%
Test protocol:
Repeated 1min µcycles, made of 4.5A6s pulses
corresponding to radio
emission followed by
CC 100mA-54s for
reception or stand-by
-Higher autonomy at 20°C (+60%) & -20°C (+180%) compared to commercial battery
-Specific pack design developed by AGLO-DEV for this « breathing » technology with high
reproducibility in term of weight (<0.5%) and resistance (<0.5%)
HIGH ENERGY BATTERY STATUS
2012 & 2013
4.5
Soft packaging
Cycle C/8 @ 40°C
[4.3-2.5V] 10x140x140mm
4
~ 9 mm
145 mm
Voltage (V)
High Energy Battery
Prismatic Soft Pouch
10 x 140 x 140mm
310Wh/kg (@C/8) 44Ah
NMC/Si-C technology 3.4V
150 mm
3.5
3
2.5
2
0
10.140.140 cell
Nominal capacity:
Unom:
Mass:
Energy density:
Internal resistance (cell) (1kHz)
300
Electrical specifications
43 Ah @ C/8 initial
3,4V
490g
300 Wh/kg @C/8 initial
4mOhm
100
200
Energy density (Wh/kg)
Temperature Range:
Max charging voltage
Min discharge voltage:
Imax charge (TBC)
Imax discharge (TBC)
CEA PROPRIETARY
-20/ +45°C
4.3-4.4V
2.5V
8A
11A
| PAGE 20
CEA 40 Ah Li-Ion Cells based on Si-C
Negative Electrode – Under Progress
NMC / Si-C 40Ah High energy Cells (C/2 max)
-Soft pouch: 315 Wh/kg BoL Loss ~ 1%/cycle
NMC electrode High
energy density
Separator
Si-C electrode High
energy density
End 2013
Specifications aimed:
>250Wh/kg EOL at cell level
Loss<0.2% per cycle
Winding
140x140mm Prismatic Cell
Assembly
CEA PROPRIETARY
EXAMPLE:
HIGH ENERGY BATTERY FOR ELECTRIC AIRCRAFT
2013
High Energy Battery
Prismatic Soft Pouch
10 x 140 x 140mm
310Wh/kg (@C/8) 44Ah
NMC/Si-C technology 3.4V
EADS Show Room
Le Bourget meeting show 2013
6000
CEA PROPRIETARY
5000
180
160
140
4000
120
3000
100
80
2000
60
40
1000
design
TBD
power design
0
200
225
250
20
energy design
large energy density
better cycle life+continuous power
275
Cell energy density (Wh/kg)
300
Normalized cell Impedance 1ms
(mOhm.Ah)
Energy versus Power Optimization
Energy Density: 250 to 270Wh/Kg or
530Wh/L to 615Wh/L; Ri : ~2mΩ
Continuous Power max: 760-790W
Weight: 70kg (55kW)
Energy: 19kWh
Continuous C-rate max: 4C
Cell power @50% DoD (W/kg)
NEXT
200
10.140.140
Pmax 1ms
Pmax (1ms)
performance
Pmax 10s
Pmax 10s
Ri 1ms (mOhm.Ah) simulation
Ri 1ms (mOhm.Ah)
0
325
Simulation
ALSO FORESEEN AUV (DRONES, UNDERWATER…)
APPLICATIONS
Unmanned Aerial Vehicles System Electrical Requirements
Voltage: ~30V
Energy: ~ 700Wh
Temp. range: -10° – +50 °C
CEA Battery Technology:
10 x 140 x 140 mm
NMC/Si-C technology
Positive Electrode = NMC
Negative Electrode = Si / C composite
Cell package = Prismatic Soft-Packaging
Cell voltage: 2,5 – 4,3 V
Targeted Energy Density: 275Wh/kg BOL (12Ah
@3C)
Battery Pack (9s2p) for 3-4h operating fly
| PAGE 23
CEA PROPRIETARY
HIGH SPECIFIC ENERGY SILICON BASED Li-ION PROTOTYPES
FOR SATELLITES
Specifications aimed:
-From Aeronautic: Soft pouch
C ~ 40Ah, E ~ 300Wh/kg BOL at
cell level. Loss ~ 0.4%/cycle
(100%DOD)
OK
ca. 300Wh/kg (C/8 @40°C)
40Ah Prismatic shape for electric aircraft
10 x 140 x 140 mm; NMC/Si-C technology
OK
-To Spatial: Aluminum hard casing
C ~ 35Ah, E > 250Wh/kg BOL at
cell level Loss < 0.07% per cycle
(80%DOD)
20 cells (18650) 3 Ah 240Wh/kg
First step prototyping for space
NEXT
*Technology: Li rich/Si-C, 250Wh/kg BoL in D-Cells like
300 cycles with C/10 charge rate and C/2 discharge rate at 80%DoD
Criterion: The remaining cell capacity after 300 cycles shall be higher or
equal to 80% of initial capacity
CEA
2014
PROPRIETARY
Rechargeable Li-ion cell
Li Rich/Si-C Technology
>250Wh/kg BoL*
50125-cells
| PAGE 24
Li-ion
System level
HIGH ENERGY ROADMAP OVERVIEW
High Energy Density
Medium-Low Power Density
Today,
Space
Today,
EV
SAFT: VES 180 SA 180Wh/kg
Panasonic18650 180Wh/kg
>2000 Cycles
Lithium metal
System level
High Energy Density
Low Power
Safety Integration
150Wh/kg // 230Wh/L
750 cycles
High Energy Density
Probably Need
Hybridization for Power
GEN
1
GEN
2
3 years
Li rich – SiC (3 years)
240Wh/kg // 325Wh/L
300-500cycles
Li-rich – Li (3 years)
290Wh/kg // 375Wh/L
200-500 cycles
5 years
Li rich – SiC (5 years)
240Wh/kg // 325Wh/L
500-1000cycles
Li-S (3-5 years)
300Wh/kg // 260Wh/L
300-500 cycles
10years
Lithium Air
System level
CEA PROPRIETARY
GEN
3
Li-Air (10years +)
280Wh/kg //240Wh/L
300-500 cycles
| PAGE 25
Emphasis on High Power Li-ion Technology
for Pulse-Load Operations
Heavy Duty Vehicles / Start & Stop /
Storage-Enhanced Grid Charging Systems
…
Florence Fusalba, Battery Program Manager
Rechargeable
Ultra High Power
Safe
Long life
| PAGE 26
OUTLINE
Power Li-ion Batteries, EDLC, LICs…
e-Buses, Start & Stop, Heavy Duty Vehicles... High
Power needs
High Power KPIs
Perspectives
High Power Liion Batteries for
High Rates &
Pulse Discharges
with Energy
LTO Fast Charge
EDLC large
Cells
Ultracapacitors
For High Power
with Long
Operating Life
Li-ion Capacitors (LICs)
as Hybrid devices
which combine the
intercalation
mechanism of Lithium
Batteries with the
cathode of an EDLC
| PAGE 27
Ragone Diagram: High Power Cells
LICs
Li-ion
Missing data : Cycle Life, Discharge rates, Pulses or Continuous, Temperatures…
| PAGE 28
Power Technologies Typically
Supercapacitor
LIC
LIB
2.3 to 2.75V
2.2 to 3.8V
2.75 to 4.2V
5 (typical)
10 (typical)
100 to 200
Specific Power (W/kg)
Up to 10000
Up to 3500
1000 to 3000
Charge T°
-40 to 65°C
-30 to 70°C
0 to 45°C
Discharge T°
-40 to 65°C
-30 to 70°C
-20 to 60°C
1 million to 30000h
100 000
500 and higher
Service life
10 to 15 years
?
5 to 10 years
Cost per Wh
20$ (typical)
?
0.50 to 1$ (large system)
Cell voltage
Specific Energy (Wh/kg)
Cycle life
Suppliers Data
Lack of experience on LICs
Self-Discharge data ? (supercapacitors: 50-100% /month)
LIBs not High Power Sized here
| PAGE 29
LICs CEA EXPERIMENTAL DATA
3300F Prismatic Li Ion Capacitor,
Power applications (means 1.5 Ah, 4.4Wh)
12Wh/kg & 20Wh/L; DC-IR 1.3mΩ @25°C
Source JSR Micro
Voltage range [3.8-2.2V]
About 2500 cycles (10C/10C)
1% capacity fade
Discharged capacities vs. C-Rate and Temperatures far more efficient than any battery
technology… but still relatively low Energy…
CEA PROPRIETARY
| PAGE 30
CEA Li-ion Cell Technologies for High Power
GEN1: LFP for High Power Discharge
LFP/G
Cylindrical Hard Casing (Al)
Wound cell
Dimensions :125 mm Height – 50mm Diameter
Practical Capacity : 16Ah [3,6V-2,5V]
120Wh/Kg – 3C Rate
Mean Discharge Voltage: 3.2V
Lithium Iron Phosphate Technology – Cycle Life in a power mode (5C chargedischarge rates) exhibits only -0.0017% capacity loss per cycle upon 7500cycles…
CEA PROPRIETARY
| PAGE 31
CEA PILOT LINE LFP CELLS DEVELOPMENTS
EXAMPLE : Power-Sized versus Energy-Sized LFP chemistry
Performances
assesments started
Specifications
#Customers
LFP/G Energy
V1
LFP/G High
Energy
E0
LFP/G Power
PG0
LFP/LTO Power
P0
Q2/12
Q3/12
Q4/12
Q4/12
16.5Ah – 3.3V
112Wh/kg220Wh/L
C-2C* Charge
2C-5C* Discharge
19Ah – 3.3V
130Wh/kg250Wh/L
C/2-C* Charge
C-2C* Discharge
4
2
10Ah – 3.3V
11Ah – 1.9V
70Wh/kg-135Wh/L
50Wh/kg-100Wh/L
3C-5C* Charge
10C-30C* Charge
10C-30C*
10C-30C* Discharge
Discharge
1
1
*Continuous-Pulsed
CEA PROPRIETARY
| PAGE 32
Li-ion Cell Technologies for Very High Power
CEA Li-ion Power Cells GEN1
LFP/LTO
66
LMO/LTO
3,5
64
Umax
3
62
60
2,5
Voltage (V)
Temperature (°C)
50125 Capacity :
11Ah
45-50Wh/Kg 15-30C
Rate
Mean Discharge
Voltage: 1.9V
58
100A 3s
37C
56
2
200A 3s
74C
Tc1-2_amb
54
Tension
1,5
300A 3s
148C
52
3s pulses every 10% SOC @ 65°C
50
36000000
56000000
76000000
96000000
116000000
136000000
Umin
156000000
1
176000000
test time (ms)
⇒ Extended cycle life
⇒ No Capacity Loss after 10000 cycles
100%DOD@C-Rate (RT)
High Power Short Pulses Li-ion for F1 KERS:
150C charge-discharge max limit
Lithium Titanate Technology
⇒ Fast charge / Ultra High Power
⇒ Long cycle life
⇒ Low self-discharge
⇒ Stable/Safe behavior
⇒ Very good low temperature capability
NMC/LTO also possible for higher
energy density (~90Wh/kg)
LTO Technology competitive for Power modes if C-rates >15C
CEA PROPRIETARY
| PAGE 33
Silicon Technology for High Energy Medium Power
Nano sized Silicon -> 90% restituted capacity at -30°C @ C/4 (ref. -ALEC @PSC 2012)
Si-C relatively good high rate discharge capability, not good in high rate charge mode (ref.
EaglePicher* @SPW 2013)
NMC/Si-C high performances up to 2C rate @-20°C; +70% of the capacity recovered &
Low self discharge (<2%/month) (ref. CEA** @PSC 2012, SPW 2013…)
*
**
Good Power capability at low T°
°
May find already some applications in security,
Low Self-discharge
military & aerospace markets where low cyclelife is
Low Cycle-Life to be improved… sufficient
| PAGE 34
CEA PROPRIETARY
Interest in High Voltage Spinel Oxides
“5V Spinel”
Generic composition is LiNi0.5Mn1.5O4
Theoretical capacity = 146.7 mAh/g at ~4.7 V vs. Li+/Li (Ni4+/Ni2+)
High cycle life, High rate capability, Energy density increase strategy
Intensity (u.a.)
Spinel structure with a ~ 8.18Å
Medium power
design
Target ~150 Wh/kg
in hard casing
10
20
30
40
50
60
70
80
Angle 2θ
θ (°)
CEA PROPRIETARY
| PAGE 35
CEA High Voltage Spinel Oxide: LiNi0.4Mn1.6O4
5V Spinel/Graphite prototype:
Cell design
Soft Prismatic 40x70mm
Cell capacity
2,4 Ah
Electrodes loading
3 mAh/cm2
Positive electrode
LiNi0.4Mn1.6O4
Negative electrode
Graphite
Electrolyte
LiPF6 in carbonates + additives
Separator
2500-type Celgard®
Potential at equilibrium
4.6 V
Specific energy
200Wh/kg
Target: Similar Energy Density to current commercial Power sized
cells but with Higher Power rate capability due to higher cells
voltage (4.6V versus 3.6V) and lower battery oversizing due to higher
discharge rate capability especially at low Temperature
Lithium Titanate Technology
⇒ Fast charge / Ultra High Power
⇒ Higher low temperature capability
CEA PROPRIETARY
Versus LTO:
LFP: 1.9V
LCO, NMCs: 2.1V
LiMn2O4: 2.4V
5V Spinel : 3.2V
| PAGE 36
Li-ion Power Technologies Perspectives / Next Gen.
CEA Li-ion Power Cells GEN2
‘3V’ Li-ion Cell by coupling of 5V Spinel with LTO
5V Spinel versus LTO
Higher Power capability at low temperature
Higher DOD (higher useful capacity or lower
oversizing)
No Li plating event (safer)
Lower Self-discharge (compared to graphite)
Target: 10kW/kg
BUT (Compared to Graphite)
More cells in series to increase
battery voltage
Lower energy density <100Wh/kg
CEA PROPRIETARY
| PAGE 37
CEA POWER TECHNOLOGIES
CEA Batteries Power
Technologies
Fast charge / High Cycle Life
LTO-based
Li-ion
LICs
Power LMP
LMNO (5V Spinel)
Power LFP
NMC/Si-C
Hybrid SC
Low cost / Low T°
CEA SC/LIC Power
Technologies
High Energy/ Power @Low T°
CEA PROPRIETARY
| PAGE 38
HIGH POWER ROADMAP OVERVIEW
2014
2016
Auxiliary power unit
(APU)
Propulsion
(hybrid)
Propulsion
(full electric)
High Safety
durability
Power density
durability
Energy density
GEN
1
GEN
1
GEN
1
LFP-G hard casing
100 Wh/kg
5000 cycles
LFP-LTO hard casing
2000 W/kg
>10000 cycles
NMC – G
200 Wh/kg
1000 cycles
GEN
2
GEN
2
GEN
2
LFP blend-G
130 Wh/kg
5000 cycles
Blend-LTO
3000 W/kg
10000 cycles
NMC – Si/C
250 Wh/kg
300 cycles
CEA PROPRIETARY
| PAGE 39
Power Technologies versus Applications (Examples)
eBUS >200kW, 10-20kWh
Start & Stop: 2-3kW, 250Wh
Autonomous Heavy Duty Vehicles >500kW, >20kWh
Study of Case
Stationary ESS: Other targeted application field (not discussed here)
10-10MW
Energy & Power
1-50MW
High Power
100kW-1MW
Energy & Power
Source: ESA (RT Efficiency versus Cycle Life)
5-50kW
Energy
| PAGE 40
OUTLINE
Power Li-ion Batteries, EDLC, LICs…
e-Buses, Start & Stop, Heavy Duty Vehicles... High
Power needs
High Power KPIs
Perspectives
Rechargeable
Ultra High Power
Safe
Long life
| PAGE 41
LI-ION TECHNOLOGY IN POWER MODE
e-BUSES
Electric Energy Storage with Power Capability
Demonstrating Project under progress (ElLiSup)
Round trip : Battery pack charged at the end of the bus line. Lifetime of the bus : 15 years
(ca. 15000 cycles)
Embedded energy 12 kWh (Mini) discharged in 26min. Charge Max Power :
180 kW, 4 min (at least 20% of capacity). Voltage of the battery : between 400V and 600V
CEA Work:
Design and manufacturing of packs
Key issues : end of bus line charge = 250
kW in 5mn => cooling / mechanical
integration and validation
System integration tests on the CEA test
bench. Bus integration.
In use tests
CEA PROPRIETARY
CEA Grenoble Scale 1 Demonstration
| PAGE 42
LI ION TECHNOLOGY IN POWER MODE
e-BUSES
Electric Energy Storage with Power Capability
Battery Design
4 battery packs, their cooling system and BMS
480 kW DCDC converters for the main power
Power box (fuses, contactors)
4 inverters (for communication) and 1 motor for
power
2 DCDC converters for the 24V auxiliaries bus
Vehicle central unit
Station Design
Key issues : harmonics, noise, perturbation on the
grid, 250 kW safe interface with the bus
Electrical and thermal architecture
Power electronics definition
Manufacturing by sub-contractor
System tests with the bus
CEA PROPRIETARY
CEA Battery Modules
250kW charging station
| PAGE 43
12V Li-ion Starter Battery for Stop & Start Vehicles
Concern
• Exemption Risk on Lead Starter Batteries reviewed in 2015
Goal: decrease
• Lead : Today 25-27kg (full display)
embedded
• Average current life time = ca. 5 years (i.e. : 80% of French users)
capacity
=> Take advantage of Li-ion in term of charge sustaining (CO2 reduction)
Performances requirements are summarized below:
Battery Target Design with Li-ion
Current Design with Lead-Acid Battery
Typical requirement: C(20h)= 70 Ah
Energy C(20h)= 70 Ah
Typical requirement: 760A (EN)
Power 760A (EN)
Typical requirement: [- 30°C ; 75°C]
Working Temp [-30°C ; 75°C]
Fully compatible with 12V network
12Vnet Fully compatible with 12V network
CEA PROPRIETARY
Li-ion Starter Battery Specifications:
Unom = 12V
Imax =
760A, 10s @-18°C 100% SOC
475A, 10s @-30°C 100% SOC
988A, 1s @23°C 80% SOC
Umin = 7.5V 10s -18°C @Imax
Charge acceptance:
100A @0°C & 50%SOC
200A @25°C & 70%SOC
Capacity: 10Ah min EOL
Weight: 10kg max Volume: 9.14L max
Energy: 120Wh EOL
Max Operating T°: 80°C (Mean 50°C)
(12Wh/kg min)
Max Calendar T°: 100°C
Pmax: 11856W
| PAGE 44
12V Li-ion Starter Li-ion Proposed Solution
⇒ Only LFP/LTO solution allows to respond to the needs with weight < 10kg
⇒ Best chemistry in SAFETY and CYCLE LIFE for such charge & discharge rates
⇒ Demonstrated by CEA under Start & Stop mission profiles with 0.7Ah 24V cells :
2,8
43C Charge (3s)
2,6
2,4
43C Charge (2s)
Voltage (V)
2,2
5,73C Charge (30s)
2
1,8
Stand By (10s)
1,6
5,73C Discharge (30s)
1,4
43C Discharge (5s)
1,2
µ hybrid profile
86C Discharge (1s)
1
123,505
123,51
123,515
123,52
Time (h)
123,525
123,53
1 HEV profile = An accelerated duty profile built from the succession of these
micro cycles (100 µcycles ~ 1 week of actual operation):
A discharge at max. current 60A and 6V cut-off voltage 60A (1s) ⇔ 80C rate
A charge at max. current 30A and 30V cut-off voltage 30A (3s) ⇔ 40C rate
Start & Stop Experimental Data
⇒ LFP/LTO accumulator allows to restitute ca. 30000 times more than 40% of its
total capacity at very high rates (>>50C) in both charge and discharge modes
CEA PROPRIETARY
| PAGE 45
LFP/LTO TECHNOLOGY FOR ULTRA HIGH POWER MARKETS
HEAVY DUTY VEHICLES
Autonomous between stations
Example of Required Specification :
-Partial Cycling Hypothesis for >100k Cycles with ability to sustain >200k peaks @15kWh
Storage Systems Sizing w/o hybridization (Super Capacitors)
- Parameters of interest:
Charge power / Discharge maximum level
Available Energy and Restituted Energy/kWh
(Power peaks to sustain not taken into account…)
⇒ LFP-LTO = End of life OK with needed DOD
⇒ Others = need SC hybridization for life cycle > 2 500 000 µcycles
CEA PROPRIETARY
| PAGE 46
Cost of Battery Pack Analysis
Case n°1 : e-BUS Specifications
• Pack Energy > 20kWh
• Charge power ability = 260kW, 20s.
Techno
Type of cell
LFP / LTO
high Power
LFP / Graphite
Energy
LFP / Graphite
Power
pack config.
Nbr of cells
cell shape
cell nominal Capacity (Ah)
cell nominal Voltage ( V)
Pack total Energy (kWh)
4P x 312S
1248
50-125 cyl.
11
1,9
26
8P x 192S
1536
50-125 cyl.
16
3,2
78,6
6P x 192S
1152
50-125 cyl.
10
3,2
36,9
213
9,1
260
8,6
213
3,0
260
3,0
213
6,4
260
6,4
100-110
4,0
404
100
1,27
385
65
1,76
Discharge Power ( kW)
Cell Discharge Rate (equiv. xC)
Charge Power ( kW) ( duration= 20s)
Cell Charge Rate (equiv. xC)
Cost calculation , hypothesis= 500 packs/year
Pack battery Global Cost (cells+ pack system) ( k€)
Pack battery - Cost of Energy (k€ / kWh)
Pack battery - Cost of power (€ / kW)
250
Cost of Power : LTO = about x 1,5 LFP/G power pack solution
Pack Weight, Volume : nearly the same in case of using LFP/G power cells
Case n°2 : Simulation in the scope of a high power charge requested application
• Pack Energy > 20kWh = Unchanged
• Charge power ability = Power pick of ~900kW, up to 5-10s
Techno
Type of cell
LFP / LTO
high Power
LFP / Graphite
Energy
LFP / Graphite
Power
pack config.
Nbr of cells
cell shape
cell nominal Capacity (Ah)
cell nominal Voltage ( V)
Pack total Energy (kWh)
4P x 312S
1248
50-125 cyl.
11
1,9
26
24P x 192S
4608
50-125 cyl.
16
3,2
236
18P x 192S
3456
50-125 cyl.
10
3,2
110,6
213
9,1
900
213
1,0
900
3,5
213
2,1
900
7,4
285
1,21
317
180
1,63
200
Discharge Power ( kW)
Cell Discharge Rate (equiv. xC)
Charge Power ( kW) ( duration= 5-10 s)
Cell Charge Rate (equiv. xC)
Cost calculation , hypothesis= 500 packs/year
Pack battery Global Cost (cells+ pack system) ( k€)
Pack battery - Cost of Energy (k€ / kWh)
Pack battery - Cost of power (€ / kW)
30
100-110 = unchanged
4,0
117
Optimistic
Cost of Power : LTO = about divided by 2
vs. LFP/G power pack solution
Pack Weight, Volume : about 3 times higher if
using LFP/G power cells
Use of LFP/G Energy cells is clearly not
competitive !!
CEA PROPRIETARY
| PAGE 47
OUTLINE
Power Li-ion Batteries, EDLC, LICs…
e-Buses, Start & Stop, Heavy Duty Vehicles... High
Power needs
High Power KPIs
Perspectives
LFP/G High
Power Li-ion
Batteries for High
Rates & Pulse
Discharges with
Energy
LFP/LTO Ultra
High Power Li-ion
Batteries for High
Rates & Pulse
Discharges with
Fast Charge
Design for High Voltage
Reduced RI & Lower heat
generation (RI2)
Better heat dissipation
Simple cell-to-cell connections
Flexible 2D form factor
| PAGE 48
High Power KPIs / Markets / Perspectives
⇒ 2020 KPIs (Ref. STRATEGIC ENERGY TECHNOLOGY PLAN © European Union, 2011) :
Li-ion Batteries KPI = 10-year battery design life and 20-year power and balance-of-system
design life; Charge-discharge T° range: -20°C to 70°C; Charge cycles: greater than 10 000
times at 70-80% DOD ; Fully installed system (All-in cost to install a step-up transformer)
under 200€ per kilowatt-hour
Supercapacitors KPI = Energy densities >15Wh/kg; A cost reduction down to maximum of 10
€/kW and a specific power > 30kW/kg
Large Volumes Markets:
Start & Stop:
2015 Market size $242.6M
Grid Enhanced Energy Storage
$16-35 Billions >2020
(for 7 - 14 GW new installed capacities per year)
Small Volumes High Added Value Markets:
Autonomous Heavy Duty Vehicles >500kW, >20kWh
Aerospace (helicopters, launchers, radar satellites…), military…
CEA PROPRIETARY
| PAGE 49
End of lecture
Thank you !
Contact: florence.fusalba@cea.fr
Commissariat à l’énergie atomique et aux énergies alternatives
Centre de Grenoble | 38054 GRENOBLE Cedex 09
T. +33 (0)4 38 78 29 20 | F. +33 (0)4 38 78 51 98
Direction de la Recherche
Technologique
Liten
Etablissement public à caractère industriel et commercial | RCS Paris B 775 685 019
| PAGE 50