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Status on safety of large lithium ionStatus on safety of large lithium-ion batteries in Japan
Central Research Institute of Electric Power Industry(CRIEPI)
Yo Kobayashi
Copyright © 2011 by CRIEPI
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Outline
• Li-ion for EV & Stationary in Japan– EV sales volume in Japan– Unfavorable / Favorable conditions for EV– Stationary Li-ion “Boom” after 3.11
• Challenge to safe Li-ion batteryg y– Choice of electrode materials for EV– New material approach in National Project (NEDO)New material approach in National Project (NEDO)
• Our approachPure polymer & Li metal free “Li ion battery”– Pure polymer & Li-metal free Li-ion battery
– Forced destruction test in NEDO projectS
Copyright © 2011 by CRIEPI
• Summary
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EV total sales in Japan
12000
10000
6000
8000i-MiEV LEAF
4000
6000
2000
0
ul-0
9
p-09
v-09
n-10
ar-1
0
y-10
ul-1
0
p-10
v-10
n-11
ar-1
1
y-11
ul-1
1
p-11
Copyright © 2011 by CRIEPI 3
Ju Sep
Nov Jan
Ma
May Ju Sep
Nov Ja
n
Ma
Ma Ju Sep
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Unfavorable condition for EV
• Deficiency in electricity after 3.11Actual rotation blackout in Tokyo– Actual rotation blackout in Tokyo
– Save on electricity: 1st priority in JapanNo TVCF about EV until August– No TVCF about EV until August
Donation from French Red Cross : €13M “Merci pour support”
Earthquake & Tsunami(11/Mar) Rotation Blackout(15/Mar)
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Favorable Wind
• EV : Recognized as also EPS*Strong adverse wind to Nuclear power• Strong adverse wind to Nuclear power generation
Li it d f l h i F il f l1st P i it– Limited fuel choice: Fossil fuel 1st Priority– EV: Still lower CO2 emission than oil
d• 2nd use of EV battery Target : Smart grid
LEAF to Home
Copyright © 2011 by CRIEPI 5 *Emergency Power System
Ref : NISSAN Web Site
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Released Stationary Li-ion after The Earthquake in Japan
KOKAM(Korea) BYD(China) SONY
2.5 kWh/ €18900 2.4 kWh/ € 8000 300 Wh/ € 1500
NEC PANASONIC TOSHIBA
6 kWh/ € 25000 3.2 kWh/ € 16800 1.6 kWh/ € 15000
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Bad New for NaS*, Warning for Li-ion?
• NaS(NGK): Fire accident on 21th/Sep.p
• Control fire: 2 weeks with “Sand”• NGK
Stop production of NaS Recommend to stop operation of NaS
• Li-ion can’t substitute such huge it i di t l
Introduction of 80MW NaS toTohoku Electric Power Company
capacity immediately. • But, should be in the future?
If Li i f EV Li i f LL**??• If so, Li-ion for EV=Li-ion for LL**??
Planed Jan/12S d d A /12*Sodium Sulfur Battery
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Suspended Apr/12Sodium Sulfur Battery**Load Leveling
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Li-ion Cell Size History in Japan NISSAN PrairieWith 100Ah Li-ion
• 1990’s: Challenge to 100 Ah– SONY: Cylindrical (1996 NISSAN Prairie)y ( )– Panasonic: Cylindrical (2000, NEDO)– GSY*: Rolled Prismatic (2000, NEDO)– MHI**: Prismatic (2003)All 100Ah cells disappeared
2000’ S f t i 1st i it f ti lPanasonic (NEDO)100Ah x 8 module• 2000’s: Safety is 1st priority for practical use
– GSY: 50 Ah Prismatic (2009, Mitsubishi i-MiEV)– AESC***: 30 Ah Laminate (2010 Nissan LEAF)
100Ah x 8 module
AESC : 30 Ah Laminate (2010, Nissan LEAF)– TOSHIBA: 20 Ah Prismatic (2011, Honda EV-Bike)– MHI: 50 Ah Prismatic (2010, LL for 100 kW PV) MHI 100Ah
*GS-Yuasa**Mitsubishi Heavy Industrial
MHI 100Ah
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Mitsubishi Heavy Industrial***Automotive Energy Supply Corporation
(Joint company of NEC&NISSAN)
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Safety Concept of EV Battery
• 2010: 100 Wh/kg“Conservative” material choice: 600
Small CellFor PC
– Conservative material choice: LiMn2O4, Graphite, Li4Ti5O12
– Not so high energy density l 400
Large cellEV(2020)
Post Li-ionEV (2030)Not so high energy density
– Not so large cell• 2020: 200 Wh/kg
Wh/
l
200• 2020: 200 Wh/kg
– High Cap. Anode/CathodeEl t l t M difi ti
100 200 300
Large cellEV(2010)
– Electrolyte Modification• 2030: >300 Wh/kg
Wh/kg
– Solvent free (TOYOTA)
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Difference in Position of Safety : Donor or Acceptor?ECS Boston 2011
SafetyLi-Air Others
Japan Battery Meeting 2011
Li-Air OthersCathode
AnodeModelingCathode
Ch t i
All-Solid
Li Air Others
CellCharacteri-zation
AnodeCharacteri-zation
ElectrolyteElectrolyteCell
• US(ECS) : Li-ion Acceptor– Cell safety and modeling are their interest
Ionic Liquid
• Japan : Li-ion Donor– “Expected” safe materials (Ionic Liquid, Solid Electrolyte)
are our interest
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are our interest
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National Project concerning Safety
No specific national project about safety in Japan1 Expected safe materials: Mainly focused on electrolyte1. Expected safe materials: Mainly focused on electrolyte Solid electrolyte(Inorganic/Glass/Polymer) Ionic liquidq Flame retardant electrolyte Ceramic coated separator/electrode
2. Safety test: Battery for PHEV (10 Ah class) Cell/Module/System: JARI C Forced destruction test: CRIEPI
3. Discussion on Regulation Li ion for residential (Tokyo Fire Department) Li-ion for residential (Tokyo Fire Department)
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Our approach・Solution for the safe battery・Estimation of event in abuse conditionEstimation of event in abuse condition
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Solvent-free & Metal-free Lithium-ion Polymer Battery[Graphite |SPE | LiNi1/3Mn1/3Co1/3O2]x3 stack in one package
Solid Polymer Electrolyte(SPE)No flammable vapor (Safety)Printing process (Large-scale)Printing process (Large-scale)High-voltage stack (High energy density)No Li metal (Low production cost)
4V 4V 4V
12V
4V 4V 4V
C/8, 50oCCycle property of stack cell
Copyright © 2011 by CRIEPI
10cm3 Stack 12 V battery (100cm2)
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Proposed Safety Test
Test Type Open SpaceTest
Accelerated Rate Calorimeter (ARC)
Forced Destructionusing Pressure VesselTest Calorimeter (ARC) using Pressure Vessel
Advantages Simulate actual event
Precise Temp. of thermal runaway
Precise pressure trace in event
No size limitationVarious testVi ibl
Reaction rate estimation by Temp.
Reaction rate estimation by pressureCombine nail testVi iblVisible Visible
Drawbacks Poor Quantitative
InvisibleSize limitation
Size limitation(<100Ah)Can’t simulate reaction
comparison Difficult to nail/crash with ambient air
Labs & SNL Thermal Hazards CRIEPILabs & Companies
SNLINERISJARI
Thermal Hazards CRIEPI
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Li-ion Forced Destruction System
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Schematic of Pressure Tight Housing
Copyright © 2011 by CRIEPI
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Proposed Forced Destruction Test • Concept
– Estimate maximum energy of cells Pmaxgyin event
– Not safety judgment
E t i ti ht h i Pres
sure
vent
• Event in pressure tight housing– Max. pressure(Pmax) & dP/dt :
Reaction rate estimation
P E dP/dt P
Reaction rate estimation– Outgas volume estimation from the
pressure before/after event (P)
time
NeedleA h• Soft (blunt) & staircase Nailing
– Simulate spot internal short circuit without using metal chip inside dl
e P
ositi
on
Temperatu
Approach
Eve
nt
without using metal chip inside
• Goal– Compare fresh & cycled cellN
eed ure1mm & pause
Copyright © 2011 by CRIEPI
Compare fresh & cycled cell– Confirm cycled≒safe cell
17
time
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Summary : Li-ion for EV & Stationary-use in Japan– Present
• Conservative battery design in EVS f t N t i t t i JSafety : Not so serious news at present in Japan
• Stationary : Quick release after 3.11. Safety check is needed Solvent free Li-ion polymer : Will be one solution Solvent free Li ion polymer : Will be one solution
– Issues• Keep battery safety after cyclesp y y y
Compare new & cycled cells using forced destruction test
– Higher energy density (for long distance EV)• High capacity electrodes : Lots of choice• Improvement of safety with high capacity electrodes
El t l t & i t f d i K t h l f f t Electrolyte & interface design : Key technology for safety
– Innovative post Li-ion (>300 Wh/kg)• Academic approach but very serious competition in Japan
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• Academic approach, but very serious competition in Japan• No solution in organic liquid electrolyte?
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Appendix: Science Museum in 1974
• My father explained the future technology of the 21th century21th century– TV phone
Electric Vehicles– Electric Vehicles
Now,I j “Vid Ch t” i t h• I can enjoy “Video Chat” using smart phones.
• But, EV is just start running..My father had told me a lie….
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But, I still have a dream..
• I don’t want to tell a lie to my son again.MerciMerci.
NISSAN LEAF
This work is financially supported from New Energy and Industrial Technology Development Organization (NEDO)
Copyright © 2011 by CRIEPI 20
Development Organization (NEDO).