Tetsuya Osaka at BASF Science Symposium 2015
Transcript of Tetsuya Osaka at BASF Science Symposium 2015
New diagnosis method for LIB health conditions using EIS
Faculty of Science and Engineering Waseda University
Tetsuya Osaka
March 10th, 2015"Science Symposium Ludwigshafen“
BASF Science Symposium 2015
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Contents
• Introduction
• Design of Equivalent Circuit for Electrochemical Impedance Spectroscopy on LIB
• Dependence of EIS on Temperature
• EIS for Degradation Analysis of LIBs
• Square Current/Potential-EIS
• Summary
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IntroductionWhat is
Electrochemical Impedance Spectroscopy (EIS)?
Input signal
-0.005
0
0.005
0.005 0.01 0.015
-Z"
/ Ω
Z’ / Ω
Frequency response
Measure Data processing
EIS can analyze electrochemical devises without destruction of the
devises, because of small-amplitude sinusoidal input. divide complicated process of electrochemical reaction into
elemental processes, because of their characteristic frequency.
EIS method can be powerful for evaluation of Lithium-ion battery (LIB)3
The Electrochemical Society Interface
PENNINGTON CORNER
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Electrochemistry plays a
A Turning Point for ECS
Journal of The Electrochemical Society
th
Tetsuya OsakaECS President
Recycling plant of battery Maintenance‐free Analysis without destruction
Substation
Smart grid
Substation
Substation
Possibilities of Innovation from Battery Systems
Plug‐in hybrid vehicles (PHEVs) Battery electric vehicles (BEVs) Fuel cell electric vehicles (FCEVs)
Home energy management system (HEMS)
Factory energy management system (FEMS)
Solar power
Wind power
Air plane
PENNINGTON CORNER
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A Turning Point for ECS
Journal of The Electrochemical Society
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Recurrence Movement of LIB Technology to Japan
Example of LIB accidents
【電気自動車】 浙江省杭州市の武林路で2011年4月11日午後3時(日本時間4時)ごろ、電動タクシーが発火・炎上した。乗客はなく、けが人はいなかった。(新華社、鞠煥宗撮影)
2011.4.11,早朝 2011.4.11,早朝
2011.4.11,16時 2011.7.10,早朝
2011.11.26
Fig1 フランスでの事故 Fig.2 ブラジルでの発火事故
iPhoneが発熱し,煙と火花が出るという怖い体験をしたユーザーたちがいる.ブラジルで1台,オーストラリアの飛行機内で1台のiPhoneから火が出た. 先に報告されたのはオーストラリアでの発火だ.11月25日,リズモア発シドニー行きのRegional Express航空の機内でのことだ.RegionalExpress社の公式声明によると,着陸後,ある乗客の携帯電話が「かなりの
寮の濃い煙を出し,やがて赤く光った」.客室乗務員が消火し,けが人は出なかったという. 機種は公表されておらず,上に掲載した写真では,「iPhone 4」か「iPhone 4S」かは判断できない. ブラジルの発火は11月22日で,オーストラリアの発火より先に起きていたが,報告されたのは最近のことだ.アイラ・モタさんが,フランスで購入した8GBのiPhone 4を充電しようとして,コンセントにつないで就寝した.夜中に目を覚ますとiPhoneから火花と煙が出ていたという.
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EVs mount LIBs made in China began to spread after Shanghai EXPO. Several years passed from the EXPO, accidents of the EVs have increased.Because safety on long cycles are not enough. Therefore Japanese technology has been attracted again, resulting in recurrence movement of LIB technology to Japan
Super dry room andProduction line of lithium secondary batteries (< 1 Ah)
【Super dry room】Floor area:ca. 14.85m3
Cleanness (Minimum):100 (JIS B9920クラス5)Dew point of air supply:‐95Dew point in the room:‐70connected directly with 2 glove boxes
(Dew point <‐95, O2 < 2ppm)
【Laminated LIB fabrication】a) Mixier, b) Electrode coaterc) Roll press, d) Ultrasonic weldere) Heat sealer, f) Vacuum sealer with electrolyte supply
Leading LIB fabrication process in academic fieldA number of evaluation equipment for LIBs
Charge‐dischargetest equipment
Glove box filled with Ar(Dew point:‐110)
Electrochemical measurement system
Second dry room was built on the basis of the experience by the first one.
Floor area:8.75 m2,Dew point in the room:‐60
Dew point of air supply:‐95(0.04 ppm)Dew point in the room:‐70
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First dry room
Floor area:14.85 m2
First introduction of a super dry room among universities in Japan (1999)
Construction of leading-edge dry room on the basis of the know-how by first super dry room (2010)
Deliver CUTTING EDGE MATERIALS and TECHNOLOGIES
Facility for production of medium sized LIB: Laminate type (~5Ah)
Final completion in March, 2014
Super dry room andProduction line of lithium secondary batteries
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【Dry room】Floor area:ca. 62.71m3
Cleanness (max.):10000Dew point of supply air :‐80Dew point in the room:‐50
【Apparatuses for Laminated LIB】・In dry room
Clicking machine,Roll press machine, Welder,Film mold machine,Heat sealer, Vacuum sealer with electrolyte injector,etc.
・Clean benchMixer, Coater
Super dry room andProduction line of lithium secondary batteries (~10 Ah)
Ultrasonic WelderCutting frame
Dry room: 60 m2 + Coating space: 6 m2
Production line of lithium secondary batteries (10 Ah class)
Full automaticlamination system
Heat sealer Electrolyte injector and vacuum sealer
LIB production ability of our laboratory
Small LIB (100 – 1500 mAh) for research can be produced by NEDO RISING projectOur LIB is comparable to commercial LIBs
Composition of pouch type batteryWaseda LIB with electrodes lab. made 55 mAhCathode = LiCoO2 /AB+KB/PVdFAnode= Graphite /AB/PVdFSeparator single PPElectrolyte 1MLiPF6/EC DEC=1 1 with VC
Waseda LIB with commercial electrodesCathode active material LiCoO2Anode active material Graphite Separator single PPElectrolyte 1MLiPF6/EC DEC=1 1
Commercial LIB for electric assisted bycicle (5 Ah)Cathode active material Mn based materialAnode active material Graphite
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30
40
50
60
70
80
90
100
0 1 2 3 4 5 6
No
rmal
ize
d C
apac
ity
%
C-rate C
BatterySystem
Evaluation
Materials
terytem
E
Anode Cathode Electrolyte
Feedback to developmentof materials and system
Material evaluation as a actual battery
Advantage of our group
Non-destructive analysis by electrochemical impedance spectroscopy
New material creation by electrochemical Nano-technology
Integration technology and system optimizationfor battery performance
Our LIB production technique enables materials we developed to be evaluated as actual battery
Higher performance than commercial LIB
One setmultiple sets
~5 Ah
Specification of lithium secondary batteries made by Osaka Lab.
~2.5 mAh~75 mAh
multiple sets
2~3Ah
70mm×30~70mm
18 mm φ70 mm×70 mm
70 mm ×70 mm70mm × 140 mm
Semi automatic assembly machine Handmade
~1.5 AhCapacityLiCoO2/C
60 mm×800 mm
One set
ElectrodeSize
Slurrypreparation
Coater
Assembly
Sheets One set
Pouch Cell Cylindrical Cell Pouch Cell Pouch Cell Button Cell
Roll to Roll (W200mm)
Desktop Coater
Powder mixing/ Slurry preparation (0.5L~5L) (0.15~1L)Mixer
Roll to Roll (W150mm)
Coating Duplex Duplex Duplex Simplex Simplex
Center of Innovation ProgramSmart Life Support Innovation R&D Center
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Visualization of BEMSSeminar room, Office room
Clean roomElectrode coating
Dry roomLIB assembling
Super dry roomLaboratory
Separated laboratories with confidentiality
Industry-academia partnership project room
Innovation design center〜
Waseda Smart Life Support Innovation R&D Center(Final completion in December, 2014)
R&D Center
Hall
Center of Innovation ProgramSmart Energy System Innovation R&D Center
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Contents
• Introduction
• Design of Equivalent Circuit for Electrochemical Impedance Spectroscopy on LIB
• Dependence of EIS on Temperature
• EIS for Degradation Analysis of LIBs
• Square Current/Potential-EIS
• Summary
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Possible Phenomena relate to LIB performance
Phenomenon in LIB LIB performance
Electron Migration・Electrode layer・Current collector / Electrode
layer・Current collector
Power decayCapacity decay
Ion migration・Electrolyte・Electrolyte in electrode layer・SEI
Power decayCapacity decay
Electrochemical reaction (Chargetransfer)
・Active material / Electrolyte (Active material / SEI)
Power decayCapacity decay
Life deterioration Safety deterioration
Diffusion in Solid of Active MaterialsPower decay
Capacity decay
Cu current collectorAl current collector Electrolyte
Anode active materialCathode active materialElectron conductive additive
SEI
SEI: Solid Electrolyte Interphase 15
Design of Equivalent Circuit for LIB
• Examples– Solid-Solid contact interface
– Active material / Electrolyte
– SEI Active material
Electron conductive additive
Current collector
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Design of Equivalent Circuit for LIB
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SEI
Active material
Electrolyte
Li+
Li+
Li+
• Examples– Solid-Solid contact interface
– Active material / Electrolyte
– SEI
Key phenomenon should selectedfor practical application of EIS to LIB evaluation. 17
Nyquist plot of a Commercial LIB
Nyquist plot obtained from a LIB at 100% of SOC. (Frequency range100 kHz ‐ 0.1 mHz)
<Conditions>Equipment:Solartron SI1287, SI1252ACharge‐discharge:Constant current (1 A)‐Constant voltage (4.2 V kept until less than 1 mA).Impedance measurement:Open circuit voltage at a SOC, Amplitude 10 mV, Frequency range 100 kHz ‐ 0.1 mHz.
Feature 1•High frequency (> 5 kHz): Inductive response
Feature 2•Middle frequency (5 kHz - 1 Hz): Several overlapped semicircles
Feature 3•Low frequency (< 1 Hz): Diffusive response and limiting capacitance
‐0.01
0
0.01
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0.05
0.06
0.07
0 0.01 0.02 0.03 0.04 0.05 0.06
‐Z"
/ Ω
Z’ / Ω
← 100 kHz
10 kHz →
← 1 mHz
1 Hz↓
0.1 mHz →
Feature1
Feature 2
Feature 3
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Fundamental Equivalent Circuit for Batteries
The equivalent circuit containsCharge transfer reactions and diffusions on anodeCharge transfer reactions and diffusions on cathode Ionic resistance of electrolyte.
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‐0.01
‐0.005
0
0.005
0.005 0.010 0.015
‐Z"
/ Ω
Z’ / Ω
Experimental Data Fitting
R2
Rs
CPE2
ZW2
R1
CPE1
ZW1
L0
R0
Fundamental equivalent circuit with inductive element
Inductive response (Feature 1)
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Equivalent circuit with inductive element
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ZD(L-1)
L-2L-1
L-1
ZD-1(L-1)
ZD-2(L-2)
Distributeddiffusion length
Uniformdiffusion length
Size distribution of active material
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Equivalent circuit counting diffusion distribution
T. Osaka, S. Nakade, M. Rajamaki, T. Momma, J. Power Sources, 119, 929 (2003)
Equivalent circuit 2 can fit the impedance responses of features 2 and 3 in a commercial LIB. 23
Solid Electrolyte Interphase on anodeSolid Electrolyte Interphase (SEI) Desolvation Electrolyte
(Solvated ion)
Li+ migration in interphase
Migrationin electrolyte
Migrationin SEI
Diffusionin graphite
http://www.jst.go.jp/kisoken/crest/report/sh_heisei10/shigen/ogumi.pdf
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Equivalent circuit counting SEIT. Osaka, T. Momma, D. Mukoyama, H. Nara, J. Power Sources, 205, 483‐486, 2012.
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Residual Errors for the Impedance Data
LIB (0.85Ah), SOC100%
T. Osaka, T. Momma, D. Mukoyama, H. Nara, J. Power Sources, 205, 483‐486 (2012). 26
Contents
• Introduction
• Design of Equivalent Circuit for Electrochemical Impedance Spectroscopy on LIB
• Dependence of EIS on Temperature
• EIS for Degradation Analysis of LIBs
• Square Current/Potential-EIS
• Summary
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-0.03
0
0.03
0 0.03 0.06
-Z"
[Ω]
Z’ [Ω]
-0.1
0
0.1
0.2
0.3
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
-Z"
[Ω]
Z’ [Ω]
RS
RF
CPEF
RI
L
RA
CPEA
RC
CPEC
SEI Anode Cathode
- 20 ˚C20 ˚C
Impedance Measurements at Low Temperature as Useful Technique to Detect SEI
T. Momma, M. Matsunaga, D. Mukoyama, T. Osaka,J. Power Sources, 216, 304, 2012.
Commercial LIB、0.83Ah、SOC 50%
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Fitting Parameters under Temperature Control
Cell B、0.83Ah、SOC 50%
000
000
000
000
001
-30 -20 -10 0 10 20 30
Log
(Res
ista
nce)
[Ω
] Cathode Anode SEI
000
000
000
001
010
-30 -20 -10 0 10 20 30
Log
(Cap
acita
nce)
[F
]
Temperature []
0
-1
-2
1
-3
0
-1
-3
-2
RS
RF
CPEF
RI
L
RA
CPEA
RC
CPEC
Cathode Anode SEI
T. Momma, M. Matsunaga, D. Mukoyama, T. Osaka, J. Power Sources, 216, 304, 2012.
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Contents
• Introduction
• Design of Equivalent Circuit for Electrochemical Impedance Spectroscopy on LIB
• Dependence of EIS on Temperature
• EIS for Degradation Analysis of LIBs
• Square Current/Potential-EIS
• Summary
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EIS Analysis for Cycling Degradation
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D. Mukoyama, T. Momma, H. Nara, and T. Osaka,Chem. Lett., 41, 4, 444 (2012).
-0.05
0
0.05
0.1
0.15
0.2
0.25
0.3
0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45
-Z"
[Ω]
Z’ [Ω]
Whole resistance represented as the real part of whole cell impedance
Limiting capacitance from low frequency impedance plots
Cell C、0.85Ah、SOC100%
Whole resistance represented as the real part
Limiting capacitance
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T. Hang, D. Mukoyama, H. Nara, N. Takami, T. Momma, T. Osaka,J. Power Sources, 2013.
LIB with Li4Ti5O12 Anode、4.2 Ah
Fig. Battery charge capacity with the number of charge–discharge cycles.
Fig. Variation of the (a) resistance and (b) limiting capacity with the number of charge‐discharge cycles at DOD of 20%
Electrochemical Impedance Spectroscopy Analysis for Lithium-Ion Battery Using Li4Ti5O12 Anode
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Contents
• Introduction
• Design of Equivalent Circuit for Electrochemical Impedance Spectroscopy on LIB
• Dependence of EIS on Temperature
• EIS for Degradation Analysis of LIBs
• Square Current/Potential-EIS
• Summary
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-0.01
-0.005
0
0.005
0.01
0.015
0.02
0.005 0.01 0.015 0.02 0.025
-Z"
/ Ω
Z’ / Ω
1 mHz
1 kHz
1 Hz
Fig. Example of a commercial LIB impedance response.Battery Capacity:5Ah, Frequency range:10k – 1mHz, V0‐p = 5mV
Recent Progress of LIBs
Battery for power grid systemThe battery capacity: Larger×The inner impedance: smaller
0.0001
0.001
0.01
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1
10
0.01 0.1 1 10 100
Re
al p
art
of
imp
ed
ance / Ω
Battery Capacity / mAh
Large‐capacity LIB
10 year before
Present
Fig. Correlation of battery capacity to real part of impedance 1k ‐ 1Hz.Samples:Several commercial LIB cells
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Concept of Battery Analysis
Conventional EIS
Square current EIS (SC‐EIS) for large capacity LIB
Input signal
High frequency range (Base model)
-0.005
0
0.005
0.005 0.01 0.015
-Z"
/ Ω
Z’ / Ω
Frequency response
Measure
Fourier Transform
Data processing
Input signal
-0.005
0
0.005
0.005 0.01 0.015
-Z"
/ Ω
Z’ / Ω
Frequency response
Measure
Data processing
0
0.2
0.4
0.6
0 200 400 600
|A|
Frequency [Hz]
|A|spectrum
0
0.005
0.01
0 200 400 600
|V|
Frequency [Hz]
|V|spectrumLow frequency range: less than 1 Hz
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Application of (SC-EIS) to Analysisfor Degradation of Lithium Ion Battery
Battery system・ Power output:60W (4V, 5Ah, 3C):Laminated cell × 1・ Nominal capacity:20Wh (4V, 5Ah)・ SOC in commercial use:50%
Charging/discharging system・ HJ3010SD8 (Hokuto) + 34410A (Agilent)×2(Current, Voltage)・ Power control
Control rate; per 10 msec Start to 100%; 1 msec
・ Property a switch that interrupts an electric circuit in the event of current cut‐
off. It takes 40 to 60 msec to return polarity.
Measurement specification
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Square-Current EIS with High Frequency
Time / s
Cu
rren
t I
/ A
IB
IP‐P
IA
tontoff
tr
ton = toff = 1, 10 msec
tr = 1 msec
IA = 1A
IB = 1mA = 20, 200 msecf = 5, 50 Hz
IP‐P = 1 A
Range of high frequency:250~5Hz
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To use another current waveform for the phase difference measurementcomparing that with high frequency, quasi sine wave current generated by puttinga multistage step of 50Hz was used.
Time / s
Cu
rren
t I
/ A
‐IA
IP‐P
IA
Range of low frequency:Less than 1Hz
Square-Current EIS with Low Frequency
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Nyquist Plots
0
0.01
0.02
0.005 0.015 0.025
‐Z''/Ω
Z'/Ω
Sweep 10p/1d0A±1A 1mHz0A±1A 10mHz0A±1A 100mHz0A±1A 1Hz0.5A±0.5A1Hz0.5A±0.5A 5Hz0.5A±0.5A 10Hz0.5A±0.5A 16.7Hz
0
0.001
0.002
0.009 0.01 0.011 0.012 0.013
‐Z''/Ω
Z'/Ω
SC-EIS Results
Bode Diagram
0
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0.03
0.04
0.0001 0.001 0.01 0.1 1 10 100 1000
|Z|
/Ω
f / Hz
0
10
20
30
40
0.0001 0.001 0.01 0.1 1 10 100 1000
θ/d
egr
ee
f / Hz
We realized the measurement of the frequency response of the electrochemistry impedance with charge‐discharge system and the simple and low‐cost measuring equipment using the
digital multi‐meter.
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Tuning of Measurement and Analysis Program
Low frequency range: less than 1 Hz
High frequency range (Base model)
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Cutting-edge Data
‐0.002
0
0.002
0.005 0.007 0.009 0.011
‐Z”
/ Ω
Z’ / Ω
EIS
SC‐EIS
SC: 50 Hz, 5 Hz, 0.5 Hz
Measurement timing between current and voltage was synchronized sampling frequency until 1 MHz.
Beautiful !!
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The square wave impedance method (SW‐EIS) isused similarly to the general FRA method. SP‐EISand SC‐EIS are proved to give the equal results tothat of FRA‐EIS. Especially, the square wave currentimpedance method (SC‐EIS) works well to the largecapacity battery with low inner impedance .
Application of Square Wave Impedance to battery analysis
New Analysis of High Capacity LIBs with Low Internal Resistance
Summary: Square Current/Potential-EIS
Contents
• Introduction
• Design of Equivalent Circuit for Electrochemical Impedance Spectroscopy on LIB
• Dependence of EIS on Temperature
• EIS for Degradation Analysis of LIBs
• Square Current/Potential-EIS
• Summary
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Summary
• EIS for commercial Li‐ion batteries is able to beanalyzed with using the proposed equivalent circuit,thus the degradation is estimated with this methodusing non‐destructive evaluation.
• The Square Wave‐EIS method proposed showed aresult similar to that of general FRA method, especially,the Square Current‐EIS method works effectively for thebattery system with lower internal impedance lessthan a few m.
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Acknowledgement
for recent our staffs and students.Karuizawa seminar House of Waseda univ 2014.8.
Thank you four your attention.
Battery Group Meeting at Kamogwa Seminar House of Wased Univ/ 2011.7.26.