design the interface carbon materials & its application in ......lithium ion capacitor (lic)...
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Design the interface carbon materials &
its application in lithium ion capacitors
LI Feng (李峰)
Shenyang National Lab for Material Science
Institute of Metal Research, CAS
72 Wenhua Road, Shenyang, China
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Outline
Carbon & Supercapacitor
Materials - From Design to High Energy
Cell - From Power to Function
Summary
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Applications of electrochemical energystorage system (ES)2
(ES)2
H. D. Yoo, Materials Today, 2014. 17. 110-121
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Requirement of Application
LIC
C. Zhong, Chemical Society Reviews. 2015, 44, 7485-7539
Larger energy capacity
Better safety
Longer life
Higher power capacity
Wider temperature range
Lithium ion capacitor (LIC)
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Separator
Electrolyte
Active Materials : CarbonCurrent Collector
U
Configuration of LICs Cell
Anode & Cathode can be same
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Advantage and disadvantages
A: D:
High energy > 20 Wh/kg
High Cell voltage > 4 V
Long Life
Low power(Graphite) Low capacitance(AC)
K. Naoi, Energy & Environmental Science. 2012, 5, 9363–9373
4.2-4.3 VLIC
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Material Level Cell Level
Capacitance
Cycle
Material
Energy
Power
Capacitance
Cycle
System
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Strategies to improve energy density
C: specific capacitance (F/g)
Q: specific capacity (mAh/g)
U: working voltage (V)
High-capacity materials High-voltage electrolytes
aqueousorganic
Energy density (E):
E : Number & potential
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1.5V
4.5 V
0 V
4.5V
Our example:
Symmetric graphene SCs in LiPF6 /EC+DMC electrolyte:
Working voltage relies on the electrode potential window.
Common Phenomena after Assembly of LICs
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Question & Solution
• How to bring electrode materials and electrolytes into full play in LIC devices?
From the Fact:C and U are determined on the potential window of
each individual electrode in LICs.
To Solution:Tuning electrode potential window (EPW).
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Tuning initial electrode potential (E0V) to
optimize EPW of each individual electrode
Our Method
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Why can EP be tuned?
For LICs, Electrode potential
(EP) depends on surface
charge density of electrode
materials.
Pote
ntia
l
the state of charge
Batteries
LICs
potential plateau
Batteries LICs
Mechanism ofenergy storage
Phase transformationin bulk
Surface double-layeradsorption,
Surface Faradic reaction
Free energy (G) −nFE (content) 1/2 CE2 =1/2 ΔQE (variable)
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Our Approach
E0V
E’0V
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Twographeneelectrodes
Discharged to 1.16V
0.01~1.16V20 cycles
ECI bygalvanostatic
charge/discharge
Postive electrode
Held at 1.16V for 2h
Held at 1.16V for 2h
Negative electrode
Process of Tuning EP
Assembledinto twohalf-cells
with Licounter
①
Disassemledfrom half cellsand assembled into a SC device
② ③
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4.3V
Performance of LIC after Tuning EP
Graphene:
U & C are improved simultaneously.
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Charge/discharge Curves of
graphene LIC at different
current densities
1C = 175 mA/g
Capacitance retention of
graphene before/after
tuning EP
fourfold
Performance of LIC after Tuning EP
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Ragone Plot
63 Wh kg-1
at 11kW kg-1
Energy density improved by 10 Times!
152 Wh kg-1
Weng Z, Li F, et al, Angew. Chem. Int. Ed. 2013. A Hot Paper selected.
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Cycle Stability after Tuning EP
Graphene SC SWCNT SC
91%75%
The last 20 cycles of graphene SLIC
4.73 V
0.42 V
E0V = 1.17 V
C of positive electrode decreases
4.3 V 4.3 V
? Why & What
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0 100 2000
1
2
3
4
Pote
ntia
l (V
vs. L
i/Li+ )
Specific Capacity
Cathode
Anode
Reason for performance decay
Unstablewindow
OO
H
OO
H
O
OH
Electrolyte reduction
Byproducts
Cathode
1 2 3 4-0.6
-0.4
-0.2
0.0
0.2
Curre
nt (m
A)
Potential vs. Li/Li+
1st
10th5thChallenge:
To minimize electrolyte reduction
e-
e-
e-
e-
Graphene cathode
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0 1 2 3 4 5 61
2
3
Volta
ge
Time (h) for PEC
Electrolyte with LiODFB
PEC Region(Protective layer formation)
Unstable window
Preliminary electrochemical coating (PEC)
1 2 3 4-0.6
-0.4
-0.2
0.0
0.2
Curre
nt (m
A)
Potential vs. Li/Li+
1st (reduction of LiODFB)
10th5th
Mechanism of PEC (Decomposition of LiODFB)
J. Electrochem. Soc., 156 (2009) A318
BF O C
ODFB-1
Li+
LiBC2O4F2 ≈ 1.7V
Ion- conductiveElectron -insulating
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Twographeneelectrodes
Discharged to 1.16V
0.01~1.16V20 cycles
PEC+ ECI bygalvanostatic
charge/discharge
Postive electrode
Held at 1.16V for 2h
Held at 1.16V for 2h
Negative electrode
ECI bygalvanostatic
charge/discharge
NEW Process for Tuning EP
Assembledinto twohalf-cells
with Licounter
①
Disassemledfrom half cellsand assembled
into a LIC device
② ③
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OO
H
OO
H
OH
OO
H
OO
H
O
OH
Electrolyte reduction
Armored graphene (A-G)
PEC
Byproducts
Graphene (G)
PEC
No electrons
Baymax Armed Baymax
What happen during PEC
XY Shan, F LI, et al, Adv Energy Mater, 2016: 1502064
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0 100 200 300 4000
200
400
600 Fresh cell 10th cycle 50th cycle 100th cycle
-Z''
(ohm
)
Z' (ohm)
G PEC-G
(a) (b)
0 200 400 600 8000
200
400
600
800 Fresh cell 10th cycle 50th cycle 100th cycle
Z' (ohm)
-Z''
(ohm
)
EIS after Cycled
Original cathode After PEC
Increasing Stable
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Electrochemical performance of A-GLISC
020406080
100120140160
5 10 20 30 50 100
GLISCA-GLISC
Spec
ific
capa
city
(mA
hg-
1)
Current density / C
0 400 800 12000
1
2
3
4
5
Volta
ge (V
)
Time (sec.)
5C 10C 20C 30C 50C 100C
102 103 104100
101
102
103
Ener
gy D
ensi
ty (W
h kg
-1)
Power Density (W kg-1)
Fe3O4/G//3D G
AG//Li4Ti5O12
AC//TiO2-RGO
AC//Li4Ti5O12
All-graphene battery
A-GLISC
GLISC
Li+ PF6-A
node
Cathode
- +
Anode
Cathode
- +
GLISC A-GLISC
PEC
G A-G-2G G
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0 200 400 600 800 10000
30
60
90
120
150
180
Cycle number
Spec
ific
Cap
acity
(mA
hg-1)
Cou
lom
bic
effic
ienc
y (%
)
0
20
40
60
80
100
GLISCCoulombic efficiency of A-GLISC
A-GLISC
Coulombic efficiency of GLISC
0
20
40
60
80
100
Cap
acity
Ret
entio
n (%
)
80 %
Lithium storage systems
Decay of 0.011% per cycle
Highest retention among lithium ion
capacitors reported up to now.
Cycling stability of A-GLISC
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Cycled GG
A-G-2 Cycled A-G-2
1µm
0
20
40
60
80
100
Ato
mic
Per
cent
age
(%) C
O F P
1µm
0
20
40
60
80
100
Ato
mic
Per
cent
age
(%) C
O F P
1µm
0
20
40
60
80
100
Ato
mic
Per
cent
age
(%) C
O F P
1µm
0
20
40
60
80
100
Ato
mic
Per
cent
age
(%) C
O F P
Results after cycled
P
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Material Level Cell Level
Smart ?!
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0 40 80 1200
2
4
Specific capacity (mAhg-1)
Volta
ge (V
) 4.3 V
SWCNTs-SLIC
Electrolyte limit
2.8 V
SWCNTs-SC
① ② ③
_On-lineECI
PE Charge
NEDischarge
Device
+
NE vs. Li discharge
PE vs. Li charge
Fulfill on-line ECI in device
2 um 10 nm
Electrode materials: SWCNTs
_
+
E’ovFull cell
Voltage modulator Energy boosting
High-Energy output
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Integrate intelligence into LICs
👍👍 Monitor per electrode
👍👍 Built-in alerts for safety
👍👍 Self diagnosis & regeneration
Smart LICs --- Transparent Box
Charge DischargeSCs
Transparent Box
How to bring interactivity and autonomy into LICs?
+_ Smart device into SCs
Sensitive to internalchange inside SCs
V1V2
Feedback
Our strategy:
XY Shan, F Li et al, Energy storage materials 1:146-151 2015
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Feedback Safety monitoring
0 50 100 1500.0
1.5
3.0
4.5
Specific capacity / mAhg-1
Pote
ntia
l vs.
Li/L
i+
Feedback:V1, V2: Voltage sensorsV1 alerts when < 0V;V2 alerts when > 4.5V
5 μm
Graphene
Ep-Max En-Min
Ep-Max
V2 alerts and device turns off!
Smart function
_
+> 4.5V Electrolyte
< 0V Li plating V1
V2
Feedback
Energyoutput
0 100 2000
50
100
150Po
tent
ial (V
vs. L
i+ /Li)
Spec
ific c
apac
ity (m
Ahg-1
)
Cycle number
Charge Discharge
0.1
0.2
0.3
4.4
4.6
Ep-Max
En-Min
Electrolyte limit
Cycle Capacity
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Feedback + Voltage modulator Self-regeneration
0 100 200 300 3500
50
100
0
50
100
Cycle number
Coul
ombi
c Effi
cienc
y (%)
Spec
ific C
apac
ity (m
Ahg-1
)
G-SLIC G-SLIC-R
Discharge
Regeneration (G-SLIC-R)
Coulombic efficiency
0.875 1.750 2.6250
50
100
150
Capa
city
(mAh
g-1)
Current density (Ag-1)
G-SCG-SLICG-SLIC-R
Smart function
_
+> 4.5V Electrolyte
< 0V Li plating V1
V2
Feedback
① ② ③
_
PE Charge
NEDischarge
+
On-line ECI
V2 alerts and device turns off!
0 50 100 1500.0
1.5
3.0
4.5
Specific capacity / mAhg-1
Pote
ntia
l vs.
Li/L
i+ Ep-Max
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Summary• Energy density of carbon based LICs are dependent
on working potential window after assembled to
LIC devices, which can be tuning.
• Optimization of potential window from materials to
cell design can attain LICs with high energy
density, long life & smart .
• Developing novel design and assemble technology
for LICs.
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Acknowledgement
• NSFC
• MOST
• CAS
• Prof. Huiming Cheng @ IMR
• Dr. Xuyi Shan @ IMR
• Mr. Yuzuo Wang @IMR
• Dr. Ze Weng @ Yale, USA
• Dr. Dawei Wang @ NSW, Australia
• Prof. Zhangquan Peng @ CIAC, CAS
Thank you very much
for your attention!