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Lithium-ion Capacitor with low footprint sacrificial material for graphite pre-lithiation
AABC EuropeMainz, January 30th- February 2nd, 2016
1P. Jeżowski, 2O. Crosnier, 2T. Brousse, 1F. Béguin
1ICTE, Poznan University of Technology, Poland
2IMN, University of Nantes, France
POZNAŃ UNIVERSITY OF TECHNOLOGY
Power Sources Group
www.powersourcesgroup.put.poznan.pl
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Operating principle of an EDLC
K. Naoi in “Electrochemical capacitors: materials, systems and applications”, F. Béguin & E. Frackowiak eds, John Wiley, Weinheim (2013)
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Operating principle of LiC hybrid Capacitor
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21 CUE
K. Naoi in “Electrochemical capacitors: materials, systems and applications”, F. Béguin & E. Frackowiak eds, John Wiley, Weinheim (2013)
Compared profiles of symmetric and hybrid capacitors
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-400 -300 -200 -100 0 100 200 300 400
E / V
vs
Li/
Li+
t / s
hybrid
symmetric
Electrolyte 2 mol.L-1 LiTFSI in EC/DMCSimilar mass of electrodes
C. Decaux, F. Béguin, et al, Electrochim. Acta, 86 (2012) 282-2864
1/C = 1/C+ + 1/C-
C+ << C-
C ~ C+0
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U / V
t / s
Hybrid capacitor 157 F/g
Symmetriccapacitor 96 F/g
Hybrid ~ 80 Wh/kgSymmetric ~ 20 Wh/kg
~4 times higher
E = ½ (Umax2- Umin
2) C
Fuji Heavy Industry patents: EP1400996A1 (2002); WO2006112068A1 (2006); US2007/0002524A1 (2007) ; EP1914764A1 (2007); etc
T. Aida, K. Yamada and M. Morita, Electrochem. Solid-State Lett. 9 (2006) A534.
Preloading from lithium auxiliary electrode
In patented/published systems, lithium is used as
auxiliary electrode to pre-dope graphite
To develop a Li-metal free hybrid capacitor
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Lithiation from composite electrode with irreversible oxide
In case of Li2MoO3 and Li5FeO4, highly irreversible extractionBut requires high potential > 4.7 V vs Li/Li+ causing side reactions
M.S. Park et al, J. Phys. Chem. C 117 (2013) 11471
To use materials from which lithium can be irreversibly extracted at lower
potential
P. Jezowski, K. Fic, O. Crosnier, T. Brousse, F. Béguin,Electrochim. Acta, 206 (2016) 440
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40% AC, 40% LRO, 15% C65, 5% PTFE1M LiPF6 in EC:DMC
0.06 mV s-1
Implementation of Li5ReO6 (LRO)
1st cycle
2nd cycle
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Effect of SEI formation current
P. Novak et al., J. Electrochem. Soc., 158 (2011) A1478
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Ca
pa
cit
an
ce
/ F
/g
Cycle no. / -
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Effect of the SEI formation currenton cycle life
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90
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150
0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000
Ca
pa
cit
an
ce
/ F
/g
Cycle number
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10 100 1000 10000
En
erg
y W
h/k
g
Power / W/kg
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LIC_LRO 2.2–4.1 V
EDLC in TEABF4/ACN @ 2.7 V
EDLC in LiPF6/EC:DMC @2.7 V
Ragone plot of the LIC per total mass of electrode materials
P. Jezowski, K. Fic, O. Crosnier, T. Brousse, F. Béguin, J. Mat. Chem. A 4 (2016) 12609
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Disadvantages of lithiated oxides
• Lithium extraction potential is relatively high
• Di-oxygen may be produced during lithium extraction
• The residual material in the positive electrodereduces its conductivity and consequently power of the system
- Renewable materials from which lithium is extracted atlower potential and which dissolve in the electrolyte
- Materials from which lithium is extracted together withinert gas evolution
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Implementation of 3,4 -dihydroxybenzonitriledilithium salt (LORG)
Low molecular mass: 147 g mol-1
High theoretical capacity ~ 365 mAh g-1
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65% LORG, 30% C65, 5% PTFE1M LiPF6 in EC:DMC
0.06 mV s-1
Anodic oxidation of 3,4 -dihydroxybenzonitriledilithium salt (LORG)
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65% LORG, 30% C65, 5% PTFE1M LiPF6 in EC:DMC
Anodic oxidation of 3,4 -dihydroxybenzonitriledilithium salt (LORG)
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Graphite
Glassy fiber separator soaked with 1M LiPF6
(in EC:DMC vol.:1:1)40% AC
40% LORG5% Binder 15% C65
Lithium pin as reference
Cell construction
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Po
ten
tial v
s. L
i|Li
+,
Vo
ltag
e /
V
Charge / mAh/g
potential of positive electrode
voltage
potential of negative electrode
Graphite pre-lithiation with LORG
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ote
ntia
l v
s. L
i|Li
+,
Vo
ltag
e /
V
Charge / mAh/g
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0.0
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0 5 10 15 20 25 30Po
ten
tial v
s. L
i|Li
+,
Vo
ltag
e
/V
Time / min
0.25 A/g
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Po
ten
tial v
s. L
i|Li
+,
Vo
ltag
e
/V
Time / min
0.50 A/g
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Po
ten
tial v
s. L
i|Li
+,
Vo
ltag
e
/V
Time / min
0.65 A/g
positive electrode
voltage
negative electrode
Charge/discharge of LORG-based LIC (2.2 – 4.0 V)
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Ca
pa
cita
nc
e /
F/g
Cycle number
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cit
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/ F
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Cycle number
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Cycle-life of LORG-based LIC (2.2 – 4.0 V)
Stable performance
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State of the cell after conditioning
After cell conditioning, mass of the positive electrode reduced by 34%
- Color of solution
turned to orange
- White separator after
extraction
Ex
trac
tion
in m
ethan
ol
Separator aftercell conditioning
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Mass spectrum of extract
Extract from separator3,4 -dihydroxybenzonitrile M - 1
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Ragone plot of the LIC based on LORG per total mass of electrode materials
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Sp
ec
ific
en
erg
y /
Wh
/kg
Specific power / W/kg
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10 100 1000 10000
Sp
ec
ific
en
erg
y/
Wh
/kg
Specific power / W/kg
LIC_LRO 2.2–4.1 V
EDLC in LiPF6/EC:DMC @2.7 V
LIC_LORG 2.2–4.0 V
EDLC in TEABF4/ACN @ 2.7 V
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20% L-Cap, 60% AC, 15% C65, 5% PTFE1M LiPF6 in EC:DMC
New high capacity material (H-Cap)
0.06 mV s-1 C/20
Irreversible capacity > 1000 mAh g-1
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Graphite
Glassy fiber separator soaked with 1M LiPF6
(in EC:DMC vol.:1:1)60% AC
20% H-CAP5% Binder 15% C65
Lithium pin as reference
Cell with H-Cap
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Po
ten
tia
l v
s. L
i/Li
+,
Vo
lta
ge
/
V
Charge / mAh/g
SEI formation @ C and graphite lithiation @ C/20
Positive
Cell
Negative
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Li extraction from H-CAP
PTFE
AC
H-CAP/AC electrode (before extraction)
AC
AC
H-CAP/AC electrode (after extraction)
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ten
tial v
s. L
i/Li
+,
Vo
ltga
e/
V
time / min
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ote
ntia
l v
s. L
i/Li
+,
Vo
ltag
e/
Vtime / min
0.25 A/g 0.50 A/gpositive electrode
voltage
negative electrode
Charge/discharge of H-CAP LIC (2.2 – 4.1 V)
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Pre-lithiation with H-Cap and cycle life of the cell
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Ragone plot of the LIC based on LHighCap per total mass of electrode materials
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10 100 1000 10000
Sp
ec
ific
en
erg
y /
Wh
/kg
Specific power / W/kg
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10 100 1000 10000
Sp
ec
ific
en
erg
y/
Wh
/kg
Specific power / W/kg
LIC_LRO 2.2–4.1 V
EDLC in LiPF6/EC:DMC @2.7 V
LIC_LORG 2.2–4.0 V
EDLC in TEABF4/ACN @ 2.7 V
LIC_LHighCap_2.2–4.1 V
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Lithium deintercalation from the investigated lithiatedmaterials is fully irreversible
Conclusion
Assembling of LIC cell based on lithiated material + AC positive electrode is simple and does not require metalliclithium auxiliary electrode
The LIC capacitors based on the sacrificial lithium source display excellent cycle life and higher energydensity than EDLCs
With the new high capacity material, the residual massin the positive electrode is very low.
The foundation for Polish Science is acknowledged for
funding the ECOLCAP project in the frame of the
Welcome programme
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Acknowledgements
Thank you for your attention
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Vo
lta
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/ V
Charge / mAh g-1
Cell failure
due to gassingAfter 1h
pre-lithiation
Triplex bodyPositiveterminal
Negativeterminal
a)
Pouch cell construction
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lta
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/ V
Charge / mAh g-1
Pouch cell construction with dead space
First stage LiC6 intercalation compound
reached