Motivation of this work...IEP-S5R5@S10 1 M KOH (%) 10 M KOH Number of cycle @ 20C at 10 M KOH the...
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method can afford nanostructured particles easy to disperse facilitating the fabrication of homogeneous electrodes with smooth surfaces Development of anthraquinone conjugated microporous polymer anode for advanced alkaline rechargeable batteries Rebecca Grieco a *, Nagaraj Patil a , Marta Liras b , Jaime S. Sanchez c , Jesús Palma a and Rebeca Marcilla a a Electrochemical Process Unit, IMDEA Energía, Avda. Ramón de la Sagra 3, 28935 Móstoles, Spain b Photoactivated Processes Unit, IMDEA Energy, Avda. Ramón de la Sagra 3, 28935 Móstoles, Spain c Chalmers University of Technology, Chalmersplatsen 4, 412 96 Göteborg, Sweden E-mail: [email protected] Acknowledgments The authors thank the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement (No 860403). References [1] Conjugated Microporous Polymers; A. I. Cooper, Adv. Mater. 2009, 21, 1291. [2] New Anthraquinone‐Based Conjugated Microporous Polymer Cathode with Ultrahigh Specific Surface Area for High‐Performance Lithium‐Ion Batteries Marcilla, R. et al. Adv. Funct. Mater. 2020, 30 (6), 1908074 [3] Electrode Engineering of Redox-Active Conjugated Microporous Polymers for Ultra-High Areal Capacity Organic Batteries; R. Marcilla et al., ACS Energy Letters 2020 5 (9), 2945-2953 The growing demand for large-scale electrochemical energy storage systems necessitates the replacement of the conventional electrodes, that employ transition metal oxides, with more safe, sustainable and low toxicity materials. Among them, redox-active conjugated porous polymers (CPPs) represents an interesting class of low cost and eco-friendly organic electrode materials for energy storage applications.[1] Miniemulsion and solvothermal synthetic route Synthesis in presence of CNTs and RGO hybrid When applied as cathode in Li-ion half-cells, high gravimetric (147 mAh g ‒1 ) and areal capacities (6.3 mAh cm ‒2 ), good rate capability, unprecedented long-term cyclability.[2,3] INTRODUCTION RESULTS Rechargeable dual-ion battery based on commercial Ni(OH) 2 Galvanostatic charge - discharge in 1M KOH, 3 - electrodes set - up 1 The dissolution issue is evident Porous structure improved the cyclability SET-UP: WE: Ink on glassy carbon RE: Hg/HgO counter: Pt mesh IEP-11 robust 3D porous structure that avoids dissolution problems faced by most previous examples in literature Application in combination with NiCoMnSx, new alternative cathode 2 0 500 1000 1500 2000 0 20 40 60 80 100 IEP-S5R5@S10 1 M KOH 10 M KOH Discharge capacity retention (%) Number of cycle @ 20C at 10 M KOH the capacity decays because of the Ni Results vs Ni(OH) 2 in a full cell, 1 M KOH CV and GCD in 3 M KOH of the full cell 1. Ni(OH) 2 cyclability is affected by high electrolyte concentration 2. innovative full-cell Ni(OH) 2 NiCoMnSx • Ni(OH) 2 cathode cyclability is strongly affected by high concentrated basic electrolytes • Polymer anodes dissolve faster in electrolytes where the concentration is low need to search for materials that are insoluble in alkaline media and that work even at low salt concentration (for instance at 1M KOH) Cyclic voltammetry in 1M KOH, 3 - electrodes set - up Linear polymer Porous polymer SET-UP: Bucky paper electrodes, 2mg/cm 2 mass loading, 10 mm diameter Results vs Ni(OH) 2 in a full cell, 10 M KOH Full-cell that outperformed most of the state-of-the-art alkaline batteries Porous polymer synthesized by our group Motivation of this work PAQS (as reference) IEP-11 Polyanthraquinone porous polymer IEP-11 || Ni(OH) 2 vs PAQS | Ni(OH) 2 No need of binder No need of current collector very high mass loadings Superior rate-capability Electrode engineering: buckypaper NiCoMnSx structure and SEM pictures -1,2 -1,0 -0,8 -0,6 -0,4 -0,2 0,0 -45 -30 -15 0 15 30 45 cycle 1 Current (A g -1 ) Potential ( V vs. Hg/HgO) Cycle 1 Cycle 100 PAQS-L cycle 1 cycle 100 -1,2 -1,0 -0,8 -0,6 -0,4 -0,2 0,0 -45 -30 -15 0 15 30 45 Current (A g -1 ) Potential ( V vs. Hg/HgO) IEP-11-P Cycle 1 Cycle 100 cycle 1 cycle 100 0 5000 10000 15000 20000 25000 0 25 50 75 100 a Cap ret 6240 cycles = 35% Cap ret 22 730 cycles = 75% @ 20 C and PAQS-L and IEP-11-P Cycle number Discharge capacity retention (%) 0 25 50 75 100 Coulombic efficiency (%) 10 20 30 40 50 60 0 50 100 150 200 200 100 500 Discharge capacity (mAh g -1 ) Cycle number 1 2 5 10 20 50 PAQS-L IEP-11-P Compare our improved porous polymer anode vs a linear polymer firstly using commercial Ni(OH) 2 as cathode Then creating an innovative full battery combining improved IEP-11 anode with a newly developed NiCoMnSx cathode
Transcript of Motivation of this work...IEP-S5R5@S10 1 M KOH (%) 10 M KOH Number of cycle @ 20C at 10 M KOH the...
method can afford nanostructured particles easy to disperse facilitating the fabrication of homogeneous electrodes with smooth surfaces
Development of anthraquinone conjugated microporous polymer
anode for advanced alkaline rechargeable batteries
Rebecca Griecoa*, Nagaraj Patila, Marta Lirasb, Jaime S. Sanchezc, Jesús Palmaa and Rebeca Marcillaa
aElectrochemical Process Unit, IMDEA Energía, Avda. Ramón de la Sagra 3, 28935 Móstoles, Spainb Photoactivated Processes Unit, IMDEA Energy, Avda. Ramón de la Sagra 3, 28935 Móstoles, Spain
cChalmers University of Technology, Chalmersplatsen 4, 412 96 Göteborg, Sweden
E-mail: [email protected]
Acknowledgments
The authors thank the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement (No 860403).
References
[1] Conjugated Microporous Polymers; A. I. Cooper, Adv. Mater. 2009, 21, 1291.
[2] New Anthraquinone‐Based Conjugated Microporous Polymer Cathode with Ultrahigh Specific Surface Area for High‐Performance Lithium‐Ion Batteries Marcilla, R. et al. Adv. Funct. Mater. 2020, 30 (6), 1908074
[3] Electrode Engineering of Redox-Active Conjugated Microporous Polymers for Ultra-High Areal Capacity Organic Batteries; R. Marcilla et al., ACS Energy Letters 2020 5 (9), 2945-2953
The growing demand for large-scale electrochemical energy storage systems necessitates the replacement of the conventional electrodes, that employ transition
metal oxides, with more safe, sustainable and low toxicity materials. Among them, redox-active conjugated porous polymers (CPPs) represents an interesting
class of low cost and eco-friendly organic electrode materials for energy storage applications.[1]
Miniemulsion and solvothermal synthetic route
Synthesis in presence of CNTs and RGO hybrid
When applied as cathode in Li-ion half-cells, high gravimetric (147
mAh g‒1) and areal capacities (6.3 mAh cm‒2), good rate capability,
unprecedented long-term cyclability.[2,3]
INTRODUCTION
RESULTSRechargeable dual-ion battery based on commercial Ni(OH)2
Galvanostatic charge-discharge in 1M KOH, 3-electrodes set-up
1
The dissolution issue is evident
Porous structure improved
the cyclability
SET-UP:
WE: Ink on
glassy carbon
RE: Hg/HgO
counter: Pt mesh
IEP-11 robust 3D
porous structure that
avoids dissolution
problems faced by
most previous
examples in literature
Application in combination with NiCoMnSx, new alternative cathode 2
0 500 1000 1500 20000
20
40
60
80
100
IEP-S5R5@S10
1 M KOH
10 M KOH
Dis
ch
arg
e c
ap
acity r
ete
ntio
n (
%)
Number of cycle
@ 20C
at 10 M KOH the capacity decays because of the Ni
Results vs Ni(OH)2 in a full cell, 1 M KOH
CV and GCD in 3 M KOH of the full cell
1. Ni(OH)2 cyclability is affected by high electrolyte concentration
2. innovative full-cellNi(OH)2 NiCoMnSx
• Ni(OH)2 cathode cyclability is
strongly affected by high
concentrated basic electrolytes
• Polymer anodes dissolve faster in
electrolytes where the
concentration is low
need to search for materials that
are insoluble in alkaline media
and that work even at low salt
concentration (for instance at
1M KOH)
Cyclic voltammetry in 1M KOH, 3-electrodes set-up
Linear polymer
Porous polymer
SET-UP:
Bucky paper electrodes,
2mg/cm2 mass loading, 10
mm diameter
Results vs Ni(OH)2 in a full cell,
10 M KOH
Full-cell that outperformed most of the state-of-the-art alkaline batteries
Porous polymer synthesized by our groupMotivation of this work
PAQS
(as reference)
IEP-11
Polyanthraquinone porous polymer
IEP-11 || Ni(OH)2 vs PAQS | Ni(OH)2
No need of binder
No need of current collector
very high mass loadings
Superior rate-capability
Electrode engineering: buckypaper
NiCoMnSx structure and SEM pictures
-1,2 -1,0 -0,8 -0,6 -0,4 -0,2 0,0-45
-30
-15
0
15
30
45
cycle 1
Cu
rre
nt
(A g
-1)
Potential ( V vs. Hg/HgO)
Cycle 1
Cycle 100
PAQS-L
cycle 1 cycle 100
-1,2 -1,0 -0,8 -0,6 -0,4 -0,2 0,0-45
-30
-15
0
15
30
45
Curr
ent (A
g-1
)
Potential ( V vs. Hg/HgO)
IEP-11-P Cycle 1
Cycle 100
cycle 1cycle 100
0 5000 10000 15000 20000 250000
25
50
75
100a
Cap ret6240 cycles = 35%
Cap ret22 730 cycles = 75%
@ 20 C and PAQS-L
and IEP-11-P
Cycle number
Dis
cha
rge c
ap
acity r
ete
ntio
n (
%)
0
25
50
75
100
Co
ulo
mb
ic e
ffic
ien
cy (
%)
10 20 30 40 50 600
50
100
150
200200100 500
Dis
ch
arg
e c
ap
acity (
mA
h g
-1)
Cycle number
1 2 5 10 20 50
PAQS-L
IEP-11-P
Compare our improved porous polymer anode vs a linear polymer firstly using
commercial Ni(OH)2 as cathode
Then creating an innovative full battery combining improved IEP-11 anode with a
newly developed NiCoMnSx
cathode
