New Vistas in Electrochemical Energy Storage · 2016-09-15 · 3.8V J. Janek et al, JACS, 2015 TTF-...
Transcript of New Vistas in Electrochemical Energy Storage · 2016-09-15 · 3.8V J. Janek et al, JACS, 2015 TTF-...
![Page 1: New Vistas in Electrochemical Energy Storage · 2016-09-15 · 3.8V J. Janek et al, JACS, 2015 TTF- TTF+/3.5-3.7V P.G. Bruce et al, Nature Chemistry, 2014 Br-/Br 2 D. Aurbach et al,](https://reader034.fdocuments.net/reader034/viewer/2022050218/5f6414214cc5e61a0105ea4e/html5/thumbnails/1.jpg)
MIT Energy Initiative
Cambridge MA
Amiens
New Vistas in Electrochemical Energy
Storage
Sept 7, 2016
Prof. Linda Nazar, FRSC
Senior Canada Research Chair
Electrochemical Energy Materials Laboratory
BASF International Scientific Network for Electrochemistry and Batteries
DOE, USA
Joint Center for Energy Storage Research
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Thanks to:
C. Xia, R. Black, R. Fernandes, D. Kundu, X. Liang, X. Sun, P. Bonnick, V. Duffort, B. Adams
Waterloo Institute for Nanotechnology and the
Quantum-Nano Centre
University of Waterloo, Waterloo ON Canada
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Introduction: Li-ion
Storing electrons and ions:- Chemical transformation
Li-Sulfur and metal-oxygen batteries-
Storing electrons and ions:- Multivalent intercalation
batteries: Mg and Zn -ion
Conclusions
3
Waterloo Institute for Nanotechnology and the
Quantum-Nano Centre
Agenda :
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“Integrated energy storage is an area where technology lags and needs intense development if systems with optimum overall efficiency
gains are to be attained”
Global Energy Assessment: Cambridge Univ Press, 2012
GEA – the first global and interdisciplinary assessment of energy challenges and solutions – identifies 41 pathways to provide sustainable energy for the world by 2050
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New electrochemical energy storage chemistry needed
Energy Storage: A Challenge of the 21st Century
Wind Solar
Exploit renewable energyresources
Electric (+ solar): Kiira Motors
kWh
Enable low cost, high range electric vehicles
Power the world: big computing, small devices
Smart energy delivery
Wh - MWhMWh
Chemicals ElectricityBatteries
Chemical energy to electrical energy and work (downhill, discharge)
Electrical energy back to chemical energy (uphill, charge)
Different energy needsDifferent materials
Different cost point
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Progress in Li-ion technology: driven by portable devices
Capacity: Electrons stored per mass
(mAh/g) or volume (mAh/L)
Light weight/dense
Capacity * Voltage = Energy densityWh/kg or Wh/L
Source: Sony (Japan)
2014
Increase in energy density by year for 18650 cellsLimit ~ 280 Wh/kg based on “intercalation”
chemistryProblems: cost, safety
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1990 2005 2015
En
erg
yd
en
sit
y
So
ny
miEV / C0 / Lion
250 Wh/kg,
800Wh/l
20072004
2 MW
Li-ion battery
Future Development
Energy storage perspective: 2x in ED, -2x in cost
So
ny L
iMn
O
Zn-a
ir
Li-SL
i-M-O
me
tal
oxid
es
Zn-io
n
Li-a
ir
LiF
eO
4
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A-
A-
A-
A-
Li+
Li+Li+
Li+
Li+
A-
Li+
A-
Li+Li+Li+
Li+Li+Li+
Li+Li+Li+
Li+Li+Li+
Li+
Li+
A-
A-
I
Li+
Li+
Li-Ion Cell Operation
LiCoO
2
graphite
Capacity (mAh/g)
Vo
ltag
e (V
)
(+) (-)
8/75
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A-
A-
A-
Li+
Li+Li+
Li+
A-
A-
Li+
A-
Li+Li+Li+
Li+Li+Li+
Li+Li+
Li+Li+Li+
Li+
Li+
A-
A-
LiCoO2 Li1-xCoO2 + xLi+ + xe- xLi+ + xe- + C LixC
e-
Li+
Li+Li+
Li+
e- Li+
e-Li+
Li+
(Charge)I
Capacity (mAh/g)
Vo
ltag
e (V
)
cell voltage
(+) (-)
9/75
Li-Ion Cell Operation
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A-
A-
A-
Li+
Li+Li+
Li+
A-
A-
Li+
A-
Li+Li+Li+
Li+Li+Li+
Li+Li+
Li+Li+Li+
Li+
Li+
A-
A-
e-
Li+
Li+Li+
Li+
e- Li+
e-Li+
Li+
(Discharge)
Li1-xCoO2 + xLi+ + xe- LiCoO2 LixC xLi+ + xe- + C
cell voltage
Capacity (mAh/g)
Vo
ltag
e (V
)
(+) (-)
10/75
Li-Ion Cell Operation
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Vehicular energy storage: looking to the far future
11
All-solid-state batteries (Li, Na, Li-S, etc) have in common with Lithium-air the requirement of strict control of electrochemical interfaces
(Toyota, MRS Bull 2015)
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Dissolution-precipitationStep change
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+-
e-e-
Li+ conducting
electrolyte
LiCoO2Graphite
charge
dischargeLi+
Li+
+-
e-e-
Li+ conducting
electrolyte
LiCoO2Graphite
charge
dischargeLi+
Li+
Intercalation cell Chemical Transformation cell
16
O
32
S
3
Se
52
Te
84
Po
21
Sc22
Ti23
V24
Cr25
Mn26
Fe27
Co28
Ni29
Cu30
Zn
Transition metal oxides: good e- transport
Ch
alcoge
ns: ligh
t we
ight
Ion intercalation vs chemical transformations
S ↔ Li2S
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Li-Oxygen
Lithium-chalcogenide (O2, Sulfur) batteries: similar
≈ 350 Wh/kg
Factor of 7
≈ 200 Wh/kg
0,7Li+ + 0.7e- + Li07MO2 LiMO2
Energy density = 220 Wh/kg
x 3
≈ 1000 Wh/kg
Factor of 3.5
650 Wh/kg possible?
..but limited cycling
Li-Sulfur
2Li+ + 2e- + S Li2S (E°= 2.27 V )
Energy density = 2500 Wh/kg2Li ++ 2e- + O2 Li2O2 (E°= 2.96V)
Energy density = 3500 Wh/kg
Earth abundant
inexpensive
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e- e- e-
(soluble)
S8 (solid) S82- Sn
2- (n: 3 to 6) S22- Li2S
O2 (gas) O2- O2
2- (Li2O2)
S8 + S62- 2S3
-
reactive
(insoluble)
” + O2)
Redox transform electrochemical systems
S2 + 2 Li+/e- ↔ Li2S O2 + 2 Li+/e- ↔ Li2O2Li+ + e- + 2 Li0.5CoO2→ 2 LiCoO2
MW/e- = 196 MW/e- = 23 MW/e- = 23
• Dissolution-crystallization and disproportionation chemistry
2LiO2
1. 14
solids)
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e- e- e-
(soluble)S8
2- S(-0.25)
O2 (gas) O2-
S8 + S62- 2S3
-
reactive
(insoluble)
(Li2O2) + O2)
Redox transform electrochemical systems
Prone to disproportionation reactions
Intermediates in the electrochemical reactions very problematic
• Dissolution-crystallization and disproportionation chemistry
2LiO2
1. 15
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Reactive radicals
1. 16
Aging
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O2 + 2 Li+/e- ↔ 2 LiO2 → Li2O2 + O2
Li-O2 batteries: a lot of hype, a lot of challenges
● minimal overpotential for oxygen reduction● reactivity of host electrode with Li2O2
nanoporous, stable conductive host● Overcome large overpotential on charge
Positive Electrode
Organic Electrolyte
● electrolyte reacts with superoxide O2.-● O2 solubility, diffusivity
● Li salt solubility
A long term prospectReview of Li-O2: D. Aurbach, B. McCloskey, L.F. Nazar, P. Bruce* Nature Energy (in press, 2016)
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But….steps forward in understanding
Discharge: Li+/e- + O2 → LiO2 →
Superoxide formed on surface: dissolution competes with 2nd reduction : dependent on current density and solvation
Favour large aggregates via O2-• transport
L. Nazar et al., JACS 2013; EES (2013); Y. Shao-Horn, JPCL, 2013
Micron-sized Li2O2
Li2-xO2 → O2 + x Li+ + x e-
Charge: Li2O2 → Li2-xO2 + x Li+/e-
M. Wagemaker, Nazar et al., JACS (2015), JPCL 2016
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Inherent solution mediation in Na-oxygen cells
O2 + Na+/e- ↔ NaO2
19
Theor: 1600 Wh/kg
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0 1 2 3 4 51.8
2.0
2.2
2.4
0 5 10 15
0
2
4
Water content [ppm]
Ca
pa
cit
y [m
Ah
cm
-2]
Capacity [mAh cm-2]
Ecell [
V]
1111111111
Crystalline NaO2 cubes
High capacity
10 ppm H2O 10 ppm benzoic acid
Na-O2 Battery: phase transfer catalysis, high capacity
1.8
2.0
2.2
2.4
E (V
vs.
Na/
Na+ )
Capacity (mAh cm-2)
Cd
is(m
Ah
cm-2
)
HA + O2•- ⇆ HO2 + A-
HO2 + Na+ → NaO2 + H+
reverse on chargeNegligible capacity
Quasi-amorphous NaO2 films
Surface Mechanism
Sol’n Mechanism
0 ppm H2O
Xia, Nazar et al. Nature Chemistry 2015, 7, 496–501
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0.0 0.1 0.2 0.3 0.4 0.5
2.1
2.2
2.3
2.4
2.5
2.6
E (
V v
s.
Na
/Na
+)
Capacity (mAh/cm2)
b)
0.0 0.1 0.2 0.3 0.4 0.5
2.5
3.0
3.5
4.0
4.5
E (
V v
s.
Li/L
i+)
Capacity (mAh/cm2)
HO2 + Na+ NaO2 + H+
H+ + O2 HO2
H2O2 Li2-xO2 + H+
E° = 2.27 V
E° = 2.96 V
Charge
NaO2 Na+ + O2
O2 O2
Li2O2 2Li+ + O2
Li-O2 echem Na-O2 echem
21
Phase transfer catalysis not possible for Li-O2
superoxide not stable
2H+ + O2 H2O2
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Redox Mediators – THE solution on charge (& discharge)
TEMPO- TEMPO+
3.8VJ. Janek et al, JACS, 2015
TTF- TTF+/3.5-3.7VP.G. Bruce et al, Nature Chemistry, 2014
Br-/Br2
D. Aurbach et al, Angew Chemie, 2016
TDPA - TDPA+ - TDPA2+
3.1/3.5 VL. Nazar et al, ACS Central Sci, 2015
Soluble molecules in the electrolyte oxidized at a potential slightly above the equilibrium potential of Li2O2.
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A Dual Step Redox Mediator for Li-O2 Cell
RM/RM+ RM/RM2+
TTF 3.5 V 3.7 V
TEMPO 3.8 V
TDPA 3.1 V 3.5 V
Kundu, Nazar et al., ACS Central Science, 2015
quantitative
Requires that the negative Li electrode be passivated
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Detrimental reactivity of HO2 with glyme electrolyteCharge
3300 3320 3340 3360 3380
500 ppm 15 min Charge
N= 6.4 G
H= 19.5 G
N= 6.4 G
H= 19.7 G
10 ppm 120 min Charge
“Operando” ESR studies show HO2 generates glyme radicals electrolyte decomposition products
Find electrolytes stable to radical (HO2) hydrogen abstraction
C. Xia, L. Nazar, J. Baugh et al., J. Am Chem. Soc (2016)
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Down the Periodic Table
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Lit
hiu
m
Sep
ara
tor
Li+
2 Li+
Li+Li2S8
a(Li2S6) + b(Li2S4)
(Li2S)
e-e-
Discharge
—maintain active mass? Li2S
Li2Sx Li2Sx/2
Charge Polysulfide shuttle
internal “short circuit”
2Li + S Li2Sx Li2S theoretical capacity 1675 mAh/g @ 2V
1. 26
The Li-S Battery and the Redox Shuttle
2500 Wh/kg (full cell)500 - 1000 mAh/g today
-> 350 Wh/kg
Lit
hiu
m
cheese milk cheese
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Desirable shuttles
1. 27
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The Problem with Carbon
The Crossroads
28
Porous carbons
High electrolyte ratios
Low sulfur loading, low sulfur fractions
“catholyte” – like cells 150 Wh/L
LiPS poorly soluble
“Pb-acid battery”
LiPS very soluble
High donor number solvents, Protected negative electrode – like Li-O2
decreased funding
no large scalecommercialization
All solid state sulfur batteries
solve the problems with multipronged approaches - find ways for dissolution/precipitation to function in low electrolyte and high sulfur loading
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Li-S for transportation applications: critical metrics
29
Calculated cell-level energy density and specific energy for a 100 kWhuse, 80 kW and 360 V Li-S battery as a function of the electrolyte vol% in the cathode (50–90%) and excess Li amount in the anode (50–400%).
high current densities (∼7 mA/cm2)high sulfur loading ~ 7 mg/cm2
electrolyte ~1.3 – 1.9 μl/mg
---- Kevin G. Gallagher et al
Challenges:
Gallagher et al., J. Electrochem. Soc., 162 (6) A982-A990 (2015)
Are these goals achievable - how?
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The Problem with Carbon Good interaction with sulfur
No interaction with intermediate lithium polysulfides OR Li2S
The Problem with Porous Carbon
30
Cuisinier, Balasubramanian, Nazar, J. Phys. Chem Lett (2014)
In situ cell: synchrotron (APS)
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During discharge: Much lower fraction of polysulfides at all stages (efficient trapping) Li2S precipitates earlier and more progressively
Solid: Ti4O7/SDash: C/S
Ti4O7-polysulfide interaction promotes charge transfer
Operando XANES: Ti4O7/S cathode shows strong interaction
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Ti-Ox e- e- e- e-
S8 Li2Sx2-
Ti4O7
e- e-
Solvated Li+
“adsorbed” Li2S
e-
Sulfur reduces and adsorbs on metallic oxide surface → “adsorbed” Li2S
Sulfur reduced and dissolves to form solvated lithium polysulfides→ Li2S isolated from electron wiring
Carbon e- e- e- e-
S8
Solvated Li+
Li2Sx2-
Carbon
“disconnected”Li2S
disproportionationUpon electrochemical reduction (receiving e- and Li+):
• Uniform deposition of Li2S• Suppress polysulfide diffusion/shuttle• Improved capacity retention
Q. Pang, D. Kundu, M. Cuisinier, L. F. Nazar, Nature Comm, 5 : 4759 (2014)
Ti4O7 - surface enhanced electrochemistry
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The Problem with Carbon
Surface interactions of LiPS with polar hosts are key
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Pristine carbon N-doped g-C3N4
First-principle calculations – quantitative study of interactions
ba c
DFT (VASP code) Simulated the adsorption of various numbers (1,2,4) of Li2S2 molecules The substrates span the same basal area
Binding energy average per Li2S2
Example optimized geometries of 2 Li2S2 adsorbed on the substrates
Interaction via a Li-N bondNo specific bonding
Pang, Nazar et al ACS Nano, (2016); Adv. Energ. Mater. (2016)
14.9 mg/cm2 sulfur loading electrolyte/sulfur ratio = 3.5: 1 µl/mg
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S/KB cell
S/MnO2 nanosheetcell
0
hr
0.5
hr
4
hr
8
hr
12
hr
B. Catenation of sulfur to form polythionate complex
A. Formation of thiosulfate via oxidation of LiPS/ reduction of Mn4+:
Polysulfide chemical trapping: surface-active mediators
MnO2 nanosheets – 10 nm thick75 wt % sulfur/ “inorganic graphene”Capacity fade rate = 0.04% per cycle over 2000 cycles
Liang, Nazar et al., Nat. Commun. 6, 5682 (2015)
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Electrochemical reactivity of different metal oxides with LiPSs as a function of redox potential vs Li/Li+
Same process occurs for graphene oxide (reduced by LiPS – thiosulfate/ polythionate)
No redoxRedox to
thiosulfateRedox to
thiosulfate & sulfate
0 1 2 3 4 V
V2O5
NiOOH
Co3O4
CoO
Ti4O7
Fe3O4*
MnO2
VO2V2O3
CuO
Cu2O
Fe2O3*
TiO2
NiO
The “Goldilocks” Principle
Nazar, Sommers et al., Adv. Energy Mater. 6, 1501636 (2015)
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Interaction between polysulfide and MnO2 or graphene oxide
Li2S4
Li2S4/MnO2
Li2S4/Grapheneoxide
Li2S4/Graphene
At 2.3 V: partial reduction or oxidation
Li-S/MnO2 cell cathodeSB (0)
ST (-1)
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Core-shell micron-sized sulfur with an inorganic coating
Liang, Nazar et al., ACS Nano (2015)
𝟔𝑴𝒏𝑶𝟒− + 𝟑𝑺 + 𝑯𝟐𝑶 → 𝟔𝑴𝒏𝑶𝟐 + 𝑺𝑶𝟒
𝟐− + [𝑯(𝑺𝑶𝟒)𝟐]𝟑− + 𝑶𝑯−
X. Liang, L. F. Nazar et al, Angewandte Chemie 2015; Adv. Mater., 2016 on-line
Sustain high sulfur areal loadings
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Concept of “sparingly soluble-solvents” for polysulfides
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Cuisinier, Nazar et al., EES 2015.
Utilize a “non-solvent” electrolyteSolid-solid transformation? Highly limited solution process?
Utilize a sparingly soluble electrolyteOptimum properties for solution-based reactivity?
Controlling preciptn of Li2S – needs a polar metallic host, RMs
S8 Li2S?
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Critical Factors for Liquid Electrolyte Cell design
40
Q. Pang, X. Liang, L.F. Nazar, Nature Energy (in press, 2016)
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The Problem with Carbon
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Electron transfer/ion mass not higher than Li+/e-
but…
Advantage: metal anode (no dendrite formation, i.e., Mg)
- greatly increases energy density compared to carbon in Li-ion cell
Chevrel phases (Mo6S8) first to be studied as cathode*
Mg insertion examined in oxides**
Disadvantage: multivalent cations exhibit (?) low mobility in most high voltage host materials (ie, oxides)
- desolvation penalty for multivalent cations high
- nascent understanding of factors at play
Divalent batteries: intercalation of Mg2+, Zn2+ ions
*D. Aurbach et al., Nature 2000** P. Novak et al, 1997
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“Soft” anions: Mg (de)intercalation in the thiospinel Ti2S4
X. Sun, Z. Rong, G. Ceder, L.F. Nazar et al., Energy Environ Sci (2016); ACS Energy Lett 2016
Mg full cell with thiospinel cathode shows 190 mAh g-1 capacity, twice that of benchmark (2000), and relatively stable capacity retention.
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Diffusion energy barriers in Ti2S4 agree with computation
Mg self-diffusion coefficients (60° C) and corresponding energy barriers for Mg diffusion in cubic Ti2S4 calculated in dilute and concentrated limits
DMg (at 333K) ≈ 0.1X DLi at 298 KA.C. James and J.B. Goodenough, Solid State Ionics, 27, 37 (1988).
DMg (at 333K) expt: 530 meV; theory: 550 meV
In collaboration with Berkeley Theory Team: M. Liu, Z. Rong, K. Persson, G. Ceder
Nanomaterials required
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Multivalent Intercalation (Aqueous)Advantages
Divalent cation does not require desolvation from solvent shell Screening of divalent cation charge in lattice by solvent – enhanced mobility
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01/05/2016 - Philippe Bourchard
2016 to be a breakout year for stationary energy storage
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3
Why Zn metal ?
Stable in water: high corrosion resistance High abundance, production; non toxic Suitable redox potential (0.76 V vs. SHE) High
volumetric energy density (d: 7.14 g cm-3) Small exchange current for HER on Zn: large
kinetic voltage window ~2.4 V for Zn basedaqueous rechargeable batteries.
Aqueous Batteries ?
Low-cost, safe, easy to manufacture and dispose
Aqueous Zn-ion Batteries >> Safe and environmentally benign alternatives to their aprotic counterparts, can have ultra-high rate capabilities.
Aqueous Zn-ion batteries
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Efficient Zn stripping and plating
Highly reversible Zn stripping and deposition
HER2H2O + 2e- → H2 + 2OH-
WE: SS rodCE: Zn disk/metalElectrolyte: 1M ZnSO4-H2O
Zn2+ + 2e- ↔ Zn with ~100 % coulombic efficiency (Qox/Qred)
Rechargeable aqueous Zn-ion batteries: ~2.4 V window
No dendritic growth at pH < 7
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Layered Host: Water Assisted Facile Zn2+ Intercalation
a b
c
Host Structure Expanded host structurein electrolyte
Zn2+ intercalatedhost
Zn2+ Zn2+
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H2O-slurryH2O-basedbinder
Nanofiber morphology - short diffusion path, easy fab
SEM/TEM images of nanofibers Free-standing electrodes
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Sustainable & High-Rate Zn2+ ion Storage
Highly reversible Zn intercalation & stable cycling 1000 cycles: ≥ 80 % capacity retention Energy density (pouch cell): 450 Wh/L Coulombic efficiency: ≥ 99% High rate capability: discharge/charge in 8 min
6
< $70/kWh
D. Kundu, B. Adams, V. Duffort, L.F. Nazar, Nature Energy (2016)
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Integrated electrochemical energy storage
EV ↔ GridHome ↔ EV
Storage ↔ Grid
Off-peak capture essential
More important today than at any time in history:
new small & large-scale demands
Na/Zn- ion
Na/Li sulfur
Redox flowLi-ion
Li sulfur/air
52
Grid ↔ Devicesmetal/air
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BASF International Scientific Network for Electrochemistry and Batteries
Prof. M. Wagemaker, TU DelftDr. Mali Balasubramanian, Argonne, USA
Prof. Jurgen Janek, Giessen/KIT
Prof. M. Saiful Islam, Univ BathProf. Gerd Ceder, Berkeley
Prof. J. Baugh, UW
1. 53
Research team and collaborators
NRCan
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Thank you – we welcome visitors
Waterloo Institute for Nanotechnology and the Quantum-Nano Centre
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