battery energy storage beyond li-ion
TRANSCRIPT
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M. Rosa Palacín
ICMAB-CSIC, Campus UAB, 08193 Bellaterra (Barcelona) SPAIN [email protected]
Battery energy storage
beyond Li-ion
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?
Volta 1792-94
Volta 1801
Planté 1859 Jungner 1899 - +
LiyC LixCoO2e-
Introduction
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R. Brodd, ATP Working Paper Series Working Paper 05–01, NIST (US)
10-19!!!
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Cost
Safety
Energydensity
Increasingsize
Application Sustainability
energy / water footprint
recycling
critical vs. abundant materials
Performance
Tarascon & Armand, Nature 414 (2001) 359
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41000 Wh
~ x 10
~ x 620
~ x 5900
… and larger if grid applications are considered !!!
Growing larger….
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www.crugroup.com
Price of Li2CO3 over time (US$/ton)
M-ion concept
analogous to Li-ion Mn+ as charge carriers instead of Li+
(migration may be an issue for n>1, coulombic interactions)
energy density not directly related to M (but to electrode material capacities & potentials)
Na-ion
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M-anode concept
0
1000
2000
3000
4000
5000
0
2000
4000
6000
8000
10000
Li C Na Mg Al Ca
Gravim
etric capacity (mA
h/g)Volu
met
ric c
apac
ity (m
Ah/
cm3 )
Li-ion
Li “unsafe” ? polymer electrolyte ? air or sulphur cathodes?
Na low melting T, “unsafe” as solid?
Na/S successful (liquid electrodes) Mg electrolytes with wide V window?
high energy density cathodes? Ca interesting potential reversible plating/stripping? Al lower potential
reversible plating/stripping?
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Na-ion batteries
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à “unlimited” Na resources 20 ppm 22700 ppm Earth’s crust
à high standard reduction potential -3.04 -2.71 vs. NHE
à alloy formation with Al yes no
Current collector (Al)
Active material
Additive
Binder
Separator
SEI
Electrode
material
--++
Current collector (Cu)
Additive
Binder
Li-ion Na-ion
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à Similar chemistry
- Faster progress à Differences
- Ionic radius – coordination – crystal chemistry
- Polarizing character – diffusion – kinetics
- Solvation energy – solubilities – SEI
Graphite // LiPF6 EC:DMC // LiFePO4
Graphite // NaPF6 EC:DMC // NaFePO4
Alike but different…
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Practical prospects
Na15Pb4 || NaxCoO2
100 ºC
th: 350 Wh/kg, 1470 Wh/l
P(EO)8NaCF3SO3
1M NaPF6 in DME
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Practical prospects
Na15Pb4 || NaxCoO2
100 ºC
th: 350 Wh/kg, 1470 Wh/l
P(EO)8NaCF3SO3
1M NaPF6 in DME
N. Yabuuchi et al. Chem. Rev. 114 (2014) , 11636.
~1990
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Some V windows too wide to be practical Air stability can be an issue
Positive electrode materials
O3 P2
O3 higher capacity & P2 higher stability
Layered materials NaxMO2 N. Yabuuchi et al. Nature Materials 11(2012) 512
Polyanionic frameworks
Frameworks typically different from Li - based
Lower capacities than layered (« inactive groups ») Poor conductivity (C coating) High stability
2.5
3
3.5
4
4.5
0 20 40 60 80 100 120
Pote
ntia
l (V
vs N
a+ /Na)
Capacity (mAh/g)
Na3V2(PO4)2F3
A. Ponrouch et al. Energy & Environ. Sci. 6 (2013) 2361.
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(a)
(b)
(c)
(d)
(e)
(f)
Negative electrode materials: hard C
Non-graphitizable (sp3 cross-linking) Prepared by pyrolisis of solid precursors (cellulose, charcoal, phenolic resins, sugar…)
graphene sheets 10 – 40 Å (1-3 layer stacks)
E. Irisarri et al. J. Electrochem. Soc. 162 (2015) A2476
Current state of the art material Very low V operation (plating risk?) 1st cycle irreversibility is an issue
capacity microstructure, electrolyte
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R. Dugas et al. J. Electrochem. Soc. 2016, 163, A867.
Reported performance: lab cells
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Sustainability
Hard C // EC0.45:PC0.45:DMC0.1 // Na3V2(PO4)2F3
Theoretical energy density : 78 Wh/kg (BatPac v1.0)
(for comparison Graphite//LP30//LiFePO4 gives 75 Wh/kg )
3.6 V cell 300 mAh/g (HC)
110 mAh/g (NVPF)
A. Ponrouch, D. Monti, A. Boschin, B. Steen, P. Johansson, M.R. Palacin J. Mater. Chem. A 2015, 3, 22.
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Reported performance: upscaling
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Reported performance: industrial cells
http://www.faradion.co.uk Na-ion presentation http://www.faradion.co.uk/technology/354-2/
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Reported performance: industrial cells
Na-ion presentation http://www.faradion.co.uk/technology/354-2/
Will performance equal / beat Li-ion?
For myself I am an optimist ,
it does not seem to be much use being anything else.
(Sir Winston Churchill, Nov. 9th, 1954 )
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Ca batteries
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Why Ca anode?
à “unlimited” resources 20 ppm 27640 ppm 46600 ppm Earth’s crust
à high standard reduction potential -3.04 -2.37 -2.87 vs. NHE
P. Canepa et al. Chem. Rev. 2017, 117, 4287.
Proof-of-concept Mg anode (Aurbach et al. Nature)
The Odyssey of Multivalent Cathodes
MV
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M anodes: the case of Ca…
Suitable electrolytes (plating) cathode development
Reduction of the WE:
Ca stripping at the CE
Oxidation of the WE: Ca deposition ???
e-
e-
e-
e- e-
Ca2+
Ca CaxA
e-
e-
e-
V
Ca2+
Ca2+ Ca2+
Ca2+
Ca2+
e-
e-
e-
e- e-
Ca2+
Ca CaxA
e-
e-
e-
V
Ca2+
Ca2+ Ca2+
Ca2+
Ca2+
1991 Ca deposition not possible in organic solvent electrolytes Aurbach et al. (SEI does not conduct Ca2+ ions)
BUT Charge/radiusCa2+ << Mg2+
Easier migration
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M anodes: the case of Ca…
Substrate
SEI
Electrolyte
Ca2+(Solvated)①
② Ca2+(Desolvated)③
Ca(Nucleationandgrowth)④
Alkyl carbonates (high Ɛ, large redox window) Commercial salts
PC EC
TFSI- ClO4- BF4
-
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Ca2+ electrolytes
EC:PC RoomT
Concentration ↑ Viscosity ↑ Conductivity ↑, ↓
Low conductivities at RT Ion pairing
High T (50-100ºC)
Is Ca electrodeposition viable?
0.3 M Ca(BF4)2
0.45 M Ca(BF4)2
0.65 M Ca(BF4)2
0.8 M Ca(BF4)2
1 M Ca(BF4)2
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-0.04
-0.02
0
0.02
0.04
-1 0 1 2
Inte
nsity
(mA
)
Potential (V vs Ca2+/Ca passivated
)
Ca(ClO4)2Ca(BF4)2Ca(TFSI)2
-0.008
-0.004
0
0.004
-1 0 1 2
Reversible redox process in Ca(ClO4)2 & Ca(BF4)2
Ca plating???
Is Ca electrodeposition viable?
0.3M 100°C
Intensity ↑ with: Ca(BF4)2
↑ temperature ↑ ionic conductivity
-0.04
-0.02
0
0.02
0.04
-1 0 1 2
Inte
nsity
(mA)
Potential (V vs Ca2+/Ca passivated)
Plating Stripping
0.3M -0.65 -0.52
0.45M -0.52 -0.42
0.65M -0.65 -0.51
0.8M -0.88 -0.48
Ca(BF4) EC:PC 100°C 0.3 M
0.45 M0.65 M0.8 M
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Is Ca electrodeposition viable?
0.3M Ca(BF4) EC:PC
100ºC, 200h, -1.5V
Higher T, longer t
thicker deposits
higher Ca/F ratio
Bubbling in H2O: H2?
CKa
OKa
CuLaClKaClKb
CaKa
CaKb
0.50 0.90 1.30 1.70 2.10 2.50 2.90 3.30 3.70 keV
-1
-0.5
0
0.5
1
1.5
2
0 5 10 15 20 25 30 35
Op
en c
ircu
it p
ote
nti
al (
V v
s C
a2+
/Ca)
time (h)
OCV before
OCV after
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Ca plating/stripping
Deposits consist of a mixture of Ca metal and CaF2 (SEI)
SEI seems stable: permeable to Ca2+ ??
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Ca plating/stripping
Good cyclability BUT high polarisation
Ca//Ca
150 µA/cm2 150 cycles, 100ºC
A. Ponrouch, C. Frontera, F. Barde, M.R. Palacin Nature Materials 15, 2016, 169
Capacity stable upon cycling
BUT: competition with electrolyte
decomposition (efficiency to be improved)
100°C
Li//Li
150 µA/cm2 150 cycles, RT
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The quest for a cathode
Insertion cathodes?
e-
e-
e-
e- e-
Ca2+
Ca CaxA
e-
e-
e-
V
Ca2+
Ca2+ Ca2+
Ca2+
Ca2+
“Technology is always limited by the materials available”
DARPA, US, 1960´s
?
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Is CaMn2O4 a viable cathode?
CM CFSP
Marokite (1200°C, 72h) Ca CN=8
Mn3+ / Mn4+ Th.capacity Δx=1: 250 mAh/g
CM CFSP
Spinel (not known) Ca Td ∼3V, migration barrier 0.5 eV Persson et al. 2015
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What about CaMn2O4 - Marokite?
M. E. Arroyo-de Dompablo, C. Krich, J. Nava-Avendaño, M.R. Palacín, F. Bardé Chemistry of Materials 28, 2016, 6886.
0.0 0.2 0.4 0.6 0.8 1.0
-0.3
-0.2
-0.1
0.0
0.1
0.2
0.3
Form
ation
Ene
rgy (
ev/f.
u.)
x in CaxMn2O4
GGA+U GGA
0.0 0.2 0.4 0.6 0.8 1.02.0
2.4
2.8
3.2
3.6
4.0
4.4
14 %
6%14%
9%
Calcu
late
d Vo
tage
(V)
x in CaxMn2O4
GGA GGA_U
(a) (b)
Ueff = 4 eV
Suitable potential BUT migration barrier > 1.5 eV
pristine
“oxidized” 100° C
OCV 100° C
Complementary characterization COMPULSORY!!!
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Other alternatives?
2
2.5
3
3.5
4
0 50 100 150 200 250
Pote
ntia
l (V
vs C
a2+/C
a)
Capacity (mAh/g)
Ca-M-X
-0.04
-0.03
-0.02
-0.01
0
0.01
0.02
0.03
1 1.5 2 2.5 3 3.5
Inte
nsity
(mA)
Potential (V vs Ca2+/Capassivated)
cycle 4 cycle 5 cycle 6 cycle 7
M-X
D. Tchitchekova et al. (in preparation)
Preliminary proof of electrochemical reactivity in some Ca-M-X and M-X phases
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Other alternatives?
Complementary characterization: XRD may not be enough…
Tomographic reconstruction Transmission X-ray Microscopy
Ca L edge XANES
M-X
Ca-M-X Standards: M-X, CaCO3, CaF2
… to be continued
Ca-M-X
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Towards Ca metal batteries?
e-
e-
e-
e- e-
Ca2+
Ca CaxA
e-
e-
e-
V
Ca2+
Ca2+ Ca2+
Ca2+
Ca2+
Positive Efficient Ca2+ migration Large specific capacity High operation potential
Negative Plating/stripping
Electrolyte Plating/stripping Large potential window
Operation T Efficiency
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I always like to look on the optimistic side of life, but I am realistic enough to know that life is a complex matter. Walt Disney
Ackowledgements
M. E. Arroyo
C. Frontera A. Ponrouch D. Tchitchekova
F. Bardé A. Sorrentino
R. Dedryvère
P. Johansson
L. Croguennec C. Masquelier
D. Monti B. Steen
E. Irisarri
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