Post on 05-Jun-2018
Patrice SIMON 1,2
1 Université Paul Sabatier, CIRIMAT UMR-CNRS 5085 Toulouse – FRANCE,
simon@chimie.ups-tlse.fr2 Réseau sur le Stockage Electrochimique de l’Energie (RS2E), FR CNRS 3459
Batteries and Supercapacitors for
electrochemical energy storage: state-
of-the art and next challenges
Electrochemical Energy Storage
Batteries:
- high energy (100-200 Wh/kg)
- low power: < 1kW/kg
- time constant: ~ 1h
Capacitors: Power
- high power density (>50 kW/kg)
- low energy density: <0,1 Wh/kg
- time constant: ~ 1 ms
Supercapacitors:
- high power (10-20 kW/kg)
- medium energy: 5 Wh/kg
- time constant: ~ 5 s
D’après P. Simon, Y. Gogotsi , Nature Materials, 7 (2008) 845-854
Combustion
(oil)
Outline
1. Batteries
- Basics
- Li-ion batteries
- Perspectives
3. The French Network on Batteries
2. Supercapacitors
- Basic principe
- Applications
- Microporous carbons
1.1 Batteries : basic principle
∆Ecell = E+-E- (V) Qcell (mAh) and Energy = ∆E x Q (Wh)
Rechargeable cells� Accumulators (Batteries)
5
(-) LiC6 � C6 + Li+ + e; E = 0.5 V vs Li, C=372 mAh/g
� Lithium ion intercalated (Li+) : Li-ion batterie
1.2 Li-ion Batteries: starting point (1990, Sony)
Anode: C graphite
(+) Li0.5CoO2 + 0.5 Li+ + 0.5 e ⇔ LiCoO2 ; 177 mAh/g
∆E = 3.7V ; C = 60 Ah/kg ; W = 150 Wh/kg
Li – ion intercalation at both electrodes
Cathode: LiCoO2
Caracteristics:
- Li+ intercalation
- no Li metal
- Non aqueous Electrolyte
Cathode chemistry defines the name
of the batteries (LFP, NMC, NCA…)
1.2 Current Li-ion batteries: the cathode chemistries
From M. Winter, AABA Conference 2011, Mainz
8
� LiNi1/3Mn1/3Co1/3O2 (1/3): NMC chemistry
Only Ni2+
(active)
Mn +4: no Ni4+
(Mn un-active)
Co+3: Active redox
CoO6
Li
CoO6
Li
CoO6
Li 1-xCoO2 + xLi+ + x e- ↔ LiCoO2
LiCoO2: E=3.8 V, energy �
BUT
- C limited to 150 mAh/g
- Thermal stability issue
(Co-O)
1.2 2D LiCoO2-based cathodes: NMC chemistry
Cathode 3D : [LiFePO4 nano + C]
LiFePO4 (LFP); 1 Li+ per mole
- E=3.45 V vs Li
- - C=170 mAh.g-1
� no thermal runaway (P-O stable)
LiFePO4
- high power (charge and discharge)
- thermal stability (no runaway)
BUT
- lower energy density (120 Wh/kg)
- Fe solubility issue for T>50°C
- needs for carbon coatings (conductivity)
www.saftbatteries.com
1.2 Cathodes 1D: LFP
FePO4 + xLi+ + xe- ↔ xLiFePO4 + (1-x)FePO4
From M. Winter, AABA Conference 2011, Mainz
Lithium-Mangenese Oxide (LMO)
LiMn2O4 spinel structure AB2O4
xLi+ + xe- + Li(1-x)Mn2O4 ↔ LiMn2O4
0.8 Li per Mn2O4; C=120 mAh/g,
Pros :
• low cost,
• high cell voltage
• high power and thermal stability
Cons :
• -20% Capacity vs NMC
•T >50°c: Mn3+ dissolution
2Mn3+ � Mn2+ (dissolution) + Mn4+ (solid).
1.2 3D cathodes : LMO spinel
L. Croguennec, ICMCB Bordeaux
0
500
1000
1500
2000
2500
3000
3500
4000
4500
In C Bi Zn Te Pb Sb Ga Sn Al As Ge Si
Ca
pa
city
in
mA
h/g
1.3 Advanced Li-ion batteries: Li alloys as anodes
Sn, Si BUT
Huge volume change (+300%)
leading to mechanical stress
No cyclability
Cgraphite limited to 370 mAh/g � higher capacitve anodes?
M° + xLi + xe- ⇔ LixM, with x ≤ 4.4Li alloying reaction:
M°LixM°⇔
1.3 Advanced Li-ion avancé: Si-based anodes
Ex of Silicium-based anodes: mechanical buffer
Nano-sizing helps in buffering mechanical stress� improved capacity (1,000 mAh/g)
Other strategies possible (ink formulation) ; commercialization in progress
G. Yushin et al., Nature Materials 2010
1.3 Advanced cathodes: Li-rich NMC phases
Classical cationic redox mechanism
Li[Li0.2Ni0.14Mn0.54Co0.13]O2
+4 +3+2
0.4 e-
Fundamental problem
� Origin of this extra capacity
Li[Li0.2Ni0.14Mn0.54Co0.13]O2
NiMnCo
Li excess
2007: Li-rich phase (M. Tackeray et al.)
Whycapacity > 280 mAh/g?
?0.9 e−
Capacity (mAh/g)
ChargeDischarge
Charge/discharge at constant current
Direct evidence of cumulative cationic (Mn+ � M(n+1)+)
and anionic (O2− � O22−) redox
processes!!
N. Yabuuchi et al. ECS meeting November 2013
Feasibility of using previously
disregarded heavy 4d-metals!!
� Opens new paths for high capacity materials
J.M. Tarascon et al, Nature Materials 9 (2013) 827-835; JM Tarascon et al., Nature (Materials 2014)
Identical capacity> 260 mAh/g
1.3 Advanced cathodes: Li-rich NMC phases
1.4 Perspectives : Li-O2 batteries
K. M. Abraham, Z. Jiang, J. Electrochem. Soc. 143 1 (1996)
T. Ogasawara et al. J. Am. Chem. Soc. 128 1390 (2006)
� Instability vs Li° and high polarization
� low reaction kinetics
� reaction G + L � S: low power
� Precipitation of Li2O2 (insulating)
� No cycle life
� Catalyst + porous material: key
Theoretically : 800-900 Wh/kg
E Theoretical : 2300 Wh/kg
0 200 400 600 800 1000
2.0
2.5
3.0
3.5
4.0
4.5
Pot
entia
l vs
Li+ /L
i0 (V
)
C apac ity o f O 2 e lec trode (m Ah/g)
Charge
2.96 V
catalyst
DischargeO2 (g) + 2Li+ + 2e- → Li2O2 (s)
=
O2 + e- → O2-.
O2-. + Li+ → LiO2 (s)
LiO2 → Li2O2 (s) + O2
Li2O2 (s) →O2 (g) + 2Li+ + 2e-
(-) 2Li ↔ 2Li+ + 2e-
(+) O2 (g) + 2e- ↔ O22- ∆E = 4V BUT
Dominique Larcher, LRCS, Amiens
Few avantages and …. Lot of issues!!!
October 30th, 20015
Use a redox mediator (I3-/I-) to oxidize OH- in H2O
during charge and dissolve LiO2 in discharge
1.4 Li-O2 batteries: breaking news…
Important improvement in the Li-O2 technology but does not solve all the issues
● Na+ to replace Li+: Na-ion
Cost :
Li2CO3: 0.9 euro/kg
Na2CO3: 0.08 euro/kg
Abundance :
Na+ = Li+ x 105 !
Potential :
Li+/Li: -3.05 V
Na+/Na: -2.71V
Capacity :
Li+/Li: 3860 mAh/g
Na+/Na: 1166 mAh/g
� Alternative to Li-ion at lower cost ; -30% energy density
� Mass storage (renewable, grids…)
1.4 Perspectives : Na vs Li
1.4 Perspectives : Li-S batteries
16Li + S8 � 8Li2S ; OCV = 2.4V
Reactions at the cathode can be schematically described as follows:
3/4 S8 + 2 Li+ + 2ē �Li2S6 (1)
2/3 Li2S6 + 2/3 Li+ + 2/3 ē � Li2S4 (2)
3/4 Li2S4 + 1/2 Li+ + 1/2 ē � Li2S3 (3)
2/3Li2S3 + 2/3 Li+ + 2/3 ē � Li2S2 (4)
1/2Li2S2 + Li+ + ē � Li2S (5)
(3) can be as well Li2S4 + 4e- + 4Li � Li2S2 + 2 Li2S
P. Bruce et al. Nature Materials 11 (2012) 19-29
One solution: sulfur confinement in porous carbon
From confinement to adsorption on polar solid electronic conductor
Q. Pang, D. Kundu, M. Cuisinier, L.F. Nazar, Nature communications 2014
200 nm
Ti4O7 / S composites (70% wt)
Li-S : old-fashion technology (50 years old) but
Recent advances in favor of a fast commercialization
…. well ahead Metal-Air systems!!!
1.4 Perspectives: Li-S batteries
Al-ion : - Cell voltage 2 V, C=60 mAh/g, ionic liquid,
- Negative electrode = Al foam, positive = Carbon foam � vol energy??
- One charge per Al complex!!!!
� grav. Energy 5 to 10 times lower, low vol. energy…
� Interesting concept but long and winding road to replace Li !!
1.5 News: Al-ion battery…
23
ENVIA (http://enviasystems.com/) made a recent announcement on the 450
Wh/kg batteries using Si-based anode.
1.5 The ENVIA battery…
400 Wh/kg: very high energy density…
…but: thick electrodes, low rates and soft packaging
Outline
1. Batteries
- Basics
- Li-ion batteries
- Perspectives
3. The French Network on Batteries
2. Supercapacitors
- Basic principe
- Applications
- Microporous carbons
Electrochemical Energy Storage devices
Supercapacitors:
- high power (15-20 kW/kg)
- medium energy: 5 Wh/kg
- time constant: ~ 10 s
From P. Simon, Y. Gogotsi , Nature Materials, 7 (2008) 845-854
Batteries:
- high energy (250 Wh/kg)
- low P : up to kW/kg
- time constant: 10’s min
Batteries and Supercapacitors : complementary devices
2.1 Charge storage mechanism in EDLCs
Charge storage: electrostatic (Double Layer Capacitance)
� Non-aqueous electrolyte
� ∆Emax = 2,7 V
� High Surface Area carbon
SSA ≈ 1500 m².g-1
� > 100 F.g-1 of carbon
Caracteristics :
- Surface Storage: low E but high P
- Vcharge = Vdischarge
- low ∆vol. : cyclability > 1 million cycles
Porous carbon
2 nm
C = (ε0 εr S) / d
C ≈ 10 – 20 µF/cm²
2.2 Applications: power delivery
16 powered by 35 V / 28.5 F modules (Maxwell)
(14 series-connected of 4 SC 100F in parallel)
• A380 door emergency opening
http://www.airbus.com (Maxwell)
2.2 Applications : energy recovery
SC modules:
1) braking energy recovery
2) electric drive (100’s m)
Collaboration Alstom / Batscap
Source : Alstom
Starter/Alternator and recovery
micro-hybrid e-Hdi Citroen C3,
C4, C5 diesel (2012)
• -15 % gasoil
• CO2 < 130g per km
Credit: Argone Nal Lab
http://www.citroen.fr/citroen-ds4/technologies/#/citroen-ds4/technologies/
2.2 Applications: HEV
http://www.leblogauto.com/2011/11/mazda-i-eloop-place-au-
supercondensateur.html
Mazda: i-ELOOP concept
http://www.turbo.fr/peugeot/peugeot-308/essai-auto/410344-essai-peugeot-308/
Peugeot: e-HDI 308 1.6 HDi 110 ch
Blue Tram de Blue Solutions (Bolloré)
- electric drive: supercapacitors
- 1.5 km autonomy
Key interest: charging rate (60 s), cyclability, cost (facteur 10)
Plant opened last February 2015
50 Blue Tram per year
2.2 Applications : electric drive
� high SSA >1500 m2/g
2.3 Active Materials in EDLCs: porous carbons
BUT
Activated carbons
Pore Size
Distribution
Activated Carbon =
Porous carbons
Carbon
powder
Coconut Shell
Capacitance increase in carbon micropores (<1nm), electrolyte AN+1M (C2H5)4+,BF4
-
Capacitance increase in nanopores < 1 nm:
� paradigm change
� new concept to prepare carbonsJ. Chmiola, G. Yushin, Y. Gogotsi, C. Portet, P. Simon and P.L. Taberna., Science 313, 1760-1763 (2006)
Pores < size of
solvated ions
accessibles to
ions!
Huge
capacitance
increase in
nanopores:
+100%!
2.3 Microporous carbons
C. Largeot, C. Portet, J. Chmiola, P.L. Taberna, Y. Gogotsi and P. Simon JACS, 130 (9), 2730 -2731 (2008)
P. Simon, Y. Gogotsi Nature Materials, 7 (2008) 845-854
Maximum C at ~ 0,72 nm � when ion size ~ pore size... WHY??
No solvent, cation size ≈ anion size:
2.3 CDCs in neat EMI,TFISI electrolyte
AC
Ionic Liquids: no solvent (only molten salts) � no solvation shell
1. Electrolyte is inside pores even at Ψ=0V: not an electrosorption driven process
2.3 MD modeling of BMI,PF6 in CDCs
électrolyte = EMI-PF6 (100°C)
CDC CDC
Potential
1. Electrolyte is inside pores even at Ψ=0V
2. Ion exchange with the electrolyte bulk !
3. Coordination number of ions decreases inside the pores (“desolvation”)
C. Merlet, B. Rotenberg, P.A. Madden, P.L. Taberna, Y. Gogotsi, P. Simon, M. Salanne, Nature Materials (2012)
C. Merlet, C. Pean, B. Rotenberg, P.A. Madden, P.L. Taberna, P. Simon, M. Salanne, Nature Communications (2013) 27010
2.3 MD modeling of BMI,PF6 in CDCs
2.4 Perspectives for supercapacitors
1. Increase carbon capacitance (EDLC)design porous carbons to maximize capacitance
� understand the ion size /carbon pore size
relationship
Increase energy density (E=1/2 C.V²) from 5 to >10 Wh/kg
� tdischarge > 10s
3. Increase the cell voltage� ionic liquids-based electrolytes
� hybrid devices (Li-ion capacitor)
2. Fast redox materials� design nanostructured materials for high
capacitance and high power
Ex: Nano-structured Nb2O5
V. Augustin, J. Come, P.L. Taberna, S. Tolbert, H. Abruna, P. Simon , B. Dunn, Nature Materials 2013
3. The French network on batteries (RS2E)
GOALS
• address scientific and technologic
issues of current and future
electrochemical storage systems for
mobile and stationary applications
• improve knowledge and technology
transfer from research to industry
• develop the French expertise in the
field
RS2E|Réseau sur le Stockage
Electrochimique de l’Energie
= Research network on
Electrochemical Energy StorageWHEN ?SINCE 2011
Director: J.-M. Tarascon
Deputy Director: P. Simon
FUTURE HEADQUARTERS IN AMIENS (12/2016)
3. The RS2E network: organization
Academic Research Center
� 15 National research labs
LRCS , LG (Amiens)
CIRIMAT (Toulouse)
ICG-AIME (Montpellier)
IPREM (Pau)
ICMCB (Bordeaux)
IMN (Nantes)
ICR & MADIREL (Marseille)
CEMHTI (Orléans)
LCMCP, PECSA (Paris)
IS2M (Mulhouse)
LEPMI (Grenoble)
IRCICA (Lille)
Technological Transfer Center
INDUSTRIAL CLUB
RESEARCH TOPICS
CROSS CUTING
RESEARCH
Advanced Li-ion (materials,
formulation, electrolytes…)
Capacitive Storage
(nanostructuredmaterials, carbons,
pseudocapacitives…)
Eco-compatible
Storage (synthesis,
biomineralization, organic redox, ACV-
recycling…)
New Chemistries
(Li-S, Na-ion, redox-flow, solid-state
batteries…)
Smart Materials
(faradic/photovolatïc, 3D microbatteries,
micro SC…)
Safety(ageing, additives,
Thermal and electrochemical
stability)
Theory(combinatory approach,
Transfer limitations,
System modelling)
Instrumentation(in-situ techniques
(XRD, HRTEM, HREELS,
Synchrotron access))
PRE-TRANSFERT
CELLS
(safety, up-
scaling materials,
BMS, pre-
prototyping)
3.1 The RS2E network: research topics
Focus on two recent achievements:
3.2 Recent achievements within the RS2E
1. Advanced Li-ion batteries: improving the capacity (Ah)
- high capacity Li-rich cathode
3. Sodium-ion batteries: an alternative to Li-ion for grid storage?
- Na-ion battery « Task Force »
2. Supercapacitor
� basic understanding of ion transfer in nanopores
3.2 The Li-rich NMC phases
N. Yabuuchi et al. ECS meeting November 2013
Direct evidence of cumulative cationic (Mn+ � M(n+1)+)
and anionic (O2− � O22−) redox
processes!!
Feasibility of using previously
disregarded heavy 4d-metals!!
� Opens new paths for high capacity materials
J.M. Tarascon et al, Nature Materials 9 (2013) 827-835 J.M. Tarascon et al, Nature Materials 14 (2014) 230-238
Focus on two recent achievements:
3.2 Recent achievements within the RS2E
1. Advanced Li-ion batteries: improving the capacity (Ah)
- high capacity Li-rich cathode
3. Sodium-ion batteries: an alternative to Li-ion for grid storage?
- Na-ion battery « Task Force »
2. Supercapacitor
� basic understanding of ion transfer in nanopores
Different storage mechanism with electrode polarity: Positive electrode: anion in / cations out � ion exchange
Negative electrode: cation in (desolvated), anions constant � counter ion adsorption
3.2 Supercapacitor: In-situ NMR
NMR spectra at various potentials: in-pore ion population
0.2
0.4
0.6
0.8
1
1.2
1.4
-1.5 -1 -0.5 0 0.5 1 1.5
ion
popu
latio
n (m
mol
/g)
Cell voltage (V)
Cations �
Anions
constant
anions
cations
PEt4+
BF4−
Cations �
Anions �
PEt4+
BF4−
J. Griffin, A. Forse, W.-Y. Tsai, P.-L. Taberna, P. Simon, C. Grey, Nature Materials, 2015, 14, 812-819
Why ? � Key concerns to address to design optimized carbon structures
Focus on two recent achievements:
3.2 Recent achievements within the RS2E
1. Advanced Li-ion batteries: improving the capacity (Ah)
- high capacity Li-rich cathode
3. Sodium-ion batteries: an alternative to Li-ion for grid storage?
- Na-ion battery « Task Force »
2. Supercapacitor
� basic understanding of ion transfer in nanopores
● Na+ to replace Li+: Na-ion
Cost :
Li2CO3: 0.9 euro/kg
Na2CO3: 0.08 euro/kg
Abundance :
Na+ = Li+ x 105 !
Potential :
Li+/Li: -3.05 V
Na+/Na: -2.71V
Capacity :
Li+/Li: 3860 mAh/g
Na+/Na: 1166 mAh/g
� Alternative to Li-ion at lower cost ; -30% energy density
� Mass storage (renewable, grids…)
1.4 Perspectives : Na vs Li
3. RS2E: Na-ion from Lab…to battery prototypes
Na-ion battery prototypes
i) 90 Wh/kg
ii) 140 Wh/l
(not optimized)
6 patents + several under progress
Next steps:
- tests (rates, cyclabiltiy, ageing with T…)
- improving the performance (material optimization, move to Sb…)
- cost model