Batteries and Supercapacitors for
electrochemical energy storage: stateof-the art and next challenges
Patrice SIMON 1,2
1
Université Paul Sabatier, CIRIMAT UMR-CNRS 5085 Toulouse – FRANCE,
simon@chimie.ups-tlse.fr
2 Réseau sur le Stockage Electrochimique de l’Energie (RS2E), FR CNRS 3459
Electrochemical Energy Storage
Capacitors: Power
- high power density (>50 kW/kg)
- low energy density: <0,1 Wh/kg
- time constant: ~ 1 ms
Batteries:
- high energy (100-200 Wh/kg)
- low power: < 1kW/kg
- time constant: ~ 1h
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
2. Supercapacitors
- Basic principe
- Applications
- Microporous carbons
3. The French Network on Batteries
1.1 Batteries : basic principle
∆Ecell = E+-E- (V)
Qcell (mAh)
Rechargeable cells
and
Energy = ∆E x Q (Wh)
Accumulators (Batteries)
1.2 Li-ion Batteries: starting point (1990, Sony)
Caracteristics:
- Li+ intercalation
- no Li metal
- Non aqueous Electrolyte
(-)
Anode: C graphite
LiC6
C6 + Li+ + e; E = 0.5 V vs Li, C=372 mAh/g
Lithium ion intercalated (Li+) : Li-ion batterie
(+)
Cathode: LiCoO2
Li0.5CoO2 + 0.5 Li+ + 0.5 e ⇔ LiCoO2 ; 177 mAh/g
Li – ion intercalation at both electrodes
∆E = 3.7V ; C = 60 Ah/kg ; W = 150 Wh/kg
5
1.2 Li-ion batteries: a large family…
1.2 Current Li-ion batteries: the cathode chemistries
Cathode chemistry defines the name
of the batteries (LFP, NMC, NCA…)
From M. Winter, AABA Conference 2011, Mainz
1.2 2D LiCoO2-based cathodes: NMC chemistry
Li 1-xCoO2 + xLi+ + x e- ↔ LiCoO2
CoO6
Li
LiCoO2: E=3.8 V, energy
BUT
- C limited to 150 mAh/g
- Thermal stability issue
(Co-O)
CoO6
Li
CoO6
LiNi1/3Mn1/3Co1/3O2 (1/3): NMC chemistry
Co+3: Active redox
Only Ni2+
(active)
Mn +4: no Ni4+
(Mn un-active)
8
1.2 Cathodes 1D: LFP
Cathode 3D : [LiFePO4 nano + C]
LiFePO4 (LFP); 1 Li+ per mole
FePO4 + xLi+ + xe- ↔ xLiFePO4 + (1-x)FePO4
- E=3.45 V vs Li
-
From M. Winter, AABA Conference 2011, Mainz
- 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 3D cathodes : LMO spinel
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
L. Croguennec, ICMCB Bordeaux
Cons :
• -20% Capacity vs NMC
•T >50°c: Mn3+ dissolution
2Mn3+ Mn2+ (dissolution) + Mn4+ (solid).
1.3 Advanced Li-ion batteries: Li alloys as anodes
Cgraphite limited to 370 mAh/g
higher capacitve anodes?
M° + xLi + xe- ⇔
Li alloying reaction:
⇔
Capacity in mAh/g
M°
4500
4000
3500
3000
2500
2000
1500
1000
500
0
LixM, with x ≤ 4.4
LixM°
Sn, Si BUT
Huge volume change (+300%)
leading to mechanical stress
No cyclability
In
C
Bi
Zn
Te
Pb
Sb Ga
Sn
Al
As Ge
Si
1.3 Advanced Li-ion avancé: Si-based anodes
Ex of Silicium-based anodes: mechanical buffer
G. Yushin et al., Nature Materials 2010
Nano-sizing helps in buffering mechanical stress improved capacity (1,000 mAh/g)
Other strategies possible (ink formulation) ; commercialization in progress
1.3 Advanced cathodes: Li-rich NMC phases
2007: Li-rich phase (M. Tackeray et al.)
Li[Li0.2Ni0.14Mn0.54Co0.13]O2
Classical cationic redox mechanism
+2
Li excess
NiMnCo
+4
+3
Li[Li0.2Ni0.14Mn0.54Co0.13]O2
0.4 eCharge/discharge at constant current
Charge
Discharge
0.9 e−
Fundamental problem
Origin of this extra capacity
?
Why
capacity > 280 mAh/g?
Capacity (mAh/g)
1.3 Advanced cathodes: Li-rich NMC phases
Identical capacity
> 260 mAh/g
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)
1.4 Perspectives : what technology for the futur ?
1.4 Perspectives : Li-O2 batteries
Few avantages and …. Lot of issues!!!
K. M. Abraham, Z. Jiang, J. Electrochem. Soc. 143 1 (1996)
T. Ogasawara et al. J. Am. Chem. Soc. 128 1390 (2006)
E Theoretical : 2300 Wh/kg
(-) 2Li ↔ 2Li+ + 2e(+) O2 (g) + 2e- ↔ O22-
BUT
∆E = 4V
Li2O2 (s) →O2 (g) + 2Li+ + 2e-
Theoretically : 800-900 Wh/kg
O2 (g) +
2Li+
+ 2e- → Li2O2 (s)
=
O2 + e- → O2-.
O2-. + Li+ → LiO2 (s)
LiO2 → Li2O2 (s) + O2
+ 0
Potential vs Li /Li (V)
4 .5
4 .0
catalyst
3 .5
Charge
2.96 V
3 .0
2 .5
Discharge
2 .0
0
200
400
600
800
1000
C a p a c ity o f O 2 e le c tro d e (m A h /g )
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
Dominique Larcher, LRCS, Amiens
1.4 Li-O2 batteries: breaking news…
October 30th, 20015
Use a redox mediator (I3-/I-) to oxidize OH- in H2O
during charge and dissolve LiO2 in discharge
Important improvement in the Li-O2 technology but does not solve all the issues
1.4 Perspectives : Na vs Li
● Na+ to
replace Li+: Na-ion
Cost :
Li2CO3: 0.9 euro/kg
Na2CO3: 0.08 euro/kg
Potential :
Li+/Li: -3.05 V
Na+/Na: -2.71V
Abundance :
Na+ = Li+ x 105 !
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 : Li-S batteries
P. Bruce et al. Nature Materials 11 (2012) 19-29
16Li + S8
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)
3/4 Li2S4 + 1/2 Li + 1/2 ē Li2S3
+
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
One solution: sulfur confinement in porous carbon
8Li2S ; OCV = 2.4V
1.4 Perspectives: Li-S batteries
From confinement to adsorption on polar solid electronic conductor
Ti4O7 / S composites (70% wt)
Q. Pang, D. Kundu, M. Cuisinier, L.F. Nazar, Nature communications 2014
200 nm
Li-S : old-fashion technology (50 years old) but
Recent advances in favor of a fast commercialization
…. well ahead Metal-Air systems!!!
1.5 News: Al-ion battery
NATURE, April 8th, 20015
The End of the Li-ion ?????
1.5 News: Al-ion battery…
Al-ion :
- Cell voltage 2 V, C=60 mAh/g, ionic liquid,
- Negative electrode = Al foam, positive = Carbon foam
- 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 !!
vol energy??
1.5 The ENVIA battery…
ENVIA (http://enviasystems.com/) made a recent announcement on the 450
Wh/kg batteries using Si-based anode.
400 Wh/kg: very high energy density…
…but: thick electrodes, low rates and soft packaging
23
Outline
1. Batteries
- Basics
- Li-ion batteries
- Perspectives
2. Supercapacitors
- Basic principe
- Applications
- Microporous carbons
3. The French Network on Batteries
Electrochemical Energy Storage devices
Batteries:
- high energy (250 Wh/kg)
- low P : up to kW/kg
- time constant: 10’s min
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 and Supercapacitors : complementary devices
2.1 Charge storage mechanism in EDLCs
Charge storage: electrostatic (Double Layer Capacitance)
C = (ε0 εr S) / d
C ≈ 10 – 20 µF/cm²
High Surface Area carbon
SSA ≈ 1500 m².g-1
> 100 F.g-1 of carbon
Porous carbon
Non-aqueous electrolyte
∆Emax = 2,7 V
Caracteristics :
2 nm
- Surface Storage: low E but high P
- Vcharge = Vdischarge
- low ∆vol. : cyclability > 1 million cycles
2.2 Applications: power delivery
• A380 door emergency opening
http://www.airbus.com
16 powered by 35 V / 28.5 F modules (Maxwell)
(14 series-connected of 4 SC 100F in parallel)
(Maxwell)
2.2 Applications : energy recovery
Source : Alstom
Collaboration Alstom / Batscap
SC modules:
1) braking energy recovery
2) electric drive (100’s m)
2.2 Applications: HEV
Credit: Argone Nal Lab
Starter/Alternator and recovery
micro-hybrid e-Hdi Citroen C3,
C4, C5 diesel (2012)
• -15 % gasoil
• CO2 < 130g per km
http://www.citroen.fr/citroen-ds4/technologies/#/citroen-ds4/technologies/
Mazda: i-ELOOP concept
http://www.leblogauto.com/2011/11/mazda-i-eloop-place-ausupercondensateur.html
Peugeot: e-HDI 308 1.6 HDi 110 ch
http://www.turbo.fr/peugeot/peugeot-308/essai-auto/410344-essai-peugeot-308/
2.2 Applications : electric drive
Plant opened last February 2015
50 Blue Tram per year
Blue Tram de Blue Solutions (Bolloré)
- electric drive: supercapacitors
- 1.5 km autonomy
Key interest: charging rate (60 s), cyclability, cost (facteur 10)
2.3 Active Materials in EDLCs: porous carbons
Carbon
powder
Activated Carbon =
Porous carbons
Coconut Shell
BUT
Activated carbons
Pore Size
Distribution
high SSA >1500 m2/g
2.3 Microporous carbons
Capacitance increase in carbon micropores (<1nm), electrolyte AN+1M (C2H5)4+,BF4-
Pores < size of
solvated ions
accessibles to
ions!
Huge
capacitance
increase in
nanopores:
+100%!
Capacitance increase in nanopores < 1 nm:
paradigm change
new concept to prepare carbons
J. Chmiola, G. Yushin, Y. Gogotsi, C. Portet, P. Simon and P.L. Taberna., Science 313, 1760-1763 (2006)
2.3 CDCs in neat EMI,TFISI electrolyte
Ionic Liquids: no solvent (only molten salts)
no solvation shell
AC
No solvent, cation size ≈ anion size:
Maximum C at ~ 0,72 nm
when ion size ~ pore size... WHY??
P. Simon, Y. Gogotsi Nature Materials, 7 (2008) 845-854
C. Largeot, C. Portet, J. Chmiola, P.L. Taberna, Y. Gogotsi and P. Simon JACS, 130 (9), 2730 -2731 (2008)
2.3 MD modeling of BMI,PF6 in CDCs
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
2.4 Perspectives for supercapacitors
Increase energy density (E=1/2 C.V²) from 5 to >10 Wh/kg
tdischarge > 10s
1. Increase carbon capacitance (EDLC)
design porous carbons to maximize capacitance
understand the ion size /carbon pore size
relationship
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. Increase the cell voltage
ionic liquids-based electrolytes
hybrid devices (Li-ion capacitor)
3. The French network on batteries (RS2E)
Director: J.-M. Tarascon
Deputy Director: P. Simon
WHEN ?
SINCE
2011
RS2E|Réseau sur le Stockage
Electrochimique de l’Energie
= Research network on
Electrochemical Energy Storage
GOALS
FUTURE HEADQUARTERS IN AMIENS (12/2016)
• 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
3. The RS2E network: organization
Academic Research Center
15 National research labs
Technological Transfer Center
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)
INDUSTRIAL CLUB
3.1 The RS2E network: research topics
RESEARCH TOPICS
CROSS CUTING
RESEARCH
PRE-TRANSFERT
CELLS
(safety, upscaling materials,
BMS, preprototyping)
Advanced
Li-ion
Capacitive
Storage
(materials,
formulation,
electrolytes…)
(nanostructured
materials, carbons,
pseudocapacitives…)
Ecocompatible
Storage
(synthesis,
biomineralization,
organic redox, ACVrecycling…)
New
Chemistries
Smart
Materials
(Li-S, Na-ion, redoxflow, solid-state
batteries…)
(faradic/photovolatïc,
3D microbatteries,
micro SC…)
Safety
Theory
Instrumentation
(ageing, additives,
Thermal and electrochemical
stability)
(combinatory approach,
Transfer limitations,
System modelling)
(in-situ techniques
(XRD, HRTEM, HREELS,
Synchrotron access))
3.2 Recent achievements within the RS2E
Focus on two recent achievements:
1. Advanced Li-ion batteries: improving the capacity (Ah)
- high capacity Li-rich cathode
2. Supercapacitor
basic understanding of ion transfer in nanopores
3. Sodium-ion batteries: an alternative to Li-ion for grid storage?
- Na-ion battery « Task Force »
3.2 The Li-rich NMC phases
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
J.M. Tarascon et al, Nature Materials 14 (2014) 230-238
3.2 Recent achievements within the RS2E
Focus on two recent achievements:
1. Advanced Li-ion batteries: improving the capacity (Ah)
- high capacity Li-rich cathode
2. Supercapacitor
basic understanding of ion transfer in nanopores
3. Sodium-ion batteries: an alternative to Li-ion for grid storage?
- Na-ion battery « Task Force »
3.2 Supercapacitor: In-situ NMR
ion population
(mmol/g)
NMR spectra at various potentials: in-pore ion population
Cations
BF4−
1.4
anions
1.2
cations
1
Anions
0.8
PEt4+
0.6
PEt4+
BF4−
0.4
Anions
constant
0.2
-1.5
-1
-0.5
Cations
0
0.5
1
1.5
Cell voltage (V)
Different storage mechanism with electrode polarity:
Positive electrode: anion in / cations out ion exchange
Negative electrode: cation in (desolvated), anions constant
Why ?
counter ion adsorption
Key concerns to address to design optimized carbon structures
J. Griffin, A. Forse, W.-Y. Tsai, P.-L. Taberna, P. Simon, C. Grey, Nature Materials, 2015, 14, 812-819
3.2 Recent achievements within the RS2E
Focus on two recent achievements:
1. Advanced Li-ion batteries: improving the capacity (Ah)
- high capacity Li-rich cathode
2. Supercapacitor
basic understanding of ion transfer in nanopores
3. Sodium-ion batteries: an alternative to Li-ion for grid storage?
- Na-ion battery « Task Force »
1.4 Perspectives : Na vs Li
● Na+ to
replace Li+: Na-ion
Cost :
Li2CO3: 0.9 euro/kg
Na2CO3: 0.08 euro/kg
Potential :
Li+/Li: -3.05 V
Na+/Na: -2.71V
Abundance :
Na+ = Li+ x 105 !
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…)
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
Thanks...
Some members of the RS2E team
www.energie-rs2e.com/en
Merci pour votre attention