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Les différentes chimies des batteries
lithium-ion et leurs usages industriels
Thomas Bibienne, PhDAgent de Recherche
Laboratoire Chimie Electrochimie des Solides
Gpe Pr. Dollé (UdeM)
Québec Mines - 23 Novembre 2016
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2/22from D. Larcher and J-M. Tarascon, Nature Chemistry, Vol 7, January 2015
Energy consumption and demand increase
TOE = Tons of Oil Equivalent
Equivalent of 10 million of oil barrel consumed since this morning!
Energy source ?
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Renewable energy supply should increase
Other: geothermal, solar, winds, heat, etc
Wo
rld
prim
ary
en
erg
y s
up
ply
(Mto
e)
?
intermittent !
International Energy Agency. 2016. Key world energy statistics
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Batteries to store energy
from electrical energy
to chemical energy
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Energy storage technology: from lead to Li-ion batteries
Specific
pow
er
(W/k
g)
= a
cce
lera
tio
n
Specific energy (Wh/kg) = autonomy
JM Tarascon, Histoire et évolution des technologies d’accumulateurs, Collège de France, 2011
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Li-ion market share
Li-Ion Batteries: principle and history
Safety
Electrode materials
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7/22modified from Avicenne Energy, 2014
Worldwide battery market dominated by lead acid
rapid growth of Li-ion batteries
Volu
me in
Volu
me in
NiMH Nickel Métal-Hydrure
NiCd Nickel Cadmium
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How does a battery work in discharge?
modified from the Li-Ion Rechargeable Battery: A Perspective, John B. Goodenough
and Kyu-Sung Park, J. Am. Chem. Soc., 2013
Positive
Li+ + e- + CoO2 + -» LiCoO2
NegativeLiC6 -» Li+ + e- + C6
LiC6LiCoO2
Electrolyte
Li+
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when lithium-metal used as negative electrode with liquid electrolyte:
formation of lithium dendrite = lithium ‘rod’
Electric short circuit -» fire
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Li-dendrite issue with Li-metal: 2 solution arose
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11/22Armand, M. B. in Materials for Advanced Batteries, 1980
Limitation of dendrite formation
No organic solvent
Operated at 80°C
Blue Solution Blue Car
2011- présent
Li-metal
polymer
1978
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12/22Issues and challenges facing rechargeable lithium batteries, J.-M. Tarascon and M. Armand, Nature 414, 359-
367, November 2001 - http://www.sonyenergy-devices.co.jp/en/keyword/
-» 1991, first Li-ion
batteries to be
commercialized (Sony)
LiCoO2/Graphite
= "rocking chair" battery
Li-ion
1983
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Li-ion battery history
LiCoO2 (LCO)
Goodenough and
Mizushima
19801975
Layered structure
of LiTiS2
Whittingham
LiMn2O4 (LMO)
Thackeray et al.
1984
LiFePO4 (LFP)Pahdi, Goodenough
1997
Graphite as
negative LixC6
Yazami
1983
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Key requirements for electrode material (theoretical)
Safety – Price
chemically stable, non-toxic, inexpensive
easy to prepare and handling
Crystal structure
empty sites to intercalate large amount of Li ion
high lithium chemical diffusion
small volume changing during electrochemical process
Electrochemical properties
possibility to be oxidized/reduced
good electronic conductor
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Li-ion technology:
many available positive and negative electrode materials
LCO
LFP
LMO
JM Tarascon, Histoire et évolution des technologies d’accumulateurs, Collège de France, 2011
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Substitution in lamellar oxides
LiCoO2 (LCO)
LiNi1-y-zCoyAlzO2 (NCA)
LiNi1-y-zMnyCozO2 (NMC)
from
to
CoO2Li+
CoO2Li+
CoO2Li+…
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Li-ion batteries main application:
EVs, light electronic
-» material’s choice depends on its application
Source: Avicenne Energy Analyses
LCO LiCoO2
NMC Li(Ni,Mn,Co)O2
LMO LiMn2O4
LFP LiFePO4
NCA LiNi1-y-zCoyAlzO2
Consumer
Electronics
LCO, NMC
Transportation
Electric Vehicles (xEV)
LMO, LFP, NCA
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Evolution of positive electrode market:
LFP quick growth prevision
modified from Avicenne Energy Analyses
market share in 2015
LFP LiFePO4
LMO LiMn2O4
NCA LiNi1-y-zCoyAlzO2
NMC Li(Ni,Mn,Co)O2
LCO LiCoO2
previsions
Asumption: Tesla use NCA and relative success 200
000 EV sold/yr in 2025
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19/22modified from Fabrice Renard, Oreba 1,0, Montréal, May 2014 and Avicenne Energy Analyses
Anne de Guibert, SAFT Batteries, Matériaux stratégiques pour l’énergie et politiques nationales
Positive electrode price:
lithium amount and price is not so significant
process has to be optimized
Metal cost processed in positive electrode
($/kWh) (before cell and pack process yield)
In a battery: only 2.5 wt.% of Li in a battery, being
<1g 3.3kg of ‘Li-metal’10g
LCO LiCoO2
NMC Li(Ni,Mn,Co)O2
NCA LiNi1-y-zCoyAlzO2
LMO LiMn2O4
LFP LiFePO4
APC Project
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Safety
Higher energy density in more powerful Li-ion batteries
Recycling ?
Source: Google image
Boeing 787 Li-battery pack
issue – 2013
LCO/Graphite
Samsung Galaxy Note 7 – 2016
LCO-NMC ? /Graphite
Tesla model S on fire – 2016
NCA/Graphite
Hoverboard after explosion – 2016
LCO-NMC ? /Graphite
Sony laptop – 2006
LCO/Graphite
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Conclusion
The Li-ion technology that will take the lead will have to sacrifice energy density to
favour security for a given application
Mitsubishi, Batteries 2012
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22/22modified from Avicenne Energy Analyses , 2014
K, Zaghib et al., Safe and fast-charging Li-ion battery with long shelf life for power applications, J Power Sources, 196, 8 (2011)
Rocking chair batteries LTO/LFP : safe, high power
to replace lead acid batteries in Electric Vehicles
Perspectives
Vo
lum
e in
Production of electrode materials with locally available precursors
xLi2CO3 + yTiO2 -» Li4Ti5O12
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Take a look inside a battery
2000m
Design Considerations for Unconventional Electrochemical, A. Vlad et al., Adv. Energy Mater. 2015, 5, 1402115
Batterie 18650
sectional view
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Annexes
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26/22https://en.wikipedia.org/wiki/File:Lithium_world_production.svg
http://www.crugroup.com/about-cru/cruinsight/Lithium-The_Problem_With_Prices
Production et prix du Lithium aujourd’hui
Evolution du prix du Li
Production mondiale de lithium
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Et demain ? 3 scénarios envisagés
Muted – towards high prices
Aggressivedrastic drop
Measuredstable prices
http://www.crugroup.com/about-cru/cruinsight/Lithium-The_Problem_With_Prices
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28/2228/29Anne de Guibert, Matériaux stratégiques pour l’énergie et politiques nationales
Cellphone:
2 billions light electronic in 2008 – 1800 tons of Li-metal
w/ 8-10% growth/year : 4500 tons in 2014
10 millions of EV
> 35 000 tons of Li-metal
10 000 systems pf 1 MWh
> 1 650 tons of Li-metal
Realistic regarding the reserves, slightly higher than the 37 ktons per year
How much Li we will need in 2020
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Réserves mondiales Lithium ≠ Gisement exploités mondiaux !
Et au Québec ?
http://minerals.usgs.gov/minerals/pubs/commodity/lithium/mcs-2016-lithi.pdf
Purity ?
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Salar de Uyuni (Bolivie) – plus grande réserve de sel de lithium
Source : Google - Uyuni et lithium desert
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Puissance spé.
= accélération
P (W) = E (V) * Intensité (A)
Une batterie se définit par son voltage et sa capacité
E (volt)
Différence de potentiel
entre électrode
négative - et positive +
Capacité (mAh)
= nombre de charges transportées
Capacité
= Autonomie
M
dxCapacity
*8.26 dx : nombre d’électrons
M: masse molaire (g)mAh/g
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Batteries Li-O2 et Li-S
Li–O2 and Li–S batteries with high energy storage, Peter G. Bruce et al, Nature Materials, Vol 11, 2012
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Evolution of positive electrode
materials production
modified from Avicenne Energy Analyses
market share in 2015 previsions
Asumption: Tesla use NCA and relative success 200
000 EV sold/yr in 2025
LFP LiFePO4
LMO LiMn2O4
NCA LiNi1-y-zCoyAlzO2
NMC Li(Ni,Mn,Co)O2
LCO LiCoO2
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Li-ion battery geometries
Button Cell
Source: Sanyo
Pouch Cell
=Li-laminateSource: A123
Source: Cadex
18650 cell
Prismatic cell
Source: Hitachi
modified from Avicenne, 2014
2014 market share
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Electrode materials limitations
cycle life
abundance
"zero strain" material
cycling - efficiencies
Graphite low energy density
LTO high voltage
Negative
LCO performance cost - resource limitations
high capacity safety
high voltage cost - resource limitations
high voltage
safety
low cost low capacity
high voltage limited cycle life
excellent safety
low cost of Fe
low toxicityLFP
cost - resource limitations
low energy density
NCA
NMC
LMO
Positive
LCO LiCoO2
NCA LiNi1-y-zCoyAlzO2
NMC Li(Ni,Mn,Co)O2
LMO LiMn2O4
LFP LiFePO4
LTO Li4Ti5O12
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36/22Thomas Bibienne - Québec Mines - 23 Novembre 2016
Utilisation Cathodes par Cathodes dans Applications
Sources: AVICENNE ENERGY Analyses
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Characteristics of the main positive electrode materials
http://batteryuniversity.com/learn/archive/understanding_lithium_ion
http://batteryuniversity.com/learn/article/types_of_lithium_ion
LCO LiCoO2
LMO LiMn2O4
LFP LiFePO4
NMC Li(Ni,Mn,Co)O2
NCA LiNi0,8Co0,15Al0,05O2