LES DIFFÉRENTES CHIMIES DES BATTERIES LITHIUM-ION ET LEURS USAGES INDUSTRIELS - THOMAS BIBIENNE, PHD
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Les différentes chimies des batteries
lithium-ion et leurs usages industriels
Thomas Bibienne, PhD
Agent de Recherche
Laboratoire Chimie Electrochimie des Solides
Gpe Pr. Dollé (UdeM)
Québec Mines - 23 Novembre 2016
1/22
Energy consumption and demand increase
Equivalent of 10 million of oil barrel consumed since this morning!
TOE = Tons of Oil Equivalent
Energy source ?
from D. Larcher and J-M. Tarascon, Nature Chemistry, Vol 7, January 2015 2/22
Renewable energy supply should increase
energy supply (Mtoe)
World primary
Other: geothermal, solar, winds, heat, etc
intermittent !
?
International Energy Agency. 2016. Key world energy statistics 3/22
Batteries to store energy
from electrical energy
to chemical energy
4/22
Energy storage technology: from lead to Li-ion batteries
Specific power (W/kg) = acceleration
Specific energy (Wh/kg) = autonomy
JM Tarascon, Histoire et évolution des technologies d’accumulateurs, Collège de France, 2011 5/22
Li-ion market share
Li-Ion Batteries: principle and history
Electrode materials
Safety
6/22
Worldwide battery market dominated by lead acid
rapid growth of Li-ion batteries
Volume in
Volume in
NiMH Nickel Métal-Hydrure
NiCd Nickel Cadmium
modified from Avicenne Energy, 2014 7/22
How does a battery work in discharge?
Negative Positive
LiC6 -» Li+ + e- + C6 Li+ + e- + CoO2 + -» LiCoO2
Li+
LiC6 Electrolyte LiCoO2
modified from the Li-Ion Rechargeable Battery: A Perspective, John B. Goodenough
and Kyu-Sung Park, J. Am. Chem. Soc., 2013 8/22
when lithium-metal used as negative electrode with liquid electrolyte:
formation of lithium dendrite = lithium ‘rod’
Electric short circuit -» fire
9/22
Li-dendrite issue with Li-metal: 2 solution arose
10/22Li-metal
polymer
1978
Blue Solution Blue Car
Limitation of dendrite formation
No organic solvent
Operated at 80°C 2011- présent
Armand, M. B. in Materials for Advanced Batteries, 1980 11/22Li-ion
1983
= "rocking chair" battery
-» 1991, first Li-ion
batteries to be
commercialized (Sony)
LiCoO2/Graphite
Issues 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/ 12/22Li-ion battery history
1975 1980 1983 1984 1997
Layered structure LiCoO2 (LCO) Graphite as LiMn2O4 (LMO) LiFePO4 (LFP)
of LiTiS2 Goodenough and negative LixC6 Thackeray et al. Pahdi, Goodenough
Whittingham Mizushima Yazami
13/22Key requirements for electrode material (theoretical)
Electrochemical properties
possibility to be oxidized/reduced
good electronic conductor
Crystal structure
empty sites to intercalate large amount of Li ion
high lithium chemical diffusion
small volume changing during electrochemical process
Safety – Price
chemically stable, non-toxic, inexpensive
easy to prepare and handling
14/22Li-ion technology:
many available positive and negative electrode materials
LMO
LCO
LFP
JM Tarascon, Histoire et évolution des technologies d’accumulateurs, Collège de France, 2011 15/22Substitution in lamellar oxides
CoO2
Li+
CoO2
Li+
from LiCoO2 (LCO) CoO2
Li+
…
to LiNi1-y-zMnyCozO2 (NMC)
LiNi1-y-zCoyAlzO2 (NCA)
16/22LCO LiCoO2
Li-ion batteries main application: NMC Li(Ni,Mn,Co)O2
EVs, light electronic LMO LiMn2O4
-» material’s choice depends on its application LFP
NCA
LiFePO4
LiNi1-y-zCoyAlzO2
LCO, NMC
Consumer
Electronics
LMO, LFP, NCA
Transportation
Electric Vehicles (xEV)
Source: Avicenne Energy Analyses 17/22LFP LiFePO4
Evolution of positive electrode market: LMO LiMn2O4
LFP quick growth prevision NCA LiNi1-y-zCoyAlzO2
NMC Li(Ni,Mn,Co)O2
LCO LiCoO2
market share in 2015 previsions
Asumption: Tesla use NCA and relative success 200
modified from Avicenne Energy Analyses 000 EV sold/yr in 2025
18/22LCO LiCoO2
Positive electrode price: NMC Li(Ni,Mn,Co)O2
lithium amount and price is not so significant NCA LiNi1-y-zCoyAlzO2
LMO LiMn2O4
process has to be optimized LFP LiFePO4
In a battery: only 2.5 wt.% of Li in a
battery, being Metal cost processed in positive electrode
($/kWh) (before cell and pack process yield)Safety
Higher energy density in more powerful Li-ion batteries
Hoverboard after explosion – 2016
Tesla model S on fire – 2016 LCO-NMC ? /Graphite
NCA/Graphite
Samsung Galaxy Note 7 – 2016
LCO-NMC ? /Graphite
Boeing 787 Li-battery pack
issue – 2013 Sony laptop – 2006 Recycling ?
LCO/Graphite LCO/Graphite
Source: Google image 20/22Conclusion 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 21/22
Perspectives
Rocking chair batteries LTO/LFP : safe, high power
to replace lead acid batteries in Electric Vehicles
Volume in
Production of electrode materials with locally available precursors
xLi2CO3 + yTiO2 -» Li4Ti5O12
modified 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)22/22Take a look inside a battery
Batterie 18650
2000m
sectional view
Design Considerations for Unconventional Electrochemical, A. Vlad et al., Adv. Energy Mater. 2015, 5, 1402115 23/2224/22
Annexes
25/22Production et prix du Lithium aujourd’hui
Production mondiale de lithium
Evolution du prix du Li
https://en.wikipedia.org/wiki/File:Lithium_world_production.svg
http://www.crugroup.com/about-cru/cruinsight/Lithium-The_Problem_With_Prices 26/22Et demain ? 3 scénarios envisagés
Muted – towards high prices
Measured Aggressive
stable prices
drastic drop
http://www.crugroup.com/about-cru/cruinsight/Lithium-The_Problem_With_Prices 27/22How much Li we will need in 2020
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
Anne de Guibert, Matériaux stratégiques pour l’énergie et politiques nationales 28/29 28/22Réserves mondiales Lithium ≠ Gisement exploités mondiaux !
Purity ?
Et au Québec ?
http://minerals.usgs.gov/minerals/pubs/commodity/lithium/mcs-2016-lithi.pdf 29/22Salar de Uyuni (Bolivie) – plus grande réserve de sel de lithium Source : Google - Uyuni et lithium desert 30/22
Une batterie se définit par son voltage et sa capacité
E (volt)
Différence de potentiel Capacité
entre électrode = Autonomie
négative - et positive +
Capacité (mAh)
Puissance spé.
= nombre de charges transportées
= accélération
P (W) = E (V) * Intensité (A)
26.8 * dx dx : nombre d’électrons
mAh/g Capacity
M M: masse molaire (g)
31/22Batteries 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 32/22
LFP LiFePO4
Evolution of positive electrode LMO LiMn2O4
materials production NCA LiNi1-y-zCoyAlzO2
NMC Li(Ni,Mn,Co)O2
LCO LiCoO2
market share in 2015 previsions
Asumption: Tesla use NCA and relative success 200
modified from Avicenne Energy Analyses 000 EV sold/yr in 2025
33/22Li-ion battery geometries
Button Cell
Pouch Cell
Source: Sanyo
=Li-laminate
18650 cell Source: A123
Source: Cadex
2014 market share
Prismatic cell
Source: Hitachi
modified from Avicenne, 2014
34/22Electrode materials limitations LCO LiCoO2
NCA LiNi1-y-zCoyAlzO2
NMC Li(Ni,Mn,Co)O2
LMO LiMn2O4
Positive
LFP LiFePO4
LCO performance cost - resource limitations
LTO Li4Ti5O12
high capacity safety
NCA
high voltage cost - resource limitations
high voltage
NMC cost - resource limitations
safety
low cost low capacity
LMO
high voltage limited cycle life
excellent safety
LFP low cost of Fe low energy density
low toxicity
Negative
cycle life
Graphite low energy density
abundance
"zero strain" material
LTO high voltage
cycling - efficiencies
35/22Utilisation Cathodes par Cathodes dans Applications
Sources: AVICENNE ENERGY Analyses
Thomas Bibienne - Québec Mines - 23 Novembre 2016 36/22Characteristics of the main positive electrode materials
LCO LiCoO2 NMC Li(Ni,Mn,Co)O2
LFP LiFePO4
LMO LiMn2O4 NCA LiNi0,8Co0,15Al0,05O2
http://batteryuniversity.com/learn/archive/understanding_lithium_ion
http://batteryuniversity.com/learn/article/types_of_lithium_ion
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