1/22

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

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 ?

3/22

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

4/22

Batteries to store energy

from electrical energy

to chemical energy

5/22

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

6/22

Li-ion market share

Li-Ion Batteries: principle and history

Safety

Electrode materials

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

8/22

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+

9/22

when lithium-metal used as negative electrode with liquid electrolyte:

formation of lithium dendrite = lithium ‘rod’

Electric short circuit -» fire

10/22

Li-dendrite issue with Li-metal: 2 solution arose

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

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

13/22

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

14/22

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

15/22

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

16/22

Substitution in lamellar oxides

LiCoO2 (LCO)

LiNi1-y-zCoyAlzO2 (NCA)

LiNi1-y-zMnyCozO2 (NMC)

from

to

CoO2Li+

CoO2Li+

CoO2Li+…

17/22

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

18/22

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

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

20/22

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

21/22

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

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

23/22

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

24/22

25/22

Annexes

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

27/22

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

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

29/22

Réserves mondiales Lithium ≠ Gisement exploités mondiaux !

Et au Québec ?

http://minerals.usgs.gov/minerals/pubs/commodity/lithium/mcs-2016-lithi.pdf

Purity ?

30/22

Salar de Uyuni (Bolivie) – plus grande réserve de sel de lithium

Source : Google - Uyuni et lithium desert

31/22

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

32/22

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

33/22

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

34/22

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

35/22

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

36/22Thomas Bibienne - Québec Mines - 23 Novembre 2016

Utilisation Cathodes par Cathodes dans Applications

Sources: AVICENNE ENERGY Analyses

37/22

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