UMR 6007 and 6218
Evaluation of redox-active organic electrode materials
for “Greener” Li-ion Batteries
P. POIZOT Laboratoire de Réactivité et Chimie des Solides, Amiens (France)
UMR 6007
In collaboration with F. DOLHEM
UMR 6218Laboratoire des Glucides, Amiens (France)
GCEP Research Symposium 2010 Wednesday, September 29, 2010
Energy challenges in short
Current Li-ion technology: pros and cons
OUTLINE
Towards a « sustainable » Li-ion battery, first materials
C=O functionalities
the lifeblood of modern society……embodied in any type of goods and foods, and needed to offer any kind of services.
ENERGY, a peculiar entity…
Life expectancy when consumed energy is < 1600 kWh/pers/year
QUALITY
of LIFEENERGY
Better Life and energy consumption
Energy consumption per inhabitant : increasing by 385% in 44 years
Energy consumption (kg of oil per inhabitant)Ex: case of JAPAN
Year
ENERGY and human needsWorld energy consumption is constantly increasing
World population is constantly increasing
Source : INED (Institut National d’Etudes Démographiques+ www. Populationmondiale.com
6.84 billions of Human beings in Jan 2010
(+ 32%)
ENERGY and human needs
Photo: Reuters
Pierre Saint-ArnaudCanadian PressQuébec
2nd issue:CO2 releases (greenhouse effect)
6.2%
25.0%
21.0%10.4% 35.2% Oil
Coal
Natural gas
Biomass/WasteRenewable sources
2.2%
Nuclear
Hydro
Reserve: 218 years
Reserve: 40 years
Reserve: 61 years
~ 85% Non-renewable
1st issue:Limited reserves
ENERGY and environment
ENERGY and environment
Motorized transportation systems consume about19% of the world’s total energy supplies (95% ofthis amount being petroleum = 60% of total worldpetroleum production)Source: International Energy Outlook 2007.
1 billion - 2010(+ 50% in 10 years)
2040/20502.9 billions
2nd issue:CO2 releases (greenhouse effect)
193030
millions
1997500 millions
HeatingCooking
LightingCooling
Motion
Transport
Smart systems…
ELECTRICAL ENERGY: a particular attention
Simple conversion (and a simple switch)
BUT direct source of electricity does not exist in practice
TWO IMPORTANT CHALLENGES1/ Favoring electricity production from renewable energies
Decreasing the CO2 footprint linked to the transportation
Renewable energies (solar, hydro, wind):
BUT diffuse & intermittent
Electrochemical power unit
(secondary battery)
Future “Smart-grid” system
Conventional car (internal combustion engine vehicle)-ICE
Renewable energies (solar, hydro, wind):
BUT diffuse & intermittent
HEV/EV
TWO IMPORTANT CHALLENGES1/ Favoring electricity production from renewable energies
2/ Decreasing the CO2 footprint linked to the transportation
Interest in batteries R&D⇒ Li-ion technology, in particular
Energy challenges: context
Current Li-ion technology: pros and cons
OUTLINE
Towards a « sustainable » Li-ion battery, first materials
Li-ion battery technology
Electrode materials based on insertion compounds:(+) LiCoO2, LiMn2O4, LiNi1/3Mn1/3Co1/3O2, LiFePO4(-) Graphite, Li-based alloys
Electrode materials (+) and (-):Based on inorganic compounds synthesized from high temperature reactions and non-renewable resources
(ores)
Common batteries
Electrode materials (+) and (-):Based on inorganic compounds synthesized from high temperature reactions and non-renewable resources
(ores)
Common batteries
The present technology still falls short of both the sustainability and CO2 footprint criteria, which can lessen the benefit of the present Li-ion technology
Ores extraction
Metal refining(pyrometallurgy)
Electrode material synthesis (ceramic route)
and other processes
Transportation-Marketing/
use
Simplified LCA of a typical Li-ion battery: HT thermal processes and CO2 releases
Recycling processes(mainly incineration)
Metals recovery: Ni, Co, Cu
When collected
Li, Mn ???
not systematically depending of the recycling process
: energy consumption: CO2 emission
A Li-Ion Battery cell (Lithium manganese oxide type)
Al, Cu, LiMn2O4 (and others), LiPF6 (via F):derived from extraction/processing of ores (mining production)
Firs
t d
ata
A Li-Ion Battery cell (Lithium manganese oxide type)
Al, Cu, LiMn2O4 (and others), LiPF6 (via F):derived from extraction/processing of ores (mining production)
Firs
t d
ata
Mining activities = energy consumption, CO2releases, destruction of the landscape for a finite
resource
1. LCA analyses: first data [1,2]~1600 MJ are necessary to store 1 kWh in a Li-ion cell
(i.e., ~444 kWh/kWh of electrochemical energy)
~80 kg of CO2 per kWh of electrochemical energy
[1] K. Ishihara et coll., The 5th International Conference on Ecobalance, Tsukuba, Japan (2002)[2] Empa - Swiss Federal Laboratories for Materials Testing and Research (current research)
1. LCA analyses: first data~1600 MJ are necessary to store 1 kWh in a Li-ion cell
(i.e., ~444 kWh/kWh of electrochemical energy)
~80 kg of CO2 per kWh of electrochemical energy
2. The Lithium element is not systematically recovered for the Li-ion batteries manufacturing
resulting speculation on metals quotation in general
(350 USD/ton of Li in 2003 ⇒ 3000 USD/ton of Li in 2008)
Extraction du minerai
Uyuni salar
1. LCA analyses: first data~1600 MJ are necessary to store 1 kWh in a Li-ion cell
(i.e., ~444 kWh/kWh of electrochemical energy)
~80 kg of CO2 per kWh of electrochemical energy
2. The Lithium element is not systematically recovered for the Li-ion batteries manufacturing
resulting speculation on metals quotation in general
(350 USD/ton of Li in 2003 ⇒ 3000 USD/ton of Li in 2008)
3. EC regulations (#2006/66/EC), at least 50% by averageweight of battery waste should be recycled by 2011 intomaterials for their original purpose or for other purposes,excluding energy recovery
Energy challenges: context
Current Li-ion technology: pros and cons
OUTLINE
Towards a « sustainable » Li-ion battery, first materials
Concept of a “greener” Li-ion battery Interest in photoautotroph organisms
Energy from sunlight to convert carbon dioxide and water into organic materials
Photosynthesis: Low yield (~1%) but large scale
Biochemistry – photosynthesisInorganic chemistry(ores: non-renewable)
organic chemistry <-> renewable resources
Easy to recycle
Concept of a “greener” Li-ion battery
Lithiated organic material(high redox potential)
Organic material(low redox potential)
BIOMASS
Drawbacks: higher solubility and lower energy density values
Biomass (crop)
Biorefinery
Battery processing
Battery utilization
Battery marketing using advanced packaging
technologies
Thermal destruction of spent batteries
Elaboration of organic raw
materials
Elaboration of active materials using Green Chemistry concepts
CO2assimilation
CO2release
Lithium recovery (ash)
Battery recycling
Concept of a “greener” Li-ion battery
H. Chen, M. Armand, G. Demailly, F. Dolhem, P. Poizot, J.-M. Tarascon, ChemSusChem, 1, 348 (2008).
Nothing new: A. Heeger (1977; conducting conjugated polymers)
Organic Molecules as electrodes materials???
OO
1st Li-ion batteries (Polyaniline/LiXAl)
Nothing new: A. Heeger (1977; conducting conjugated polymers)
Organic Molecules as electrodes materials???
OO
Such Organic molecules do not derive from natural product (biomass)
1st Li-ion batteries (Polyaniline/LiXAl)
Concept of a “greener” Li-ion battery
What chemistry? What redox-active structure?
R−C−R’||O
R−C−R’|O−
•
e−
Biological activity
OO
OO
LiO
LiO
OLiO
LiO
O
O
LiO
LiO
O
O
O
LiO
LiOOxocarbones2
Croconate
Squarate
Deltate
Rhodizonate
[1] R. West, Oxocarbon, Academic Press, 1980.[2] N. Ravet, C. Michot, M. Armand, Mater. Res. Soc. Symp. Proc 1998, 496, 263-173.
1st series: Special attention given to oxocarbons [1,2]
OO
OO
LiO
LiO
OLiO
LiO
O
O
LiO
LiO
O
O
O
LiO
LiOOxocarbones2
Croconate
Squarate
Deltate
Rhodizonate
[1] R. West, Oxocarbon, Academic Press, 1980.[2] N. Ravet, C. Michot, M. Armand, Mater. Res. Soc. Symp. Proc 1998, 496, 263-173.
OPO3H2
OPO3H2H2O3PO
OPO3H2
OPO3H2H2O3PO
Phytic acid
1st series: Special attention given to oxocarbons [1,2]
O
O
O
O
HO
HO
. 1 eq. Li2CO3
H2O, rt.
O
O
O
O
LiO
LiO
.
(1) (2)
Dehydration
O
O
O
O
LiO
LiO
(3)
2H2O 2H2O
Synthesis: A two-step process
Chemistry and electrochemistry of Li2C6O6
0
0,5
1
1,5
2
2,5
3
3,5
4
2 2,5 3 3,5 4 4,5 5 5,5 6
Pote
ntia
l (V
vs. L
i+ /Li0 )
x in LixC
6O
6
Good cyclability for potentials ranging from 1.5 to 2.4 V (i.e., Li4C6O6 <> Li6C6O6 )
Chemistry and electrochemistry of Li2C6O6
⇒ Evaluation of several potential windows
H. Chen, M. Armand, G. Demailly, F. Dolhem, P. Poizot, J.-M. Tarascon, ChemSusChem, 1, 348 (2008).
0
100
200
300
400
500
600
0 5 10 15 20 25
Cha
rge
capa
city
/mA
h g-1
Cycle number
2.5-3.5 V
2.2-3.5 V
1.45-2.5 V
1.45-2.9 V
1 Li+/10 h
Li4C6O6 : an amphoteric lithiated redox compound (never reported)
OPO3H2
OPO3H2H2O3PO
OPO3H2
OPO3H2H2O3PO
O
OH
OH
O
HO
HO
THQ
Interest in its synthesis
Highly charged anion = INSOLUBILITY
Windows: 1.45 ≤ E ≤ 2.5 V vs. Li+/Li0 (reduction)2.3 ≤ E ≤ 3.5 V vs. Li+/Li0 (oxidation)
Electrochemistry of Li4C6O6
1
1,5
2
2,5
3
3,5
4
2 2,5 3 3,5 4 4,5 5 5,5 6
Pote
ntie
l (V
vs L
i+ /Li0 )
x dans LixC
6O
6
Li6C
6O
6
Li2C
6O
6
Li4C
6O
6
Oxydation de Li4C
6O
6
Réduction de Li4C
6O
6
0
50
100
150
200
250
300
0 10 20 30 40 50
Cap
acité
de
char
ge (m
Ah/
g)
Nombre de cycles
Oxydation de Li4C
6O
6
Réduction de Li4C
6O
6
x in LixC6O6 Cycle number
Pote
ntia
l (V
vs. L
i+ /Li
0 )
OxidationReduction
Oxidation
Reduction
Cap
acity
(mAh
/g)
H. Chen, M. Armand, M. Courty, M. Jiang, C.P. Grey, F. Dolhem, J.-M. Tarascon, P. Poizot, J. Am. Chem. Soc., 131, 8984 (2009).
1 Li+/10 h
Windows: 1.45 ≤ E ≤ 2.5 V vs. Li+/Li0 (reduction)2.3 ≤ E ≤ 3.5 V vs. Li+/Li0 (oxidation)
First all-organic Li-ion cell based on renewable matter(∆V = 1 V, only but a single material for the two electrodes)
Electrochemistry of Li4C6O6
1
1,5
2
2,5
3
3,5
4
2 2,5 3 3,5 4 4,5 5 5,5 6
Pote
ntie
l (V
vs L
i+ /Li0 )
x dans LixC
6O
6
Li6C
6O
6
Li2C
6O
6
Li4C
6O
6
Oxydation de Li4C
6O
6
Réduction de Li4C
6O
6
0
50
100
150
200
250
300
0 10 20 30 40 50
Cap
acité
de
char
ge (m
Ah/
g)
Nombre de cycles
Oxydation de Li4C
6O
6
Réduction de Li4C
6O
6
x in LixC6O6 Cycle number
Pote
ntia
l (V
vs. L
i+ /Li
0 )
OxidationReduction
Oxidation
Reduction
Cap
acity
(mAh
/g)
1 Li+/10 h
OPO3H2
OPO3H2H2O3PO
OPO3H2
OPO3H2H2O3PO
OHOH
HO
OHOHHO
Dephosphorylation
Phytic Acid Myo-Inositol
Biomass
8% of the dry weight of corn-steeping liquor [1]
HNO3/O2/Li2CO3
[1] S. R. Hull, R. J. Montgomery, J. Agric. Food Chem., 43, 1516–1523 (1995)
From biomass to an active lithiated electrode material…
… easily recycled by calcination with production of pure Li2CO3
Pure Li2CO3(ash)
Clear evaluation of the LCA of such an electrode material is in progress
COMBUSTION under air (300°C)
2nd series: What next? Which functionality? Substituent?Tune Redox potential/solubility
2-Create a reliable experimentaldatabase of model chemicalstructures in relation with theirsolid state electrochemicalbehaviour
1-DFT calculations
“Molecular Design” & Experimental test
General molecular structure of 2,3,5,6-tetraketopiperazine
Derived from oxalic acid
0
50
100
150
200
0 5 10 15 20 25Sp
ecifi
c ca
paci
ty (m
Ah/
g)Cycle number
0
0.5
1
1.5
2
2.5
3
3.5
0 50 100 150
E / V
(vs.
Li+ /L
i)
Q (mA.h/g)
1.5
2
2.5
3
3.5
0 0.5 1 1.5
E / V
(vs.
Li+ /L
i)
x in PhP
Capacity fade due to solubility of active material in electrolyte
N N
O O
OO
NH HN
O O
Cl Cl
O O+
sealed tube, 120°C
52%
Synthesis and characterisation of tetraketopiperazines
PHP
Use of a polymeric approachT. Umemoto, US Patent 6737193 B2, 2004H. Aoyama, M. Ohnota, M. Sakamoto, Y. J. Omote, J. Org. Chem., 1986, 51, 247
N N
O O
O O
2 to 5% mol.of catalyst
Ph-Me or 1,2-DCE60 to 110°C; 24h
N N
O O
O On
n+ n
Catalysts: Grubbs 1st generation; Grubbs 2nd generation; Hoveyda Grubbs 2nd generation. Solvents: Toluene, 1,2-dichloroethane, trichlorobenzene.Swagelok type cell : Li metal disc as negative electrode, a Whatmann GF/D as separator, saturated in EC:DMC LiPF6 1 M as electrolyte . Powder hand-milled: active material + 50%(w/w) carbon SP. 10-12 of powder is used. Electron exchange rate 1e- /10h.
o - APAP
0
50
100
150
200
0 5 10 15 20
Q (m
Ah/
g)
cycle number
0
0.5
1
1.5
2
2.5
3
3.5
0 50 100 150 200
E / V
(vs.
Li+ /L
i)
Q (mA.h/g)
0
0.5
1
1.5
2
2.5
3
3.5
0 50 100 150 200
E / V
(vs.
Li+ /L
i)
Q (mA.h/g)
1.5
2
2.5
3
3.5
0 0.5 1 1.5
E / V
(vs.
Li+
/Li)
x in o-AP
Capacity retention can be improved by increasing the
polimerization degree
Polymeric approach via Acyclic Diene Metathesis
n = 2 - 3
1 Li+/10 h 1 Li+/2 h
Electrochemicalactive centres
N N
O
O O
Li Li
O
NN
O O
OO
O
OLiO
LiO OLi
OLi
Electrochemicalactive centres
Radicalsstabilization
Insolubility,cyclability
Electrochemicalactive centres
Radicalsstabilization
Insolubility,cyclability
PHPC6O6Li4
Pyromellitic Diimide Dilithium Salt
H. Chen, M. Armand, M. Courty, M. Jiang, C.P. Grey, F. Dolhem, P. Poizot, J. Am. Chem. Soc., 2009, 131 (25), 8984–8988.J. Geng, J.P. Bonnet, S. Renault, F. Dolhem, P. Poizot, submitted to Energy & Environmental Science. S. Renault, J. Geng, F. Dolhem, P. Poizot, submitted to Chemical Communications.
“Molecular Design” & Experimental test
HN NH
O
O
O
O
N N
O
O
O
O
Li LiLiH (2 éq.), DMF,
r.t., 18 hrs
Thermal treatment,
320°C, 2 hrsN N
O
O
O
O
Li Li2 DMF
yield = 91%
Straightforward synthesis
Electrochemistry of Pyromellithique diimide dilithium salt
0
0,5
1
1,5
2
2,5
3
3,5
4
2 2,5 3 3,5 4
x in LixC
10H
4N
2O
4
0
50
100
150
200
250
0 5 10 15 20Cycle number
Pote
ntia
l(V
vs. L
i+ /Li
0 )
Cap
acity
(mAh
/g)
Capacity retention: 91% after 20 cycles
1 Li+/10 h
CONCLUSIONS
Organic molecules can show attractive electrochemical characteristics (redox potential tuning)
Make greener and sustainable battery using organic electrode prepared from a renewable natural precursor: a new research avenue may be opened
⇒ Richness of Organic structures but complexity
A lot to do: organic active matter is still at an embryonic stage
⇒ However, organics are often soluble vs. electrolyte / lower density values vs. inorganic materials
