Lithium-Ion Battery Materials
An Energy Storage Opportunity for Southern Africa
presented by Michael Thackeray
SA Energy Storage 2017
Emperors Palace, Johannesburg, South Africa
29 November 2017
SystemNegativeElectrode
PositiveElectrode
OCV(V)
Th. Cap(Ah/kg)
Th En.(Wh/kg)
Pr. En.(Wh/kg)
1859Plante
Lead-acid Pb PbO2 2.1 83 171 20-40
1866LeClanché
Zn-MnO2 Zn γγγγ-MnO2 1.6 *208 *333 85
1898Jungner
Ni-Cd Cd NiOOH 1.35 162 219 20-40
(Theoretical values: masses of active electrode and electrolyte components only)
Dominant Battery Technologies since Volta (~1800)
* Based on alkaline cell reaction: Zn + 2MnO2 + H2O → ZnO + 2MnOOH
� Li-ion cell chemistry extremely versatile – open to further advances
1973-1974 MID-EAST OIL CRISIS(Discovery of ββββ-Al2O3 spawns high temperature Na/S and Na/MCl2 (‘Zebra’) systems
1989 Ni-MH MH alloy NiOOH 1.35 ∼∼∼∼178 240 50-70
1991 Li-Ion LixC6 Li1-xMO2(M=Co, Ni, Mn)
4.2-3.0(3.8)
158(for x=1.0)
584 100-150
BEYOND LITHIUM-IONLi/S; Li/O2, Na and Mg-based systems etc
3
� Prolific American inventor and enthusiast of electric power (>1000 patents)
� Ni-Fe battery (1901)
Edison with an electric car, 1913
Thomas Edison (1847–1931)
Images courtesy of Wikimedia and the National Museum of American History – in public domain.
1896: Thomas Edison to Henry Ford: ‘Forget Electric Cars’
“Young man, that’s the thing; you have it. Electric cars must keep near to power stations.
The storage battery is too heavy. Steam cars won’t do, either, for they require a boiler
and fire. Your car is self-contained—it carries its own power plant’.
By the 1920s, EVs were out of vogue and had been replaced by ICEs
4
Battery Research at CSIR, South Africa (1974-1994)
� Prompted by the 1973-74 Oil Crisis
� Price of oil quadruples from $3 to $12 per barrel
� Government-funded research: 1974→
- Lithium batteries – Li-ion spinel technology
� Contract research (De Beers, Anglo American): 1978→
- High temperature Na/β-Al2O3/NaAlCl4, FeCl2 ‘Zebra’ batteries
� Technologically successful ideas – despite no battery experience in 1974
National PhysicalResearch Laboratory
5
Courtesy of CSIR
Chain of Events: 1983 - 2017� 1983: Anglo American moves CSIR research team to a start up company in SA.
� 1985: Teams up with Daimler Benz to develop and implement Zebra batteries in electric vehicles.
� 1992: Zebra technology demonstrated in A-Class Mercedes and used in buses to transport athletes at the Barcelona Olympic Games
� 1999: Anglo American and Daimler Benz walk away from a multi-million dollar investment in Zebra technology because of the lack of an EV market/infrastructure.
� High temperature batteries for transportation also deemphasized by the US Department of Energy
� 2017: Technology still alive – batteries for stationary storage being produced byFIAMM (Europe), GE (USA) in a joint venture with Chaowei Lvna (China).
6
Wikimedia Commons: Data from BP workbook of historical data
Crude Oil Prices since 1861
7
Nominal
Real (2014 dollar)(inflation adjusted)
1973: 3$/barrel
1980: 36$/barrel
1998: 12$/barrel
1974: 12$/barrel
2012: 112$/barrel
2017:~50$/barrel
Justification for EVs and Renewable Energy
Ref: P. Tans, NOAA/ESRL (www.esrl.noaa.gov/gmd/ccgg/trends/); Earth images courtesy of Wikimedia – in public domain.
A planet in peril?
� Population growth – a smaller world
� Unsustainable tensions as mankindstrives for equality and a shareof resources
8
� CO2 emissions – global warming
Impact of Li-Ion Batteries
� ~$23 billion market created over the past 25 years
� Consumer electronics and communications
� Transportation (‘Li economy’ driver)
- Hybrid-electric vehicles and ‘plug-in’ HEVs
- All electric vehicles
� Stationary energy storage (grid, off-grid)
� Implantable medical devices (Neuro-stimulators, pacemakers, defibrillators)
� Aerospace, defense
� Power tools, toys etc
� Lithium batteries have become a strategic commodity
in national energy security
GM’s Chevy Volt
9
Grand View Research Report August 2017; Volvo press release, 5 July 2017; Financial Times, 24 October 2017.
� Driven by e-mobility policies
� Volvo (Geely Holding) announces that from 2019 every Volvo vehicle would have an electric motor, EV, plug-in HEV or mild HEV (48V)
� Germany, France and UK call for a ban on traditional fuel vehicles by 2030-2040
10
Global Li-ion Battery Market Predicted to be Worth ∼$93 Billion by 2025
Grand View Research Report, August 2017
U.S. lithium-ion battery market revenue by electrode product, 2014 - 2025 (USD Million)
11
� Electrode materials market expected to increase fourfold within 10 years
The Advent of Li-Ion Batteries(Sony Corporation – 1991)
� Lithium insertion/extraction reactions� Highly energetic (4 V) systems� Flammable electrolytes� Inherently unsafe; individual cells are protected from overcharge by
costly electronic circuitry� Electrode and electrolyte materials dictate performance and safety
LixC6(Anode)
LiCoO2(Cathode)Li+
e-
(Electrolyte)
⇒ Scientific and technological motivation to find alternative materials
12
Li-Ion Batteries: 3.5 - 4 V Cathode Materials
• Capacity limited to ~0.5 Li per M atom(i.e., ∼∼∼∼140 mAh/g)
• 2-D layers for Li+ transport• Co4+ and Ni4+ unstable/highly oxidizing• Structures destabilized at low Li content
• Capacity limited to <0.5 Li/Mn at 4 V(i.e., <120 mAh/g)
• 3-D channels for Li+ transport• Robust M2O4 spinel framework; • High power electrode
• Capacity limited to 1 Li/Fe; P inactive(i.e., ∼∼∼∼150 mAh/g)
• 1-D channels for Li+ transport• Excellent structural and thermal stability• Poor electronic and Li-ion conductivity• Stable in nanoparticulate form
OLIVINELiMPO4
(M=Fe)LFO
ROCKSALTLiMO2
(M=Co, Ni, Mn)LCO, NCA, NMC
SPINELLiM2O4
(M=Mn)LMO
13
Li-Ion Batteries: Anode Materials
� Carbon• Graphite: <100 mV vs. Li0
• Moderate capacity (372 mAh/g)• Highly reactive, surface protection necessary
� Metal Oxides• Li4Ti5O12 (LTO) Spinel: 1.5 V vs. Li0
• Low capacity (175 mAh/g) and energy• High power• Safe!
� Metals, Semi-metals and Intermetallic Compounds• Al, Si, CoSn, Cu6Sn5: <0.5 V vs. Li0
• High gravimetric/volumetric capacities• Large volume expansion on reaction with lithium• Reactive, surface protection required• Extremely challenging
LiC6
LiAl
••••
•••• ••••Li7Ti5O12
14
Prognosis for Li-ion Technology
� Li-ion cells with:
� Si or metallic Li anodes� effectively protected electrode surfaces� non-flammable electrolytes
would constitute significant advances in Li-ion technology that will take time to implement.
� In the interim, incremental advances in cathode design and performance can be expected.
15
Major Materials Challenges for Li-ion Batteries
� Increase the energy density of cells – both volumetric and gravimetric for
portable/mobile applications
� Increase cell voltage ⇒ e.g., LiMn2O4 (4 V) → LiMn1.5Ni0.5O4 (4.7 V)
� Increase electrode capacity ⇒ Mn rather than Co-, Ni-rich oxide cathodes
� Reduce cost and toxicity ⇒ Mn-rich rather than Co, Ni-rich oxide cathodes
� Reduce/Eliminate Safety Hazard
� Control electrochemical and chemical reactions to eliminate the risks of
thermal runaway
⇒ Mn-rich rather than Co, Ni-rich oxide cathodes
⇒ Non-flammable electrolytes
⇒ Voltage control
16
Recent Trends
� Demand for Li-ion batteries is increasing dramatically
� Competition for world’s mineral reserves of battery materials is intensifying
� Anodes: Li, Ti, C (natural graphite)� Cathodes: Co, Ni, Mn� Electrolytes: F (e.g., LiPF6 salt)� Current collectors: Cu, Al
� Ni-rich cathodes (NCA, NMC – 811 and 622) are in vogue (power)
� Safety concern� Cost concern (Co, Ni, Li)
� Mn-rich cathodes still provide an exploitable opportunity
17
� Electrodes comprised of ‘active’ LiMO2 and ‘inactive’ Li2MnO3 components
� Gen 1 cathodes commercialized (160-170 mAh/g)
� Gen 2 cathodes provide 240-300 mAh/g, if activated at 4.6V
MO2 (ideal CdCl2-type)
“inactive”
Li2MnO3 LiMO2
(M=Mn, Ni, Co)
“active”
x=0.3
-Li
xLi2MnO3•(1-x)MO2
<4.4V
Net loss
′′′′Li2O′′′′(oxygen loss)
>4.5V
xLi2MnO3•(1-x)LiMO2
Li(1-x)MO2
±±±±Li (~140 mAh/g to ~4.3V)
±±±±Li ±±±±Li (~160 mAh/g to ~4.3V – Gen 1)
±±±±Li (~240 mAh/g to ~4.6V – Gen 2)
Li- and Mn-rich Composite Electrode Structures (M=Mn, Ni, Co)
18
US Patent 6,677,082 US Patent 6,680,143
High Capacity Li- and Mn-rich CathodesThe Voltage Fade Limitation
Li/0.5Li2MnO3•0.5LiNi0..375Ni0.375Co0.25O2 Cell
� 250 mAh/g
� Voltage decays if cells are charged to high potential, reducing energy output
� Voltage fade attributed to structural instability
19
Stabilization of High Capacity Cathodes
� Embed transition metal pillars (spinel) to stabilize structures
� Prime motivation: Design Mn-rich electrodes that can compete with ‘in vogue’ Ni-rich compositions, e.g., NMC - 811 and 622, to reduce cost and safety concerns
20
Cycling Stability and Rate Performance (4.45-2V)
MERF Facility - LixMn0.53Ni0.28Co0.19Oδ
Cycling Stability
Cycle number
150
170
190
210
0 10 20 30 40
Series5
Series6
Series7
Series1
2% spinel
5% spinel
10% spinel
15% spinel
Ca
pa
city
, m
Ah
/g
Cycle 1: 4.6 – 2.0 V, 15 mA/g
Cycle 2-40: 4.45 – 2.0 V, 15 mA/g
Rate Performance
Cycle number
100
120
140
160
180
200
220
0 5 10 15 20 25 30 35 40
Series3
Series4
Series6
Series5
20mA/g 40mA/g 67mA/g 100mA/g 200mA/g 400mA/g 600mA/g 200mA/g
2% spinel
5% spinel
10% spinel
15% spinel
Ca
pa
city
, m
Ah
/g
Cycle 1: 4.6 – 2.0 V, 15 mA/g
Cycle 2-40: 4.45 – 2.0 V, 15 mA/g
■ Electrodes containing 5-10% spinel (targeted amount) show significantly improved capacity and rate capability
■ Stable cycling at relatively low rate (power)
Croy, Shin et al., J. Power Sources (2016) 21
22
0 50 100 150 200 250
2.5
3.0
3.5
4.0
4.5
5.0
Vo
ltag
e v
s. L
i/L
i+
Capacity (mAh/g)
Cycle 2
Cycle 50
Commercial ‘532’ NMC Elecrode
4.45-2.5V
15mA/g, 30 °C
740 Wh/kg
697 Wh/kg
0 50 100 150 200 250
2.5
3.0
3.5
4.0
4.5
5.0
Vo
ltag
e v
s. L
i/L
i+
Capacity (mAh/g)
4.45-2.5V
15mA/g, 30 °C
Cycle 2
Cycle 50
Mn-rich LLS ‘532’ MNC Electrode
790 Wh/kg
753 Wh/kg
Comparison of a Commercial Ni-rich ‘532’ NMC Electrode
with a Mn-rich ‘532’ MNC Electrode
� A Mn-rich ‘532’ MNC electrode outperform cells with a commercial Ni-rich
‘532’ NMC electrode at a low current rate.
Mineral Resources in Southern Africa: Li-Ion Batteries
� Cathodes:� Mn – South Africa (80% of world reserves)� Ni – South Africa, Botswana� Co – Democratic Republic of the Congo, Zambia
� Anodes:� C (natural graphite) – Madagascar, Namibia� Li – Zimbabwe, Namibia (small, relative to world resources)� Ti – South Africa
� Electrolytes: F (e.g., LiPF6 salt) – South Africa
� Current collectors:� Cu – Zambia, South Africa� Al – South Africa, Mozambique
⇒ Major opportunity for materials beneficiation in South and Southern Africa
⇒ Need for partnerships to gather know-how and accelerate production
⇒ Time is of the essence
23
� Plant to manufacture precursor materials for Li-ion cathodes launched in Mpumulanga on 10 October 2017
� Focus on manganese based materials – LMO and NMC
24
“Beneficiation of raw Mn ore into lithium-ion battery precursor
materials will add value of at least twenty fold” – Danie Theron
� Builds on expertise and competence of past Delta EMD employees
“Energy storage solutions critical for the nation”
-- Naledi Pandor
� It’s never to late to innovate, no matter how inexperienced you are
� Opportunities to innovate:
� Processing techniques to produce high quality products reproducibly
� Improved electrode and electrolyte materials’ design
25
Support from the Office of Vehicle Technologies of the
US Department of Energy is gratefully acknowledged.
This presentation has been created by UChicago Argonne, LLC, Operator of Argonne National Laboratory (“Argonne”). Argonne, a U.S. Department of Energy Office of Science laboratory, is operated under Contract No. DE-AC0206CH11357. The U.S. Government retains for itself, and others acting on its behalf, a paid-up nonexclusive, irrevocable worldwide license in said article to reproduce, prepare derivative works, distribute copies to the public, and perform publicly and display publicly, by or on behalf of the Government.
Acknowledgments