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

2

Content

� A historical perspective

� Li-ion battery materials

� A Southern African opportunity

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By the 1920s, EVs were out of vogue and had been replaced by ICEs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