Bruno Scrosati Lithium batteries: a look into the future. Department of Chemistry, University of Rome “Sapienza”

Bruno Scrosati

Lithium batteries: a look into the future.

Department of Chemistry, University of Rome “Sapienza”

To fight the global warming a large diffusion in the road of low emission vehicles (HEVs) or no emission vehicles (EVs) is now mandatory

Electrified Vehicle sales forecastfor Asia Pacific countries

20152014201320122011

1,400,000

1,200,000

800,000

1,000,000

600,000

400,000

( V

eh

lcle

s )

Rest of Asia Pacific Korea China Japan

0

200,000

2010

Source: The Korean Times

Source: http://aspoitalia.blogspot.com/2011/02/gli-scenari-dellagenzia-internazionale.html

Will it be a tank of lithium to drive our next car?

Key requisite: availability of suitable energy storage, power sourcesBest candidates: lithium batteries

Courtesy of Dr. Jürgen DeberitzCHEMETALL GmbH

Where lithium is taking us?

7

Li-ion battery system: a scheme of operation

Electrochemical Reactions

• CathodeLiCoO2 Li1-xCoO2 + xLi+ + x e-c

d

Cn + xLi+ + x e- CnLixcd

• Anode

• OverallLiCoO2 + Cn Li1-xCoO2 + CnLix

c

d

(From: K. Xu, Encyclopedia of Power Sources, Elsevier, 2010)

The present Li-ion batteries rely on intercalation chemistry!

Further R&D is still required to improve their performance especially in terms of energy density to meet the HEV, PHEV, EV requirement

Although lithium batteries are established commercial products

Lithium Batteries

Jumps in performance require the renewal of the present lithium ion battery chemistry, this involving all the components, i.e., anode, cathode and electrolyte

Energy Density (Wh/kg)

EV driving range (km)

Middle size car (about 1,100 kg) using presently available lithium batteries (150 Wh/kg) driving 250 km with a single charge 200 kg batteries

Enhancement of about 2-3 times in energy density is needed!

THE ENERGY ISSUE

Electric Vehicle Applications- The energy issue

Li-ion Batteries

Present

140 Wh/kg*

170 Wh/kg*

200 Wh/kg*

Estimated progress of the conventional Lithium-Ion

Technology in terms of battery

weight in EVs

200kg

140 kg

200kg

140 kg

Near future

Modified by courtesy of Dr. Stefano Passerini, Munster University, Germany

Midterm evolution of the lithium ion battery technology

Some examples of new-concept batteries developed our laboratory.

Stena Metall AB.

Main goal: complete the development of the battery starting from a further optimization of the electrode and electrolyte materials, to continue with their scaling up to large quantities and then on their utilization for the fabrication and test of high capacity battery cells, to end with the definition and application of their recycling process.

Collaborative participation of nine partners. Consorzio Sapienza Innovazione (CSI), Italy, managing coordinator

HydroEco Center at Sapienza including Dept Chemistry (scientific coordinator) , Dept Physics, Universities Camerino and Chieti;

Chemetall

Chalmers University of Technology

Ente Nazionale Idrocarburi ENI SpA

Zentrum für Sonnenenergie- und Wasserstoff-Forschung (ZSW)

SAES Getters SpA

ETC Battery and Fuel Cells Sweden AB

The APPLES SnC/ GPE / LiNi0.5Mn1.5O4

lithium ion polymer battery

anode GPE cathode

http://www.applesproject.eu

1 μm

The Li[Ni0.45Co0.1Mn1.45]O4 / SnC lithium ion cell

J.Hassoun, K-S. Lee, Y-K.Sun,B.Scrosati, JACS 133 (2011)3139

The Li[Ni0.45Co0.1Mn1.45]O4 / SnC lithium ion battery

Projected energy density: 170 Wh/kg

Li[Ni0.45Co0.1Mn1.45]O4 + SnC Li (1-x)[Ni0.45Co0.1Mn1.45]O4 + LixSnC

Li4Ti5O12 / Li[Ni0.45Co0.1Mn1.45]O4 lithium ion battery

500 nm 10 nm

Crystallized carbon

Primary

particles

A B

0 20 40 60 80 100 120 140 160

1.0

1.5

2.0

2.5

3.0

3.5

1.0-3.0 V, 1 C charge

0.5 C, 0.85 A g-1, 1 C, 0.17 A g-1

3 C, 0.51 A g-1, 5 C, 0.85 A g-1

10 C, 1.7 A g-1, 20 C, 3.4 A g-1

Voltage / V

Capacity / mAhg-1

A

0.0 0.2 0.4 0.6 0.8 1.02.8

3.2

3.6

4.0

4.4

4.8

5.2

Pote

ntial V

s. L

i / V

X in Li1-x

[Ni0.45

Co0.1

Mn1.45

]O4

A

 H-Gi Jung, M. W. Jang, J. Hassoun, Y-K. Sun, B. Scrosati, Nature Communications, 2 (2011) 516

Li4Ti5O12 / Li[Ni0.45Co0.1Mn1.45]O4 lithium ion battery

0 20 40 60 80 100 120 1401

2

3

4

0.2C 0.5C 1C 3C 5C 7C 10C 2C

Capacity / mAh g-1

Voltage /

V

2.0 - 3.4 VA

0 4 8 12 16 2060

80

100

120

140

83.5%

10C

1C

7C5C

3C2C

0.5C0.2C

2.0 - 3.4 V

Capacity /

mA

h g

-1

Number of Cycle

0.1C

B

0 100 200 300 400 5000

20

40

60

80

100

120

140

1C

Capacity /

mA

h g

-1

Number of Cycle

C

Projected energy density: 200 Wh/kg

Li4Ti5O12 + Li[Ni0.45Co0.1Mn1.45]O4

Li4+xTi5O12 + Li (1-x) [Ni0.45Co0.1Mn1.45]O4

Electric Vehicle Applications- The energy issue

>500 Wh/kg

Super- Battery < 100kg

Li-ion Batteries

Year Present 2012 2017

140 Wh/kg*

170 Wh/kg*

200 Wh/kg*Estimated

limit of Lithium-Ion Technology

250 kg

140 kg

250 kg

140 kg

Revolutionary Technology-

Change

Modified by courtesy of Dr. Stefano Passerini, Munster University, Germany

Cathode side: Li Metal Chemistries

"4V"

Li-IonOxide

Cathodes

1

2

3

4

5

6

250 500 750 1000 1250 1500 1750 40003750

Pote

ntial

vs.

Li

/Li+

00

Capacity / Ah kg-1

Li Li metalmetal

O2 (Li2O)

F2

S

O2 (Li2O2)

Lithium-Element Battery Cathodes

Where should we go ?

Intercalationchemistry

CarbonanodesCarbonanodes

Modified by courtesy of Dr. Stefano Passerini, Munster University, Germany

Li2S8 : 209 mAh/g-S, Li2S4 : 418 mAh/g-S

Li2S2 : 840 mAh/g-S, Li2S : 1675 mAh/g-S

Li2S8 : 209 mAh/g-S, Li2S4 : 418 mAh/g-S

Li2S2 : 840 mAh/g-S, Li2S : 1675 mAh/g-S

< Theoretical capacity of lithium polysulfides >

Ch

arg

e p

roce

ssC

har

ge

pro

cess

Dis

char

ge

pro

cess

Dis

char

ge

pro

cess

S8

Li2S8

Li2S6

Li2S4

Li2S2

Li2S

LithiumSulfur

Li

Li+

Li2S

Li+ + S

e-

Li+Li+

e-

•Electrolyte(polymer or liquid)

Anode Cathode

Anodic rxn.: 2Li → 2Li+ + 2e-

Cathodic rxn.: S + 2e - → S2-

Overall rxn.: 2Li + S → Li2S,

ΔG = - 439.084kJ/mol

OCV: 2.23V

Theoretical capacity : 1675mAh/g-sulfur

The lithium-sulfur battery

B. Scrosati, J. Hassoun, Y-K Sun, Energy & Environmental Science, 2011

Cobalt: 42,000 US$/ton Sulfur: 30 US$/ton

The lithium-sulfur battery

solubility of the polysulphides LixSy in the electrolyte (loss of active mass low utilization of the sulphur cathode and in severe capacity decay upon cycling)

low electronic conductivity of S , Li2S and intermediate Li-S products (low rate capability, isolated active material)

Reactivity of the lithium metal anode (dendrite deposition, cell shorting, safety)

Major Issues:

Ji, X., Lee, K.T., Nazar, L.F., Nat. Mater 8, 500 (2009)

N. Jayprakash,J. Shen, S.S. Morganty, A. Corona, L.A. Archer, Angew. Chemie Intern. Ed. 50, 5904 (2011)

Lai, C. Gao, X.P., Zhang, B., Yan, T.Y., Zhou, Z J. Phys. Chem. C 113, 4712 (2009).

The lithium-sulfur batterySleeping for long time……. booming in the most recent years…………

Ji, X., S. Ever, R. Black, L.F. Nazar, Nat. Comm., 2, 325 (2011)

Ji, X., L.F. Nazar, J. Mat. Chem, ., 20, 9821 (2010)

and others

……. however mainly focused on the optimization of the sulfur cathode still keeping Li metal anode

E.J. Cairns et al, JACS, doi.org/10.1021/ja206955k

Our approach:

Jusef Hassoun and Bruno Scrosati, Angew. Chem. Int. Ed. 2010, 49, 2371

ANODEConventional :Li metal our work : Sn-C nanocomposite

(gain in reliability and in cycle life)

ELECTROLYTEConventional : liquid organic our work : gel-polymer

membrane (gain in safety and cell fabrication)

CATHODEConventional : sulfur-carbon our work : C- Li2S composite Conventional : liquid organic (Li-metal-free battery ) (Li metal battery)

SnC nanocomposite / gel electrolyte/ Li2S-C cathode sulfur lithium-ion polymer battery

SnC/ Li2S lithium ion battery

J. Hassoun & B. Scrosati, Angew. Chem. Int. Ed. 2010, 49, 2371

Potentiodynamic Cycling with Galvanostatic Acceleration, PGCA, response in the CPGE. Li counter and reference

electrode. Room temperature.

THE CATHODE

Anode peak area = cathode peak area (integration)

Reversibility of the overall electrochemical reaction!

30 35 40 45 50 55

Support

JCPDS-772145

Li2S

Inte

nsity

/ cp

s

2 / degree

1 2 3 4 5

In situ XRD analysis run on a Li/CGPE/Li2S cell at various stages of the Li2S → S+ 2Li charge

process.

0 150 300 450 600

1.6

2.4

3.2

4.0

4.8543

2

1

Ce

ll vo

ltag

e /

V

Capacity / mAhg-1

Jusef Hassoun, Yang-Kook Sun and Bruno Scrosati, J. Power Sources, 196 (2011) 343

SnC/ Li2S lithium ion polymer battery

0 20 40 60 80 1000

100

200

300

400

500

600

700

0

200

400

600

800

1000

1200

1400

Cap

acity

(Li

2S-C

mas

s) /

mA

hg-1

Capacity (Li

2 S-C

mass) / m

Ahg

-1

C/10 C/20

C/6

C/5

Cycle number

Projected energy density: 400 Wh/kg

SnC+ 2.2Li2S Li4.4SnC+ 2.2S

Safety

Capacity decay upon rate

increase. Slow kinetics!

Some Li2S particles remain uncoated by carbon

Optimization of the cathode material morphology is needed. Work in progress in our laboratories

The kinetics issue

0 20 40 60 80 1000

100

200

300

400

500

600

700

0

200

400

600

800

1000

1200

1400

Cap

acity

(Li

2S-C

mas

s) /

mA

hg-1

Capacity (Li

2 S-C

mass) / m

Ahg

-1

C/10 C/20

C/6

C/5

Cycle number

SEM

FIB EDX

Scheme

Improved sulfur-based cathode morphology

Hard carbon spherule-sulfur (HCS-S) electrode morphology, showing the homogeneous dispersion of the sulfur particles in the bulk and over the surface of the HCS particles. The top right image illustrates the sample morphology as derived from the SEM image (top left) and the EDX image (bottom right) in which the green spots represent the sulfur

J.Hassoun, J. Kim, D-J. Lee, H.-Gi.Jung,S-M.Lee,Y-K.Sun, B. Scrosati, J.Power Sources, Doi:10.1016/jpowsour.2011.11.60 

Improved sulfur-based cathode morphology

J.Hassoun, J. Kim, D-J. Lee, H.-Gi.Jung,S-M.Lee,Y-K.Sun, B. Scrosati, J.Power Sources, Doi:10.1016/jpowsour.2011.11.60 

Cycling response room temperature 0 C

Rate capability

LiSiC/ S-C lithium ion battery

0 200 400 600 800

0.0

0.5

1.0

1.5

2.0

2.5

3.0

0 3 6 9 12 15 18 210

400

800

1200

0.2 A g-10.5 A g-1

1 A g-1

0.1 A g-12 A g-1

Vol

tage

(V)

Capacity (mAh g-1)

0.1 A g-1

Cycle number

Cap

acity

(mA

h g

-1)

20 40 60 80 100

0

600

1200

1800

2400

0 500 1000 1500 2000

1.0

1.5

2.0

2.5

3.0

Ca

pa

city (

mA

h g-1

(S) )

1 A g-1

(S)

Cycle number

Vo

lta

ge

(V

)

Capacity (mAh g-1

(S) )

J.Hassoun, J. Kim, D-J. Lee, H.-Gi.Jung,S-M.Lee,Y-K.Sun, B. Scrosati, J.Power Sources, Doi:10.1016/jpowsour.2011.11.60 

LiSiC/ S-C lithium ion battery

0 10 200

500

1000

1500

2000

0 250 500

0.5

1.0

1.5

2.0

2.5

3.00.5 A g-1

Ca

pa

city (

mA

h g

-1

(S) )

Cycle number

1th

2nd

3th

4th

Volta

ge

/ V

Capacity (mAh g-1

(S) )

0 20 40 60 80 100

0

300

600

900

1200

1500

18000.5 A g-1

(S)

Ca

pa

city (

mA

h g

-1

(S) )

Cycle number

Projected energy density: 400 Wh/kg

The lithium-air battery. The ultimate dream

Potential store 5-10 times more energy than today best systems

Two battery versions under investigation

Lithium-air battery with protected lithium metal anode and/or protected cathode (aqueous electrolyte)2Li + ½ O2 + H2O 2LiOHTheor. energy density : 5,800 Wh/kg

Lithium-air battery with unprotected lithium metal anode (non aqueous electrolyte)Li + ½ O2 ½ Li2O2

Theor. energy density : 11,420 Wh/kg

Present Lithium Ion technology (C-LiCoO2: Theor energy density: 420 Wh/kg

The lithium-air battery (organic electrolyte)Unprotected electrode design

Organic electrolytes

Remaining issues: high voltage hysteresis loop, limited cycle life, stability of the organic electrolytes, reactivity of the lithium metal anode…..

Courtesy of Prof O.Yamamoto, Mie University, Japan

Reaction mechanism

Lithium superoxide formationLithium

peroxide formation

Lithium oxide formation

Y-C. Lu, Z. Xu, H.A. Gasteiger, S. Chen, K. Hamad-Schifferli, Y. Shao-Horn, 2010, JACS, 132, 12170-

12171

Y-C. Lu, H.A. Gasteiger, Y. Shao-Horn, Electrochem Solid State Lett , 2011, 14, A70-A74

Very low charge -discharge hysteresis with efficiency

approaching 90% !

J. Hassoun, F. Croce, M. Armand & B. Scrosati, Angew. Chem. Int. Ed., 2011, 50,

2999

Oxygen electrochemistry in the polymer electrolyte lithium cell at Oxygen electrochemistry in the polymer electrolyte lithium cell at RTRT

Li / Polymer electrolyte / SP,O2 cell study by PCGA

P.G. Bruce et al., IMLB, Montreal, Canada, June 27-July 2, 2010

P.G. Bruce et al., ECS, Montreal, Canada, May 01-06, 2011

Electrolyte decomposition !

Polymer electrolytePolymer electrolyte

EC:DMC, LiPFEC:DMC, LiPF66

J. Hassoun, F. Croce, M. Armand & B. Scrosati, Angew. Chem. Int. Ed., 2011, 50,

2999

Oxygen electrochemistry in the polymer electrolyte lithium cell at Oxygen electrochemistry in the polymer electrolyte lithium cell at RTRT

Reduction products

XRD of the SP electrode

Li / polymer electrolyte / SP,O2 galvanostatic discharge

Oxygen electrochemistry in the polymer electrolyte lithium cell at Oxygen electrochemistry in the polymer electrolyte lithium cell at RTRT

The last concern: are lithium metal reserves sufficient for allowing large electric vehicle production?

Main Lithium Deposits

B.Scrosati, Nature, 473 (2011) 448

Laboratory structurePrincipal investigator:

Prof Stefania Panero

Post Docs:

Priscilla Reale

Maria Assunta Navarra

Graduate students: average 3 Visitors : average 2 Master students : average 4

Total : average 15

Inchul Hong

Researchers:

Jusef Hassoun

Sergio Brutti

ACKNOWLEDGEMENT

This work was in part performed within the 7th Framework European Project APPLES (Advanced, Performance, Polymer Lithium batteries for Electrochemical Storage )