Lithium batteries: a look into the future
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Lithium batteries: a look into the future. Bruno Scrosati. 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.

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Lithium batteries: a look into the future.

Bruno Scrosati

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

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 sources

Best candidates: lithium batteries


Courtesy of Dr. Jürgen DeberitzCHEMETALL GmbH

Where lithium is taking us?


  • Li-ionbattery system: a scheme of operation

Electrochemical Reactions

  • Cathode

  • Anode

  • Overall

The present Li-ion batteries rely on intercalation chemistry!

7

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


Lithium Batteries

Although lithium batteries are established commercial products

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

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


THE ENERGY ISSUE

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!


Electric Vehicle Applications- The energy issue

Estimated progress of the conventional Lithium-Ion Technology in terms of battery weight in EVs

200 Wh/kg*

170 Wh/kg*

200kg 140 kg

140 Wh/kg*

Li-ion Batteries

Near future

Present

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.


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;

Chalmers University of Technology

Chemetall

Ente Nazionale Idrocarburi ENI SpA

Zentrum für Sonnenenergie- und Wasserstoff-Forschung (ZSW)

SAES Getters SpA

ETC Battery and Fuel Cells Sweden AB

Stena Metall AB.


TheAPPLESSnC/ 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

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

Projected energy density: 170 Wh/kg


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

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

Li4Ti5O12 + Li[Ni0.45Co0.1Mn1.45]O4 Li4+xTi5O12 + Li (1-x) [Ni0.45Co0.1Mn1.45]O4

Projected energy density: 200 Wh/kg


Electric Vehicle Applications- The energy issue

Revolutionary Technology-Change

Super- Battery< 100kg

>500 Wh/kg

200 Wh/kg*

Estimated limit of Lithium-Ion Technology

170 Wh/kg*

250 kg 140 kg

140 Wh/kg*

Li-ion Batteries

Present

2012

2017

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

Year


Cathode side: Li Metal Chemistries

Where should we go ?

6

Li-Ion

Oxide

Cathodes

F2

Lithium-Element

Battery Cathodes

5

Potential vs. Li/Li+

"4V"

4

O2 (Li2O2)

O2 (Li2O)

3

Intercalation

chemistry

S

2

Carbon

anodes

Li

metal

1

0

4000

0

3750

1250

250

500

1000

1500

1750

750

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

Capacity / Ah kg-1


The lithium-sulfur battery

< Theoretical capacity of lithium polysulfides >

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

e-

e-

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

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

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

Li+ + S

Li+

Li+

Li+

  • Electrolyte

  • (polymer or liquid)

Li2S

Li

S8

Li2S8

Charge process

Li2S6

Discharge process

Li2S4

Li2S2

Li2S

Lithium

Sulfur

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


The lithium-sulfur battery

Major Issues:

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)


The lithium-sulfur battery

Sleeping for long time……. booming in the most recent years…………

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

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

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

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

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

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

and others

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


Our approach:

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

ANODE

Conventional :Li metal  our work : Sn-C nanocomposite (gain in reliability and in cycle life)

ELECTROLYTE

Conventional : liquid organic  our work : gel-polymer membrane (gain in safety and cell fabrication)

CATHODE

Conventional : sulfur-carbon  our work : C- Li2S composite

Conventional : liquid organic (Li-metal-free battery )

(Li metal battery)

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


SnC/ Li2S lithium ion battery

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


THE CATHODE

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

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

Anode peak area = cathode peak area (integration)

Reversibility of the overall electrochemical reaction!

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


SnC/ Li2S lithium ion polymer battery

SnC+ 2.2Li2S  Li4.4SnC+ 2.2S

Projected energy density: 400 Wh/kg

Safety


The kinetics issue

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


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

Rate capability

Cycling response room temperature 0  C

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

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

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 2LiOH

Theor. 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

Oxygen electrochemistry in the polymer electrolyte lithium cell at RT

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

  • 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

Lithium superoxide formation

Lithium peroxide formation

Lithium oxide formation

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 RT

Polymer electrolyte

Electrolyte decomposition !

EC:DMC, LiPF6

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

J. Hassoun, F. Croce, M. Armand & B. Scrosati, Angew. Chem. Int. Ed., 2011, 50, 2999


Oxygen electrochemistry in the polymer electrolyte lithium cell at RT

Reduction products

Li / polymer electrolyte / SP,O2 galvanostatic discharge

XRD of the SP electrode


The last concern:

are lithium metal reserves sufficient for allowing large electric vehicle production?


Main Lithium Deposits


B.Scrosati, Nature, 473 (2011) 448


LAB-FCT

Laboratory structure

Principal investigator:

Prof Stefania Panero

Researchers:

Jusef Hassoun

Maria Assunta Navarra

Priscilla Reale

Post Docs:

Sergio Brutti

Inchul Hong

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

Total : average 15


ACKNOWLEDGEMENT

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


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