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STATO DI SVILUPPO DELL’ACCUMULO ENERGETICO PER VIA ELETTROCHIMICA LE BATTERIE AL LITIO. Bruno Scrosati L aboratory for A dvanced B atteries and F uel C ell T echnology. LAB-FCT. Dipartimento di Chimica Centro Hydro-ECO SAPIENZA Università di Roma. Research background. Wind. Geothermal.

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slide1

STATO DI SVILUPPO DELL’ACCUMULO ENERGETICO PER VIA ELETTROCHIMICA

LE BATTERIE AL LITIO

Bruno Scrosati

Laboratory for Advanced Batteries

and Fuel CellTechnology

LAB-FCT

Dipartimento di ChimicaCentro Hydro-ECOSAPIENZA Università di Roma

slide2

Research background

Wind

Geothermal

Cost of Oil (WTI)

Solar

Intermittent alternative energy sources (REPs) , as well as electric transportation, require convenient energy storage systems, e.g., batteries

  • Global warming : suppression of CO2
  • Demand of oil in the world

(particularly in BRICs)

 Energy Storage, Vehicle

Kyoto protocol

http://www-gio.nies.go.jp

Courtesy of Dr. Ahiara, Samsung Research, Yokohama, Japan

slide3

Li-ionbattery system

Electrochemical Reactions

  • Cathode
  • Anode
  • Overall

Figure. Schematic illustration of a rechargeable lithium battery

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

3

slide4

Charge

Lithium-Ion Battery

Electrolyte

AL Current

Collector

Cu Current

Collector

Graphite

LiMO2

SEI

SEI

slide5

Discharge

Lithium-Ion Battery

Electrolyte

AL Current

Collector

Cu Current

Collector

Graphite

LiMO2

SEI

SEI

slide6

Lithium Batteries

Lithium batteries: high energy density (3 times lead-acid). Power sources of choice for the consumer electronics market

The application of lithium batteries spans beyond the electronics market

slide7

HEV, EV and FCV in Japan

Hybrid (HEV) and electric (EV) vehicles are already on the road

HEV in market

PHEV

FCHV

?

Their diffusion is expected to drammatically increase in the next few years

EV

Courtesy of Dr. Ahiara, Samsung Research, Yokohama, Japan

Reference: Institute of Information Technology, Japan

slide8

Lithium Batteries

Although lithium batteries are established commercial products

further R&D is still required to improve their performance to meet the REP andHEV-EV requirement

Enhancement in safety, energy density andcostare needed!

slide11

SAFETY

Actions:

Replacement of the oxygen releasing cathode material (LiCoO2) with structurally stable alternative compounds, e.g. LiFePO4

Replacement of the flammable liquid organic electrolyte with more stable materials, for example

Polymer ionic conducting membranes

cost of lithium batteries in comparison with other rechargeable systems

THE COST ISSUE

Cost of lithium batteries in comparison with other rechargeable systems

AVERAGE PRICE PER CELL IN 2005

Source : The rechargeable battery market, 2005-2015, June 2006

Source :TIAX, based on MEDI data

slide13

COST

Actions:

Replacement of the expensive cathode material (LiCoO2) with low cost, abundant alternative compounds, ideally iron or sulfur – based cathodes

slide14

Cost

Comparison of various raw materials for lithium secondary batteries.

Materials in use: LiCoO2 (cathode) ; Cu (current collector)

Alternative materials: LiFePO4, LiMn2O4, S (cathode) ; Stainless Steel (current collector)

slide15

THE ENERGY ISSUE

Energy Density (Wh/kg)  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
Electric Vehicle Applications- The energy issue

Revolutionary Technology-Change

500 km Battery

Super- Battery < 200kg

Pb-acid 3000 kg

Ni-MH 1200 kg

>500 Wh/kg

200 Wh/kg*

Estimated limit of Lithium-Ion Technology

170 Wh/kg*

700 Kg 500 kg

140 Wh/kg*

Li-ion Batteries

Present

2012

2017

Year

Courtesy of Dr. Stefano Passerini, Munster University, Germany

slide17

ENERGY DENSITY

Actions:

Replacement of the present electrode materials with alternative compounds having much higher values of specific capacity

slide18

High-Energy Battery Technologies

X

Where should we go?

500 km Battery

6

5

Potential vs. Li/Li+

4

Oxide

Cathodes

High capacity

cathodes

"4V"

3

Li-ion

Super- Battery <200kg/500km

Li/O2 , Li/S

2

Intercalation

materials

1

Carbon

anodes

"0V"

High capacity

0

0

1250

250

500

1000

1500

1750

750

Capacity / Ah kg-1

Courtesy of Dr. Stefano Passerini, Munster University

slide19

 Why Li/S battery?

Anode

Cathode

e-

e-

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

Li+ + S

Li+

Li+

Li+

Electrolyte

(polymer or liquid)

Li2S

Li

Future Li-S performance region

Li-S, 2005

Sion Power Corp.

Li-S, 2001

Prismatic Li-Polymer

Prismatic Li-ion

Cylindrical Li-ion

SION POWER CORPORATION

PBFC-2, Las Vegas, Nevada, USA,

June 12-17, 2005

Ni/MH

Ni/Cd

Fig. Energy density comparison with commercial secondary batteries.

slide20

 Why Li and S for electrode active material? (1)

Lithium

Sulfur

-. Atomic weight: 32.06g/mol

-. Light yellow solid

(2.07g/cm3)

-. Non-toxic, “green” material

-. Abundant and cheap

(28 US$/ton)

-. Theoretical capacity:

1.675 Ah/g

-. Atomic weight: 6.94g/mol

-. Lightest alkali metal

(0.54g/cm3)

-. Silvery, metallic solid

-. Theoretical capacity:

3.86Ah/g

-. E = -3.045VSHE

Courtesy of Prof. K.Kim, Gyeongsang National University, Korea

http://periodic.lanl.gov

slide21

Why Li / S battery ?

Comparison of various secondary batteries.

Comparison of various raw materials for lithium secondary batteries.

Courtesy of Prof. K.Kim, Gyeongsang National University, Korea

slide22

The lithium-sulfur battery

The Li/S concept is not new. However, so far limited progress due to a series of practical issues

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)

slide23

R&D is required to improve the performance of super-batteries, such as Li-S or Li-O2 to meet the HEV-EV requirement

Large investments are in progress worldwide to reach this important goal

.

slide24

Our approach:

Total renewal of the battery chemistry, including all three components, i.e. anode, electrolyte and cathode.

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

http://www.wiley-vch.de/vch/journals/2002/press/201010press.html

slide25

THE BATTERY

Specific advantages

 Control of lithium sulphide solubility (specifically designed polymer electrolyte)

Easiness of fabrication (polymer configuration; match between anode and cathode specific capacity)

 Safety ( no lithium metal anode; no LiPF6 in the electrolyte; chemical stability of electrodes)

 Low cost ( abundant materials; simple preparation)

slide26

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

 High energy density (about 3 times that offered by common lithium ion batteries) and plastic design.

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

http://www.wiley-vch.de/vch/journals/2002/press/201010press.html

slide27

Acknowledgement

Funds

Italian Ministry of Education , University and Resarch, MIUR , PRIN 2007 Project

and

SIID Project “REALIST” (Rechargeable, advanced, nano structured lithium batteries with high energy storage) sponsored by Italian Institute of Technology.