Lithium Air Batteries: The Future For Electric Vehicles?

Lithium Air Batteries: The Future For Electric Vehicles?

Loading
Loading Social Plug-ins...
Language: English
Save to myLibrary Download PDF
Go to Page # Page of 37

Description: Our research group is active in the field of electrochemistry and electrocatalysis from more than 80 years… In the last decade, the experimental work carried out in our Labs is focussed on the development of innovative, low-cost and environmentally friendly materials for energy storage and production devices by new, reliable and sustainable synthesis procedures, and the assessment of their structural-morphological characteristics and electrochemical behavior.

 
Author: Amici Julia, Francia Carlotta, Zeng Juqin, Alidoost Mojtaba, Nerino Penazzi, Francesco Trotta, Silvi  | Visits: 351 | Page Views: 732
Domain:  Green Tech Category: Battery & Fuel Cell 
Upload Date:
Link Back:
Short URL: https://www.wesrch.com/energy/pdfTR1YL6000DEYP
Loading
Loading...



px *        px *

* Default width and height in pixels. Change it to your required dimensions.

 
Contents:
Amici Julia1, Francia Carlotta1, Zeng Juqin1, Alidoost Mojtaba1,
Nerino Penazzi1, Francesco Trotta2, Silvia Bodoardo1

1Department

of Applied Science and Technology – Politecnico di Torino – c.so Duca degli Abruzzi, 24 –
10129 Torino – Italy – silvia.bodoardo@polito.it

2Department

Silvia Bodoardo (silvia.bodoardo@polito.it)

of Chemistry – University of Torino – via Giuria 9 – Torino Italy
Silvia Bodoardo silvia.bodoardo@polito.it

1

Politecnico di Torino
International context

Approx. 400 agreements with international universities
and international networks
National context
Leader in engineering and
architecture studies

Regional network
Italy

Education, research, technology
transfer, services for local institutions

Piedmont

PoliTO
Silvia Bodoardo (silvia.bodoardo@polito.it)

2

Main research activities
Our research group is active in the field of electrochemistry and electrocatalysis from more than 80 years…
In the last decade, the experimental work carried out in our Labs is focussed on the development of innovative, low
cost and environmentally friendly materials for energy storage and production devices by new, reliable and
sustainable synthesis procedures, and the assessment of their structural-morphological characteristics and
electrochemical behaviour.

Li-ion cells

Electrochromic devices
Li-air and Li-S batteries

Fuel Cell,

from nano-micro-thin Lab-scale to preindustrial-scale assembly
Equipments and knowledge for full electrochemical characterisation
Silvia Bodoardo (silvia.bodoardo@polito.it)

Silvia Bodoardo

3

facilities
Testing tools (5 V 5A and more than 200 A)
Dry box and dry room . Facilities for synthesis and complete characterization of materials.

Silvia Bodoardo (silvia.bodoardo@polito.it)

4

outline






Introduction Energy needs
Li-ion issues
Li-air characteristics and issues
Li-air protective membrane
Conclusions

Silvia Bodoardo (silvia.bodoardo@polito.it)

Silvia Bodoardo

5

More batteries or
Better batteries?

Silvia Bodoardo (silvia.bodoardo@polito.it)

6

7

Silvia Bodoardo (silvia.bodoardo@polito.it)

7

Lithium Ion Battery
• The most advanced batteries on the market today are the Li-ion batteries.
• High operating voltage: a single cell has an average operating potential of approx. 3.6 V-4V,
about twice that of sealed Pb-acid batteries.
• High discharge rate: up to 3-5C are easily attainable.
Superior cycle life: service life of a battery is around 1000
cycles.


The societal needs in the present energy scenario
require the development of inexpensive, thermally
stable, long cycling and safe lithium batteries with high
energy and power densities

• Li-ion will reach its maximum performance in 2025… and
then?
• Production of Li-ion cells is OUT of Europe
Silvia Bodoardo (silvia.bodoardo@polito.it)

8

Li-ion raw materials issues : Cobalt !!
• Annual cobalt production : 63000 tons
Originally LiCoO2 :

• batteries are consumer n°1

• CRM : High price ; volatile for
geopolitical reasons (Congo, Chinese
competition for African resources)
• Cobalt (CoO, Co(OH)2) is also used in
alkaline NiCd, NiMH and NiZn
• For Li-ion, it exists technical solutions to
decrease cobalt content, or to eliminate
for less stringent applications

Cost

10 years at
40oC
50% SOC

Cathode
reactivity

Voltage vs. SOC

Reference

Lower than
NCA
Opportunity to
improve

Cathode
reacticity

Voltage control
vs. SOC

Close to
reference

Voltage control
vs. SOC

Lower
cathode
material cost
Balance of
system same

Specific
strategy

Lower
cathode
material cost
Systems cost
same

Chemistry

Calendar
life

Li(NiCoAl)O2

529 Wh/kg

Li(NiMnCo)O2

LiMn2O4

LiFePO4

Silvia Bodoardo (silvia.bodoardo@polito.it)

Safety

Battery
manageme
nt

Energy(mat
erials only)

Silvia Bodoardo

476 Wh/kg

419 Wh/kg

Lower than
NCA
Mn dissolution

Cathode
reactivity

424 Wh/kg

Lower than
NCA
To be
demonstrated

Limited by
electrolyte
reactivity

9

Annie de Guibert SAFT Brussels 2010

Silvia Bodoardo (silvia.bodoardo@polito.it)

Lithium - oxygen

Need of
higher
energy
density

10

Why Li-Air?
• Extremely high specific capacity of Li anode material (3842 mAh g-1 for lithium)
• The Li-air battery has theoretical specific energy of 11500 Wh/kg,
• when fully developed, Li-air could have practical specific energies of 1000-3000 Wh kg-1
• They can be produced without CRM

• Use of air which is highly available and no cost
 Unlike the Li-ion battery, the Li–air battery does not exploit the concept of intercalation
electrodes as the Li+ ions react directly with O2 in a porous electrode.
 The roadmap of the Li-air technology is predicted to be extended to a 10 or 20 years
window because of a large number of unresolved issues
Where does 11,000 Wh/kg come from?
Start with Li - (6.9 g/mole)
Assume oxygen is “free” and we don’t need to worry about its mass.
Spec. E. = 3 V x 96500 C/mol 3600 C/Ah 0.0069 kg/mol

Silvia Bodoardo Wh/kg
Spec. E. = 11,500 (silvia.bodoardo@polito.it)

Vol. E. = 3500 Wh/kg (assuming only Li2O2)

Silvia Bodoardo

11

Product:
Li2O
Li2O2

Source - IBM 2010
Silvia Bodoardo (silvia.bodoardo@polito.it)

12 12

The Li-air battery
Nonaqueous:
2Li+ + 2e- + O2 ↔Li2O2
E0= 2,96V vs Li+ / Li

Lithium oxides have low electrical conductivity: during
ORR their precipitation inside the cathode pore
structure results in subsequent high charge overpotentials and voltage losses.
-As the oxygen dissolved in the electrolyte is carried
through the pore network of the cathode, precipitation of
insoluble products narrow such network lowering
oxygen diffusivity

Silvia Bodoardo (silvia.bodoardo@polito.it)

13

Li-air Issues

Silvia Bodoardo (silvia.bodoardo@polito.it)

L. Grande, E Paillard J. Hassoun, J-B Park, Y-J Lee, Y-K Sun, S. Passerini, B. Scrosati, Adv. Mater. 2015, 27, 784-800

14

STable high-capacity lithium-Air Batteries
with Long cycle life for Electric Cars
GC.NMP.2012-1-314508

The STABLE Project focused on innovations of battery anode, cathode, electrolyte materials and technologies of
Li-air cells.
One important objective was to obtain a Li-air battery with an improved cycle life of more that 100 cycles.
This can be achieved through the use of suitable catalysts at the cathode, the protection of a protective membrane
at the cathode (to avoid moisture entrance) and through the use of electrolytes that increase the solubility of Li2O2
Cathode: Pd doped mesoporous carbon nanofibers (Pd CNFs) produced by electrospinning
technique were prepared to be used as electrocatalysts at the air cathode

Electrolyte: we considered the role of different solvents, namely: DMSO, TEGDME and
EMITFSI, on the cell electrochemical performance.

Silvia Bodoardo (silvia.bodoardo@polito.it)

15

CATHODE
Pd/CNF
A)

Pd(Ac)2

O2

PALLADIUM ACETATE

Li2O2

C)
AEAPTS
1. ELETTROSPINNING

B)

2. THERMAL TREATMENT
3. PYROLISIS

A+B

A+B+C

Pd2.5A/CNF

Pd5/CNF

Pd2.5/CNF

G.S. Park, J.S.Lee, S.T.Kim, S. Park, J. Cho, J. Power Sources, 2013, 243, 267-273
Z. Favors, H.H. Bay, Z. Mutlu, K. Ahmed, R. Ionescu, R. Ye, M. Ozkan, C. S. Ozkan , Scientific Reports, 2014, 5, 8246

Silvia Bodoardo (silvia.bodoardo@polito.it)

16

Metal catalysts the effect of Pd

Pd/CNF
Pd2.5/CNF

Cathode: CNFs or Pd/CNFs, binder
PVDF Kynar
(90:10) on GDL24BA
(Sigraget)
Anode: Lithium foil 2,54cm2
Electrolyte: TEGDME/LiClO4
Continuous O2 flow 3.5ml/min
Applied current: 20mA/g
10h discharge/10h charge

Pd5/CNF

Silvia Bodoardo (silvia.bodoardo@polito.it)

17

ELECTROLYTE
Ru/ITO & the effect of the electrolyte
1. Most of the electro-catalysts for Li/air are supported on different structured carbons. This is because
carbon is lightweight material with good electronic conductivity and with a suitable porous structure, which
acts favourably for both oxygen diffusion and Li2O2 deposition during discharge. Recent studies emphasized
the instability of carbon-based cathodes in Li-O2 cells, suggesting a strong dependence on the
hydrophobic/hydrophilic nature of the carbon surface and its ability of promoting electrolyte
decomposition during cell cycling.
Indium tin oxide replaced carbon to support
Ruthenium nanoparticles

2. Of great significance is the sensitivity of the electrochemical response of the Li-O2 cell to the electrolyte
composition. All polar aprotic solvents used in the electrolyte react with species generated from oxygen
reduction. To date, some rather stable electrolyte solvents such as tetraethylene glycol dimethyl ether
(TEGDME) and dimethyl sulfoxide (DMSO) have been identified.

Silvia Bodoardo (silvia.bodoardo@polito.it)

18

TEM

Ru/ITO
ethylene glycol
ITO NPCs
1. REFLUX in Ar
2. + formic acid
3. Filtering and drying

RuCl3.6H2O
NaOH

EDX

Silvia Bodoardo (silvia.bodoardo@polito.it)

Element
OK
Ru K
In L
Sn L

Weight%
7.33
4.27
78.33
10.07

Totals

XRD

Atomic%
36.14
3.34
53.83
6.69

100.00
19

Ru (4%wt)/ITO
TEGDME

DMSO

Silvia Bodoardo (silvia.bodoardo@polito.it)Ru/ITO 85 wt. % + PVDF 10 wt. % on GDL24BC. Discharge-charge current density 0.05mAcm-2, at the curtailed capacity
of 1,0 mAhcm-2 Continuous O2 flow 3.5mlmin-1

20

Protective membrane preparation and
characterization
PVDF+SiO2
NPs
in DMF

Casting with doctor
blade on HDPE

2’’

24h
H2O

Methanol

HF bath 2h

Drying in air for 24h

Si Oil loading
Mb

Mb SiO2

Mb SiOil

120

Section

Surface

Section

CHARACTERISTICS OF DEHYDRATION MEMBRANE
O2
H2O
Contact
MbSiO2
permeability
permeability
angle
0,426 Barrer
733,246 [g/(m2.24h)]
148,72 ± 16,4
Mb
0,940 Barrer
815,861 [g/(m2.24h)]
93,5 ± 5,1

80

Weight [%]

Surface

100

60

40

20

0

MbPVDF.SiO2
MbPVDF.HF
100

200

300

400

500

600

700

T [°C]

Silvia Bodoardo (silvia.bodoardo@polito.it)
0,487 Barrer

MbSioil

28,875 [g/(m2.24h)]

120,76 ± 11,6

21

800

Electrochemical characterization
ECC-AIR (EL-CELL).

Membrane
Current collector
Cathode: GDL (SIGRAGET GDL-24BC with microporous layer).
Separator: ECC1-01-0012-A/L 18 mm x 0.65 mm glass
fibre separator (EL-CELL) + Electrolyte: 0,5M LiClO4 in
Tetraethylene glycol dimethyl ether (TEGDME).
Anode: Lithium disc ( Chemetall s.r.l.).

CYCLING TESTS: I=0,05mAcm-2, 20h discharge, between 2,25V and 4,35V
No membrane
PURE O2 FLOW 3ml/min

Silvia Bodoardo (silvia.bodoardo@polito.it)

Si-oil/PVDF membrane
Dry-room AIR , 17%RH

22

Silvia Bodoardo (silvia.bodoardo@polito.it)

23

New membranes with selective
super hydrofobic additive
the cyclodestrines

Silvia Bodoardo (silvia.bodoardo@polito.it)

Silvia Bodoardo

24

Li-air cell prototype

Silvia Bodoardo (silvia.bodoardo@polito.it)

Silvia Bodoardo

25

Conclusions
Li-air

Specific energy
Energy density
Charge/discharge
efficiency
Cycle durability
Nominal cell
voltage

11140 Wh/kg
(theor)

LiS
Na-ion
500 W·h/kg
demonstrat 100-400
ed
Wh/kg
350 W·h/L

C/10
prototype

2,9 V

C/5 nominal
150 disputed
2,5-3 V

Li-ion
100-300
Wh/kg
250-700
Wh/kg
till 10C

1000
3 - 3.4 V

1000
3,5 -4.3 V

• Several issues need to be overcome
• In order to use electrochemical batteries with low environmental impact with
really high energy Li-air can become one solution
• Li-ion is a lost competition with Asiatic countries.
• The competition on post-lithium ion is still open  EC can help in this direction
Silvia Bodoardo (silvia.bodoardo@polito.it)

Silvia Bodoardo

26

Acknowledgments:
Julia Amici
Daniele Versaci
Mojtaba Alidoost
Usman Zubair
Vankova Svetoslava
Juqin Zeng
Francesca Di Lupo
Carlotta Francia
Nerino Penazzi
Francesco Trotta (University of Turin)

Acknowledgments to All the Partners of:

Silvia Bodoardo (silvia.bodoardo@polito.it)

STABLE FP7 project
“STable high-capacity lithium-Air Batteries with Long cycle life for Electric cars "
Grant agreement no: 314508

27

Aknowledgement to STABLE FP7 project
“STable high-capacity lithium-Air Batteries with Long cycle life for Electric cars "
Grant agreement no: 314508

Silvia Bodoardo (silvia.bodoardo@polito.it)

Silvia Bodoardo

28

Silvia Bodoardo (silvia.bodoardo@polito.it)

Silvia Bodoardo

29

Pd/CNF
Sample

Pd 1

Pd 2,5

Pd5

Pd 2,5A

CNF

measured(wt%)

2.39

7.06

10.65

4.78

-

theorethical (wt%)

3.28

7.3

15.29

6.28

-

542.635
37.042
505.593

211.244
67.649
143.595

626.96
66.369
560.591

139.552
98.01
41.592

15.8
15.8
0

pore size (nm)

3.2

3.7

3.6

3.9

3.2

total pore volume (cm3/g)

0.24

0.12

0.31

0.113

0.046

microporous

0.20

0.062

0.21

0.014

0

mesoporous

0.04

0.058

0.10

0.099

0.046

total surface area (m2/g):
mesoporous
microporous

Silvia Bodoardo (silvia.bodoardo@polito.it)

30

Pd/CNF

Pd2.5/CNF

Silvia Bodoardo (silvia.bodoardo@polito.it)
Cathode composition 90wt% catalyst -10 wt% binder (PVDF Kynar). Discharge-charge applied current 20mA/g , Continuous O2 flow 3.5mlmin-1

31

Metal catalysts the effect of Pd & mesoporosity

Silvia Bodoardo (silvia.bodoardo@polito.it)

32

TEGDME

DISCHARGED

Ru/ITO 85 wt. % + PVDF 10 wt. % on GDL24BC. Discharge-charge current density 0.05mAcm-2,
at the curtailed capacity of 1,0 mAhcm-2 Continuous O2 flow 3.5mlmin-1

CHARGED

DMSO

DISCHARGED

CHARGED

Clearly, the electrolyte plays a tremendous role on the performance of Li-O2 batteries, affecting the morphology of the lithium peroxide &
the cell recharge ability.

Silvia Bodoardo (silvia.bodoardo@polito.it)

33

TEGDME

ITO

DMSO

ITO 85 wt. % + PVDF 10 (silvia.bodoardo@polito.it)
Silvia Bodoardo wt. on GDL24BC. Discharge-charge current density 0.05mAcm-2, at the curtailed capacity of 1,0 mAhcm-2 Continuous O2 flow 3.5mlmin-1

34

DMSO

TEGDME & the BINDER
10000

CMC vs. PVDF




RuITO_PVDF_pristine

RuITO_PVdF_TEGME _ fully discharged/recharged
RuITO_CMC_pristine
RuITO_CMC _TEGME_ fully discharged/recharged

a.u.

GDL
 ITO



 Li2O2
 Li2CO3









15

20







 

 





0



 

25

30

35



40

45

50

55

60

65

70

2

PVDF strongly
ITO substrate

affects

the

Ru/ITO 95 wt. % + CMC 5wt. % on GDL24BC. Dischargecharge current density 0.05mAcm-2, at the curtailed
capacity of 0,5 mAhcm-2 Continuous O2 flow 3.5mlmin-1
Ru/ITOSilvia Bodoardo (silvia.bodoardo@polito.it)
95 wt. % + CMC 5wt. % on GDL24BC. Discharge-charge current density 0.05mAcm-2, at the curtailed capacity of
0,5 mAhcm-2 Continuous O2 flow 3.5mlmin-1

35

The ionic liquid EMITFSI possesses such a high viscosity that significantly hinders the mass transport. The DMSO solvent has a high O2 diffusion coefficient
and low viscosity, which enhance the O2 transfer in the electrolyte-flooded cathode. The addition of EMITFSI significantly improved the ionic conductivity of
electrolyte, from 6.1 ms cm-1 for the DMSO electrolyte increased to 9.5 ms cm-1 for the EMITFSI-DMSO electrolyte.

DMSO

Ru/ITO 95 wt. % + CMC 5 wt. % on GDL24BC. Discharge-charge current density 0.05mAcm-2, at the
curtailed capacity of 1,0 mAhcm-2. Continuous O2 flow 3.5mlmin-1

Silvia Bodoardo (silvia.bodoardo@polito.it)

DMSO+ 20wt%EMITFSI

Ru/ITO 95 wt. % + CMC 5 wt. % on GDL24BC. Discharge-charge current density 0.05mAcm-2, at the
curtailed capacity of 1,0 mAhcm-2. Continuous O2 flow 3.5mlmin-1

36

Electrochemical characterization

No membrane
PURE O2 FLOW 3ml/min

Silvia Bodoardo (silvia.bodoardo@polito.it)

Si-oil/PVDF membrane
Dry-room AIR , 17%RH

37