R&D of novel power sources Ariel Rosenman Prof. Gregory Salitra - - PowerPoint PPT Presentation

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R&D of novel power sources Ariel Rosenman Prof. Gregory Salitra - - PowerPoint PPT Presentation

Jun 21, 2023 293 likes •576 views

On the Dynamic Frontier of Dr. Ran Elazari R&D of novel power sources Ariel Rosenman Prof. Gregory Salitra Doron Aurbach Daniel Sharon Bar Ilan university, Israel Prof. Boris Mrkovsky In collaboration with Prof. Elena Markevich

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SLIDE 1

On the Dynamic Frontier of

R&D of novel power sources Doron Aurbach Bar Ilan university, Israel

  • Dr. Ran Elazari

Ariel Rosenman

  • Prof. Gregory Salitra

Daniel Sharon

  • Prof. Boris Mrkovsky
  • Prof. Elena Markevich

And many others.. In collaboration with BASF,GM,Pellion

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SLIDE 2

2

Main xEV`s Makers 2013

PHEV HEV BEV

Audi BMW GM BYD Dodge Fisker Ford Honda Hyundai Jaguar Land Rover Lotus Daimler/Merced es Mindset Mitsubishi Porsche Suzuki Toyota VIA Motors Volvo Volkswagen Acura/Honda Audi Azure BMW GM Daimler/Mercede s Eaton Fiat Ford Honda Hyundai Jaguar Kia Land Rover Mitsubishi Nissan Porsche Subaru Toyota Volvo Volkswagen Audi BMW BYD GM Chrysler Daimler/Merc edes Fiat Ford Honda Hyundai Kia Mazda Mitsubishi Nissan Porsche Proterra Saab Tesla Toyota Volvo Volkswagen Wheego

Full EV can drive only 160 km between charges. Nevertheless, it is now a business!!! Li ion batteries take the lead!

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SLIDE 3

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Most Rechargeable Li+ ion Batteries in Use Today

Cathodes LiXCoO2 LiFeO4

Li[MnNiCO2

Anode LiXC6 Electrolyte solution: Ethylene-Carbonate & Di-Methyl Carbonate/ LiPF6 Voltage: 3.7 V, Average Energy Density: 150 Wh/Kg

Cathode Surface films Anode Surface films

  • D. Aurbach et Al., Materials Today, 2014
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SLIDE 4

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Advanced Li ion batteries : the challenge of new anodes

Si anodes (Li4.2Si > 3500 mAh/g), but need unique morphology

A 10 µm 10 µm C 1 µm 10 µm D 1 µm 10 µm B 1 µm

EC-DMC/LiPF6 Cycled in: DMC-FEC/LiPF6 EC-DMC-FEC/LiPF6 Monolithic electrodes comprising Si nano-wires Pristine Surface films formed in FEC-containing solutions were much thinner and compact

D.Aurbach et Al., Langmuir, 28, 6175 (2012)

Monolithic Si electrodes by sputtering

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SLIDE 5

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Galvanostatic cycling of monolithic Si electrodes in DMC:FEC 4:1 1M LiPF6 (“magic”) solution at 30oC

500 1000 1500 2000 2500 3000 20 40 60 80 100 120 140 Charge Discharge

Capacity [mAh/g]

500 1000 1500 2000 2500 3000 10 20 30 40 50 60 70 Charge Discharge

Current 0.132 mA (C/5 rate)

Cycle no. Capacity [mAh/g]

Current 0.258 mA (C/2.5 rate)

Cycle no.

Electrodes based on Si NW Electrodes based on Si sputtered on Cu

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SLIDE 6

C/8 C/2 C/2

FEC-based electrolyte FEC-based electrolyte 6

High voltage cathodes: LiNi0.5Mn1.5O4 /Si cells (Monolithic Si electrodes prepared by sputtering)

Markevich, Salitra & Aurbach, Electrochem. Comm., 2013

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SLIDE 7

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1 2 3 4 5 6 50 100 150 200

Capacity, mAh/g Voltage, V

LiCoPO4 LiMnPO4 LiMn0.8Fe0.2PO4 LiFePO4

For LiFePO4, LiMnPO4, LiMn0.8Fe0.2PO4:

  • Low cost, reasonable capacity
  • Good safety:low toxicity, high thermal stability
  • High rate capability

For LiCoPO4

  • High voltage, lower capacity, stability???

Cathodes, the limiting factor

The LiMPO4 olivine Family

theoretical Energy Density (mAh/ g) Voltage Range (V) Olivine 170 (165 practical) 3.4 LiFePO4 170 (150 practical) 4.2 LiMnPO4 170 (160 practical) 4.2 LiMn0.8Fe0.2PO4 170 (130-140 practical) 4.8 LiCoPO4

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SLIDE 8

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C2/m monoclinic phase: Li2MnO3 = Li[Li1/3Mn2/3]O2 R3M rhombohedral LiMO2: M=transition metal ion)

M

  • It appears that XRD is less sensitive than HRTEM in studies of the phase transitions and cation
  • rdering in the integrated layered material.

Molecularly integrated material Unique morphology of the BASF cathode materials

Li & Mn rich Li1+x[MnyNizCow]O2 high capacity cathodes

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SLIDE 9

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HC-MNC activated at 4.8 V in 1st cycle, further cycled up to cut-off potential 4.6 V

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SLIDE 10

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100 200 300 400 2.0 2.5 3.0 3.5 4.0 4.5 5.0

C/14 C/20

C/7 1C 2C

1-st Cycle

Discharge capacity / mAhg

  • 1

Voltage / V

AlF3-Coated Uncoated

The Irreversible capacity loss of the AlF3 coated electrode is less due to lesser oxidation reactions at high anodic potentials Significant increase of the discharge capacity of the AlF3 coated electrodes is due to higher Li storage capability of these electrodes.

100 200 300 400 2.0 2.5 3.0 3.5 4.0 4.5 5.0

C/14C/20

C/7 1C 2C

Cycle-1

Discharge capacity / mAhg

  • 1

Voltage / V

ICL = 23.2 % ICL = 5.1 %

Aurbach, Garsuch, Lampert, Schulz-Dobrick et Al., J. Electrochem. Soc., 160, A2220 (2013)

Typical voltage profiles at various currents applied C-rate

  • f the xLi2MnO3. (1-x)Li[MnNiCo]O2 electrodes
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SLIDE 11

Advantages of Li-S and Li-O2 over Li-ion systems

  • Higher Theoretical capacity, energy and power density.
  • Low cost (1$ per 100g) and abundant raw materials (350 ppm).
  • Operability at low temperature (-40˚C).

Bruce, P. G., Freunberger, S. A., Hardwick, L. J., Tarascon, J.-M.. Nature materials 11, 19–29 (2012). 11

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SLIDE 12

Bar Ilan University 12

Working Mechanism

Formation and re-oxidizing Li2Sn

Discharge Charge

+ S8 Li2S8 Li2S6 Li2S4 Li2S2 Li2S

Insoluble products

12

+

Sulfur-cathode LiNO3 Li-anode

Li-Polysulfudes diffuse to the anode

Shuttle effect

12

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SLIDE 13

Rechargeable lithiated silicon-sulfur (SLS) cells

  • vs. Li-S reference cells, an important new direction

Li –Sulfur Cells (reference) Sulfur/Lithiated a-Si Li-Ion Cells

13

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SLIDE 14

S S8

8

S S8

8

S S8

8

S S8

8

S S8

8

S S8

8

S S8

8

S S8

8

S S8

8

S S8

8

S S8

8

S S8

8

S S8

8

S S8

8

S S8

8

S S8

8

S S8

8

S S8

8

S S8

8

S S8

8

a b a b

Activated carbon cloth impregnated with sulfur as possible cathodes for Li-S system.

Electrode Preparation

14

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SLIDE 15

Charge/Discharge capacity vs. cycle number Charge/Discharge profiles vs. voltage

  • ~3.12 mg/cm2 of sulfur impregnated on activated

carbon cloth disc (kynol 2000 m2/g, 14 mm φ) under vacuum in a sealed glass ampulla at 200 °C for 10h.

  • Cell where cycled at current density of ~1 mA/cm2

(~C/5) unless indicated otherwise between the voltage range of 2.5V and 1.9V.

Electrochemical performance of S/kynol 2000 Discharge potential is limited to 1.9V

 Binder Free.  Rigid Structure.  High Porosity & Surface Area.

1.3 mA/cm2 0.65 mA/cm2

15

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SLIDE 16

Li2S Li2S Red. Ox. Proposed mechanism for redox mediated Li2S oxidation

b)

Li2S Pristine Electrode No Additive With Redox Couple

a)

Li-L2S cells: towards Li ion sulfur systems

The best red-ox mediator we found so far: Decamethylferrocene Fe(η5-C5Me5)2

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SLIDE 17

Using monolithic high surface area activated carbon cloth electrodes Decoration by α-MnO2 nano-particles can reduce the oxidation potential

via electro-catalysis ACM ACM α-MnO2

The over-potential dropped to in more then 0.5 V by introducing MnO2 catalyst

4.3 V

  • D. Aurbach et Al.,J. Mater. Chem. A, 1, 5021(2013)

The most relevant electrolyte solution: CH3O(CH2CH2O)nCH3 / LiTFSI LiN(SO2CF3)2

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SLIDE 18

Proposed degradation mechanism of polyether solvents during oxygen reduction (in the presence of Li ions)

       5

6b

Li2O2

7

LiOCO2Li CO2 + LiOLi O H Li Li O O Li Li Li CH3OCH2CH2OCH2 Li CH3O OCH2CH2O CH3OO 1 3 2 4 H2C O Li2O2 HCO2Li CH3CHO Li2O2 H3CCO2Li

a b c b a

OCH2CH2OCH2 +

c

O O Li Li

d d

:B HB  

6a

10

The lithium cation is a hard electrophile which is expected to bond strongly to the hard Lewis base oxygen anions. This in turn helps to convert the alkoxy groups into better leaving groups and facilitates nucleophilic attacks by Li2O2.

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SLIDE 19

Are rechargeable Li-O2 batteries realistic?

Electrolyte solution stability

ORR- reactivity with the oxides OER- low solution oxidation potential

  • 1. Carbonates
  • 2. Polyether ?
  • 3. DMSO
  • 4. DMF ???

Carbon stability

Enhances electrolyte solution degradation Reacts with O2, super-oxides & peroxides

Catalyst integration

Enhances solution degradation and oxidation Introducing more contaminations

Carbon replacement?

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SLIDE 20

O2 O2 O2

5 nm

The “perfect” system

Still not found

GAS

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SLIDE 21

O2 O2

Non functional system

Carbonates solvents

GAS

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SLIDE 22

O2 O2

500 nm

+

Complex system

Polyethers, DMSO, Sulfolane, DMF, Etc...

GAS

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SLIDE 23

Inert cathode

O2 O2

5 nm

+

Complex system with inert cathode

More studies should be done

Negligible

GAS

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SLIDE 24

Chemical reactions of oxides may be very different from those observed under electrochemical reactions that involve primarily electron transfer processes. In fact, the main side reactions should occur during the formation of the reduced oxygen species in the anionic form (catalyzed by Li ions in solutions, before precipitation as solid Li2O2 deposits. Substrates:

  • rganic Moieties /

Solvent molecules

The effect of the lithium oxides source

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SLIDE 25

Conclusions and open questions

  • There are no stable polar-aprotic solvents suitable for ORR in the presence of Li ions.
  • The high reactivity relates to oxides and Li ions in solution phase. Solid Li2O2 is not too

reactive.

  • Li ions are hard electrophiles. Moving to other cations (Na+) may change the game.
  • Carbon electrodes are also problematic. They react with O2, oxides and degrade.
  • At this stage, we have serious problems in the course of ORR. Too early to discuss
  • catalysis. Finally, when we will solve all the above problems, we will face the real
  • nes……….a lot of hard work needed! Do not promise anything .
  • Li ion battery technology is reaching its limits.
  • Load leveling becomes more & more important: Super –Capacitors, Na ion batteries ,

Mg batteries, flow batteries, Li ion batteries with LTO (Li4Ti5O12, 1.5V) anodes vs. LiMn2O4, LiFePO4 or LiMn0.8Fe0.2PO4 cathodes (2.5-2 V highly stable batteries)

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SLIDE 26

Just capacitive, electrostatic interactions

Anions Adsorption desorption Li ions Intercalation De-intercalation

s

Super- capacitors (high power, prolonged cycling)

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SLIDE 27

Low voltage, long life Li ion batteries, based on LTO anodes. A contribution of Li ion technology for load leveling applications?

2V 2.5V 3.3V

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SLIDE 28

Warning

  • During the last several decades, the battery community demonstrated

highly important progress.

  • The development and commercialization of Li ion batteries is the most

impressive success of modern electrochemistry.

  • Our modern life which are characterized by an intensive use of mobile

electronic equipment: cellular phones, laptops, cameras and more…are affected so much by the high fidelity and reliability of Li ion battery technology.

  • Now we are challenged by the demands for electrochemical propulsion.

We are expected to provide fast revolutions (see for instance the 5-5-5 program…)

  • The risk is very serious. It took us so many years of excellent scientific

hard work to reach our prestige. We should not loose it!!!

  • We should not promise thinks that we may not be able to deliver. It is

much better to be a-priori moderate and then surprise……