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Development of Novel Lithium Salts for Battery Applications. Outline of the presentation. Introduction – searching for new salts for lithium batteries Synthesis and characterization of novel family of organic covalent lithium salts

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Presentation Transcript
outline of the presentation
Outline of the presentation
  • Introduction – searching for new salts for lithium batteries
  • Synthesis and characterization of novel family of organic covalent lithium salts
  • Properties of polymer and liquid electrolytes containing newly developed salts:
      • conductivity
      • lithium transference number
      • formation of ionic aggregates
      • electrochemical stability
      • performance in lithium batteries
  • Conclusions
anions
Anions:

• Control dissociation and conductivity

• Control transport numbers t+ /t-

• are an important part of SEI build-up

at +/- electrodes

• Control aluminium corrosion

slide4

ClO4-

BF4-

Explosive !

Toxic !

PF6-

AsF6-

SbF6-

Classics…

Tendency to décompose according to equilibrium:

LiBF4  BF3+ <LiF>

LiPF6  PF5 + <LiF>

Fast reaction above 80°C

 Destruction of electrolyte and interfaces

conceptual approach to anion design
Conceptual approach to anion design
  • “O” is not a favorable building block:

Strong Li—O interactions  ion pairing, ≠ ClO4-, BOB-

  • “N, C” are favorable:

Weak interactions Li—N but easy oxidation

If O present, F or CnF2n+1 is required

stability domains
Stability Domains

Li metal

Fluorinated anions

Non fluorinated anions

h ckel anions
Hückel anions…

Aromaticity 4n + 2 «  » electrons

pKA = 10-60

pKA = 10-20

X = N, C-CN, CRF, S(O)RF

Gain of > 1 eV by resonance

See P. Johansson et alPhysical Chemistry Chemical Physics, volume 6, issue 5, (2004).

lidcta
LiDCTA

DCTA

Stable to 3.8 V (La Sapienza, KZ)inexpensive

Gives quite fluid ILs

slide9

Most Stable Lithium Imidazole Configurations

1.93 Å

1.87 Å

1.88 Å

1.92 Å

LiTDI

LiPDI

B3LYP/6-311+G(d)

Scheers et al. 2009

slide10

Gas Phase Ion Pair Dissociation Energies

Ion pair (g) Li+ (g) + Anion- (g)

LiTDI < LiPDI < LiDCTA < LiTFSI < LiPF6

MP2/6-31G(d)

LiTDI LiPDI LiDCTA LiTFSI LiPF6

Scheers et al. 2009

litdi 2 trifluoromethyl 4 5 dicyanoimidazole lithium salt
LiTDI (2-trifluoromethyl-4,5-dicyanoimidazole lithium salt)

- Easy, low‑demanding, inexpensive, one‑step, high yield syntheses;

- Salts are pure, stable in air atmosphere, non‑hygroscopic, stable up to 250°C, easy to handle;

conductivity in peo
Conductivity in PEO

SS / PEO20LiX / SS

cooling scan

LiDCTA

LiPDI

LiTDI

lihdi peo conductivity
LiHDI-PEO Conductivity

1:25 Ea=76.4 kJ∙mol-1 1:50 Ea=121.8 kJ∙mol-1

slide15

PEO20LiTDI

PEO20LiPDI

Hot-Pressing

PEO20LiTDI

PEO20LiPDI

PEO20LiBOB/ LiBF4

Hot-Pressing

PEO20LiDCTA

Hot-Pressing

PEO20LiCF3SO3+ ZrO2SA

Casting

slide16

Anodic stability

Li / PEO20LiX / Super P

LiDCTA

LiPDI

LiTDI

slide17

Interphase resistance - PEO

Li / PEO20LiX / Li

LiTDI

LiDCTA

LiPDI

slide18

Interphase resistance - PEO

Li / PEO20LiX / Li

LiPDIa

LiPDIb

LiTDIa

LiTDIb

LiDCTAa

LiDCTAb

rate capability peo
Rate capability (PEO)

% of capacity at C/20

rate capability peo21
Rate capability (PEO)

% of capacity at C/20

cycling limn 2 o 4 4 3 v ec dmc
Cycling LiMn2O4 4.3 V (EC-DMC)

Swagelok cell , Al plunger

new imidazole derived salts
New imidazole-derived salts
  • Easy, low‑demanding, inexpensive, one‑step, high yield syntheses;
  • Salts are pure, stable in air atmosphere, non‑hygroscopic, stable up to 250°C, easy to handle;
  • 20°C ionic conductivity exceeds:

10‑3 S∙cm-1 in PC, 10‑4 S∙cm‑1 in PEGDME500

10‑6 S∙cm‑1 in PEO (10‑4 S∙cm‑1 at 40°C)

6 mS∙cm‑1 in EC:DMC

  • T+ at ionic conductivity maximum reaches:

0.45 in PC, 0.40 in EC-DMC, 0.25 in PEGDME500 (but overall max 0.62);

  • Stable over time against Li;
  • Stable up to 4.4 V vs. Li against metallic lithium anode;
  • Stable up to 5.0 V vs. Li against aluminum;
  • Much smaller association rate than commercially available salts;
research team working on new salts
Research team working on new salts

Presentation of research team

working on new lithium salts:

Warsaw University of Technology:

- L. Niedzickiand W. Wieczorek – characterization of salts and low molecular weight polyether electrolytes

- J. Prejzner, P. Szczeciński, M. Bukowska - synthesis of new salts

- Z. Żukowska – spectroscopic studies

Universite de Picardie Jules Verne, Laboratoire de Reactivite et de Chimie des Solides

- S. Grugeon, S. Laruelle - characterization of solid polymeric electrolytes, studies of electrochemical stability and battery performance

- and M. Armand – development of new salt systems

Faculty of Chemistry, University of Rome, “ La Sapienza

- S. Panero, P. Reale and B. Scrosati, - characterization of solid polymeric electrolytes; conductivity, transference numbers and electrochemical stability

Department of Applied Physics, Chalmers University of Technology,

- J. Scheers, P. Johansson, P. Jacobsson – modeling and spectroscopic studies

slide43
For inquiries about buying LiTDI(lithium 4,5-dicyano-2-(trifluoromethyl)imidazolate)please contact:Leszek Niedzickiasalm@ch.pw.edu.pl