Spiro-ammonium imide salts as electrolytes for lithium batteries

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Spiro-ammonium imide salts as electrolytes for lithium batteries

Spiro-ammonium Imide salts as electrolytes for

Lithium batteries

Yaser Abu-Lebdeh, Emily Austin, Isobel Davidson

Institute for Chemical Process and Environmental Technology

National Research Council of Canada, Ottawa, CANADA

Organic salts: Ionic liquids

and Plastic crystals

•

Ionic liquids



Good thermal (volatile,

Non-flammable) properties.



chemical and electrochemical

properties.

•

Plastic crystalline phases



Below melting: sustain high ionic

conductivity,



plastic solid material

•

Lithium batteries

Spiro-ammonium imide

salts

Strong base

DSC of neat salts

SP-56

SP-66

SP-55

XRD as a function of T

Regular Crystal

Monoclinic

C-centered

Regular Crystal

Monoclinic

primitive

Plastic Crystal I

Plastic Crystal II

TFSI¯

Br¯

PF

₆

¯

• Salts synthesized as

Br

-• Exchanged for

TFSI

-

_and

PF

₆

-• Melting Point:

TFSI

_<

_PF

<

Br

-• PC phases:

Br

_{: One transition at 50}

_C

PF

_{: No transitions}

Effect of anion type on

SP-56

Effect of salt content on

SP-56

Conductivity of the salts

•

SP-56 showed the highest

conductivities

-40

-20

0

20

40

60

80

100

120

140

-8

-6

-4

-2

0

-8

-6

-4

-2

-5

-4

-3

-2

T(

C)

Neat SP salts

L

o

g

(C

o

n

d

u

ct

ivi

ty

/

S/

cm)

SP salts+5mol% LiTFSI

SP:EC (1:) 1M LiTFSI

Electrochemical stability of

SP-56

-5.E-07

0.E+00

5.E-07

-4

-3

-2

-1

0

1

2

3

4

E/ V vs. Li

+

/Li

I/ A

Molten neat SP-56

T = 125 °C

1mM SP-56 solution in Propylene carbonate

Lithium battery performance

•

SP-56 and SP-55 mixtures

with EC (1:1) showed high

capacities with good

retention.

•

SP-66 showed the lowest

capacity

0

20

40

60

80

100

0

50

100

0

50

100

150

0

50

100

150

Cycle Number

SP-56

Sp

e

ci

fic

D

isch

a

rg

e

C

a

p

a

ci

ty(mAh

/g

)

SP-55

SP-66

Summary

• Spiro-ammonium imide salts exhibit:

 high melting points ( >100

o

_C)

 Plastic crystalline phases

 More than one regular and one plastic crystalline phases

 low cathodic stability

• Mixing the salts with conventional solvents (1:1 w.t.) gave

Acknowledgements

• Dr. Pamela Whitfield

• Danny Min