non lithium-ion batteries - argonne blogs...non lithium-ion batteries ... fig. xrd patens of lagp...

Yanli MIAO, Xueling WU, Jinpeng YU, Xingjiang LIU*

National Key Lab. of Power Sources,

Tianjin Institute of Power Sources, China

9th US-China EV & Batteries Workshop, 18-19, Aug. 2014, Seattle, USA

Non Lithium-ion Batteries

新型非锂离子电池体系

Tianjin Institute of Power Sources

Tianjin Institute of Power Sources (TIPS) is the

earliest founded and largest comprehensive institute

in China, specialized in technical research and

product development, manufacture and application

of chemical and physical power sources.

TIPS has developed over 40 series, 500 more

spices of new products and set its technical

advantage in solar cell, lithium battery, alkaline

rechargeable battery, and electronic controller.

It has also carried out transfer of some

technologies, of which, the biggest project is that

TIPS set up Tianjin Lishen Battery Ltd.

Brief Introduction of TIPS


Advanced Chemical

Power Sources.

Advanced Physical

Power Sources.

Evaluation &

Simulation

National Key Lab. of Power Sources

Novel ch

emical

pow

er sources

PE

MF

C &

RF

C

Non

-aqueo

us

electroch

emistry

Micro

pow

er

source sy

stem

Photo

voltaic

Tech

nolo

gy

Thin

film so

lar

cell

Material

evalu

ation

Com

puter

simulatio

n

Brief Introduction of NKLPS


Outline

Introduction

Effects of carbon/LAGP interlayer on

Li/S cell performance

SC & HC as anode material for SIB

Conclusion


Electric vehicles Energy storage applications

What’s the next generation battery for energy storage

applications and EVs?

Introduction

Li-S? Li-Air? SIB? MIB? FIB? RFB? or…


Reaction Mechanism of Li/S Cell


Fig. LAGP modified PP separator. (a) front view,

(b) side view.

Inte

nsi

ty (

a.u

.)

(012)

(134)

(315)

(137) (4

10)

(228)

AlPO4●

●

10 20 30 40 50 60

2 Theta / (degree)

(104)

(110)

(113)

(006)

(024)

(211)

(116)

(300)

(206)

(119)

(131)

(312)

PDF: 80-1924

LiGe2(PO4)3

Fig. XRD patens of LAGP glassy ceramic

electrolyte.

LAGP Modified Separator

Li PP LAGP S

LAGP modified Separator

Fig. Image of Li-S cell with LAGP

modified Separator


0 10 20 30 40 50400

500

600

700

800

900

1000

1100

1200

Sp

ecif

ic C

ap

acit

y (

mA

h g

-1)

Cycle Number

LAGP modified separator

normal PP separator

(a)

0 200 400 600 800 1000 1200

1.6

1.8

2.0

2.2

2.4

2.6

Po

ten

tia

l (V

vs.

Li/

Li+

)

Specific capacity (mAhg-1)

normal PP separator

LAGP modified separator

1st

(b)

Fig. Comparison on discharge characteristics

for Li-S cell with PP separator and LAGP

modified PP separator.

Fig. Comparison on Cycleability for Li-S cell

with PP separator and LAGP modified PP

separator.

Effects of LAGP Modified Separator


Elt. Line Intensity

(c/s)

Conc Units Error

2-sig

MDL

3-sig

C Ka 18.82 18.726 wt.% 1.085 1.006

O Ka 100.38 64.317 wt.% 1.328 .520

F Ka 6.59 12.020 wt.% 1.364 1.519

S Ka 24.17 4.937 wt.% .232 .177

100.000 wt.% Total

Elt. Line Intensity

(c/s)

Conc Units Error

2-sig

MDL

3-sig

C Ka 74.34 31.653 wt.% .783 .415

O Ka 157.78 59.974 wt.% .971 .269

F Ka 1.88 1.465 wt.% .413 .541

S Ka 86.13 6.908 wt.% .161 .092

With PP With LAGP-PP

SEM Image of Li Surface


0 20 40 60 80 100 120 140

0

200

400

600

800

1000

1200

Without carbon interlayer

With Super-P interlayer

With Actived Carbon interlayer

Cap

acit

y (

mA

h/g

)

Cycle

S: 70wt%

正极集流体金属锂负极硫正极

碳膜隔膜

Carbon Coated Separator

Fig. Image of Li-S cell with carbon

coated separator.

Fig. Comparison on cycleability for Li-S cell with

PP separator and carbon coated PP separator.


0 10 20 30 40 500

10

20

30

-ZIm

/Ω

ZRe

/Ω

With KB interlayer

With MWCNTs interlayer

With SP interlayer

With out interlayer

0 10 20 30 400

400

800

1200

1600

KB interlayer

MWCNTs interlayer

SP interlayer

Spec

ific

Cap

acit

y（

mA

h•g

-1）

Cycle Number

Carbon Coated Separator

0 200 400 600 800 1000

1.8

2.0

2.2

2.4

2.6

2.8

Cel

l p

ote

nti

al (

V)

Capacity (mAh/g)

Carbon interlayer is

helpful on improving

the capacity and

cycleability of Li-S cell


Na-ion Battery: SIB


Bottlenecks for SIB

Category Lithium Sodium

Cation radius(Å) 0.76 1.06

Atomic weight 6.9 g mol-1 23 g mol-1

EO (vs. Li/Li) 0 0.3V

Cost, Carbonates $5000/ton $150/ton

Capacity(mAh g-1), metal 3829 1165

Coordination preference Octahedral and tetrahedral Octahedral and prismatic

Radius:Na ion > Li ion

Graphite can't used as the anode material


Coal tar pitch/

Coal tar pitch

+30%wt H3PO4

（85%）

400℃，4h

0 MP

Pitch coke bulk

Cru

sh

Pich coke

grains

CSC/PSC

900℃，6h

Carbonization

Preparation of SC and PSC


Soft Carbon—SEM

CSC

PSC

Phosphorus doping can change the micro-structure of the soft carbon.


Soft Carbon-XRD

Sample 2θ002 /° 2θ100 /° d002 /A

CSC 25.736 44.132 3.4588

PSC 25.289 43.947 3.5188

20 40 60 80

Inte

nsi

ty a

.u.

2Theta deg.

CSC

PSC

The (002) diffraction peak of the CSC

became weaker after doping phosphorus.


Soft carbon—Raman

0

200

400

600

800

Inte

nsity

(cn

t)

800 1 000 1 200 1 400 1 600 1 800 2 000

Raman Shift (cm-1)

160

0.3

252

4.7

134

4.4

0

100

200

300

400

500

600

700

800

Inte

nsity

(cn

t)

800 1 000 1 200 1 400 1 600 1 800 2 000

Raman Shift (cm-1)

159

4.2

134

1.4

Sample Average

D/G (area)

Average

D/G (a)

Average

D (w)

Average

G (w)

D-band

(cm-1)

G-band

(cm-1)

CSC 1.137 0.708 102 71 1344.4 1600.3

PSC 1.163 0.757 100 71 1341.4 1594.2

CSC

PSC


SC—Electrochemical Performance

0 50 100 150 200 250 300 350 4000.0

0.5

1.0

1.5

2.0

Po

ten

tia

l(V

) v

s. N

a/N

a+

Specific Capacity(mAh/g)

CSC

PSC

5 10 15 20

0

50

100

150

200

250

0

10

20

30

40

50

60

70

80

90

100

110

Cou

lom

bic

eff

icie

ncy

(%)

Sp

ecif

ic C

ap

aci

ty(m

Ah

/g)v

.s.N

a/N

a+

Cycle Number

PSC

CSC

Fig. Cycle performance of the CSC &

PSC at the current density of 100 mA g-1

in 1M NaClO4 (EC:DMC=1:1)

Fig. The 1st charge/discharge curves of

the CSC & PSC at the current density of

100 mA g-1 in 1M NaClO4 (EC:DMC=1:1)


Hard Carbon—SEM & XRD

10 20 30 40 50 60 70 80 90

Inte

nsi

ty a

.u.

2Theta deg.


Fig. Cycle performance of the HC at

the current density of 100 mA g-1 in 1M

NaClO4 (EC:DMC=1:1)

5 10 15 20160

180

200

220

240

260

280

S

pecif

ic C

ap

acit

y(m

Ah

/g)

Cycle Number

0 50 100 150 200 250 300 3500.0

0.5

1.0

1.5

2.0

Po

ten

tia

l(V

)v.s

. N

a/N

a+

Specific Capacity(mAh/g)

Fig. The 1st charge/discharge curves of the

HC at the current density of 100 mA g-1 in

1M NaClO4(EC:DMC=1:1)

HC—Electrochemical Performance


Conclusion

Cycleability of Li-S has been improved using carbon

coated or LAGP modified separator.

Phosphorus doping can significantly improve the

electrochemical performance of SC in SIB. The PSC

delivered a high specific capacity of 251 mAh/g at the

1st cycle and a better cycle performance.

A low-cost material - bamboo based hard carbon

exhibited an excellent electrochemical activities for SIB.


Thank you for your attentions!

9th US-China EV & Batteries Workshop, 18-19, Aug. 2014, Seattle, USA

non lithium-ion batteries - argonne blogs...non lithium-ion batteries ... fig. xrd patens of lagp...

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