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SAND2012-7857C

Carbon-Enhanced VRLA
Batteries
September 27, 2012
David G. Enos, Summer R. Ferreira
Sandia National Laboratories
Rod Shane
East Penn Manufacturing

Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed
Martin Corporation, for the U.S. Department of Energys National Nuclear Security Administration under contract DE-AC04-94AL85000.

Carbon Enhanced VRLA Batteries


Pb-Acid batteries are inexpensive, but have a poor cycle life
when subjected to high-rate, partial state of charge (HRPSoC)
operating conditions.
The addition of some carbon materials have been
demonstrated to dramatically improve the cycle life, enabling
use of VRLA batteries under HRPSoC conditions.
Some additions enhance, others detract not clear why.

The overall goal of this work is to quantitatively define the


role that carbon plays in extending the cycle life of a VRLA
battery.

The Advanced VRLA Battery

Recently, there have been several manners in which carbon has been added to a PbAcid battery
The work presented here deals with the Advanced Battery, where carbon has
been added to the negative active material

Advanced VRLA Battery


PbO2

Pb

Lead-Acid
Cell

Ultrabattery

PbO2

Carbon

Asymmetric
Supercapacitor

PbO2

PbO2

Separator

Pb + C

Activities in FY12
As reported in FY11, initial efforts focused on characterizing
the basic materials of construction of the carbon modified
batteries, and their impact on battery plate morphology and
basic functional characteristics. Initial cycle testing was also
completed.
In FY12, longer term cycle testing was completed (10k cycles
and then continuing to battery death)
Cycle life as a function of battery type
Changes in battery performance as a function of cycle life
Morphological changes in the negative plate material as a function of
cycle life
4

Cycle Life Under HRPSoC Conditions


Batteries cycled until the remaining capacity was below 80%
of the initial capacity
4 Battery types were evaluated
Control, Carbon Black + Graphite, Acetylene Black, Activated Carbon
80000

ALABC PSoC cycle test


50% SoC
1 Minute charge/discharge
at 2C rate
10s pause between cycles
2.45V high cutoff
1.75V low cutoff

Cycles to Failure

60000

40000

With Recovery Charges


Control: 61116
CB+G: 103923+
AB: 85271+
AC: 79675

20000

Control

CB+G

AB

AC

HPPC Performance
300

250

200

CT 28 - Uncycled
CT 30 - Uncycled
CT 28 - 10k Cycles
CT 30 - 10k Cycles

150

100

350

Regen

Pulse Power Capability (W)

Pulse Power Capability (W)

Control

350

20

40

60

80

300

250

200

CT 28 - Uncycled
CT 30 - Uncycled
CT 28 - 10k Cycles
CT 30 - 10k Cycles

150

100

100

Discharge

20

Depth of Discharge

Pulse Power Capability (W)

Pulse Power Capability (W)

Activated Carbon

200

150

20

40

60

Depth of Discharge

80

350

Regen

AC 14 - Uncycled
AC 25 - Uncycled
AC 14 - 10k Cycles
AC 25 - 10k Cycles

250

100

60

100

Depth of Discharge

350

300

40

80

100

Discharge

300

250

200

AC 14 - Uncycled
AC 25 - Uncycled
AC 14 - 10k Cycles
AC 25 - 10k Cycles

150

100

20

40

60

Depth of Discharge

80

100

HPPC Performance

350

Regen

300

Pulse Power Capability (W)

Pulse Power Capability (W)

Acetylene Black

350

250

200

150

Discharge

300

250

200

150
AB 30 - Uncycled
AB 30 - 10k Cycles

AB 30 - Uncycled
AB 30 - 10k Cycles
100

20

40

60

80

100

100

20

Pulse Power Capability (W)

Pulse Power Capability (W)

Carbon Black + Graphite

200

150

20

40

60

Depth of Discharge

80

350

Regen

CB+G 20 - Uncycled
CB+G 30 - Uncycled
CB+G 20 - 10k Cycles
CB+G 30 - 10k Cycles

250

100

60

100

Depth of Discharge

Depth of Discharge
350

300

40

80

100

Discharge

300

250

200

CB+G 20 - Uncycled
CB+G 30 - Uncycled
CB+G 20 - 10k Cycles
CB+G 30 - 10k Cycles

150

100

20

40

60

Depth of Discharge

80

100

Plate Morphology
1

Cross sectional analysis (SEM)


Cathodoluminescence
BET surface area
Hg porosimetry

Surface Area as a Function of Cycles


BET surface area measurements (in m2/g) for all four battery types as a
function of HRPSoC Cycles
Recovered battery was cycled to death with periodic recovery charges

BET Surface Area (m /g)

2.0
CB+G
1.5

1.0

0.5

AB

Control

0.0

Uncycled

1k Cycles

10k Cycles

Death

Recovered

Uncycled

1k Cycles

10k Cycles

Death

Recovered

Control

0.40

0.33

0.36

0.35

0.47

CB+G

1.74

1.57

1.71

1.32

1.47

AB

0.94

0.89

0.85

0.95

0.95

AC

9.30

6.46

8.45

4.21

Structural Evolution: 1k Cycles


Control

Activated Carbon

Acetylene Black

Carbon Black + Graphite

100 microns

10

Differences at 1k Cycles

Begin to see development of a dendritic structure in the near surface regions (top 50-100
microns) of carbon containing cells
Fissures visible in carbon containing cells, most prominent in CB+G

Carbon Black + Graphite

Activated Carbon

Acetylene Black

Carbon Black + Graphite

Acetylene Black

11

Structural Evolution: 10k Cycles


Control

Activated Carbon

Acetylene Black

Carbon Black + Graphite

100 microns

250 microns

12

Differences at 10k Cycles

In control and AC containing cells, sulfation took place along the surface of interior voids as
well as the exterior surface
In carbon black containing cells, appeared similar to 1k, though with a more pronounced
dendritic structure

Control

Acetylene Black

Control

13

Differences at End of Life

In most cases, just more of what was observed at 10k cycles


Large pores/voids in carbon containing plates (esp. carbon black) become more prominent
Sulfation ranged from almost complete/through thickness to almost none visible in some of
the carbon black containing cells

Carbon Black + Graphite

Acetylene Black

Activated Carbon

Acetylene Black

Activated Carbon

14

Summary/Conclusions
Batteries of all 4 chemistries have been subjected to HRPSoC
cycling and evaluated as a function of cycle life
Carbon additions increase the active area within the negative
active material and are clearly electrochemically active, but
surface area isnt everything
All of the carbon modified batteries exhibited an increased
cycle life. Suggests production methodology may be of
comparable importance to the nature of the carbon additive.
Carbon black additions provided most significant
improvement, but also result in internal damage to the plate
Failure mechanism for the conditions evaluated here may be
tied to positive plate degradation
15

Future Tasks
Evaluation of the positive plates from select batteries to
establish if that is dominating failure
Hg Porosimetry of NAM as a function of cycle life
Wrap up of experimental program by December 2012.

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Contact Information
PI: David Enos (Sandia National Labs), dgenos@sandia.gov
Co-Authors
Summer Ferreira (Sandia National Labs), srferre@sandia.gov
Rod Shane (East Penn Manufacturing), rshane@dekabatteries.com

The authors gratefully acknowledge the support of Dr. Imre Gyuk and the
Department of Energys Office of Electricity Delivery and Energy Reliability

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