A New Vanadium Redox Flow Battery

Using Mixed Acid Electrolytes

Liyu Li, Soowhan Kim, Wei Wang, M. Vijayakumar, Zimin Nie, Baowei
Chen, Jianlu Zhang, Jianzhi Hu, Gordon Graff, Jun Liu, Gary Yang*
Funded by the Energy Storage Systems Program of the U.S. Department Of Energy through Pacific
Northwest National Laboratories

November 2, 2010
US DOE Energy Storage Systems (ESS) Program Review
Washington DC

Redox Flow Battery (RFB)

A redox flow battery is a promising technology for large scale energy

storage .

Potential RFB Systems

+
2+
V3+/V2+ All V Redox Flow BatteryVO2 /VO

H2 evolution

Zn2+/Zn
Cr3+/Cr2+
Ti3+/Ti2+ S/S2-

-1.0

-0.5

Br2/Br-

VO2+/V3+
Cu2+/Cu+

TiOH /Ti

0.0

3+

3+

2+

Fe /Fe

0.5

Mn3+/Mn2+
MnO
/MnO2
4
Cl /Cl
-

BrCl2-/Br3+

O2 evolution

Ce4+/Ce3+

Cr5+/Cr4+
Co3+/Co2+

1.0

1.5

2.0

Standard potential (V) of redox couples

The use of vanadium in both the anolyte and catholyte effectively

eliminate the cross-contamination between the electrolytes through
the ion-exchange membrane.

Challenges for All Vanadium Sulfate RFB

V specie
V2+

V3+

V4+ (VO2+)

V5+ (VO2+)

Vn+, M
2
2
2
2
2
2
2
2
2
2
2
2.2
1.8

H+, M
6
6
6
4
4
4
6
6
6
8
8
7.8
8.4

SO42-, M
5
5
5
5
5
5
5
5
5
5
5
5
5

Temp, oC
-5
25
40
-5
25
40
-5
25
40
-5
25
40
40

Time for p.p.

419 hr
Stable (>30 d)
Stable (>30 d)
634 hr
Stable (>30 d)
Stable (>30 d)
18 hr
95 hr
Stable (>30 d)
Stable (>30 d)
Stable (>30 d)
95 hr
358 hr

Low energy density: Vn+ concentration <1.7M, decided by the low

solubility of V4+ at low temperatures and the poor stability of V5+ at high
temperatures.
Limited operation temperature window: 10 to 40oC, requiring active
electrolytes temperature management during hot/cold weathers.

Stability of Vn+ Cations in HCl Solution

Vn+ specie
V2+

V3+

V4+ (VO2+)

V5+ (VO2+)

Vn+, M
2.3
2.3
2.3
1.5
1.8
2.3
2.3
2.3
2.3
2.3
2.3
2.3
2.3
2.3

H+, M
5.4
5.4
5.4
3.0
3.0
3.1
3.1
3.1
5.4
5.4
5.4
7.7
7.7
7.7

Cl-, M
10
10
10
7.5
8.4
10
10
10
10
10
10
10
10
10

T, oC
-5
25
40
-5
-5
-5
25
40
-5
25
40
-5
25
40

Time for precipitation

Stable (>10 d)
Stable (>10 d)
Stable (>10 d)
Stable (>10 d)
124 hr
96 hr
Stable (>10 d)
Stable (>10 d)
Stable (>10 d)
Stable (>10 d)
Stable (>10 d)
Stable (>10 d)
Stable (>10 d)
Stable (>10 d)

Cl- anions can effectively stabilize V5+, V4+, and V2+.

It is likely that high concentration of V2+, V3+, V4+, and V5+ cations can be
stabilized in a mixed sulfate and chloride electrolyte solution.

Vn+ Stability in SO42Cl- Mixed Solutions

Vn+
specie

Vn+, M

T, oC

Time for
precipitation

Vn+
specie

Vn+, M

T, oC

Time for
precipitation

V2+

-5

Stable (>10 d)

-5

Stable (>10 d)

2.5

-5

Stable (>10 d)

V4+
(VO2+)

2.5

-5

Stable (>10 d)

2.5

25

Stable (>10 d)

2.5

25

Stable (>10 d)

2.5

40

Stable (>10 d)

2.5

40

Stable (>10 d)

40

Stable (>10 d)

40

Stable (>10 d)

-5

192 hr (8 d)

-5

Stable (>10 d)

2.5

-5

Stable (>10 d)

2.5

-5

Stable (>10 d)

2.5

25

Stable (>10 d)

2.5

25

Stable (>10 d)

2.5

40

Stable (>10 d)

2.5

40

Stable (>10 d)

40

Stable (>10 d)

40

Stable (>10 d)

2.7 V5+
0.3 V4+

50

Stable (>10 d)

2.7 V5+
0.3 V4+

60

Stable (>10 d)

V3+

The overall stability of vanadium is

decided by V3+ at low temperatures.

V5+
(VO2+)

SO42-/Cl- mixtures can effectively stabilize >2.5M V5+, V4+, V3+ and V2+.
Much broad operation temperature window (-5 to 60 oC) can be achieved using
SO42-/Cl- mixed electrolytes.

Solution Chemistry of the Mixed ElectrolytesDFT Study

Cl

O
O
O

O
O

In sulfate solution, V5+ exists as [VO2(H2O)3]+, which tends to convert to V2O5-3H2O

precipitation via:
[VO2(H2O)3]+

VO(OH)3 + [H3O]+

2VO(OH)3

V2O5-3H2O

Solution Chemistry of the Mixed ElectrolytesNMR Study

51V

in mixed acid

51V

in sulfuric
acid
51V

in VOCl3
standard

35Cl

35Cl

in mixed acid

in VOCl3
35Cl

in HCl

Temperature Dependence of VO2Cl(H2O)2 Formation

80

-540
Chemical Shift-Sulfuric Acid
Chemical Shift Mixed Acid
Line Width Sulfuric Acid
Line Width Mixed Acid

51

70

-550
50

40

-555

30
-560

V Line Width (k Hz)

60

51

V Chemical Shift (ppm)

-545

20
-565
10

-570

0
-30

-20

-10

10

20

30

40

50

60

Temperature, oC

VO2Cl(H2O)2 complex starts to form in the mixed solutions when

temperatures reaching ~20oC.

Solution Chemistry of the Mixed ElectrolytesDFT and Stability Studies

Same V2+, V3+ and V4+ -containing structures was predicted
in both electrolyte solutions: [V(H2O)6]2+, [V(H2O)6]3+ and
[VO(H2O)5]2+.
According to SEM-EDS, and XRD analysis, in the mixed
systems, the stability of V4+ is controlled by the solubility of
VOSO4, the stability of V3+ is controlled by the solubility of
V2(SO4)3 and VOCl, the stability of V2+ is controlled by the
solubility of VSO4.
The improvement of stability of V2+, V3+, and V4+ in the mixed
system over the current sulfate systems is due to the
decrease of SO42- concentration in the solutions.

Electrochemical Properties of Mixed Solutions

0.3

V4+

V5+

Current Density (A/cm2)

0.2
V2+

V3+

0.1
0.0
-0.1
V4+

-0.2

V5+

2.5 M V4+ + 2.5 M SO2-4 + 6 M Cl-

-0.3
2+

V
-0.4
-0.8

3+

V
-0.4

1.5 M V4+ +
0.0

0.4

5 M SO2-4
0.8

Potential (V vs. SHE)

No chlorine gas evolution.

1.2

1.6

Electrode and Cell Reactions (T<10oC)

Cathode:
Anode:
Cell:

VO2+ + H2O e
V3+ + e
VO2+ + H2O + V3+

Charge
Discharge

VO2+ + 2H+

E = 1.00V

Charge
Discharge

V2+

E=-0.25V

Charge
Discharge

VO2+ + 2H+ + V2+

E=1.25V

Electrode and Cell Reactions (T>10oC)

Cathode:
Anode:
Cell:

VO2+ + Cl- + H2O e

V3+ + e
VO2+ + Cl- + H2O + V3+

Charge
Discharge
Charge
Discharge
Charge
Discharge

VO2Cl + 2H+
V2+
VO2Cl + 2H+ + V2+

Cell Testing and RFB Evaluation

- Cell and reservoirs are inside the environmental chamber.

- Circulating pump is out side of the chamber.
- Pressure monitoring.

Cell Performance at Ambient Temperature

100
95

1.8
Charging

90

1.4

Voltage (V)

Efficiency (%)

1.6

85

Discharging

1.2
1.0
0.8

80
75
70

0.6

Coulomb
Energy
Voltage

10

15

20

25

30

35

10

20

30

40

50

60

70

80

Capacity / Charging Capacity (Ah%)

40

45

50

55

Cycle Number
Stable performance with 88% energy efficiency at 50 mA.cm-2

90

100

Cell Performance at Varied Temperatures

100

95

Coulombic Efficiency
Voltage Efficiency
Energy Efficiency

Efficiency, %

90

85

80

50oC

40oC

75

5oC

0oC

70
0

10

20

30

40

50

60

70

80

90

Cycle number

A VFB with 2.5 M V mixed acid electrolyte can be operated under a

broad temperature range of 0 to 50 oC.
Redox reactions are temperature dependent.
No noticeable gas evolution over 25 days.

Cell Performance at Varied Current Densities

Discharge
Current,
(mA.cm-2)

Columbic
Efficiency

Energy Density
(Wh.L-1)
Mixed

sulfate

Mixed

Energy
Efficiency
sulfate

Mixed

sulfate

2.5MV

3MV

1.6MV

2.5MV

3MV

1.6MV

2.5MV

3MV

1.6MV

100

36.2

39.5

22.3

0.95

0.95

0.94

0.81

0.76

0.83

75

37.5

40.8

22.4

0.96

0.96

0.94

0.84

0.81

0.85

50

38.5

41.8

22.6

0.96

0.97

0.94

0.87

0.85

0.87

25

39.2

43.1

22.6

0.96

0.97

0.94

0.90

0.89

0.88

Cell operation conditions: 10 cm2 flow cell, Charged to 1.7V by 50 mA/cm2 current.

The VRBs using mixed sulafte-chloride electrolytes

were able to deliver 70 to 80% more energy than the
sulfate system, while still being highly efficient.

Summary
A new vanadium redox flow battery with a significant improvement
over the current technology was developed.

This battery utilizes sulfate-chloride mixed electrolytes, which are

capable of dissolving 2.5 M vanadium, representing about 70%
increase in energy density over the current sulfate system.

More importantly, the new electrolyte remains stable over a wide

temperature range of -5 to 60oC, potentially eliminating the need of
energy-consuming solution temperature management.

Battery tests indicated no concern of chlorine gas evolution during the

battery operation.

Further Work
Optimize the mixed electrolyte for further improvement in energy
density and stability.
Demonstrate a 2.0 kWh (0.3 kW) bench-top prototype FRB with the
newly developed mixed electrolyte.
Build up strong collaborations with industry, university, and other
national laboratory partners.
Prepare for larger systems demonstration within 2-3 years.

Acknowledgements
Financial support :
1.

DOE Office of Electricity Delivery and Energy Reliability

Energy Storage Program (Manager: Dr. Imre Gyuk)

2.

PNNL LDRD program for NMR and DFT-related work.

The NMR work was carried out at the Environmental and Molecular
Science Laboratory, a national scientific user facility sponsored by
the DOEs Office of Biological and Environmental Research (BER).