5
On the zinc side, the end products of a still-unknown reaction pathway require
the overall stoichiometry to follow
Zn OH
Zn OH
e at Vvs Zn
l
4
2
0 0
4
2
.
.
(6)
Zn OH
ZnO H O OH voltage independent
l
4
2
2
2
(7)
where in the failure mechanism is usually reported as “shape change” in which
the zinc balled up in isolated locations and refused to cycle.
The stringent economics of grid-scale energy storage became important during the
US Department of Energy’s ARPA-E GRIDS program of 2009–2013. In that program a pathway was discovered via Mn-Zn technology for battery system cost to be
reduced to nearly $100 per kWh and maintain long cycle life. This technology
employed a Mn cathode in which only 0.1–0.3 electrons cycle per Mn atom (EMD)
and only 0.1 electrons cycled per Zn atoms. Cycle life was 1500–4000 and costs were
below ~$200 per kWh energy storage [27, 28]. This Mn-Zn technology could replace
Pb-acid batteries and eliminate significant environmental pollution from lead. Also,
life cycle assessment finds the greenhouse gas emissions from Mn-Zn technology to
be better than Ni-Zn or lead-acid batteries if the Mn is cycled at more than 20% of the
first electron of MnO 2 [29]. Commercialization of such technology is under developTable 1 Performance comparison of the manganese electrodes from recent publications, where
n.r. denotes “non-reported” measurements in a publication
Reference
capacity per area
(mAh cm
−2
)
capacity per
mass
(mAh g
−1
)
capacity per
solids
a
(mAh g
−1 )
capacity per
volume
a
(mAh cm
−3
)
Cycle life
Wroblowa and
Gupta [106]
17
521
n.r.
n.r.
20
Kannan et al.
[107]
n.r.
~375
~187
n.r.
600
Raghuveer and
Manthiram
[108]
n.r.
210
147
n.r.
30
Ingale et al. [27] 5
31
15
50
4000
Hertzberg et al.
[109]
n.r.
~250
~125
~100
50
Hertzberg et al.
[110]
26
~425
~255
~200
60
Rus et al. [111] n.r.
225
147
~110
30
Pan et al. [23]
1.4
280
196
~140
5000
Yadav et al. [14] 29
617
370
315
3500
Zhang et al. [24] 2.5
225
~200
~110
2000
a “Total solids” and “total volume” are for the manganese electrode and pore-electrolyte only, and
do not include the mass or volume of the Zn anode electrode
b
Also see Kordesch et al. [25]
Aqueous Mn-Zn and Ni-Zn Batteries for Sustainable Energy Storage
On the zinc side, the end products of a still-unknown reaction pathway require
the overall stoichiometry to follow
Zn OH
Zn OH
e at Vvs Zn
l
4
2
0 0
4
2
.
.
(6)
Zn OH
ZnO H O OH voltage independent
l
4
2
2
2
(7)
where in the failure mechanism is usually reported as “shape change” in which
the zinc balled up in isolated locations and refused to cycle.
The stringent economics of grid-scale energy storage became important during the
US Department of Energy’s ARPA-E GRIDS program of 2009–2013. In that program a pathway was discovered via Mn-Zn technology for battery system cost to be
reduced to nearly $100 per kWh and maintain long cycle life. This technology
employed a Mn cathode in which only 0.1–0.3 electrons cycle per Mn atom (EMD)
and only 0.1 electrons cycled per Zn atoms. Cycle life was 1500–4000 and costs were
below ~$200 per kWh energy storage [27, 28]. This Mn-Zn technology could replace
Pb-acid batteries and eliminate significant environmental pollution from lead. Also,
life cycle assessment finds the greenhouse gas emissions from Mn-Zn technology to
be better than Ni-Zn or lead-acid batteries if the Mn is cycled at more than 20% of the
first electron of MnO 2 [29]. Commercialization of such technology is under developTable 1 Performance comparison of the manganese electrodes from recent publications, where
n.r. denotes “non-reported” measurements in a publication
Reference
capacity per area
(mAh cm
−2
)
capacity per
mass
(mAh g
−1
)
capacity per
solids
a
(mAh g
−1 )
capacity per
volume
a
(mAh cm
−3
)
Cycle life
Wroblowa and
Gupta [106]
17
521
n.r.
n.r.
20
Kannan et al.
[107]
n.r.
~375
~187
n.r.
600
Raghuveer and
Manthiram
[108]
n.r.
210
147
n.r.
30
Ingale et al. [27] 5
31
15
50
4000
Hertzberg et al.
[109]
n.r.
~250
~125
~100
50
Hertzberg et al.
[110]
26
~425
~255
~200
60
Rus et al. [111] n.r.
225
147
~110
30
Pan et al. [23]
1.4
280
196
~140
5000
Yadav et al. [14] 29
617
370
315
3500
Zhang et al. [24] 2.5
225
~200
~110
2000
a “Total solids” and “total volume” are for the manganese electrode and pore-electrolyte only, and
do not include the mass or volume of the Zn anode electrode
b
Also see Kordesch et al. [25]
Aqueous Mn-Zn and Ni-Zn Batteries for Sustainable Energy Storage