Battery Technologies For Large-Scale Stationary Energy Storage

CH02CH23-Soloveichik ARI 9 May 2011 7:35
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Grigorii L. Soloveichik
General Electric Global Research, Niskayuna, New York 12309; email: [email protected]
Annu. Rev. Chem. Biomol. Eng. 2011. 2:503–27 Keywords

First published online as a Review in Advance on electrochemistry, secondary battery, fuel cell
March 23, 2011
The Annual Review of Chemical and Biomolecular Abstract

Engineering is online at chembioeng.annualreviews.org
In recent years, with the deployment of renewable energy sources, advances
This article’s doi: in electrified transportation, and development in smart grids, the markets
10.1146/annurev-chembioeng-061010-114116
for large-scale stationary energy storage have grown rapidly. Electrochemi-
Copyright c 2011 by Annual Reviews. cal energy storage methods are strong candidate solutions due to their high
All rights reserved
energy density, flexibility, and scalability. This review provides an overview
1947-5438/11/0715-0503$20.00 of mature and emerging technologies for secondary and redox flow batter-
ies. New developments in the chemistry of secondary and flow batteries as
well as regenerative fuel cells are also considered. Advantages and disad-
vantages of current and prospective electrochemical energy storage options
are discussed. The most promising technologies in the short term are high-
temperature sodium batteries with β -alumina electrolyte, lithium-ion bat-
teries, and flow batteries. Regenerative fuel cells and lithium metal batteries
with high energy density require further research to become practical.
503
INTRODUCTION
The very nature of electricity generation, distribution, and usage requires a method to balance
supply and demand. The simplest way to solve this problem is to store energy in some form when
the demand is low and to return it to the electric grid when the demand is high. Implementation
of large-scale electric energy storage (EES) will avoid the building of excessive energy generation
capacity to meet short-term peak demand for electricity. Based on an analysis by the U.S. De-
partment of Energy (DOE), EES should be approximately 1.7% of new generation capacity to
minimize the effect of the system’s variability (1). In addition, stationary energy storage is a key
enabler for the smart grid concept and for wide implementation of intermittent renewable energy
sources such as solar and wind.
Several different types of energy storage can be used for large-scale stationary applications,
namely mechanical, electrical, chemical, and electrochemical (Table 1). The Electricity Storage
Association (ESA; http://www.electricitystorage.org) identified twelve specific energy storage

technologies based on these four types of energy storage. Examples of mechanical energy storage
systems are flywheels, pumped-storage hydroelectricity (also known as pumped hydro), and com-
pressed air energy storage (CAES). Electrical energy storage systems are based on supercapacitors
and superconductive electromagnetic storage. An example of chemical storage is the energy stored
in the form of hydrogen or other chemicals. Secondary (rechargeable) and redox flow batteries
(in which a solution of one or more electroactive species flows through an electrochemical cell)
as well as regenerative fuel cells, which can be operated both in direct and reverse (consuming
electricity and producing energy rich chemicals), are examples of electrochemical energy storage.
Table 1 Energy storage technologies for stationary applications

Typical Discharge Storage capacity Life time, Efficiency,
Technology power, MW time cost, $ kWh−1 cycle/years % Drawbacks
Flywheels 1 <5 min 1,000–2,000 100,000/>10 >90 Cost, power
applications
Compressed air 2,700 2–10 h 90–200 >5,000/>10 50 Site specific, storage
energy storage and transmission
(CAES) cost
Pumped-storage 4,000 (up to 4–12 h 75–100 >10,000/>25 75–80 Site specific,
hydroelectricity 22,500) transmission cost,
(pumped hydro) environment
Supercapacitors 0.25 <1 min 500–3,000 500,000/20 >90 Explosion hazard, low
energy density, cost
Superconductive 10a 1–30 min 2,000–10,000 100,000/20 97 High capital cost,
electromagnetic cryogenics
storage (SMES)
Chemical (hydrogen) 10a >5 h 13 40–50 Low density storage,
high cost, safety
Secondary batteries 0.5–1 1–8 h 250–3,500 1,000– 75–80 High cost, low cycle
(lead-acid, Li-ion, 4,500/7–20 life
NAS)
Flow battery 12 10 h 150–2,500 500–2,000/10 70 Low energy density
(vanadium redox
battery)
a
Projected.
504 Soloveichik
Several reviews comparing different energy storage options for stationary applications have been
published recently (2–9).
This review gives an overview of the past ten years of progress in electrochemical storage
methods at different stages of development, from mature technologies to emerging technologies
to new chemistries.
APPLICATIONS
Utility-scale applications of energy storage are both energy related, such as peak shaving (0.1–
10 MW), load leveling (1–100 MW), and energy arbitrage (50–500 MW), and power related, such
as frequency and voltage regulation (spinning reserve), power quality regulation, and bridging
power (1–30 MW) (10). The necessary response times for energy storage vary from seconds in
power quality applications to hours for energy management applications. In addition, it is antici-
pated that increased market penetration of intermittent renewable energy sources (solar and wind)
will require their smooth integration into the power grid and enable advanced smart grid opera-
tions. Commercial electrochemical energy storage systems have 100 kW to 20 MW of power and
from 50 kWh to 40 MWh of energy capacity (7). For telecommunications (telecom) applications,
EES needs several hours of operation to balance electricity supply outages. In contrast, for uninter-
ruptible power supply (UPS) systems, which are usually smaller than 500 kW, an EES system must
supply very high currents over short times (minutes) until the backup system responds. Safety, relia-
bility, and durability are the most important criteria for stationary applications. Multi-MW systems
must be built as turnkey systems, whereas smaller systems may be developed as modular ones.
Grid-scale stationary EES system revenues are expected to grow from $1.5 billion in 2010 to
$25.3 billion over the next 10 years, according to a new report from Pike Research (11). Pike
predicts that the most significant growth will be in CAES, Li-ion batteries, and flow batteries.
Although only lead-acid batteries currently meet cost targets for EES, it is anticipated that flow
batteries and high-temperature sodium batteries will increase their market share (12).
SECONDARY BATTERIES
A secondary battery, also known as rechargeable or storage battery, is a group of electrically
connected electrochemical cells based on reversible electrochemical reactions. During the charge
process, the anode active material is oxidized to generate electrons, and the cathode active material
is reduced, which consumes electrons flowing through the external circuit. The charge balance
is provided by ion flow between electrodes through an ion-conducting electrolyte. During the
discharge process, these processes run backward. In secondary batteries, at least one of the active
materials is present in a solid state.
Mature Technologies
Several battery technologies have been in use long enough to be considered mature technologies.
These batteries, such as lead-acid, nickel-cadmium, and nickel-metal hydride, are produced by
multiple manufacturers in different sizes for different stationary applications.
Lead-acid batteries. The lead-acid secondary battery was invented in 1859 by Gaston Planté
and is based on simple chemistry (Equation 1):
Pb + PbO2 + 2 H2 SO4 ⇔ 2 PbSO4 + 2 H2 O E0 = 2.04 V. 1.
www.annualreviews.org • Batteries for Stationary Energy Storage 505

The mature lead-acid battery technology is widely used in many mobile and stationary applications.
For stationary applications, the valve-regulated lead-acid (VRLA) battery is the battery of choice
but, to lesser extent, traditional flooded batteries are also used. The VLRA battery, also known as
the sealed lead-acid battery, uses the recombination of the oxygen evolved at the positive plates
with the hydrogen evolved on the negative plates, thus generating water and eliminating the
requirement for water addition in the traditional lead-acid battery.
Some recent improvements in lead-acid battery technology were aimed at automotive ap-
plications but could be used in stationary batteries as well. For example, it was found that the
solid lead anode could be partially replaced with carbon to convert it into a battery-supercapacitor
hybrid named the UltraBattery (13–16). In addition, Kelley & Votoupal (17) proposed a corrosion-
resistant current collector made of high–surface area carbon foam. This technology was used by
FireFly Energy to develop lighter batteries with higher energy density, but the company went
out of business in March 2010. In other research, coating lead plates with a thin layer of graphite
prevented sulfation of the negative plate (18).

Pure lead electrodes are not sufficiently mechanically strong that they can be made big enough
for large-scale applications, and they cannot tolerate high currents. Lead-antimony alloys display
better corrosion resistance and can be made into taller plate designs, but they are not suitable for
standby applications because of antimony poisoning. Addition of selenium and other elements to
lead-antimony alloys overcomes this deficiency (19).
Recent advances in lead-acid batteries are associated with development of new gel electrolytes
and separators (20, 21). For example, in VRLA batteries a novel polysiloxane-based gel electrolyte
with an open 3D network structure showed higher discharge capacity and better temperature
tolerance than the traditional fumed-silica gel electrolyte (22).
Both flooded and valve-regulated lead-acid cells are used in large-scale EES installations
for UPS, peak shaving, and voltage and frequency control (500 kW–20 MW/500 kWh–
40 MWh). Key manufacturers are Exide Technologies (http://www.exide.com), C&D
Battery (http://www.cdpowercom.com), Hagen Batterie AG (http://www.hagen-batterie.de),
and Storage Battery Systems (http://www.sbsbattery.com).
Nickel-cadmium batteries. Alkaline NiCd batteries are well developed for consumer applica-
tions but also used for large-scale applications. Compared to lead-acid batteries, they have lower
cell voltage, as shown in Equation 2,
Cd + 2 NiOOH + 2 H2 O ⇔ Cd(OH)2 + 2 Ni(OH)2 E0 = 1.29 V, 2.
but higher energy density and longer cycle life. However, other batteries are replacing NiCd bat-
teries in all markets owing to their substantial negative temperature coefficient that limits charging,
voltage depression (memory effect), high cost, and environmental concerns (3). Key manufacturers
of NiCd batteries are Storage Battery Systems and Saft Batteries (http://www.saftbatteries.com).
The latter installed the biggest NiCd battery for a stationary application (a spinning reserve and
power stabilization system) in Alaska (a 40-MW unit built with 13,760 cells).
Nickel metal-hydride batteries. Although they have been on the market for more than 20 years
as portable and then traction batteries, secondary nickel-metal hydride (NiMH) batteries have
only recently been considered for stationary applications such as UPS and telecom (23). NiMH
batteries have higher specific energy and better heat tolerance (up to 70◦ C), which are impor-
tant for telecom applications, plus they do not exhibit the memory effect that NiCd batter-
ies do. Ovonic Battery Company (http://www.energyconversiondevices.com) (23) advertises
506 Soloveichik
a 560-kW battery for UPS, telecom, and solar applications with one-third of the lead-acid battery
footprint.
The cell chemistry of NiMH batteries is described by Equation 3,
MH + NiOOH ⇔ M + Ni(OH)2 E0 = 1.35 V. 3.
M in this equation is an intermetallic compound of composition AB5 , where A is a combination of

La, Ce, Pr, and Nd, and B is a combination of Ni, Co, Mn, Al, or AB2 , where A is a combination
of Ti, V, and Zr, and B is a combination of Ni, Co, Cr, Mn, Al, and Sn. The partial substitution
of Ni by Al or Mn in the La(Ni,M)5 phase yields increased discharge capacity, and addition of
Co greatly improves the cycle life (24). Optimization of alloy composition and an increase in
the structural disorder allowed increased specific energy and stability to the alkaline environment
(25). It is necessary to balance the effects of different additives; for example, addition of Fe to AB2
compositions decreases specific power but increases cycle life, whereas addition of Sn decreases
storage capacity but reduces the cost (26).
The electrolyte is usually aqueous 30% potassium hydroxide with added LiOH to improve the
cathode charging efficiency. Gelation of the electrolyte with polyethylene oxide (PEO) improves
reversibility and electric efficiency up to 80% (27).
Sodium-sulfur batteries. Sodium-sulfur (NAS) batteries are considered one of the most promis-
ing candidates for stationary EES. They are used for load leveling and peak shaving as well as spin-
ning and standby reserves. They are also proposed for smoothing the output from intermittent
renewable energy sources. The battery consists of a molten sulfur cathode and molten sodium
anode separated by Na+ -conducting ceramics, usually β -alumina (β -Al2 O3 ). During discharge
sodium is oxidized and sulfur is reduced to form sodium polysulfides Na2 Sx (x = 3–5) in the
cathode compartment, as shown in Equation 4:
2Na + x S ⇔ Na2 Sx E0 = 2.07 − 1.78 V. 4.
At the battery working temperature (300–350◦ C) all electroactive materials are in liquid form.
To compensate for the low conductivity of sodium polysulfides in sulfur, carbon felt is used as a
current collector, thus increasing the battery cost. Sodium is stored inside a tubular container made
of the primary solid electrolyte that is surrounded by the cathode (the central sodium geometry).
The NAS battery has zero self-discharge and high electrical efficiency. Due to high working
temperatures, the heat losses may be substantial enough during standby or floating charge (ohmic
heating when the battery is charged or discharged usually compensates for the heat losses) to be
practically equivalent to a self-discharge. It should be noted that the reaction between molten
sodium and sulfur is highly exothermic, thus increasing the fire hazard, and, in the absence of
electronics to detect and shunt around failed cells, the broken cell turns off the whole string
because sulfur and sodium sulfides are insulators.
The current chemistry-related research work on the NAS battery mainly targets corrosion-
resistant sealing and containment materials and a low-resistance β -alumina separator with a
dense and fine-grained microstructure (28). Addition of yttria-stabilized zirconia (YSZ) or ceria
(cerium dioxide) using a novel vapor phase process that involves exposure of sintered mixture
of α-alumina and YSZ to soda vapor at ∼1,450◦ C to convert α-alumina into β -alumina yields
fine-grain ceramics (29, 30). The use of ζ -aluminates, M2 O. 5Al2 O3 (M = Na, Li), as precursors
has allowed the production of ceramic tubes with low resistivity (31).
A novel room-temperature NAS battery with a solid Na anode, solid sulfur or metal sul-
fide cathode, liquid glyme or carbonate electrolyte, and a Celgard separator has been proposed

(32, 33). The initial discharge capacity (489 mAh/g sulfur) was close to that of the high-temperature
NAS battery but rapidly decreased with cycling (32).
NGK Insulators Ltd. of Japan (http://www.ngk.co.jp) is currently the only supplier of NAS
batteries. The size of NAS installations coupled with renewable sources varies from 1 to 65 MW
(6 to 150 MWh). Recently, Pacific Gas & Electric Company announced it would install a 4-MW
NAS system with a 28-MWh storage capacity, which would be the biggest battery-based EES in
California (http://www.energy.ca.gov).
Emerging Technologies
Some battery technologies, such as Li-ion, are well developed for the consumer market but only
recently began to penetrate into the stationary EES market. Experimental data in the field are
limited, and therefore these technologies are considered as emerging ones.

Lithium-ion batteries. Lithium-ion batteries use lithium intercalation in both the positive
(lithium metal oxides) and negative (usually graphitic carbon) materials in an organic electrolyte,
as shown in Equation 5:
Lix C + Li1−x MO2 ⇔ LiMO2 + C E0 = 3.3 − 4.2 V. 5.

Lithiated carbon is protected from reaction with the electrolyte by a solid-electrolyte interphase
(SEI) (34). The advantages of Li-ion batteries include high cell voltage and energy density, low
self-discharge, and excellent rate capabilities. Major shortcomings are high cost, low temperature
tolerance, and the need for protective circuitry to prevent cell degradation and thermal runaway.
Lithium polymer batteries use the same chemistry but a solid polymer as the electrolyte; they
provide improved safety and more flexible cell design but at the expense of increased cost and
decreased scalability.
Li-ion technology (35) is currently a favorite for consumer and mobile applications and received
a boost with the development of plug-in and electric cars. Major breakthroughs in this technology
were the use of LiFePO4 as cathode material (36), especially in the doped nanosized form (37);
a safer anode material, Li4 Ti5 O12 (38); and advanced electrolytes (39). Recent advances in this
technology have translated into increasing numbers of EES installations (40). For example, A123
Systems (http://www.a123systems.com) has built a Li-ion grid storage battery for AES Energy
Storage (12-MW installation in Chile and 20 MW in New York for frequency regulation) and
for Southern California Edison. Altair Nanotechnologies (http://www.altairnano.com), working
with AES Energy Storage, has deployed a 1-MW, 250-kWh Li-ion battery system using lithium ti-
tanate capable of full charging and discharging in 15 minutes (4C rate) for grid regulation. Valence
Technology (http://www.valence.com) will install EES based on batteries with a LiFeMgPO4
cathode for the first smart grid solar-powered residential development in Texas. Saft Batteries has
developed large Li-ion batteries with maximum power 150 W kg−1 at two hour (C/2) discharge
rate, maximum energy 65 Wh kg−1 at 15 minutes discharge (4C rate), low self-discharge (less than
5% per year), and a faradic efficiency close to 100% for telecom and stationary applications. Ener1
Battery Company (http://www.ener1.com) is already building five 1-MW Li-ion battery grid
storage trailers for Oregon’s Portland General Electric. Similarly, Sony and Lithium Technology
Corporation have announced LiFePO4 -based packs for integration with household photovoltaic
systems (http://www.gaia-akku.com).
Sodium metal chloride batteries. The sodium metal chloride battery was invented more than
25 years ago within the ZEolite Battery Research Africa (ZEBRA) project by Coetzer’s group in
508 Soloveichik
South Africa (41). The chemistry is based on the electrochemical reaction of molten sodium in
the anode with transition metal chloride in the cathode (discharge) and the reverse reaction of the
transition metal with NaCl (charge) (Equation 6):
MCl2 + 2 Na ⇔ M + 2 NaCl E0 = 2.58 V(M = Ni), 2.35 V(M = Fe). 6.
As in the case of a NAS battery, the anode and cathode are separated by the Na+ -conductive β -
Al2 O3 ceramic membrane. Ionic conductivity in the cathode is provided by a secondary electrolyte,
molten sodium aluminum tetrachloride (NaAlCl4 ). Many transition metals (42, 43, 30) have been
tested as active cathode materials; nickel and iron (Equation 6) are the most practical. Current
commercial ZEBRA batteries contain a mixture of nickel and iron, which is added to improve
the battery power (44, 45). The cathode contains an excess of nickel powder, which serves as
an extended current collector and reduces cell resistance. The downside of this approach is low
utilization (25–30% or even lower in NiFe cells) of expensive nickel.

This simple chemistry, however, cannot provide long cycle life. Morphology changes have
been proposed as the mechanism of capacity loss during cycling (46). Addition of elemental sulfur
(1–5%) to the dense cathodes yielded significant improvement in the capacity retention (46). The
reduction of S, which was found in the cycled cathode by the X-ray diffraction in the form of
Ni3 S2 , prevented grain growth of the Ni particles in the cathode and promoted formation of a
modified high–surface area, active metallic phase that was stable for hundreds of cycles (47). The
β -alumina electrolyte tube was stable in contact with the S-doped Ni cathode electrolyte for more
than 2,000 cycles. Combination of sulfur with NaI and NaBr additives reduced the area-specific
impedance of the nickel chloride electrode (48).
Recent research on sodium metal chloride batteries has focused on improvement of the cathode
composition to increase energy and power. Optimization of the concentration of FeS (instead of
elemental sulfur) and NaI cathode additives yielded an energy increase from 94 Wh kg−1 to
120 Wh kg−1 in commercial batteries (45). It was suggested that NaI generates nickel iodide that
serves as a charge transfer mediator (49).
Sodium metal chloride batteries are assembled in the discharged state, with the cathode con-
sisting of nickel and iron, NaCl, and small amounts of additives to improve performance, and
then impregnated under vacuum with molten NaAlCl4 . In contrast to NAS batteries, the pre-
ferred design for ZEBRA batteries has a central cathode geometry. Instead of round β -alumina
tubes, cruciform (cloverleaf )-shaped tubes are used to increase the battery power by increas-
ing the surface area of the secondary electrolyte and the reaction front (50, 51). EaglePicher
(http://www.eaglepicher.com), in partnership with the Pacific Northwest National Laboratory
and funded by Advanced Research Projects Agency–Energy, is developing a battery with a planar
configuration of thinner electrodes that may provide higher power. Sodium is generated in the
anode compartment during the first charge. This feature makes sodium metal chloride batteries
safer to manufacture than NAS batteries because no elemental sodium is involved in cell assembly.
In addition, the most common failure mode of molten sodium batteries—a broken β -alumina
separator tube—in this case yields a relatively mildly exothermic reaction between Na and the
electrolyte (Equation 7):
NaAlCl4 + 3 Na → Al + 4 NaCl. 7.
The aluminum metal generated in this reaction shorts the cell, which keeps the whole string
operational, as opposed to what occurs in NAS batteries (51). In addition, sodium metal chloride
batteries are much more tolerant to freeze-thaw cycles than NAS batteries owing to smaller
differences in thermal expansion coefficients between the ceramic separator and other battery
components.

The cells are packaged in a double-walled vacuum-insulated metal box equipped with an air
cooler and an ohmic heater controlled by the battery management system (BMS) to keep the cell
temperature constant at approximately 300◦ C (45, 52). As in the case of NAS batteries, the heat
losses should be compensated and can be considered as equivalent to self-discharge.
ZEBRA batteries have been developed primarily for mobile applications. MES-DEA of
Switzerland (now FZ Sonick SA; http://www.cebi.com/cebi) currently produces batteries
for mobile applications (e.g., electric buses) with a production capacity of 90 MWh annu-
ally. Additionally, systems for vehicle-to-grid (V2G), telecom, and distributed energy gen-
eration coupled with renewable sources applications are planned (53, 45). Recently, GE
(http://www.geenergystorage.com) announced plans to build an improved sodium metal chlo-
ride DurathonTM battery plant with the capability of generating 900 MWh of energy per year to
serve mainly UPS, telecom, utility, and heavy-duty transportation applications. Xylene Power Ltd.
(http://www.xylenepower.com) is developing a sodium-sulfur-nickel chloride (Na-S-NiCl2 )

electrochemical cell that the company claims will combine the best properties of NAS and sodium–
nickel chloride batteries. This 18-kWh battery is reported to have a lifetime of approximately 2,000
cycles and a specific energy density of approximately 100 Wh kg−1 (812 Wh kg−1 theory).
New Chemistries
To improve the safety of Li-ion batteries, batteries with aqueous electrolytes (LiNO3 , Li2 SO4 )
have been proposed (54). The cell voltage is limited by water, and the cycle life of such batteries
is short. However, it was recently shown that exclusion of oxygen and pH adjustment in the
LiTi2 (PO4 )3 /Li2 SO4 /LiFePO4 cell allowed good capacity retention (10% capacity loss over 1,000
cycles) (55).
A major research direction aims to replace materials with limited capacity, in particular carbon
as an anode material and metal oxides as cathode materials, with potentially much higher capacity
materials: lithium metal and transition metal fluorides, respectively. Badway et al. (56) provided the
first practical demonstration that FeF3 as a nanocomposite with carbon may be reversibly cycled
at 235 mAh g−1 to FeF2 and at 600 mAh g−1 (770 mAh g−1 theory) to metal iron, which is much
higher than the capacity of LiCoO2 (150 mAh g−1 ). Other promising cathode materials are TiF3 ,
VF3 , CuF2 , BiF3 , CoF2 , and NiF2 (57, 58). Metal fluorides (as well as sulfides and nitrides) that
transfer two or three electrons overcome the one-electron limitation of the complex metal oxides.
Unfortunately, these materials are insulators and react with lithium to form new phases (LiF and
metal or mixed phases). In contrast, transition metal oxides that form intercalation compounds
have essentially the same crystal structures as their parent mixed oxides. Suggestions to make Li
transport reversible include decreasing the particle size and optimizing the cathode composite
(which includes a conductive additive) microstructure as well as using material doping.
When used as an anode material, lithium metal has approximately 10 times more capacity than
the lithium-carbon intercalated materials currently used in Li-ion batteries. Lithium reacts with
oxygen (Equations 8 and 9) and sulfur (Equation 10) as follows:
Li + 1/4O2 + 1/2H2 O ⇔ LiOH(in aqueous electrolyte) E0 = 3.44 V, 8.
2 Li + O2 ⇔ Li2 O2 (in non-aqueous electrolyte) E0 = 2.96 V, 9.
2 Li + S ⇔ Li2 S E0 = 2.2 V. 10.

Such couples have the highest theoretical energy density among rechargeable batteries (3,860,
3,500, and 2,460 Wh kg−1 , respectively). However, poor Li reversibility that requires a large
510 Soloveichik
excess of the metal (three- to fourfold) as well as safety issues (dendrite formation and the inherent
thermodynamic instability of Li metal in organic solvents) limits its use in batteries. Li-air batteries
also suffer from poor reversibility of oxygen reduction (59). Nevertheless, the potential increase
in energy density, especially in combination with energy-dense sulfur and oxygen cathodes, has
stimulated further research on protection and cycling reversibility of lithium metal in such batteries
with different cathodes.
In the case of aqueous electrolyte [usually basic but an acidic electrolyte also could be used
(60)], reaction products are soluble and do not block the membrane. Solid-state electrolytes
are considered promising for lithium metal batteries to provide safety and long cycle life. A
protective layer for Li called LISICON [LiM2 (PO4 )3 ] has been patented (61) and used by
PolyPlus (http://www.polyplus.com) and SION Power (http://www.sionpower.com) in
rechargeable Li-air and Li-S batteries. An all-solid-state Li-S battery with a glass ceramic lithium
thiophosphate electrolyte also exhibited excellent capacity retention (62). Furthermore, Seeo
(http://www.seeo.com) is developing an all-solid lithium metal battery with LiFePO4 or sul-

fur cathodes (63) and a novel PEO-based solid polymer electrolyte invented at Lawrence Berkeley
National Laboratory (64, 65).
The Japan National Institute of Advanced Industrial Science and Technology (AIST)
(http://www.aist.go.jp) is developing a rechargeable lithium-air battery that uses two types of
electrolytes. An organic electrolyte conducts Li+ ions from/to metal lithium in the anode, which
is separated from the cathode by a solid ionic conductor (e.g., LISICON). LiOH formed in the
cathode by oxygen reduction is soluble in aqueous alkaline electrolyte. Inexpensive Mn3 O4 on
carbon is used as the oxygen reduction catalyst in alkaline media (66, 67). A separate electrode
in the cathode is used for battery charging. An all-solid Li-air battery with a layered membrane
made from glass-ceramic and polymer-ceramic materials and a solid-state composite air cathode
demonstrated a potential energy density of 1,000 Wh kg−1 (68).
A Li foil anode protected by a solid-state Li+ -conducting membrane in combination with an
organic electrolyte was used for a novel Ni-Li battery with the common Ni(OH)2 cathode in an
alkaline electrolyte (69). This battery has high cell voltage (3.49 V) and energy density (935 Wh
kg−1 theoretical and >400 Wh kg−1 projected practical) (69).
The reversibility of a Li-S battery is much better than that of a Li-air battery. The chemistry of a
Li-S battery is more complex than that described by Equation 10 and includes equilibria between
several lithium polysulfides with different solubility and redox potentials (70–74). Polysulfides
react with lithium to cause substantial self-discharge, which may be reduced by selection of mixed
solvents for the electrolyte (75). A practical energy density of 350 Wh kg−1 for this battery has been
demonstrated (76). In addition, silicon nanowires have been used as a low-expansion matrix for
lithium electroplating in a lithium-sulfur battery. A battery with a Li2 S-impregnated mesoporous
carbon cathode and a Si nanowire anode has low resistance and high theoretical energy density
(1,550 Wh kg−1 ) but, unfortunately, poor capacity retention (77).
To address the problem of lithium instability in organic electrolytes, Arizona State University,
in collaboration with Fluidic Energy, Inc. (http://fluidicenergy.com/), is developing a new class
of metal-air batteries using ionic liquids as electrolytes. It was claimed that these batteries would
have lower cost and a target energy density more than six times higher than that of available
Li-ion batteries (78). A battery with a molten alkali bis(trifluoromethylsulfonyl) amide mixture
as an electrolyte with a Li metal anode and LiFePO4 cathode at 100–180◦ C demonstrated good
capacity retention (79).
Cairns et al. (80) introduced the concept of an all-liquid membraneless battery in which reaction
products are dissolved in a fused salt electrolyte. In such high-temperature battery liquid, lithium
was used as the anode, a lithium halide eutectic as the electrolyte, and bismuth, selenium, tellurium

(80), or P4 S10 (81) as the cathode. Sadoway et al. (82) have introduced a new all-liquid battery for
stationary applications based on Equation 11,
3 Mg + 2 Sb ⇔ Mg3 Sb2 E0 = 0.42 V, 11.
and consists of three layers of liquids—magnesium, sodium sulfide, and antimony—that are natu-
rally separated by gravity owing to significant density differences. The battery works at 700◦ C, and
the reaction product, Mg3 Sb2 , is dissolved in the sulfide electrolyte during the battery discharge.
The simple design, absence of a separator between anode and cathode, and high current density
make this battery attractive for large-scale applications. However, low cell voltage and extremely
high temperature of operations (which means expensive materials of construction and heat losses)
are clear disadvantages.
FLOW BATTERIES
The redox flow battery concept has been around since the 1970s but is still a less developed
technology compared with lead-acid and NiCd secondary batteries (4). Only two types of flow
batteries (all-vanadium and polysulfide-bromine) have reached commercialization on a large scale.
A flow battery consists of two usually aqueous electrolytes that contain two redox couples and are
pumped through an electrochemical cell in which chemical energy is converted to electricity. The
two electrolytes are stored in separate tanks and separated in the electrochemical cell by an ion
exchange (cation or anion) membrane (Figure 1). Ideally, the membrane should be impermeable
to redox-active species but allow the transport of cations (usually protons or Na+ ) or anions, and
sometimes water, to maintain electroneutrality and electrolyte balance. There are seven redox
couples suitable for flow batteries (V/V, S/Br2 , Zn/Br2 , V/Br2 , Fe/Cr, Ce/Zn, and Pb/Pb) that
are in different stages of pilot testing (4). Two other redox couples Zn/Cl2 and H2 /Br2 are at the
laboratory testing stage.
The most important feature of redox flow batteries is the potential to separate the energy
capacity and the power. The battery energy capacity is determined by the size of the electrolyte
tanks, whereas the battery power is defined by the size of the electrochemical cell. This allows
for a flexible layout, which is attractive for stationary applications. Additional advantages of redox
flow batteries include the ability to fully charge and discharge without damaging the cell, the long
Bipolar
flow cell stack
Positive Negative
electrolyte
tank + – electrolyte
tank
Pump Pump
Figure 1
Redox flow battery concept.
512 Soloveichik
life of the electrolytes (basically, the battery lifetime is defined by the lifetime of the ion-selective
membrane), flexible operation, modular design, and moderate cost. For instance, the projected life
of vanadium redox batteries is 8 years, after which the membrane could be replaced to extend the
lifetime (83). In addition, thermal management of flow batteries is easier than that of other types
of batteries owing to the flow of liquid electrolytes. The main drawbacks of flow batteries are the
low energy density, which is limited by solubility of redox-active species; the cross-contamination;
and the longevity of ion-selective membranes. Because a stack of electrochemical cells with bipolar
electrodes is typically used, the shunt current may substantially decrease the battery efficiency.
This negative effect could be reduced by increasing the manifold length of the cell ports, but this
increases energy losses for pumping, so trade-offs should be made. Furthermore, the plumbing,
pumping, and connections in flow batteries are complex and prone to leakage, which increases
maintenance cost.
Mature Technologies
Several redox flow battery technologies have been tested in the field long enough to collect data
on their reliability and efficiency. As a result, the initial concept of storing energy in big electrolyte
tanks has been changed to a modular design with a much smaller scale for a single unit.
Vanadium redox flow battery. The concept of vanadium-vanadium, also known as the all-
vanadium redox battery (VRB), was suggested in 1984 at the University of New South Wales,
Australia (83). The battery uses the VV /VIV and VIII /VII redox couples in sulfuric acid as the
positive and negative half-cell electrolytes, respectively (84). The cell chemistry is represented by
the total Equation 12:
VO+ +
2 +2 H + V
2+
⇔ VO2+ + H2 O + V 3+ E0 = 1.26 V. 12.
The initial electrolyte is prepared as a mixture of 1 M VIII and VIV by chemical reduction or
electrolytic dissolution of V2 O5 in H2 SO4 . To balance electroneutrality, protons should move
between cathode and anode via a proton exchange membrane.
The VRB can be recharged both electrochemically and mechanically by replacing spent solu-
tions with fresh ones. In the discharged state, the positive and negative electrolytes are essentially
the same, which prevents migration of ions between anolyte and catholyte. Ion migration in the
charged state causes a self-discharge that may reach 3% per day. However, this is not fatal for the
battery because it can be recharged back to the full capacity. Turning off the pumps effectively
reduced the self-discharge. Additionally, much lower self-discharge was found for the proton ex-
change membranes modified with polyethyleneimine (85), polypyrrole (86), or alternating layers
of a polycation and polyanion (87). A novel fluoropolymer-based amphoteric ion exchange mem-
brane and sulfonated poly(fluorenyl ether ketone) membrane exhibited lower vanadium crossover
and higher efficiency than Nafion R
membranes (88, 89). Hybrid-structure membranes based on
a sulfonated poly(fluorenyl ether ketone) ionomer with embedded silica demonstrated enhanced
proton selectivity in a VRB (90). Furthermore, addition of a conductive material to the elec-
trolyte decreased the cell resistance and increased power (91). According to a recent study, the
net energy storage efficiency is higher and the environmental impact is substantially lower for the
vanadium-vanadium battery than for the lead-acid battery (92).
The major suppliers of vanadium redox batteries are VRB Power Systems, Inc. (now Prudent
Energy, China; http://www.pdenergy.com) and Sumitomo Electric Industries (SEI). VRB Power
built a 250-kW, 2-MWh prototype system for PacifiCorp in Utah and several systems from 100 kW
to 4 MW for peak shaving, UPS, and renewables in Japan. SEI installed a 450-kW/1-MWh,

2-h VRB load-leveling demonstration system and a 3-MW UPS system in Japan (93). Ashlawn
Energy will install a 1 MW/8 MWh VRB in Ohio under the DOE’s Smart Grid program using
VFuel Pty Ltd. (http://www.vfuel.com.au) technology. In addition, Cellennium Co. (Thailand;
http://www.vanadiumbattery.com) is developing a 50-kW VRB made of horizontal bipolar flow
cells arranged in a vertical pile that greatly reduces shunt current.
Polysulfide-bromine flow battery. The chemistry of the polysulfide-bromine (PSB) flow bat-
tery is based on the redox reaction of sodium polysufides and the couple Br− /Br3 − , as shown in
Equation 13:
2 Na2 S2 + NaBr3 ⇔ Na2 S4 + 3 NaBr E0 = 1.36 V 13.
(94). The open circuit voltage depends on the concentration of active species and varies from 1.7 to
1.5 V. Ideally, only Na+ cations pass through a cation-selective membrane, e.g., Nafion R
. Due to
the higher solubility of electroactive species, PSB has a higher energy density (30 W h kg−1 ) than
other flow batteries. In one study, replacing a carbon current collector in the negative electrode
with nickel foam increased the efficiency of a PSB up to 77% (95). One of the challenges for PSB
batteries is maintaining the water balance to avoid dilution of one of the electrolytes. The use
of a buffer chamber could alleviate this problem (96). Other challenges are cross-contamination,
deposition of insoluble sulfur species on the membrane, and gas (H2 S, Br2 ) evolution.
Regenesys successfully tested a 1-MW prototype and had ambitious plans to build 12-MW,
120-MWh plants in Little Barford, UK, and in Columbus, Mississippi. However, a new owner,
German utility company RWE, canceled these projects in 2003. The PSB technology has been
acquired by VRB Power (now Prudent Energy).
Emerging Technologies
Redox flow batteries reviewed here vary from rather old to recently introduced. However, they
all are built at a relatively small scale and have not had enough time in the field to be considered
mature.
Zinc-bromine and zinc-chlorine flow batteries. The zinc-bromine flow battery (ZBB) con-
sists of a zinc anode and a bromine cathode separated by a microporous separator. An aqueous
solution of zinc bromide, which is the battery discharge product, is circulated through the two
compartments of the cell from two separate tanks. Bromine is stored adsorbed on porous media
or in the form of a complex with quaternary ammonium cations that is in equilibrium with an
aqueous bromine-containing phase (97). The reaction chemistry is:
Zn + Br−
3 ⇔ ZnBr2 + Br
−
E0 = 1.85 V. 14.
The battery uses an inexpensive porous diaphragm to separate anolyte and catholyte. Because the
electrode kinetics of a Zn/Zn2+ couple is much faster than that of a Br2 /Br− couple, high–surface
area carbon electrodes are used on the cathode side.
The major drawbacks of ZBB are the high cost of electrodes, zinc dendrite formation during
charge, low energy efficiency, and poor cycle life (4). Nevertheless, due to its high energy density
(75–85 Wh kg−1 ), insignificant electrode polarization, and low cost, ZBB has been considered for
load leveling applications.
ZBB Energy Corp. (http://www.zbbenergy.com) sells ZESS POWRTM modules with up to
250 kW power and up to 400 kWh storage capacity as well as systems built from up to 20 modules
with 8,000 kWh storage capacity total. Recently ZBB Energy Corp. and SunPower announced
514 Soloveichik
the pairing of a 500-kWh system with photovoltaic solar for a commercial building application.
Premium Power (http://www.premiumpower.com) builds the modular PowerBlock R
150 and
TransFlow 2000 utility-grade energy management systems, which use the zinc-bromide Zinc-
Flow R
technology and provides 100 kW or 500 kW of uninterrupted power and 150 kWh or
2.8 MWh of energy storage capacity, respectively. RedFlow (http://www.redflow.com.au) mar-
kets a modular 200-kW/400-kWh zinc-bromine flow battery mostly for telecom and solar applica-
tions. Primus Power (http://www.primuspower.com) participates in a project to commercialize
a 25-MW/75-MWh system in California as part of DOE’s Smart Grid Demonstration Program.
The zinc-chlorine flow battery has similar features and chemistry (Equation 15):
Zn + Cl2 ⇔ ZnCl2 E0 = 2.02 V. 15.
It uses liquefied chlorine and a NaCl electrolyte and has higher open circuit voltage than the
bromine analog (98).
Cerium-zinc flow battery. The recently suggested cerium-zinc flow battery forms a solid during
charge (Equation 16),
2 Ce(CH3 SO3 )4 + Zn ⇔ 2 Ce(CH3 SO3 )3 + Zn(CH3 SO3 )2 E0 = 2.48 V, 16.
similar to the zinc-bromine battery (99). Both anode and cathode compartments include methane
sulfonic acid (MSA) as an electrolyte, so both cerium and zinc are present in solution as salts
with the MSA anion. Only protons pass through the proton exchange membrane (e.g., Nafion R
)
during charge and discharge, and their concentration is high enough to dissolve dendrites formed
from the electrodes. To prevent hydrogen evolution, the hydrogen overpotential was increased
by addition of small amounts of indium or tin (99). Remarkably, the battery is not sensitive to
cross-contamination, which may even be beneficial (100).
Plurion (http://www.plurionsystems.com) is developing a 250-kW modular cerium-zinc sys-
tem for UPS and renewables made of four 65-kW batteries.
Iron-chromium flow battery. The iron-chromium flow battery was invented by Thaller (101)
and has the chemistry
Cr2+ + Fe3+ ⇔ Cr3+ + Fe2+ E0 = 1.18 V. 17.
The cell was later improved by NASA in the 1980s (102, 103) and at the University of Alicante in
the 1990s (104–106). Two one-electron redox couples (FeII /FeIII and CrII /CrIII ) in hydrochloric
acid are used as the positive and negative reactants. The ion-selective membrane should allow
only protons and chloride anions to pass but in reality cannot prevent cross-contamination.
The open circuit voltage changes with the charge state because of the dominance of different
hydrated complexes of CrIII at different stages (107). The slow chromium redox kinetics called for
the development of redox catalysts such as bismuth or bismuth-lead on carbon (108). Alternatively,
addition of ethylenediaminetetraacetic acid (EDTA) to the chromium electrolyte stabilizes CrV ,
which makes an all-chromium battery possible, but the kinetics of the anodic reaction is slow
(109).
Deeya Energy (http://www.deeyaenergy.com) commercializes the iron-chromium flow bat-
tery. The product, Energy Storage Platform 24 KTM , is a module capable of delivering 24 kWh
day−1 . The company claims that due to improved performance, cost, and life (10,000 cycles) the
system cost is approximately three times less expensive than lead-acid batteries.

New Chemistries
The high cost of vanadium redox flow batteries has stimulated research on a vanadium-bromine
battery, which uses vanadium only in the negative half-cell and a bromine/bromide couple in the
positive half-cell of the battery, as shown in Equation 18:
2 V 2+ + Br2 ⇔ 2 V 3+ + 2 Br− E0 = 1.32 V 18.
(110). This approach reduces the battery cost by approximately 40% and almost doubles the
energy density (up to 50 Wh kg−1 ) owing to the higher solubility of bromide. Another possible
couple is chromium-bromine, which has a theoretical energy density of 57 Wh kg−1 (111). A
cerium-vanadium couple demonstrated a higher open circuit voltage of 1.87 V with a coulombic
efficiency of 87% (112).

Pletcher et al. (113–120) recently proposed a new soluble lead-acid flow battery. The electrode
reactions are the same as in the classic lead-acid battery (Equation 1) and have been studied in
different electrolytes (4), but the high solubility of PbII in methanesulfonic acid allows it to be
carried in a flowing solution. Because both charge products, Pb and PbO2 , are insoluble, and the
soluble discharge product Pb(MSA)2 is common for both electrodes, the cell can be run in the
undivided mode. The voltage during discharge is approximately 1.55 V, and the energy efficiency
is 65% (113). It is possible to deposit thick layers of PbO2 , but its reduction is difficult. Additives
such as sodium lignin sulfonate give uniform deposits without dendrites (116). However, the
current density of this battery is limited because of the high overpotential for the PbO2 deposition
and oxygen evolution (117).
Another undivided flow battery employing porous flow through electrodes and Ru(acac)3
(acac = acetylacetonate) and Fe(bpy)3 (ClO4 )2 (bpy = bipyridyl) in acetonitrile has been sug-
gested (90), but low concentrations of redox active species make it impractical despite the cell
design simplicity.
Uranium β-diketone complexes in polar aprotic solvents were proposed as excellent active
materials in an all-uranium redox flow battery with UVI /UV solution as the positive electrolyte
and UIV /UIII solution as the negative electrolyte (121). The concentrations of uranium solutions
may be as high as 0.8 M and the open circuit cell voltage 1 V for acetylacetone and higher for
ligands with greater basicity (121). Tetraketones form even stronger complexes with uranium and
are better suited as active materials (122).
Several electroactive couples for redox flow batteries have been suggested, one of which is a
MnIII /MnII redox couple for the cathodic electroactive material (123). Complexes of iron with
triethanolamine, EDTA, or citrate in combination with bromine were used in a flow battery
and exhibited an open circuit voltage of nearly 2.0 V at full charge and an energy efficiency of
approximately 70% (124, 125). Complexing cerium with diethylenetriaminepentaacetate improves
the electrode kinetics of the CeIV /CeIII couple for the positive electrolyte (126).
In another example, a novel hybrid single-flow Zn/NiOOH battery demonstrated a high energy
efficiency of 86% over 1,000 cycles. A highly concentrated ZnO solution in aqueous KOH was
used as the electrolyte, and the positive electrode was the nickel oxide used for secondary alkaline
batteries. At battery charging, Ni(OH)2 is oxidized to NiOOH and zincate ions are reduced to
zinc, which is electroplated onto the anode; no membrane is required (127). Another new single-
flow acid battery, a Cu-PbO2 battery with H2 SO4 -CuSO4 electrolyte, has been proposed (128).
Only one electrolyte is pumped through the battery during charge and discharge; no membrane
is needed. Preliminary tests showed energy efficiency of 83% during 450 cycles at a discharge
voltage of 1.29 V (128).
516 Soloveichik
REGENERATIVE FUEL CELLS

A regenerative fuel cell (RFC) can operate both as a fuel cell (discharge mode) and as an electrolyzer
(charge mode). Only hydrogen proton exchange membrane (PEM) fuel cells can work in both di-
rections. During charge the RFC generates hydrogen and oxygen that are stored in storage tanks,
and during discharge it electrochemically oxidizes hydrogen to generate power (129). The elec-
trolyzer and the fuel cell may be separate units or integrated in a single stack (unitized RFC). The
theoretical specific energy of the hydrogen/oxygen couple is 16,470 Wh kg−1 . Current RFC sys-
tems have demonstrated an overall specific energy density from 400 to 1,000 Wh kg−1 , which is still
several times higher than that of any secondary battery. Therefore, regenerative H2 /O2 fuel cells
have potentially the highest specific energy densities among known energy storage systems (130).
GE (131) proposed a rechargeable fuel cell combining a metal hydride electrode with the air
electrode. Hydrogen produced by water electrolysis is stored in the anode during charging and
then consumed during discharge to generate power. The theoretical specific energy density of a
rechargeable fuel cell with an anode containing LaNi5 H6 or MgH2 can reach 458 and 1,900 Wh
kg−1 , respectively. The main disadvantages of such systems are electrode deterioration during the
oxygen evolution reaction and alkaline electrolyte poisoning by CO2 . To prevent this, a second
cathode (132) and a scrubber (133) were added to the system, which reduced the overall energy
density.
Adding gas diffusion electrodes to a common NiMH battery and supplying hydrogen to the
anode and oxygen to the cathode yields a combination of a fuel cell and a secondary battery (134).
Small amounts of MnO2 in the Ni(OH)2 cathode convert it into the catalytically active oxygen
electrode of the fuel cell. The system can be used as a secondary battery if hydrogen and oxygen
are not supplied.
Another way to avoid the oxygen reduction problem is to replace O2 with chlorine or
bromine. The H2 /Br2 couple has a lower cell voltage than the H2 /O2 couple (0.555 V ver-
sus 1.229 V) but much higher efficiency in the fuel cell mode (135, 136). EnStorage (Israel;
http://www.enstorageinc.com) is developing EES systems based on regenerative H2 /Br2 fuel
cells having significantly higher efficiency (∼90%) than H2 /O2 fuel cells (∼40%) (137). Recently,
Lawrence Berkeley National Laboratory (http://www.lbl.gov) announced plans to develop a
hydrogen-bromine system for grid applications in cooperation with DuPont, Bosch, 3M, and
Proton Energy.
To overcome the problems of slow kinetics and high overpotential for the oxygen reduction
reaction (ORR), several attempts to use hydrogen peroxide instead of oxygen have been made. A
novel, though more complicated, pathway for EES using a combination of an electrolyzer and a
fuel cell based on the two-electron reduction of oxygen has been suggested (138). Energy is stored
in the form of aqueous H2 O2 produced by electrolysis and is released by electrolytic decomposition
of H2 O2 to H2 and O2 , which are directed to a PEM fuel cell. The energy density of aqueous
H2 O2 in this case is 136 Wh kg−1 , which is higher than that of common flow batteries, but the
overall efficiency is lower (35%) (138).
Hydrogen storage and transportation is energy inefficient and expensive. Therefore, several
approaches have been used to avoid handling of hazardous hydrogen gas. A new NaBH4 /H2 O2
all-liquid fuel cell with an OH− -ion-conducting anion exchange membrane has a much higher
cell voltage, as seen in Equation 19,
NaBH4 + 4 H2 O2 ⇔ NaBO2 + 6 H2 O E0 = 2.11 V, 19.
than a hydrogen fuel cell, as well as high efficiency (75%) and extremely high energy density
(theoretical 2,580 Wh kg−1 , experimentally demonstrated greater than 1,000 Wh kg−1 , predicted

Liquid diffusion Catalyst Polymer electrolyte

electrode (anode) layer membrane (PEM)
Backing Gas diffusion
layer electrode
(cathode)
L O2(air)
H2-depleted liquid (L)

H+
H2-charged liquid (L*H2)

L*H2 H2O
e– e–
Load
Figure 2
Direct organic fuel cell/flow battery concept.
practical 200 Wh kg−1 ) (139, 140). The claimed reaction reversibility that would make this system
suitable for EES (140) needs to be demonstrated on both cathode and anode sides. However, a
recent study showed that electrosynthesis of NaBH4 from NaBO2 is difficult (141).
A novel RFC concept, a direct organic fuel cell/flow battery that uses a hydrogen-rich organic
liquid as a reversible fuel in an electrochemical cell, has been proposed (142, 143). In this concept
(Figure 2), in the discharge mode the organic liquid is fed directly to the anode of a PEM fuel
cell, where it is electrochemically dehydrogenated to form a stable, hydrogen-depleted organic
compound without ever generating gaseous H2 to produce power. In the charge mode, water is
electrolyzed to hydrogenate the spent liquid back to the starting liquid compound (Equation 20):
L∗ nH2 + n/2 O2 ⇔ L + n H2 O E0 = 1.0−1.1 V. 20.
The system works as a hybrid of a fuel cell and a flow battery. An example of such an organic
liquid fuel is decalin, which can be oxidatively dehydrogenated to naphthalene to produce 10
protons and 10 electrons that, taking into account decalin’s molecular weight of 128.17, makes
it an anode material with specific energy density only approximately two times less than lithium
metal. The theoretical energy density of the organic liquid-oxygen couple may reach 1,350 Wh
kg−1 , approximately 20–40 times higher than that of common flow batteries. As other examples,
electrochemical dehydrogenation of cyclohexane vapor in a PEM fuel cell has been demonstrated
(144, 145), and electrocatalytic hydrogenation of aromatic compounds is also known (146).
To make this concept a reality, an effective hydrogenation/dehydrogenation electrocatalyst, a
low-humidity PEM, and a compatible high–energy density organic fuel should be developed. To
solve these challenging problems, a DOE-funded Energy Frontier Research Center on Electro-
catalysis, Transport Phenomena, and Materials has been created (http://ge.geglobalresearch.
com/technologies/chemical-technologies-materials-characterization/efrc/).
COMPARISON OF ELECTROCHEMICAL ENERGY STORAGE SYSTEMS

Growing energy demand will drive a substantial increase in the installed electricity genera-
tion capacity (up to 77% by 2030) and a corresponding increase in EES capacity (147). It is
518 Soloveichik
estimated that the United States alone will need to build, in the next few years, approximately
13 GW of EES systems to support the grid, and evidently even more when the increasing share
of intermittent renewable sources is taken into account. The most important parameters that will
determine successful deployment of electrochemical EES systems are cost, reliability, robustness,
flexibility, and environmental impact. Another factor is availability of electroactive materials.
For example, mass production of electric cars might strain the lithium supply and make it less
available for stationary applications. Estimates of global extractable lithium reserves vary from
13.4 million metric tons by Tahil (148) to a more optimistic 28.4 million tons by Keith Evans
(149). These reserves are more than enough to provide Li-ion batteries for the whole global
fleet of cars. However, for much larger scale stationary storage, lithium availability may be a
problem.
Electrochemical EES technologies have several advantages compared with other options.
Pumped hydro and CAES have advantages for large-scale storage, but they are location specific
and, therefore, cannot be used in many places. They also suffer from high energy transmission
costs.
According to a recent cost analysis (Table 2), redox flow batteries and sodium nickel chloride
batteries are the least expensive for energy applications, whereas Li-ion batteries may be preferred
for high power applications. Clearly, no single technology is equally suitable for all applications,
or even for the same application in different locations. Case-by-case analysis should be performed
to select the best EES option.
The best choice within electrochemical EES depends on scale and application. For example,
Li-ion batteries are best for smaller scale power applications, whereas redox flow batteries are
more appropriate than secondary batteries for large-scale energy applications. Molten sodium
batteries, especially the promising Na-NiCl2 batteries, could be used in the intermediate scale
(kW to MW).
Secondary batteries with solid active materials have a fundamental problem of the ther-
modynamic instability of their complex 3D electrode structures owing to material expan-
sion/contraction, reaction with electrolyte, and stratification due to different densities; this in-
stability leads to an unavoidable degradation of electrodes and capacity loss. Reducing the size
Table 2 Technical and economic parameters of batteries for electric energy storage (148)
Specific energy,
Wh kg−1
Specific Self-
power, Round trip discharge, Power cost, Energy cost,
Technology Theory Practical W kg−1 efficiency, % % day−1 Cycle life $ kW−1 $ kWh−1
VRLA 170 30–50 75–300 70–80 0.1–0.3 500–1,000 300–600 200–400
NiCd 315 50–75 150–300 60–70 0.2–0.6 2,000–2,500 500–1,500 800–1,500
NAS 755 150–240 150–230 75–90a 0 2,500 1,000–3,000 300–500
NaNiCl2 790 100–120 150–200 85–90a 0 2,500+ 150–300 100–200
Li-ion 560 75–200 150–315 85–98 0.1–0.3 1,000–10,000 175–4,000 500–2,500
Zinc- 217 30–50 – 65–75 Small 2,000+ 700–2,500 150–1,000
bromine
VRB 34 10–25 – 75–85 Small 12,000 600–1,500 150–1,000
a
Total efficiency is 5–7% lower owing to heat losses to maintain cell operating temperatures.
Abbreviations: VRLA, valve-regulated lead-acid; NAS, sodium-sulfur; VRB, vanadium redox battery

of particles, using composite cathodes and anodes, designing support scaffolds, and optimizing
porosity effectively may reduce the degradation rate but cannot eliminate it.
Li-ion batteries with high power and energy density are under intensive study for mobile
applications and are under consideration for stationary applications. However, they have many
disadvantages (high cost, limited lifetime, restricted electrode thickness that complicates the cell
design, temperature sensitivity, and safety) that should be addressed before large-scale imple-
mentation in stationary EES. To address major challenges, research is focused on the design of
inexpensive cathode materials with low expansion and increased capacity (e.g., multielectron ma-
terials such as transition metal fluorides), electrolytes with improved safety and conductivity (e.g.,
aqueous electrolytes), new anode materials, and improved protection and plating of lithium metal.
The scalability of Li-ion batteries to large EES units will present additional challenges.
Molten sodium batteries are well positioned for intermediate (up to MW)-scale EES. Sodium
metal chloride batteries are safer than NAS batteries and can deliver more power. These batteries
are independent of ambient temperature and have high efficiency and zero self-discharge, but
energy must be spent to compensate for heat loss during idle periods. This may be not an issue
if these batteries are used continuously, e.g., in hybrid telecom applications. Their major disad-
vantage is low power, for example, relative to Li-ion batteries. To increase power, new designs,
novel electrolytes, and sodium-conducting materials need to be explored. The battery cost can
be further reduced through development of inexpensive cathode materials and by increases in
production volume.
The regenerative hydrogen-oxygen fuel cells, coupled with even current hydrogen storage, have
by far the highest energy density (450–800 Wh kg−1 ) (150), more than 2–3 times that forecast for
any secondary batteries. They also have low environmental impact and are easily scalable but suffer
from low round-trip energy efficiency, high catalyst and membrane cost, ineffective hydrogen
storage, and slow transition from charge to discharge. Round trip efficiency of regenerative fuel
cells depends on the efficiencies of both fuel cell and electrolyzer operations. The theoretical
efficiency of the hydrogen PEM fuel cell (ε = G/H) is 84%, and that of a PEM electrolyzer
is 93% at reasonable cell potentials (151), which gives an overall efficiency of 78%. The real
efficiency of an RFC is much lower, as small as approximately 40%, owing mostly to the ORR
overpotential (152). If oxygen is not recuperated, this value is reduced to 26% (153). Replacement
of oxygen with other oxidants, e.g., bromine, eliminates the ORR issue but introduces the problems
of corrosion and toxicity. Substitution of stored hydrogen with organic liquids with high energy
density (142, 143) may be promising, but the fundamental problems in developing electrocatalysts
and low-humidity membranes need to be solved.
Flow redox batteries are better suited for large-scale applications. They have high efficiency,
are easily scalable, and may be fully discharged and charged without overcharging. In addition,
they may be instantly charged by mechanical replacement of discharged electrolytes with charged
ones. The main problems of flow batteries are low energy density, short membrane lifetime,
complex plumbing, and pumping that could lead to leaks of corrosive and toxic materials. It seems
that the current trend in flow battery deployment is to build modular kW-scale systems that
can be scaled up by combining the required number of independent systems rather than simply
to increase the electrolyte tank size. Such systems are more resilient because the failure of one
module will result in minimal loss of capacity, and maintenance and electrolyte replacement is
less expensive. Comparative analysis of these flow cells showed that vanadium/vanadium batteries
are superior to zinc/bromine batteries (toxic bromine, corrosion) and iron/chromium batteries
(low capacity retention because of electrolyte crossover) (154). To increase energy density and
efficiency, research will need to target new electroactive materials and ion-selective membranes
that effectively stop transport of redox materials but maintain high a flux of ions and water.
520 Soloveichik
CONCLUSIONS
To be competitive with other energy storage options, the capital cost of electrochemical EES
should be decreased and the cycle life and reliability increased. This will define future research
and development in the electrochemical EES area.
Currently, lead-acid (VRLA and flooded) batteries are the most frequently used in all types of
stationary applications. However, other emerging electrochemical technologies likely will soon
meet and exceed the required technical specifications and challenge lead-acid batteries in this
market (155). The most promising technologies in the short term are high-temperature sodium
batteries with β -alumina electrolyte, Li-ion batteries, and flow batteries. In the long run, assuming
further technical advances, regenerative fuel cells and lithium metal batteries with high energy
densities may obtain substantial market share.
DISCLOSURE STATEMENT
The author is a General Electric Global Research employee and a director of the Energy Frontier
Research Center funded by the U.S. Department of Energy, Office of Basic Energy Sciences,
which might be perceived as affecting the objectivity of this review.
ACKNOWLEDGMENTS
The author would like to thank Drs. G. Merfeld, R. Perry, J. Rijssenbeek, and G. Zappi for help in
manuscript preparation and helpful discussions. This material is based on work supported as part
of the Center for Electrocatalysis, Transport Phenomena, and Materials (CETM) for Innovative
Energy Storage, an Energy Frontier Research Center funded by the U.S. Department of Energy,
Office of Science, Office of Basic Energy Sciences under Award Number DE-SC00001055.
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Chemical and
Biomolecular
Engineering
Contents Volume 2, 2011

My Contribution to Broadening the Base of Chemical Engineering

Roger W.H. Sargent p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 1
Catalysis for Solid Oxide Fuel Cells
R.J. Gorte and J.M. Vohs p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 9
CO2 Capture from Dilute Gases as a Component of Modern Global
Carbon Management
Christopher W. Jones p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p31
Engineering Antibodies for Cancer
Eric T. Boder and Wei Jiang p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p53
Silencing or Stimulation? siRNA Delivery and the Immune System
Kathryn A. Whitehead, James E. Dahlman, Robert S. Langer,
and Daniel G. Anderson p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p77
Solubility of Gases and Liquids in Glassy Polymers
Maria Grazia De Angelis and Giulio C. Sarti p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p97
Deconstruction of Lignocellulosic Biomass to Fuels and Chemicals
Shishir P.S. Chundawat, Gregg T. Beckham, Michael E. Himmel,
and Bruce E. Dale p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 121
Hydrophobicity of Proteins and Interfaces: Insights from Density
Fluctuations
Sumanth N. Jamadagni, Rahul Godawat, and Shekhar Garde p p p p p p p p p p p p p p p p p p p p p p p p p 147
Risk Taking and Effective R&D Management
William F. Banholzer and Laura J. Vosejpka p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 173
Novel Solvents for Sustainable Production of Specialty Chemicals
Ali Z. Fadhel, Pamela Pollet, Charles L. Liotta, and Charles A. Eckert p p p p p p p p p p p p p p p p 189
Metabolic Engineering for the Production of Natural Products
Lauren B. Pickens, Yi Tang, and Yit-Heng Chooi p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 211
vii
CH02-FrontMatter ARI 16 May 2011 9:7
Fundamentals and Applications of Gas Hydrates

Carolyn A. Koh, E. Dendy Sloan, Amadeu K. Sum, and David T. Wu p p p p p p p p p p p p p p p p 237
Crystal Polymorphism in Chemical Process Development
Alfred Y. Lee, Deniz Erdemir, and Allan S. Myerson p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 259
Delivery of Molecular and Nanoscale Medicine to Tumors: Transport
Barriers and Strategies
Vikash P. Chauhan, Triantafyllos Stylianopoulos, Yves Boucher,
and Rakesh K. Jain p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 281
Surface Reactions in Microelectronics Process Technology
Galit Levitin and Dennis W. Hess p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 299
Microfluidic Chemical Analysis Systems

Eric Livak-Dahl, Irene Sinn, and Mark Burns p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 325
Microsystem Technologies for Medical Applications
Michael J. Cima p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 355
Low–Dielectric Constant Insulators for Future Integrated Circuits
and Packages
Paul A. Kohl p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 379
Tissue Engineering and Regenerative Medicine: History, Progress,
and Challenges
François Berthiaume, Timothy J. Maguire, and Martin L. Yarmush p p p p p p p p p p p p p p p p p p 403
Intensified Reaction and Separation Systems
Andrzej Górak and Andrzej Stankiewicz p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 431
Quantum Mechanical Modeling of Catalytic Processes
Alexis T. Bell and Martin Head-Gordon p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 453
Progress and Prospects for Stem Cell Engineering
Randolph S. Ashton, Albert J. Keung, Joseph Peltier, and David V. Schaffer p p p p p p p p p p 479
Battery Technologies for Large-Scale Stationary Energy Storage
Grigorii L. Soloveichik p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 503
Coal and Biomass to Fuels and Power
Robert H. Williams, Guangjian Liu, Thomas G. Kreutz, and Eric D. Larson p p p p p p p p p 529
Errata
An online log of corrections to Annual Review of Chemical and Biomolecular Engineering

articles may be found at http://chembioeng.annualreviews.org/errata.shtml
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CH02CH23-Soloveichik ARI 9 May 2011 7:35

• Top cited articles

• Top downloaded articles

Annu. Rev. Chem. Biomol. Eng. 2011. 2:503–27 Keywords

The Annual Review of Chemical and Biomolecular Abstract

Association (ESA; http://www.electricitystorage.org) identiﬁed twelve speciﬁc energy storage

Table 1 Energy storage technologies for stationary applications

Pb + PbO2 + 2 H2 SO4 ⇔ 2 PbSO4 + 2 H2 O E0 = 2.04 V. 1.

www.annualreviews.org • Batteries for Stationary Energy Storage 505

prevented sulfation of the negative plate (18).

Cd + 2 NiOOH + 2 H2 O ⇔ Cd(OH)2 + 2 Ni(OH)2 E0 = 1.29 V, 2.

MH + NiOOH ⇔ M + Ni(OH)2 E0 = 1.35 V. 3.

M in this equation is an intermetallic compound of composition AB5 , where A is a combination of

2Na + x S ⇔ Na2 Sx E0 = 2.07 − 1.78 V. 4.

www.annualreviews.org • Batteries for Stationary Energy Storage 507

limited, and therefore these technologies are considered as emerging ones.

Lix C + Li1−x MO2 ⇔ LiMO2 + C E0 = 3.3 − 4.2 V. 5.

MCl2 + 2 Na ⇔ M + 2 NaCl E0 = 2.58 V(M = Ni), 2.35 V(M = Fe). 6.

utilization (25–30% or even lower in NiFe cells) of expensive nickel.

www.annualreviews.org • Batteries for Stationary Energy Storage 509

(http://www.xylenepower.com) is developing a sodium-sulfur-nickel chloride (Na-S-NiCl2 )

Li + 1/4O2 + 1/2H2 O ⇔ LiOH(in aqueous electrolyte) E0 = 3.44 V, 8.

2 Li + O2 ⇔ Li2 O2 (in non-aqueous electrolyte) E0 = 2.96 V, 9.

2 Li + S ⇔ Li2 S E0 = 2.2 V. 10.

(http://www.seeo.com) is developing an all-solid lithium metal battery with LiFePO4 or sul-

www.annualreviews.org • Batteries for Stationary Energy Storage 511

3 Mg + 2 Sb ⇔ Mg3 Sb2 E0 = 0.42 V, 11.

www.annualreviews.org • Batteries for Stationary Energy Storage 513

Zn + Cl2 ⇔ ZnCl2 E0 = 2.02 V. 15.

bromine analog (98).

2 Ce(CH3 SO3 )4 + Zn ⇔ 2 Ce(CH3 SO3 )3 + Zn(CH3 SO3 )2 E0 = 2.48 V, 16.

Cr2+ + Fe3+ ⇔ Cr3+ + Fe2+ E0 = 1.18 V. 17.

www.annualreviews.org • Batteries for Stationary Energy Storage 515

2 V 2+ + Br2 ⇔ 2 V 3+ + 2 Br− E0 = 1.32 V 18.

efﬁciency of 87% (112).

REGENERATIVE FUEL CELLS

NaBH4 + 4 H2 O2 ⇔ NaBO2 + 6 H2 O E0 = 2.11 V, 19.

www.annualreviews.org • Batteries for Stationary Energy Storage 517

Liquid diffusion Catalyst Polymer electrolyte

H2-depleted liquid (L)

H2-charged liquid (L*H2)

COMPARISON OF ELECTROCHEMICAL ENERGY STORAGE SYSTEMS

www.annualreviews.org • Batteries for Stationary Energy Storage 519

www.annualreviews.org • Batteries for Stationary Energy Storage 521

chemical performance of sodium/nickel chloride cells. J. Appl. Electrochem. 30:1229–33

www.annualreviews.org • Batteries for Stationary Energy Storage 523

the iron-chromium redox energy storage system. J. Electrochem. Soc. 132:1058–62

www.annualreviews.org • Batteries for Stationary Energy Storage 525

Presented at Intl. Energy Convers. Eng. Conf., 1st, Portsmouth, VA

www.annualreviews.org • Batteries for Stationary Energy Storage 527

Contents Volume 2, 2011

My Contribution to Broadening the Base of Chemical Engineering

Fundamentals and Applications of Gas Hydrates

Microﬂuidic Chemical Analysis Systems

An online log of corrections to Annual Review of Chemical and Biomolecular Engineering

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