XYLENE POWER LTD.

SODIUM-SULFUR-NICKEL CHLORIDE ELECTRO-CHEMICAL ENERGY STORAGE

By C. Rhodes

INTRODUCTION:
The sodium-sulfur-nickel chloride (Na-S-NiCl2) electro-chemical cell is of fundamental importance for manufacture of truck or rail transportable multi-MWh energy storage systems. This electro-chemical technology provides a practical means for utility scale daily storage and recovery of electrical energy at either urban or rural locations.

ELECTRO-CHEMICAL ENERGY STORAGE TECHNOLOGIES:
Presently the practical electro-chemical technologies for storing energy for later recovery are lithium ion batteries, sodium-sulfur-nickel chloride batteries and vanadium flow batteries. Lithium ion batteries are believed to be too expensive for large scale stationary energy storage. Vanadium flow batteries are thought to be too bulky and too environmentally dangerous for widespread use in residential and small commercial applications. Hence, this web page focuses on sodium-sulfur-nickel chloride energy storage technology.

EMERGENCE OF THE SODIUM-SULFUR-NICKEL CHLORIDE CELL:
The modern sodium-sulfur-nickel chloride energy storage cell is the result of about 40 years of patient research and development in the areas of sodium-sulfur batteries and sodium-chloride (zebra) batteries. However it is only very recently that these two technologies have merged into a commercially viable technology. The purpose of this web page is to briefly describe this merged technology.

The initial cost of implementing a Na-S-NiCl2 energy storage system is a strong function of the price of nickel. The other materials are comparatively inexpensive. The nickel and other cell materials are not consumed and hence can be recycled as often as required to extend the energy storage system service life. A modern Na-S-NiCl2 cell is good for about 2000 full charge-discharge cycles before its materials should be recycled. There is ongoing development aimed at increasing the number of charge-discharge cycles between cell material recycling. The life limiting mechanism appears to be an increase in internal resistance due to agglomeration of nickel that reduces the exposed nickel surface area.

Na-S-NiCl2 energy storage systems have the advantage that they can easily be fabricated in modules which lend themselves to truck or rail transport. Battery, inverter, transformer and switchgear modules are easily interchanged for service. Presently the energy density is about 1 MWh / 10 tonnes. One 18 wheel boom truck load (40 tonnes) can consist of 4 MWh of Na-S-NiCl2 energy storage. There is ongoing development aimed at increasing the energy density.

Na-S-NiCl2 energy storage cells operate at about 300 degrees C. The thermal insulation required to efficiently thermally isolate Na-S-Cl2 batteries is bulky. Hence the smallest commercially available Na-S-NiCl2 battery is rated at about 18 kWh. Larger batteries are more thermally efficient due to larger mass to surface area ratios.

CHOICE OF REACTING ELEMENTS:
If the object is to make an electro-chemical cell with the highest possible energy content per unit weight, the periodic table of elements indicates that the cell's active elements must come from the top left and top right corners of the periodic table. On the top left are hydrogen, lithium and sodium. On the top right are fluorine and chlorine. However, use of some of these elements is impractical for various reasons.

Over the temperature range of interest hydrogen is a gas that is difficult to store in quantity, except in a large, heavy and expensive pressure tank.

Lithium is not a common element and it is in high demand for use in automotive propulsion batteries, which makes it too expensive for most stationary energy storage applications.

Fluorine forms strong chemical bonds that are difficult to break for energy storage following energy discharge.

The next best choices for energy storage are sodium (Na) and chlorine (Cl). However, chlorine is a dangerous gas. The practical way to use chlorine is to weakly chemically bind it to another element. This element must be chosen so that the resulting compound does not spontaneously decompose at the highest anticipated operating temperature. Hence the chlorine is stored as nickel chloride (NiCl2).

In theory a simple Na-NiCl2 molten salt cell could be made which when it discharges forms NaCl and Ni. However, to enable ion mobiity such a simple cell must be operated above the melting point of NaCl (801 C). That temperature is too high to be practical.

The key is to introduce sulfur to form a Na-S-NiCl2 cell. In this cell there are two ongoing reverseable chemical reactions of the form:
2Na+ + 5S = Na2S5++
and
Na2S5++ + NiCl2 = 2 NaCl + S5 + Ni++
The sodium, sulfur and sodium polysulfide all melt at less than 275 degrees C allowing these electro-chemical reactions operate efficiently at about 300 degrees C.

CELL GEOMETRY:
A Na-S-NiCl2 cell typically consists of a outer stainless steel enclosure and an inner co-axial thin wall closed end tube formed from beta Al2O3. The space between the outer stainless steel wall and the Al2O3 tube is filled with liquid sodium which forms the anode. Inside the beta Al2O3 tube is a mix of liquid sulfur, liquid sodium polysulfide, NaCl, NiCl2 and a large surface area carbon cathlode with a Ni plated surface. Air is excluded. Small amounts of other substances and an excess of nickel are added to the cathlode structure to improve its electrical conductivity. The Al2O3 tube is usually enclosed inside another open end tube of slightly larger diameter. This enclosing tube limits the chemical reaction rate in the event that the Al2O3 tube fractures. It is important that the liquid sodium be on the outside of the Al2O3 tube. If the liquid sodium was on the inside of the Al2O3 tube the Ni requirement would be greater and there could be enclosure wall failures due to chlorine corrosion during the charging cycle.

CHEMICAL CHANGES:
The beta Al2O3 has the property that it conducts Na+ ions but does not conduct either electrons or neutral Na atoms. During cell discharge Na+ ions formed in the liquid Na pass through the beta Al2O3 and combine with sulfur to form liquid sodium polysulfide which in turn reacts with the chlorine in the NiCl2 to form 2NaCl, liberating Ni. After all the NiCl2 is exhausted the remaining sulfur acquires more Na and fully converts to Na2S5.

During cell charging the Na2S5 converts to sulfur which then combines with the sodium in NaCl. The Na+ ions pass back through the beta Al2O3, acquire electrons and accumulate in the anode outside the Al2O3. The Cl- released by the NaCl combines with the cathlode's nickel coating to form NiCl2, releasing electrons to the external circuit. After all the NaCl is exhausted the remaining sodium polysulfide continues giving up Na until the Na2S5 is exhausted. The sulfur so released can form NiS or Ni3S2 which must be eliminated via complete cell discharge. The primary role of the sulfur/sodium polysulfide is to act as a Na+ transport agent between the Al2O3 inner surface and the reservoirs of solid NiCl2 and solid NaCl. The sulfur/sodium polysulfide also provides some energy storage.

MULTI-STAGE OPERATION:
The Na-S-NiCl2 energy storage cell operates in two stages during both charging and discharging. There is a distinct change in cell voltage and cell internal resistance at the interstage transition. The interstage transition, in combination with a current integrator, can be used to estimate the remaining useful cell charge. In general the cell is most efficient when it is converting NiCl2 to 2NaCl during cell discharge and when it is converting 2NaCl to NiCl2 during cell charging. At the top and bottom ends of the charge-discharge range the internal resistance is higher and nickel sulfides form or are eliminated. The nickel sulfide formation/elimination process reduces the cell's efficiency. In applications involving high charge-discharge rates the cell should be operated in the middle 80% of its operating range where the internal resistance is relatively low and where formation/elimination of nickel sulfides is not an issue.

DISCHARGE CYCLE FIRST STAGE:
Initially, when the cell is fully charged, all the Na is in the anode and all the chlorine is contained in NiCl2. During the cell discharge each participating Na atom in the anode gives up an electron to the external circuit and forms an Na+ ion according to the equation:
Na = Na+ + e-
The Na+ ions move through the solid beta Al2O3 electrolyte and react with the liquid sulfur to form Na2S++. The Na2S++ is unstable and spontaneously takes on more sulfur to form Na2S4++ or Na2S5++. The net equation is:
2Na++ + 5S = Na2S5++
The Na2S5++ circulates, finds a NiCl2 molecule and forms 2NaCl according to the equation:
Na2S5++ + NiCl2 = 2NaCl + 5 S + Ni++.
Each released Ni++ ion drifts to the cathlode where it neutralizes itself by acquiring two electrons from the external circuit and plates Ni metal onto the cathlode. This process continues until all the available NiCl2 is exhausted. The cathlode must be designed so that the Ni plating onto its surface does not significantly reduce its surface area.

DISCHARGE CYCLE SECOND STAGE:
In the discharge cycle second stage there is no NiCl2. The cell behaves as a pure Na-S cell. Na ions from the anode pass through the solid beta Al2O3 electrolyte and react with the sulfur. The sulfur, which during the discharge cycle first stage only partially converted to Na2S5 now continues to react with Na+ causing all the remaining sulfur to convert to Na2S5 according to the equation:
2Na+ + 5S = Na2S5++
Each Na2S5++ ion drifts to the cathlode where it acquires two electrons from the external circuit. This discharge process continues until all of the available sulfur has converted to Na2S5. At that point there is no energy source to drive the external circuit and the cell is fully discharged. The cell internal resistance during the discharge cycle second stage is higher than during the discharge cycle first stage. There is a surplus of Na to ensure that the process is not Na constrained.

CHARGE CYCLE FIRST STAGE:
Initially, when the cell is fully discharged, all of the sulfur is contained in Na2S5, NiS, Ni3S2 and all of the chlorine is contained in NaCl. In the charge cycle first stage the Na2S5 at the Al2O3 surface breaks down according to:
Na2S5 = 2Na+ + 5S + 2e-
and the Na+ ions move back through the solid beta Al2O3 electrolyte to the Na anode where they acquire neutralizing electrons from the external circuit. The two negative charges in the sulfur attract another two Na+ ions from the NaCl reservoir, which restore the Na2S5 concentartion, leaving Cl- ions. These Cl- ions drift to the Ni cathlode where they give up their electrons to the external circuit and combine with the nickel cathlode material to form NiCl2. This process continues until all of the available NaCl is exhausted. There is a surplus of Ni to ensure that the process is not constrained by the available supply of Ni.

The free Cl- ions may also combine with any NiS or Ni3S2 according to:
2Cl- + NiS = NiCl2 + S--
or
6Cl- + Ni3S2 = 3NiCl2 + 2S---
thus converting any NiS or Ni3S2 to NiCl2 plus free sulfur ions.
Since the sulfur is liquid the sulfur ions can migrate to the cathlode. There the sulfur ions do not chemically combine with the nickel during the charge cycle first stage because of the preference of nickel to combine with chlorine.

CHARGE CYCLE SECOND STAGE:
In the charge cycle second stage there is no NaCl. The cell behaves as a pure Na-S cell. The Na2S5 continues giving up Na+ ions which pass through the solid beta Al2O3 electrolyte to the Na anode. The negatively charged sulfur ions left behind circulate and give up their negative charge at the Ni coated cathlode and form the nickel sulfides NiS or Ni3S2. The negative charge flows in the external circuit. This process continues until all the Na2S5 is exhausted, at which point the cell is fully charged. The cell internal resistance during the charge cycle second stage is higher than during the charge cycle first stage.

OVERCHARGING:
However, there is an issue with nickel sulfide formation during the charge cycle second stage. The sulfur and sodium polysulfide are liquids at 300 degrees C but the NiS and Ni3S2 are not liquids. Formation of nickel sulfides reduces the amounts of liquid sulfur and liquid sodium polysulfide that are available to provide cathlode structure conductivity. The nickel sulfides can be removed by completely discharging and then recharging the cell. However, while that process is taking place the cell is not fully available for random energy storage. Hence, a practical energy storage system involves multiple series connected strings of Na-S-NiCl2 cells. Then, with the aid of a suitable control system, each cell string can be completely discharged, partially recharged to clear any nickel sulfides, operated in an alternating charge-discharge mode and then charged only to the point where nickel sulfides start to form. A practical Na-S-NiCl2 energy storage system should have a microprocessor based charge controller to monitor and control the charging and discharging of each series connected string of Na-S-NiCl2 cells. This controller is essential for minimizing the nickel sulfide concentration in the cells and hence maximizing cell string performance.

OPERATING TEMPERATURE:
The sodium in the anode must be above the Na melting point of 97.81 C in order to emit Na+ ions. The sulfur must be above its melting point of 112.8 C in order to circulate. As the discharge process continues the sodium polysulfide must be above its melting point of 275 C in order to circulate and react as described herein. In order to ensure proper operation the cell is kept in the temperature range:
300 C < T < 350 C.

MATERIAL DATA:

CHEMICAL NAME	SYMBOL	MELTING POINT	DENSITY R gm/cm^3	HEAT OF FORMATION
Sodium	Na	97.81 C	.97
Sodium Chloride	NaCl	801 C	2.165	-98.168 kcal/mole
Nickel Chloride	NiCl2	1001 C	3.55	-73.077 kcal/mole
Nickel mono-Sulfide	NiS	797 C	5.5
Nickel sub-Sulfide	Ni3S2	790 C	5.82
Sulfur	S8	112.8 C	2.07
Sodium Iodide	NaI	660 C	3.67
Sodium Hydroxide	NaOH	318.4 C	2.13
Sodium Monosulfide	Na2S	1180 C	1.856
Sodium Tetrasulfide	Na2S4	275 C	1.268
Sodium Pentasulfide	Na2S5	251.8 C
Nickel	Ni	1455 C	8.90
Nickel Iodide	NiI2	797 C	5.834

NOTES:
1) The Al2O3 failures tend to occur during the charge cycle.

2) Due to their different densities the cell components tend to stratify. Over time the Ni cathlode tends to reform at the bottom of the cell. Stratification of components by density R in gm / cm^3 at 350 degrees C causes:
S8 top R = 1.66
Na2Sx next R = 1.85 to 1.91
NaCl next R =2.16
NiCl2 next R = 3.55
NiS next R = 5.5
Ni3S2 next R= 5.82
Ni bottom R = 8.9

3) Note that the NaCl and the NiCl2 tend to sink in the liquid sulfur/sodium polysulfide. An important part of cell design is ensuring adequate fluid circulation in the cathlode structure. Note that Na2S5 and S8 are immiscible. Additives are required to make sulfur electrically conduct. Note that at low temperatures the density of S8 is 2.07 and is denser than the Na2Sx. The temperature at which the density of S8 equals the density of Na2Sx may represent an optimum operating point.

4) The net chemical reaction is:
2Na + NiCl2 = 2NaCl + Ni
Energy is mainly stored as sodium metal and as nickel chloride. Nickel chloride is used because it stores chlorine at the working temperature with minimum binding energy. Sulfur provides some additional energy storage at the expense of nickel sulfide formation that increases internal resistance.

5) The energy liberated per mole of NaCl is:
98.168 kcal/mole – (73.077 / 2) kcal/mole = 61.63 kcal/mole

6) 61.63 kcal/ mole NaCl X 1 mole NaCl / (22.99 + 35.45) gm
=61.63 / 58.44 kcal/gm
=1.0545 kcal/gm X 1000 gm / kg = 1054.5 kcal/ kg
= 1054.5 kcal/ kg X 4.18 kJ/kcal
= 4407.8 kJ/kg X 1kW s/kJ X 1h/3600s
= 1.22 kWh / kg NaCl

7) Active chemical weight is further increased by nickel weight.
Total active chemical weight / NaCl weight
= (2(58.44) + 58.71) /2(58.44)
= 175.59 / 116.88
= 1.5023

8) Hence theoretical maximum energy / kg is:
1.22 kWh / 1.5023 kg
= .812 kWh / kg active chemical
By comparison the presently achieved total energy storage system weight is about 0.1 kWh / kg. Thus there is an opportunity for about a four fold increase in energy storage per unit weight via improved energy storage system engineering.

9) The theoretical minimum weight of nickel required to fabricate the energy storage cell is given by:
(1.22 kWh / kg NaCl) X ((2 X 58.44 kg NaCl)/(58.71 kg Ni)) X (.454 kg Ni) / (lb Ni)
= 1.102 kWh / lb Ni
Experience at MES-DEA indicates that the actual amount of Ni used is 3 times the theoretical minimum, indicating that the Ni requirement is:
3 lb Ni / 1.102 kWh = 2.72 lb Ni/ kWh
In early September 2009 the cost of Ni was about $8.12 US / lb, giving a cost of Ni for energy storage of:
$8.12 US / lb Ni X 2.72 lb Ni / kWh = $22.09 US / kWh
At $8.12 US / lb the cost of Ni is tolerable provided that an efficient Ni recycling program is used.

10) In industrial quantities the cost of sodium is about $4.00 / kg
In industrial quantities the cost of sulfur is about $.10 / kg

11) The cost of the chemical inventory required to store 1 kWh is:
= $25.00 / kWh of electrical energy storage capacity, which suggests that the large scale fabricated battery price will likely be in the range of $100 / kWh to $200 / kWh.

12) The basic energy storage cell components are:
a) stainless steel enclosure
b) liquid Na anode
c) Al2O3 barrier
d) liquid S8/Na2S5
e) NaCl/NiCl2 reservoir
f) Ni cathlode

13) The usual cell failure mode is an internal short circuit. If energy storage systems are designed with numerous series connected cells, the storage system design can be engineered to tolerate a few internal short circuit cell failures.

PRACTICAL NUMBER OF CELLS PER CELL STRING:
Practical energy storage systems contain multiple series connected strings of Na-S-NiCl2 cells. The minimum number of cells in a string is determined by the minimum required discharge voltage. Since the required charging voltage is higher than the available discharge voltage, generally two cell strings are series connected to obtain the required discharge voltage but are parallel connected for charging. For example an inverter that provides a 120V/208V 3 phase wye output can obtain its DC power from two series connected cell strings where each cell string has a minimum output voltage of:
1.41 X 120V = 169.2 volts.
Allowing for a 3.0 volt drop across switching devices and reactors increases this voltage requirement to 172.2 volts / cell string.

According to the MES-DEA specifications the minimum operating voltage per cell is 1.722 volts, so the minimum number of cells per string is:
(172.2 volts/ cell string) / (1.722 volts / cell) = 100 cells / cell string

In order to accommodate a few cell short circuit failures before the cell string must be recycled, it is prudent to design for 108 cells / cell string. This number of cells is geometrically convenient as it permits a rectangular 9 X 12 cell array.

Application of similar design rules to a system with a 277V/480V 3 phase wye output results in a minimum output voltage per cell string of:
(1.41 X 277V) + 3V = 393.57 volts / cell string.
The corresponding minimum number of cells / cell string is:
(393.57 volts / cell string) / (1.722 volts / cell) = 228.5 cells / cell string
A geometrically convenient number is 240 cells / cell string.

Application of similar design rules to a system with a 347V/600V 3 phase wye output results in a minimum output voltage per cell string of:
(1.41 X 347V) + 3V = 492.27 volts / cell string.
The corresponding minimum number of cells / cell string is:
(492.27 volts / cell string) / (1.722 volts / cell) = 285.9 cells / cell string
A geometrically convenient number of cells is 300 cells / cell string.

PRACTICAL MAXIMUM INDIVIDUAL CELL WEIGHT:
From the point of view of both electrical and thermal isolation it is convenient to package all of the cells of a cell string in a single module. From the point of view of practical handling with readily available lifting equipment, it is desirable to keep the maximum individual module weight less than 10 tons (20,000 pounds). Hence the individual cell weight including its enclosure allowance must be less than:
20,000 pounds / 300 cells = 66.67 pounds / cell = 30.2 kg / cell.
A related constraint is the maximum available size of suitable thin wall beta Al2O3 tube material. The Al2O3 tube material must support much of the cell's active chemical weight.

CELL STRINGS AND MODULES:
In order to meet charging/discharging voltage requirements a practical energy storage system has a minimum of 2 cell strings. In order to permit full charge-discharge cycling without imposing input or output constraints it is necessary to have additional cell strings. Generally there is one module per cell string. Since each cell string may have a different number of shorted cells, there must be separate switching devices dedicated to each cell string. Each cell string needs its own voltage and current monitoring for optimum charging and discharging.

INVERTERS:
Generally with Ni-S-NiCl2 energy storage systems, to accommodate the variable cell string voltages, there is one power inverter for each pair of cell strings. Each power inverter must be designed to accommodate the wide variations in DC bus voltages and to provide controlled rates of cell charging and discharging. Frequently there is a requirement for AC bus voltage control. The inverters must be fitted with integrators that monitor the Na-S-NiCl2 cell charge/discharge conditon to prevent over charging. The inverters must provide input/output signals to allow efficient control and monitoring of the energy storage system. There must be a means to ensure that the total load is appropriately and efficiently shared by the various inverters. There must be a means of automatically isolating a defective cell string or inverter such that the failure of a single unit does not cause a failure of the entire energy storage system.

LOAD CONTROL:
Usually the energy storage system charging rate and discharging rate are controlled by an external energy management system that is programmed to minimize the facility owner's total electricity cost and/or maximize his distributed generation revenue. The energy transfer rate into or out of the energy storage system may be adjusted by changing the tap setting of the transformer between the AC line and the energy storage system.

ACCESS:
Due to the requirement to recycle energy storage modules over time, the energy storage modules need to be installed in a location with easy boom truck access. Such locations have load bearing constraints.

HEAT DISSIPATION:
Typically about 30% of the overall electrical energy that is input into the energy storage system is not recovered as electricity but instead is converted into heat. During the charging cycle there are rectification losses, switching losses and internal resistance losses. While energy is in storage there are continuous static heat losses. During the discharging cycle there are switching lossses and internal resistance losses. Ideally the energy storage system should be located such that the heat losses are recoverable and are used for a useful function such as preheating supply air or domestic hot water. However, the energy storage system must be located such that at all times all of its heat output can be safely dissipated. The combination of access and heat dissipation requirements makes practical heat recovery a challenge.

FIRE AND WATER PROTECTION:
When the energy storage system is fully charged it contains a substantial mass of liquid sodium. It is essential to prevent this liquid sodium reacting with either water or air. If water penetrates a cell seal large amounts of hydrogen will be released, that can lead to an explosion in a confined space. For this reason Na-S-NiCl2 energy storage modules should be installed in a well ventilated dry above grade location where flooding is extremely unlikely. Similarly there should be an adequate fire separation between these energy storage modules and any adjacent structure.

This web page last updated August 3, 2011.