This is a personal pre-press copy (for non-commercial use) of the paper that has been published in Energy (currently still on-line only). The published version is available at: http://www.sciencedirect.com/science/article/pii/S0360544216301803. To cite this article: Á. Cunha, F. P. Brito, J. Martins, N. Rodrigues, V. Monteiro, J. L. Afonso, P. Ferreira, Assessment of the use of Vanadium Redox Flow Batteries for Energy Storage and Fast Charging of Electric Vehicles in Gas Stations Energy (published online March 2016, in-press), DOI:10.1016/j.energy.2016.02.118 1 2
Assessment of the use of Vanadium Redox Flow Batteries for Energy
3
Storage and Fast Charging of Electric Vehicles in Gas Stations
4
Álvaro CUNHA* a
5
F. P. BRITO*, b
6
Jorge MARTINS* c
7
Nuno RODRIGUES** d
8
Vitor MONTEIRO*** e
9
João L. AFONSO*** f
10
Paula FERREIRA****g
11 12
* Department of Mechanical Engineering, Universidade do Minho, Azurém 4800-058
13
Guimarães, Portugal.
14
** Petrotec, Inovação e Indústria SA., Parque Industrial de Ponte, Pavilhão C2, S. João
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de Ponte, 4805-661 Guimarães, Portugal.
16
*** Centro Algoritmi, Universidade do Minho, Azurém, 4800-058 Guimarães, Portugal.
17
**** Research Centre for Industrial and Technology Management (CGIT),
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Universidade do Minho, Azurém, 4800-058 Guimarães, Portugal
19 20
a – e-mail: alvarogcunha@hotmail.com
21
b – e-mail: francisco@dem.uminho.pt
22
c – e-mail: jmartins@dem.uminho.pt
23
d – e-mail: nuno.rodrigues@petrotec.pt
24
e – e-mail: vmonteiro@dei.uminho.pt
25
f– e-mail: jla@dei.uminho.pt
26
g – e-mail: paulaf@dps.uminho.pt
27
Keywords:
28
Flow Battery
29
Vanadium Redox Flow Battery
30
Energy Storage
31
Peak Shaving
32
Electric Vehicle
33
Fast Charging
34
35
ABSTRACT A network of conveniently located fast charging stations is one of the possibilities to
36
facilitate the adoption of Electric Vehicles (EVs). This paper assesses the use of fast
37
charging stations for EVs in conjunction with Vanadium Redox Flow Batteries
38
(VRFBs). These batteries are charged during low electricity demand periods and then
39
supply electricity for the fast charging of EVs during day, thus implementing a power
40
peak shaving process. Flow batteries have unique characteristics which make them
41
especially attractive when compared with conventional batteries, such as their ability to
42
decouple rated power from rated capacity, as well as their greater design flexibility and
43
nearly unlimited life. Moreover, their liquid nature allows their installation inside
44
deactivated underground gas tanks located at gas stations, enabling a smooth transition
45
of gas stations' business model towards the emerging electric mobility paradigm. A
46
project of a VRFB system to fast charge EVs taking advantage of existing gas stations
47
infrastructures is presented. An energy and cost analysis of this concept is performed,
48
which shows that, for the conditions tested, the project is technologically and
49
economically viable, although being highly sensitive to the investment costs and to the
50
electricity market conditions.
51
NOMENCLATURE Greek letters ε ηCh ηAC-DC η ηtotal VRFB ηsystem μ v ρ
Roughness CHAdeMo charger efficiency VRFB charger with an efficiency (AC/DC) Efficiency of the VRFB without pumping losses VRFB efficiency with pumping losses Overall system efficiency Dynamic viscosity Cinematic viscosity of the fluid Specific mass of the liquid electrolyte
Acronyms DoD EV G1 G2 GHG ICE PHEV PSB RFB SoC VRFB ZBB ZCB
Depth of discharge Electric Vehicle All vanadium redox flow batteries Vanadium bromide redox flow battery Greenhouse gases Internal Combustion Engine Plug-In Hybrid Electric Vehicles Polysulfide/Bromide technology Redox Flow Battery State of Charge Vanadium Redox Flow Batteries (G1 and G2 technologies) Zinc/Bromine technology Cerium/Zinc technology
Variables A Acs Ar Cin C CF Cout D DpY E E EBITDA Er Ea Esold F f g H I Inv i i’ k L Le l le MARR N Nd
Amortizations Permeated cross section area of the electrodes Amortization rate per year Concentration of vanadium in the solution before the cell Costs associated Cash-Flows Concentration of vanadium in the solution after the cell Internal diameter of the pipe operating days per year Energy density of the liquid electrolyte Equilibrium potential Earnings before interest, taxes, depreciation and amortization Real discharged energy Available stored energy Energy supplied/sold to charge a car Faraday constant Coefficient of friction Gravitational acceleration Head loss Current Investment Inflation rate Real interest rate Coefficient of head loss Length of the section Equivalent piping length Permeated specimen length of the electrode Thickness Minimum acceptable rate of return Number of cells Number of cars per day
mm N.s/ m2 m2/s kg/m3
€ m2 mol/L € € mol/L m Wh/L V € W W W 9.6485 x 104 C.mol-1 m/s2 m A € m m m m -
NPV OCVdisch OCVchg Ppump Δp Δpstack Δppipe P PLeaf Pr Pout Pin Pt p R r Re re RBT LR S SoCmin s Tax T TOG t tchg tdisch V V Vdisch Vchg
Net present value Open circuit voltage of the stack during discharge Open circuit voltage during charge Pumping power Total pressure loss Pressure loss in the Stack Pressure loss in the pipes Permeability of the electrodes Power consumption of the Nissan Leaf during charge Real discharge power Power output Input power Payback time Electrical energy purchasing price Electrical resistance Universal constant of ideal gases Reynolds number Resistivity Results before taxes Liquid result Gain from sales Minimum state of charge of VRFB during cycle Electrical energy selling price Taxes Temperature Taxes over gain Time Defined time to charge VRFB Defined time to discharge VRFB Volume of liquid stored Velocity of the fluid Voltage output of stack during discharge Intput voltage of the stack during charge
Subscripts chg disch in n out
Charge Discharge Input Year Output
€ V V kW Pa Pa Pa m2 kW kW kW kW years € Ω 8,3145 J.mol-1.k-1 Ωm € € € € € K s s s m3 m/s V V
52
53
1. INTRODUCTION
54
The disruptive increase of urban traffic along the last decades is posing serious
55
sustainability concerns, mainly those related to urban air quality and greenhouse gases
56
(GHG) emissions, as well as the excessive dependency of developed economies on
57
fossil fuels. It is expected that in 2030 the transportation sector will be responsible for
58
55% of total oil consumption [1]. It is also expected that the population will grow 1.7
59
times and the number of cars even more (3.6 times) between 2000 and 2050 [2]. In this
60
context, the current policies promoting emissions reduction and the improvement of the
61
energy efficiency of Internal Combustion Engines (ICE) are contributing to palliate
62
these issues [3]. Various strategies have been explored along time to address these
63
issues, such as engine downsizing achieved with turbo-charging [4], the strategy of over
64
expansion explored by the authors [5, 6] and used in several efficient hybrid powertrains
65
or waste energy harvesting such as exhaust thermal energy recovery in form of Organic
66
Rankine Cycle or Seebeck effect thermoelectric generators [7, 8].
67
Nevertheless, the increase of the overall efficiency of conventional powertrains does
68
not seem sufficient by itself to achieve the efficiency and emissions goals set by
69
national and international agreements, nor does it improve the desired diversity of
70
energy sources. Nowadays, the main alternatives to the traditional ICE are the Plug-In
71
Hybrid Electric Vehicles (PHEVs) and the full Electric Vehicles (EV) [9]. These
72
alternatives allow the reduction of the global fossil fuels consumption that is allocated
73
to the traditional transports systems and are a key technology to the future smart grids
74
[10]. Some of these alternatives are now available in the market with substantial success
75
[11], such as Toyota Prius (PHEV) or the Nissan Leaf (EV). These vehicles are globally
76
more efficient than ICE vehicles, mainly under urban traffic since they have no idling
77
losses, they have good low end torque without the need for inefficient clutching, and
78
they can recover some of the kinetic energy lost during the braking [3, 11]. In [12] a
79
comparative environmental life cycle comparison between conventional and electric
80
vehicles has been presented. As an example, using EVs, the global GHG emissions can
81
decrease from 10% to 24% when compared with conventional diesel or gasoline
82
vehicles. In [13] a study highlighted the EV as a means to contribute to the overall
83
reduction of the fossil sources and energy used for transportation, although certainly this
84
will depend on the electricity production performance.
85
Unfortunately, the success of PHEVs and EVs is currently hampered by some
86
notable disadvantages, mostly related with energy storage and power grid charging [14].
87
The main disadvantages are their typically low autonomy (usually up to 150 km) which
88
results from the low energy density of current battery technologies and the long time
89
required to perform standard battery charging processes (typically, a full charge will
90
require around 8 hours to complete) [11, 15]. The combination of these two factors is
91
known to induce the so-called range anxiety phenomenon which, along with the high
92
cost of batteries is preventing the wide adoption of electric mobility [16]. A range
93
extender unit may be added to the powertrain to prevent this, and in fact the authors
94
have confirmed the merits on a Life Cycle basis, of efficiency-oriented range extenders
95
[17], but the use of such systems increases design complexity and cost, as the price tag
96
of some existing models incorporating range extenders indicate.
97
In order to minimize some of the aforementioned shortcomings related to energy
98
storage, some EVs allow to perform a fast battery charging. The CHAdeMo (CHArge
99
de MOve) protocol [18] is one of the most popular DC fast charging protocols in
100
electric mobility, normally displaying a maximum power output of 50 kW. Fig. 1 shows
101
an example of a CHAdeMO fast charging station developed by a partner (PETROTEC)
102
of the team. With this charging mode the battery of many existing models can be
103
charged up to 80% of their State-of-Charge (SoC) in less than half an hour [19]. This
104
substantially reduces the inconveniences associated with small range, provided that fast
105
charging stations are available along the main roads. Of course, BEVs are not practical
106
for frequent long trips due to the need for frequent charging stops. Nonetheless, it would
107
be highly valuable for electric mobility that these long trips would be possible to do if
108
necessary. The range of mass market Battery Electric Vehicles is often around 100-150
109
km, so the suitable distance between two consecutive charging stations should be lower
110
than that distance to allow for occasional long trips.
111
Unfortunately, the high power output required by these chargers is demanding in
112
terms of local infrastructure. A high power consumption plan must be contracted with
113
the electric grid service provider, representing a substantial fixed cost even without any
114
energy consumption. Moreover, EV charging demand will normally occur at daytime,
115
coinciding with costly electrical peak demand periods.
116
Fortunately, many of the aforementioned disadvantages of fast charging may be
117
averted by decoupling grid consumption and the consumption due to vehicle charging
118
by means of stationary energy storage systems. In fact, the energy needed for high
119
power vehicle charging may be stored previously and more gradually (with lower
120
average power) at off-peak demand schedules than in the case of direct grid vehicle
121
charging. This allows reducing both the installed power consumption limit and the
122
average cost of electricity. Also, power quality problems associated with power grid
123
voltage, stability and frequency are minimized [20]. In this context, the present work
124
explores the use of a specific energy storage technology to perform EV fast charging
125
during daytime using electricity previously stored during low demand periods.
126
Moreover, the proposed energy storage technology could also be integrated into
127
microgrids, to store the energy produced from renewable power sources contributing to
128
smooth their intermittent production and adapt it to power demand [21].
129
The load levelling process and the peak shaving process rely on the storage of
130
energy during low demand periods, releasing that energy when the electrical load is
131
high [22, 23]. The main goal of the load levelling process is to stabilize the electrical
132
load, avoiding fluctuations in the consumed power, while in the case of peak shaving
133
process the main goal is to use the stored energy solely to remove the load peaks
134
consumption. For both processes, the energy stored during the night is equal to the
135
energy supplied by the storage system during the day. The comparison between peak
136
shaving and load levelling is illustrated in Fig. 2.
137
Typically, these two processes are implemented in low output power applications,
138
such as domestic grids or small factories with a few kW of power. They have several
139
advantages, the first of all being the reduction of the maximum power consumed from
140
the power grid and consequently the reduction of the installed power, which results in
141
lower prices [24]. Secondly, it permits a better management of the energy demanded
142
from the power grid, taking into account the different energy prices depending of the
143
schedule, because it is possible to buy cheaper power during off-peak periods, such as
144
during night-time [24]. Thirdly, it permits a greater incorporation into the grid of energy
145
derived from renewable sources like solar and wind, which are unpredictable sources,
146
often with the peak power generation occurring in counter-cycle with demand. This
147
means that the availability of an energy storage buffer will avoid wasting the energy
148
produced during low demand periods storing it and releasing it later during high
149
demand events. This will enable a real substitution of electricity obtained from fossil
150
fuel by electricity from renewable energy sources [25, 26].
151
Nowadays, reversible hydroelectric power plants are being often used since they can
152
use the excess of energy produced by renewables (generally the wind energy produced
153
during night hours) to pump water back to the hydroelectric dam, which creates a
154
gravitational energy storage. However, this resource is not always available or sufficient
155
to solve the problem and so, the integration of large scale batteries systems in the
156
electrical power grid seems to be a good solution for complement this energy storage
157
system.
158
There are several energy storage technologies that can be used for load levelling and
159
peak shaving processes besides the pumped hydro storage. They are compressed air
160
storage and batteries. Regarding for batteries, many research groups have been studied
161
the use of lead acid [27, 28], sodium sulphur (NaS) [22], lithium ion [29] and also
162
Redox Flow Batteries (RFB) [30] for these applications.
163
Many of the aforementioned systems have requirements not easily achieved for the
164
application proposed in this work. Among the various battery technologies, the RFB
165
have several advantages over the remainders, namely because their energy capacity is
166
uncoupled from their rated power [31].This is so because energy depends mainly on the
167
amount of electrolyte stored, while rated power is a function of the cell stack. Other
168
advantages of these batteries are related with their liquid nature and their storage (in
169
tanks), which can be of any shape. In [32] and [33]the recent developments and studies
170
of RFB concerning electrolytes, electrodes, membranes, and aqueous and non-aqueous
171
systems have been reviewed. There are many types of RFB with various redox couples
172
used, however, the Vanadium Redox Flow Battery (VRFB) is currently among the most
173
studied and promising technologies of this kind. These batteries have the advantage of
174
using the same chemistry in both half cells. The main advantage of this is that the cross-
175
contamination of the electrolytes will not render the resulting mix unsuitable for the
176
function as would be the case of electrolytes with different chemistries [34]. This is one
177
of the main reasons for their fairly extended life even when compared with the latest
178
Lithium ion battery chemistries. As main disadvantage, complete VRFB systems are
179
still expensive, although the growing maturity of this technology and its attractiveness
180
as an enabler for the wide adoption of intermittent renewable sources is likely to
181
decrease its cost in the midterm [35-37].
182
The recent economic crisis affecting several western economies was accompanied
183
by a reduction in the demand of transportation fuel [38], this reduction is showed in Fig.
184
3 and it can be seen that in the European Union the fuel consumption dropped by almost
185
4% between 2007 and 2011. In the same period, some of the most pronounced drops
186
occurred in Ireland and Spain, which reduced around 23% and 15%, respectively. Other
187
sharp reductions can be also observed, like the one occurred in Greece, which reduced
188
about 17% between 2009 and 2011, and in case of Portugal there was a sharp decline of
189
about 7% between 2010 and 2011.
190
As an alternative to the costly and laborious deactivation/disposal of surplus large
191
fuel storage tanks in gas stations, a retrofit of these deposits could be performed,
192
adapting them for VRFB electrolyte storage and using the storage system for EV fast
193
charging with the strategy explained before. One merit of such an approach would be to
194
easily obtain EV fast charging spots in places which are already strategically located for
195
vehicle traffic, optimizing otherwise wasted space and infrastructures and
196
complementing the ICE vehicle fuel supply business with the emerging plug-in vehicle
197
charging business in one place.
198
Following previous work by the authors in electric mobility and gas station equipment,
199
including a review article on the VRFB technology and its prospects to the electric
200
mobility area [33], the present work assesses this philosophy by carefully describing the
201
operating principles of a VRFB, the use of energy storage technologies for load levelling
202
and peak shaving and by performing a draft design of a VRFB system capable of fast
203
charging simultaneously two electric vehicles. This design is then analysed in terms of
204
energy performance and economic viability.
205
206
Operating Principles of a Vanadium Redox Flow Battery
207
The operating principle of RFBs is partly similar to the operation of a conventional
208
battery, but a major distinction is the fact that the energy storage unit (the active materials)
209
is physically separated from the energy production unit (the cell stack) [39]. So, in a
210
VRFB the active materials are not permanently sealed inside the cell (like in a
211
conventional battery), but are stored separately in tanks and pumped into the cell
212
according to the energy demand [34].
213
This process is represented in Fig. 4, which represents the two tanks, one for positive
214
electrolyte (cathode) and other for negative electrolyte (anode), the cell and the pumps
215
[39]. When the liquid electrolytes are injected into the cell an electrochemical reaction
216
(oxidation-reduction or redox) occurs, with movement of electrons along the electric
217
circuit, as there is an exchange of ions through the membrane to maintain charge
218
neutrality between the different ionic solutions [31].
219
The positive and negative electrodes in vanadium redox flow batteries are typically
220
carbon based materials, such as carbon or graphite felts, carbon cloth, carbon black,
221
graphite powder and so on [40]. These electrodes have shown a good potential in terms
222
of operation range, a good stability and a high reversibility. Similarly to other battery
223
technologies, the electrodes are a very important component on the performance of the
224
vanadium redox flow batteries.
225
There are many types of redox flow batteries, such as: the zinc-bromine (ZBB) [41]; the
226
polysulfide-bromide (PSB) [42]; the Cerium-Zinc (ZCB) [43]; and the Vanadium Redox
227
Flow Batteries (VRFB), which include the first generation (G1 - the all vanadium system,
228
normally called VRB in the literature) and the second generation (G2 - the vanadium
229
bromide system) [33, 44].
230
The G1 is now the most studied technology and involves solely vanadium species in both
231
half cells at different valence states. It operates in an electrochemical couple based on two
232
different reactions of vanadium ions in a dilute acid solution. This is possible because
233
vanadium oxide is a stable material in four different valence states [45].
234
The cathodic and anodic reactions can be represented as follows [46]:
235 +
+
-
2+
236
VO2 + 2H + e ↔ VO + H2O
237
V ↔V +e
2+
238
3+
-
E+ = 1.00 V E- = - 0.26 V
239
And the overall reaction is [46]:
240 +
241
+
2+
2+
3+
VO2 + 2H + V ↔ VO + H2O + V
242 243
The G1 has an advantage relatively to the other redox flow batteries, which is that in the
244
event of a cross mixing between the two liquid electrolytes, the regeneration of the
245
solution may be performed simply by recharging the fluids, unlike systems with different
246
metals in which the mixed liquids would have to be replaced or removed and treated
247
externally or disposed [34].
248
Unfortunately, VRFBs still have a low energy density when compared with conventional
249
batteries. This is due to the maximum concentration of Vanadium that can currently be
250
dissolved in the supporting electrolyte. In the case of the G1 technology, typically the
251
maximum vanadium ion concentration is 2 M or less, which corresponds to an energy
252
density of 25 Wh/kg or 33 Wh/L, and that concentration is limited by the stability of the
253
V5+ ions at temperatures above 40 ºC and the solubility limit of V2+ and V3+ ions in
254
supporting electrolyte at temperatures below 5 ºC. Nonetheless, several studies have been
255
made in the last few years testing the incorporation of additives in the positive electrolyte
256
in order to inhibit the vanadium precipitation and enable the use of higher concentrations
257
and thus increase the energy density.
258
The G2 technology employs a vanadium bromide solution in both half-cells and shares
259
all the benefits of the G1 technology, including the fact that the cross contamination is
260
eliminated [47]. Since the bromide/polyhalide couple has lower positive potential than
261
the V(IV)/V(V) couple, the bromide ions will preferentially oxidize at the positive
262
electrode during the charging [48].
263
The cathodic reactions
264
ClBr2-+ 2e ↔ 2Br-+ Cl-
-
of this technology are as follows [49]:
265
or
266
BrCl2-+ 2e ↔ Br -+ 2Cl-
267
And the anodic reaction is as follows [49]:
268
V ↔V +e
269
However, the G2 technology has a disadvantage, which is the propensity for the formation
270
of bromine vapours during charging. This requires the use of expensive bromine
271
complexing agents which limit the attractiveness of the G2 technology [48].
272
Since the G2 technology is not yet in a mature state and the G1 technology is the most
273
studied and there are already several companies commercializing it [50-55], the present
274
work has focused on this technology. In Fig. 5 a typical charge/discharge cycle of a VRFB
275
at 40 mA/cm2 is shown [56]. It can be seen that the maximum voltage during charge is
276
1.74 V, while during discharge the voltage varies from 1.42 V down to 0.8 V. However, it
277
can also be seen that below approximately 1.15 V, the slope of the curve becomes very
278
sharp, which means that the SoC is close to zero.
279
Currently there are already several VRFB battery manufacturers and some operating
280
plants worldwide. A previous revision article by the authors provides some insight into
281
this subject [33].
-
2+
282
3+
-
VRFB System for Charging EVs In Gas Stations
283
This paper proposes an energy storage technology to be used by electric vehicle fast
284
charging stations to make a peak shaving process, enabling the simultaneous charging of
285
several EVs without having to incur into excessive power availability (e.g. supply
286
capacity) charges.
287
Following several decades of vehicle traffic, existing gas stations are now generally quite
288
conveniently located and evenly distributed for vehicle access. Therefore, the location of
289
EV charging spots at those places is highly attractive since it will not be necessary to
290
captivate additional real estate to build a network of new charging spots suitably located.
291
An EV owner could charge his vehicle using, for instance, a fast charging CHAdeMo
292
station located at such places in roughly half an hour, enabling the use of EVs for
293
occasional long travels, should these stations be conveniently distributed along the main
294
driveways. Furthermore, gas stations could adapt their business size as a function of the
295
increase of EV market penetration.
296
System Layout
297
Fig. 6 shows a typical steel fuel tank used in gas stations [57], among the various fuel
298
tanks available in the market. Capacities vary from 1 000 litres of capacity, to the giant
299
tanks with 100 000 litres of capacity [57, 58], but one of the most commonly used in gas
300
stations is the 20 000 litre tank with around 2.5 m of diameter and around 4.7 m in length.
301
Typically, the gas station underground tanks that are deactivated are not removed and are
302
left unused. It would therefore be advantageous to retrofit these leftover tanks to store the
303
liquid electrolytes. It would inclusively be a way of gradually migrate from a fossil fuel-
304
based business to an electric mobility services business as the market slowly adapts from
305
one paradigm to the other. The present work has considered these tanks for the storage of
306
the liquid electrolytes, but surface tanks are also possible to use and they will facilitate
307
the installation and service of the system.
308
The shape and material of the tanks raises some difficulties. Since they are typically made
309
from steel [57, 58], the liquid electrolytes cannot be in direct contact with them due to
310
their acid nature. To avoid that contact, the tanks may be coated with an acid resistant
311
material. In such case, each fuel tank can only be used for one electrolyte (positive or
312
negative). Alternatively, one or several smaller flexible tanks made from an acid resistant
313
may be installed inside the steel tanks. In this latter case, two smaller flexible tanks, each
314
one containing a different liquid electrolyte, may be accommodated inside one steel tank.
315
As can be seen in Fig. 6, the diameter of the main tank opening (only 60 cm) may hamper
316
the insertion of the flexible tanks inside it. Several small solid tanks made from PVC or
317
other acid resistant material could also be used. However, the best solution seems to be
318
the use of flexible rubber tanks as those firstly proposed by Sumitomo Electric Industries
319
Ltd. These were made specifically to take advantage of the fluidic form of these batteries
320
and to allow their insertion in unused spaces such as underground cisterns, through
321
manholes [59].
322
Rubber tanks with a shape which reasonably conforms to the interior of the steel tanks
323
should be made, as illustrated in Fig. 7 (a), including a support structure to separate both
324
tanks and leaving free space below the manhole to allow the entry of installation and
325
service staff. This structure can be done simply with Landsquare PVC beams and mounted
326
in loco with stainless steel screws.
327
Another alternative, is to use four tanks (two for positive and two for negative electrolyte).
328
This facilitates their introduction into the fuel tank. On the other hand, this configuration
329
allows the existence of two VRFBs using the same gas tank so it is possible to have one
330
battery to charge EVs and the other one being charged at low power input from the electric
331
grid. The four tank configuration is represented in Fig. 7 (b).
332
To make these tanks, the appropriate rubber should be selected. It must be highly
333
resistant to the corrosion with sulphuric acid under the prescribed concentration.
334
Typically, the two liquids electrolytes (anolyte and catholyte) of a G1 are prepared by
335
dissolving around 2M VOSO4 (vanadyl sulphate) into around 5M H2SO4 aqueous
336
solution, to form tetravalent vanadium ions [34], which means that the volume
337
concentration of sulphuric acid may be between 0.005% and 27%.
338
Table 1 which has been compiled from several references [60-62], shows the chemical
339
resistance of the most common rubber types, and it can be seen that there are various
340
types of rubber which are resistant of acid sulphuric for the concentrations needed, like
341
the EPDM, Butyl and Teflon.
342
However, the Vanadium oxides are also corrosive and their presence within the electrolyte
343
must be considered, so a rubber which is resistant to both substances is needed. After
344
analysing Table 1, as a first approximation it seems that Butyl rubber will be a good
345
candidate material for the rubber tanks.
346
2. MODELLING
347
The modelling of the system under analysis is presented in this section. The aim is
348
to evaluate its technological viability in order to characterize the charge/discharge
349
cycles, the flow rate and the required pumping power. This will allow the estimation of
350
the overall efficiency of the system. These calculations do not exclude the importance of
351
building and testing a physical prototype to compare the theoretical and real conditions
352
of operation in order to confirm the accuracy of the present simulation, but show an
353
initial approach to the design of such a system.
354
This project involves the use of a VRFB to store energy from the electrical grid
355
during low demand schedules (and also from renewable sources, if required). The stored
356
energy is then supposed to supply two CHAdeMo fast chargers to charge EVs similar to
357
the ones manufactured by Petrotec [63]. Fig. 8 outlines the architecture of the proposed
358
system. Renewable energy sources could be present at the gas station (e.g., solar or
359
wind energy) in order to reduce the energy consumed from the grid and to benefit from
360
the energy storage facility. However, all the energy included in the present calculations
361
is considered to come from the grid.
362
Electric Model (VRFB discharge)
363 364
During the fast charge of an EV the voltage, current and power output from charger
365
will vary, and these parameters were monitored by Bai et al. [64] for a Nissan Leaf. The
366
evolution of the power output is represented in Fig. 9. This charging cycle was
367
performed by a Terra 51 charger manufactured by ABB and the Nissan Leaf was
368
charged up to 80% SoC. By integrating the power against time it can be concluded that
369
in this particular cycle about 14.8 kWh were supplied to the car (actually, due to the
370
EV’s battery efficiency, the energy effectively stored in the vehicle will be lower, but
371
this is not relevant for the present analysis). This confirms that the vehicle was not fully
372
discharged when the charge began. In a real case each EV will have a different initial
373
SoC, but for the present analysis it seems fit to consider that all EVs will be in the same
374
initial conditions and will be submitted to the same charging cycle as the car monitored
375
in Fig. 9.
376
The power output (Pout) can be calculated for each time step by equation 1:
377
đ?‘ƒđ?‘œđ?‘˘đ?‘Ą =
đ?‘›đ?‘?đ?‘Žđ?‘&#x;đ?‘ đ?‘ƒđ??żđ?‘’đ?‘Žđ?‘“
Ρđ??śâ„Ž
(1)
378 379
The voltage output of the stack during discharge (Vdisch) can be calculated as a
380
function of the open circuit voltage of the stack during discharge (OCVdisch), its internal
381
resistance (R) and the discharge current (I) in each time step by the equation 2: đ?‘‰đ?‘‘đ?‘–đ?‘ đ?‘?â„Ž = đ?‘‚đ??śđ?‘‰đ?‘‘đ?‘–đ?‘ đ?‘?â„Ž − đ?‘…đ??ź
(2)
382 383 384
The instantaneous discharge current (I) of the stack can be calculated as a function of the output power and the output voltage through equation 3:
đ??ź= 385
đ?‘ƒđ?‘‚đ?‘˘đ?‘Ą Vđ?‘‘đ?‘–đ?‘ đ?‘?â„Ž
(3)
The open circuit voltage of the stack is a function of the number of cells (N), the
386
equilibrium potentials E+ and E-, the universal constant of the ideal gases (r), the
387
temperature (T), the Faraday constant (F) and the state of charge, through equation 4
388
[65]:
389
đ?‘‚đ??śđ?‘‰đ?‘‘đ?‘–đ?‘ đ?‘?â„Ž
đ?‘&#x;đ?‘‡ đ?‘†đ?‘‚đ??ś 2 = đ?‘ (đ??¸ − đ??¸ + ln ) đ??š (1 − đ?‘†đ?‘‚đ??ś)2 +
−
(4)
390 391
However, due to the internal resistances, the output voltage will always be lower
392
that the open circuit voltage of the stack, which means that there are losses associated
393
and the real discharge power (Pr) is considered to be the sum of the power output and
394
the losses as represented in Fig. 10, and can be calculated by equation 5:
395
đ?‘ƒđ?‘&#x; = đ?‘‚đ??śđ?‘‰ đ?‘‘đ?‘–đ?‘ đ?‘?â„Ž đ??ź
(5)
396 397 398
So, for a given time lapse (�t=tf-t0), the real discharged energy (Er) of the stack can be calculated through:
399 đ?‘Ąđ?‘“
đ??¸đ?‘&#x; = âˆŤ đ?‘ƒđ?‘&#x; đ?‘‘đ?‘Ą
(6)
đ?‘Ą0
400
On the other hand, the open circuit voltage of the stack depends on the SoC of the
401
VRFB, which will vary during the discharge according to the real discharged energy
402
(Er).
403
The SoC at a given moment can be calculated as a function of the energy density of
404
the liquid electrolyte (E), the volume of liquid stored (V), the maximum state of charge
405
of the VRFB (SoCmax) and the real energy discharged up to that moment, through
406
equation 7:
407
đ?‘†đ?‘‚đ??ś =
đ??¸ đ?‘‰ đ?‘†đ?‘‚đ??śđ?‘€đ?‘Žđ?‘Ľ − đ??¸đ?‘&#x; đ??¸ đ?‘‰
(7)
408 409 410 411
The computation of the results will be iterative and the output power (Pout) over time will be considered to be a known input (profile of Fig. 9). When the electrodes are carbon felts (as proposed in the present work), they must be
412
compressed in order to prevent the leakage of the liquid electrolyte and, at the same
413
time, reduce the electric resistance. Their electric resistance varies with the compression
414
ratio as illustrated in Fig. 11 for a specific model. For instance, for a compression ratio
415
of 20%, the electric resistance reduces by around 70% [66].
416
Often, the available information regarding electrodes and bi-polar plates is, rather than
417
resistance, their resistivity (re). Therefore, the electrical resistance (R) must be
418
calculated as a function of their section area (A) and thickness (le) through equation 8: đ?‘… = đ?‘&#x;đ?‘’
đ?‘™đ?‘’ đ??´
(8)
419
420
2.1.1. Electric Model (VRFB charge)
421 422
With the knowledge of the discharge profiles of Fig. 9 it is possible to define the
423
charge cycle for the VRFB. Firstly, the available stored energy, Ea, (shown in Fig. 12)
424
coincides with the real discharged energy, calculated through equation 9. So, for a given
425
SoC during charge, the available energy stored is calculated as follows:
426
đ??¸đ?‘Ž = đ??¸ đ?‘‰ đ?‘†đ?‘‚đ??ś − đ??¸ đ?‘‰ đ?‘†đ?‘‚đ??śđ?‘šđ?‘–đ?‘› 427 428 429
(9)
The open circuit voltage during charge (OCVchrg) can be calculated as a function of the SoC, as it was done previously for the discharge phase with equation 4. Considering the real power (equal to the input power minus the losses) during a
430
given charge time lapse (tch), the evolution of OCVchrg as a function of time can be
431
estimated. In this way, considering a constant power charge, it is then possible to
432
calculate the current during each time step:
433 ∑ đ??¸đ?‘Ž
đ??ź=
đ?‘Ąđ?‘?â„Ž
đ?‘‚đ??śđ?‘‰đ?‘?â„Žđ?‘&#x;đ?‘”
(10)
434 435 436
With this information it is possible to calculate the output voltage of the stack during charge (Vchrg):
437
đ?‘‰đ?‘?â„Žđ?‘&#x;đ?‘” = đ?‘‚đ??śđ?‘‰đ?‘?â„Žđ?‘&#x;đ?‘” + đ?‘…đ??ź
(11)
438 439
Note that in this case the input voltage will be the sum of the open circuit voltage
440
and the losses. This means that the input voltage is always higher that the open circuit
441
voltage. This is the opposite of what happens during the discharge of the VRFB.
442
So, the input power (Pin) can be calculated as follows:
443
đ?‘ƒđ??źđ?‘› = đ?‘‰đ?‘?â„Žđ?‘&#x;đ?‘” đ??ź 444 445 446
And the efficiency of the VRFB (Ρ) can be obtained through:
(12)
đ?‘Ą
đ?œ‚=
âˆŤ0 đ?‘ƒđ?‘œđ?‘˘đ?‘Ą đ?‘‘đ?‘Ą đ?‘Ą
đ?‘?â„Ž âˆŤ0 đ?‘ƒđ??źđ?‘› đ?‘‘đ?‘Ą
(13)
447 448
An important factor in the viability study of a VRFB system is the required mass
449
flow rate, as it represents an extra energy consumption which will reduce the overall
450
system efficiency. Typically, higher flow rates induce higher voltages due to lower
451
concentration of the reaction products within the cells in each side of the membranes
452
during operation [67]. However, there is an extra consumption of energy which reduces
453
the overall energy efficiency due to the increase of flow rate. Therefore, it is useful to
454
find the optimal value which will result in the maximum efficiency of the system.
455
It is necessary to divide the number of moles of vanadium oxidized per second by
456
the molarity of vanadium ions in the solution in order to calculate the minimum
457
required flow rate [68]. So, knowing the number cells (N), the current (I), and the
458
concentration of vanadium in the solution (Cv) and the Faraday constant (F) it is
459
possible to calculate the stoichiometric flow rate (Q) through equation 13 [68]:
460
đ?‘„=
đ??źđ?‘ (đ??żâ „đ?‘ ) đ??š đ??śđ?‘Ł
(14)
461 462
Since the flow rate depends on the concentration of vanadium, it is necessary to take
463
into account the variation of the concentration of the vanadium reactant in the solution
464
due to the variation of the SoC of the liquid stored in tank during the charge and
465
discharge cycles. The total concentration of vanadium is constant. However, during the
466
discharge, the concentration of reactants decreases, while the concentration of products
467
increases, and vice-versa.
468
Knowing the vanadium reactant and product concentration in the solution, the SoC
469
can be calculated in two ways, regarding to the concentration at the anode or at cathode
470
respectively [69, 70]:
471
đ??śđ?‘‰ 2+ đ??śđ?‘‰đ?‘‚2+ đ?‘†đ?‘‚đ??ś = = đ??śđ?‘‰ 2+ + đ??śđ?‘‰ 3+ đ??śđ?‘‰đ?‘‚2+ + đ??śđ?‘‰đ?‘‚2+
(15)
472 473
And the Depth-of-Discharge (DoD) can be calculated as follows [69]:
474
đ??ˇđ?‘‚đ??ˇ = 1 − đ?‘†đ?‘‚đ??ś =
(16)
Electrolyte Flow Model
475 476
đ??śđ?‘‰ 3+ đ??śđ?‘‰đ?‘‚2+ = đ??śđ?‘‰ 2+ + đ??śđ?‘‰ 3+ đ??śđ?‘‰đ?‘‚2+ + đ??śđ?‘‰đ?‘‚2+
Equation 14 does not take into account the variation of the SoC through the
477
membrane. This variation would be negligible for very high flow rates. Although it is
478
not quite the case in the present work, this effect has been neglected for the sake of
479
simplicity.
480
Note that when the VRFB is charging Cv of equation 14 refer to the concentration of
481
V2+ or VO2+ . On the other hand, when the VRFB is discharging, Cv refer to the
482
concentration of V3+ or VO2+. This means that the flow rate will have to vary during the
483
operation of the VRFB. It will increase during the increase of the SoC (when charging)
484
and during the increase of DoD (when discharging). This is consistent with the study
485
made by Ma et al. [71].
486
Note that the flow rate calculated by equation 14 is the flow rate for each electrolyte
487
(i.e., anode and cathode solutions). However, this value represents the minimum flow
488
rate necessary to produce the desired current if all vanadium ions existing within the
489
solution were oxidized while flowing through cells. In practice, this does not happen
490
and some authors suggest the use a flow rate which is higher than the one theoretically
491
calculated.
492
Unfortunately, to the authors’ knowledge, there is not sufficient information
493
available in the literature concerning the difference between the theoretical and the real
494
flow rate needed, so in this paper it will be considered that the VRFB will operate with
495
the stoichiometric flow rate calculated from equation 14. In this way, the calculated
496
efficiency with pumping power might be somewhat overestimated.
497 498
So, knowing the flow rate, the pumping power (Ppump) can be estimated through equation 17:
499 đ?‘ƒđ?‘?đ?‘˘đ?‘šđ?‘? = đ?‘›đ?‘?đ?‘Žđ?‘&#x;đ?‘ đ?‘„ ∆đ?‘?
(17)
500 501
With Δp representing the total pressure loss in the system, calculated through:
502
∆đ?‘? = ∆đ?‘?đ?‘?đ?‘–đ?‘?đ?‘’đ?‘ + ∆đ?‘?đ?‘ đ?‘Ąđ?‘Žđ?‘?đ?‘˜
(18)
503 504
The pressure loss in the Stack (Δpstack) is due to the flow of the liquid through the
505
graphite felt electrodes and can be calculated based on the flow rate, the dynamic
506
viscosity (Îź), the permeated specimen length (l), the permeability (P) and the permeated
507
cross section area (Acs) [66]:
508
∆đ?‘?đ?‘ đ?‘Ąđ?‘Žđ?‘?đ?‘˜ = 509
đ?‘„đ?œ‡đ?‘™ đ?‘ƒ đ??´đ?‘?đ?‘
(19)
510
It is necessary to consider that the permeability of the electrodes will vary with the
511
compression of the electrodes, according to the chart represented in Fig. 13. Of course, a
512
trend-off must be made here due to the dependence of the resistivity on this parameter
513
(recall Fig. 11).
514
The pressure loss in the pipes (Δppipe) should also be calculated according to the
515
specific piping geometry chosen. To calculate the total pressure drop, it is necessary in
516
the first place, to calculate the Reynolds number (Re) in each pipe section [72]:
517
đ?‘…đ?‘’ =
4đ?‘„ đ?œ‹đ??ˇđ?‘Ł
(20)
518 519
where v represents the kinematic viscosity of the fluid (resulting from the division of the
520
dynamic viscosity by the density) and D the inner diameter of the pipe. The coefficient
521
of friction (f) can be calculated from the Colebrook expression, which is the basis for
522
the Moody Diagram [72]:
523
đ?œ€â „ 1 2,51 = −0,86 ln ( đ??ˇ + ) đ?‘“ 3,7 đ?‘…đ?‘’ √đ?‘“
(21)
524 525 526
The localized head losses can be considered as an equivalent piping length (Le) calculated as a function of the coefficient of head loss (k) [72]:
527
đ??żđ?‘’ =
∑đ?‘˜ đ??ˇ đ?‘“
(22)
528 529 530
So, the total head loss (H) for each section can be calculated function of the parameters calculated previously by equation 23 [72]:
531
đ??ť=đ?‘“
đ??ż + đ??żđ?‘’ đ?‘‰ 2 đ??ˇ 2đ?‘”
(23)
532 533
where V corresponds to the velocity of the fluid, L corresponds to the length of the
534
section and g is the gravitational acceleration. The pressure drop for each section can be
535
calculated as follows [72]:
536
∆đ?‘?đ?‘?đ?‘–đ?‘?đ?‘’ =
đ??ť đ?œŒđ?‘”
(24)
537 538 539 540
541
542
where Ď is the density of the liquid electrolyte. The total pipe pressure loss will be the sum of the pressure losses in each section and the pumping power can be calculated using equations 17 and 18.
Economic Analysis The technological analysis made would be incomplete without a suitable economic
543
analysis. Firstly, it is necessary to roughly estimate the total cost of the proposed
544
system, even if there is a substantial uncertainty degree concerning its real cost.
545
Nevertheless, estimations based on the information obtained from the manufacturers are
546
valuable for this purpose.
547
Firstly, it is necessary to calculate the overall system efficiency using this VRFB
548
connected to two CHAdeMo chargers each with a given efficiency (ΡCh ) and one VRFB
549
AC/DC charger with a given efficiency (ΡAC-DC). So the overall system efficiency
550
(Ρsystem) can be calculated by equation 25.
551
đ?œ‚đ?‘†đ?‘Śđ?‘ đ?‘Ąđ?‘’đ?‘š = đ?œ‚đ??´đ??śâˆ’đ??ˇđ??ś đ?œ‚đ??śâ„Ž đ?œ‚đ?‘Ąđ?‘œđ?‘Ąđ?‘Žđ?‘™ đ?‘‰đ?‘…đ??šđ??ľ
(25)
552 553
For the economic evaluation of the project, both the NPV (net present value) and the
554
payback time (PT) criteria will be computed. The economic evaluation is then based on
555
a traditional discounted Cash-Flow (CF) approach, including overall financial
556
assumptions on the depreciation rate, taxes, inflation rate and discount rate and also
557
estimation of the project expected sales and operational costs.
558
So, firstly, the calculation of the gains from sales (S) for the first year (n = 1) is
559
computed as a function of the energy sold for the charging of each vehicle (Esold), the
560
number of EVs charged per day (Nd), the number of operating days per year (DpY) the
561
price of the electricity sold (s) and the average inflation rate (i). Sales for the first year
562
(n = 1) can then be calculated by equation 26.
563
S n=1 = (đ??¸đ?‘ đ?‘œđ?‘™đ?‘‘ Nd s DpY) (1 + i)
(26)
564 565
Considering that all the assumed parameters remain constant during the whole life
566
cycle considered, sales for the following years can be calculated as described in
567
equation 27.
568
S n = S n−1 (1 + i)
(27)
569 570 571
The associated costs (C) for the first year (n = 1) are calculated according to equation 28, depending on the price of the electricity bought to charge the batteries (p).
572
C n=1 =
(đ??¸đ?‘ đ?‘œđ?‘™đ?‘‘ Nd DpY) p (1 + i) ΡSystem
573 574
The costs for the following years are calculated by equation 29.
(28)
575
C n = C n−1 (1 + i)
(n > 1)
(29)
576
577
3. RESULTS AND DISCUSSION
578
Simulation Conditions
579
It is assumed that there will be always two vehicles charging simultaneously (two
580
chargers connected to the VRFB) and that the CHAdeMo charger efficiency (ηCh) will
581
be around 95%, so the power output (Pout) can be calculated for each time step by
582
equation 1.
583
Table 2 and Table 3 show the specific input values used to simulate the VRFB
584
system proposed for this project, but the analysis proposed may be used for different
585
values.
586 587
The permeability and resistance of the electrodes depends on the compression of the
588
electrodes (recall Fig. 11 and Fig. 13). The chosen compression of 20% therefore yields
589
a permeability of the electrodes around 4.7x10-11 m2 and a 70% drop in the original
590
electrode resistance [66].
591
Therefore, the internal resistance (R) of this system can be calculated by the sum of
592
the single components. In the case of electrodes and bi-polar plates it is calculated by
593
equation 8 and the total resistance of the system will be around 4.897 mΩ.
594
Regarding the hydraulic calculations, it is considered that each liquid electrolyte has
595
a height difference between the tank and the stack of 1 m. The tubes used are considered
596
to be made of PVC with low roughness (ε = 0.005 mm). The first section of the piping
597
is a circular tube with 40 mm of inner diameter, a length of 12 m and three 90º bends,
598
which carries the liquids from the tanks to the cell. The second section of the piping is a
599
collector with one output for each cell, with 3 mm of inner diameter and 20 cm of
600
length. The third section is another collector attached to each output of section 2. This
601
collector has 5 outputs, which means that the entry of the liquid into the cell is made
602
through 5 different locations in order to uniformize the flow. Each output is also a
603
circular tube with 3 mm of inner diameter and 20 cm of length. The return circuit
604
displays an identical circuit, symmetrical to the one just described. The pressure losses
605
in collectors have been neglected. Regarding the localized head losses a coefficient of
606
head loss (k) of 0.9 has been considered for each one of the bends [72]
607
608
System Performance
609
Fig. 14 (a) and (b) represent the variation of the voltage and the current,
610
respectively, during a simulation of a VRFB used for 14 consecutive fast charging
611
cycles of 2 EVs simultaneously. The strong variations of voltage and current are due to
612
the variable power profile of each vehicle charge according to Fig. 9.
613 614
The vehicles simulated have the characteristics of the Nissan Leaf, while the
615
charging profile was the one represented in Fig. 9. This means that a total of 28 vehicles
616
were charged in a 7.5 hour period, with the final state of charge of the VRFB having
617
dropped to around 1%, with no energy left to perform another vehicle charge. The rise
618
in current observed in Fig. 14 (b) is a natural consequence of the drop in voltage
619
observed in Fig. 14 (a), to ensure the programmed power cycle. The slight ripple
620
observed in the SoC curve is due to the non-constant power profile (Fig. 9).
621 622
Considering a system with 250 cells and a membrane area of 0.5 m2, the internal resistance can be calculated using the information from manufacturers (as the
623
information gathered in Table 2) along with the membrane area and the number of cells.
624
The present work considers that the membranes have a square geometry, but a
625
rectangular shape could also have been adopted.
626
The voltage and current, as a function of charge time, are showed in Fig. 15 (a) and
627
Fig. 15 (b) respectively. The calculated theoretical energy efficiency was 93.7% without
628
considering the pumping losses.
629
Fig. 16 (a) and (b) display the variation of the flow rate for each liquid electrolyte
630
during discharge and charge cycles, respectively. It can be seen that there is an
631
exponential increase of the flow rate along time during both charge and discharge.
632
It can be seen that this system will have very high flow rates during the ending of
633
the charge and it very high pumping power will be needed, resulting in a very low
634
efficiency, around 9%.
635
So, in order to reduce the pumping power and increase the system efficiency, a
636
reduction of the SoC interval used is proposed. A good compromise seems to be
637
choosing a maximum SoC obtained during charge of 97% (which reduces the total
638
number of cycles to 13). The result is shown in Fig. 17 (a) and (b) for the discharge and
639
charge respectively.
640
Under these conditions the minimum SoC achieved during discharge will be 4.7%,
641
and the VRFB efficiency considering pumping losses (ΡtotalVRFB) will be 91.7% (93.8%
642
without pumping losses). However the reduction of the SoC range used also resulted in
643
a reduction of the system capacity used, from 462 kWh to only 426 kWh. On the other
644
hand, these 426 kWh available are affected by the discharge efficiency with means that
645
in these conditions the VRFB will only provide to the fast charger around 405 kWh.
646
This energy is sufficient to charge 26 EVs.
647 648
Economic Analysis
The cost of the system has been considered to be that provided by a manufacturer
649 650
for a complete system (324 000 €) with the power and capacity similar to the values
651
required by this project (100 kW and 405 kWh). This commercial system includes
652
tanks, pumps, control system, cell stack and liquids electrolytes. However, this is a
653
typical system in which all the components are sealed in a box. The present work
654
considers that switching the solid tanks by the rubber tanks will not impact the final
655
price of the system.
656
A 20 year life cycle is considered for the project, with 26 EVs being charged per
657
day, during all 365 days of the year. For the electricity prices, the values were estimated
658
according to the Portuguese electricity time-differentiated tariffs that can reach at nigh a
659
value close to 0.08 €/kWh. This was assumed as the price of electricity bought to charge
660
the batteries (p). As for the selling price, the estimation departed from the values
661
reached during day for the Portuguese household consumers added of a premium value.
662
This premium can be justified by the fast charging possibility offered to the EV user and
663
also by the strategic location of the charging stations (e.g., motorways). The selling
664
price is then assumed to be 0.4 €/kWh. The sales per vehicle depend on the energy
665
supplied to charge the vehicle (Esold) (14.8 kWh according to the charge profile of Fig.
666
9). The inflation rate (i) is considered to be 1.8%, a value corresponding to the average
667
Harmonized Index of Consumer Prices for the EU1. The tax over gain was assumed to
668
be (TOG) 25%, and the minimum acceptable rate of return was settled as (MARR) 5%
669
for the base case analysis. The savage value of the equipment was considered to be null
670
at the end of the 20 years life time. The efficiency of the CHAdeMo chargers and VRFB
671
AC/DC charger considered are showed in Table 3. Under the assumed conditions the
672
global NPV reaches 109 906 €, which demonstrates the potential financial interest of the
Average value for the euro area for the period 1996-2015. Information obtained from the European Central Bank on https://www.ecb.europa.eu/stats/prices/hicp/html/inflation.en.html, consulted on September 2015. 1
673
project for private investors. As for the simple payback period, it can be reached
674
between the 8th and 9th years.
675
However, the present approach represents an innovative project and the uncertainty
676
of the financial and even technical assumptions should be recognized. In particular,
677
aspects such as the number of EVs charging per day, technical assumptions on
678
efficiency, the investment cost, the electricity prices differential or the discount rate are
679
important parameter whose values can have a high impact on the financial viability of
680
the investment. In fact, the assumed required investment for this system is still high
681
because it is not yet a mature technology and there are still not a lot of manufacturers
682
worldwide. It is expected that during the next few years the price of this technology will
683
decrease. The electricity prices, the access or not to differentiated tariffs or even the
684
existence of different electricity tariff schemes are country or region dependent, which
685
turns important the computation of the minimum prices differential to ensure the project
686
interest. The number of EVs charged and the technical efficiency of the system have a
687
direct impact on the sales and as such have also a major role on this analysis. Finally the
688
discount rate (which is the MARR affected by the inflation rate) can influence
689
significantly the obtained values and it is on the other hand highly influenced by the
690
perceived risk of the investment.
691
692
Sensitivity Analysis
693
In the previous subchapters the system viability was analysed both technologically and
694
economically. However the results of the analysis performed are specific for the input
695
parameters assumed and presented in Table 2 and Table 3. So in this subchapter a
696
sensitivity analysis is made in order to evaluate the effect of the variation of the main
697
input parameters on the viability of the project.
698
The technological viability is mainly dependent on the efficiency of the system, which
699
is its most important characteristic. It can be seen in Fig. 18 thru Fig. 21 that this system
700
has a high efficiency and it is still possible to increase it by varying, on one hand, some
701
of the construction parameters, like the number of cells and the membrane area and on
702
the other hand, it is also possible to adjust the operational parameters, like the number
703
of EVs in simultaneous charging and the VRFB charging time. In another way, it can be
704
seen in these figures that the efficiency does not change abruptly with the variation of
705
any parameter studied, which means that this system has a good flexibility of design and
706
operation.
707
Another important parameter that must be studied is the maximum current in the
708
system, since if too high currents are present, they might require the use of excessive
709
cable sections.
710
The first parameter studied is the number of EVs charged simultaneously. When
711
comparing the original two EVs against only one car, higher currents and flow rates will
712
result, yielding lower efficiencies. In practice, however, the average number of EVs
713
being charged at a given moment will be somewhere between one and two, with the
714
system efficiency being located somewhere between these two cases. This is illustrated
715
in Fig. 18, where a total of 26 EV charges were simulated for both situations.
716
Another important parameter that influences the system efficiency is the number of cells
717
used. The use of more cells will result in higher output voltages and lower currents,
718
which will result in lower losses. On the other hand, the use of more cells will mean
719
higher system costs. Estimating the variation of system cost as a function of the size of
720
the system is out of the scope of the present work, but the size chosen seemed to be a
721
good compromise between a reasonable system size, efficiency and maximum current
722
during the discharge.
723
Analysing Fig. 19 it can be seen that for a system with 125 cells the efficiency is low
724
(around 86%) and the current is around 800 A, which is very high and would require the
725
use of cables with high section. 250 cells seems to be a good choice because it results in
726
reasonable values of maximum current and efficiency.
727
The membrane area is also an important parameter. It can be seen in Fig. 20 that the
728
efficiency increases with the increase of the membrane area. On the other hand, the
729
maximum current density during the discharge also decreases. However, bigger
730
membranes means higher costs. Therefore, like in case of the choice of the number of
731
cells, it would be also necessary to take this into account. A membrane area of 0.5 m2
732
was chosen as being to be a good compromise.
733
The last parameter analysed is the VRFB charging time. Higher charging times
734
represent a lower charging power and therefore a higher efficiency due to the lower
735
required flow rates and currents. But it also increases the period of unavailability of the
736
system for EV charging. However, the charging time can be reduced by increasing the
737
charging power but it also increases the maximum current needed. This is a key part of
738
the economic viability of the project. When analysing Fig. 21 it can be seen that the
739
variation of system efficiency with varying charging time is not that significant. This
740
work considers that the system will be charged in 12 hours at constant power, during the
741
night, when both the demand and the electricity costs will be lower.
742
Regarding to the economic viability, it will depend on the NPV and the payback time.
743
Although a positive NPV the project can be considered as economically viable, long
744
payback times might render the project unattractive.
745
The relationship between the technological and the economic viability is provided
746
by the VRFB system efficiency (with pumping) which is the main parameter directly
747
affecting the total efficiency of the system (equation 25). This efficiency will be
748
translated into the relationship between the energy consumed from the grid and the
749
energy sold to charge the electric vehicles. Therefore, the economic viability of this
750
project will be strongly affected by the reduction of the efficiency of the system. Fig. 22
751
shows the variation of the NPV and payback time as a function of the VRFB efficiency
752
(with pumping).
753
The 80% efficiency is the value announced by a manufacturer, as previously referred.
754
Also, the efficiency calculated in section 4.3 for two EVs (91.7%) is also presented. It is
755
possible to see that the pumping influences greatly the NPV, so in order to improve the
756
efficiency it is possible to reduce the pumping losses by using a lower compression rate,
757
which can be seen in Fig. 12, increasing the permeability. However, it can be seen in
758
Fig. 11 that reducing the compression rate will also increase the resistivity, which will
759
reduce the efficiency, so an optimal trade-off between these two effects should always
760
be pursued in a real application.
761
Another important factor that affects the economic viability of this project is the
762
MARR, which has been considered to be 5% in the previous section.
763
The NPV almost increases 50% when decreasing the MARR from 5 to 4%. However, it
764
can be seen in Fig. 23 that for values of 9% and below the NPV is already negative,
765
which means that this project would only be economically viable for lower values of
766
MARR. Recognizing this as an innovative project, the value of the MARR seems to be
767
a critical aspect demonstrating the need to reduce costs or resource to public support
768
schemes at least in the initial demonstrative phase of the technology.
769
The number of EVs charged per day is also an important factor and it can be seen in
770
Fig. 24 that NPV is positive if more than 19 EVs are charged per day during 20 years.
771
The NPV nearly doubles when increasing from 22 EVs to 26 EVs per day.
772
As already mentioned, it is expected that the price of this kind of system will tend to
773
decrease along time. Therefore, it is useful to analyse the variation of the NPV with the
774
variation of the system cost, as represented in Fig. 25. It can be seen that it is possible to
775
nearly double the NPV with a 40% reduction in the system initial investment cost.
776
However, it is also clear that if the investment increases by more than around 30% the
777
project will no longer be financially viable. Once more, this demonstrates the need to
778
further develop the technology reducing the risk for the investors.
779
Finally it is worth to analyse how the electricity selling prices and their differential
780
represents a fundamental parameter for the project financial attractiveness. Fig. 26
781
shows the obtained NPV for different electricity selling prices, showing that a price
782
differential above 0.22â‚Ź/kWh (0.30â‚Ź/kWh - 0.08â‚Ź/kWh) must be ensured for the project
783
to be considered attractive.
784
785
4. CONCLUSIONS
786
The proliferation of Electric Vehicles (EVs) will bring a higher demand for battery
787
fast charging locations. Also, the high power demanded for fast charge stations is a
788
disadvantage. The use of energy storage systems, and in particular, Vanadium Redox
789
Flow Batteries (VRFBs) seems to be a good solution for reducing the installed power
790
with a peak shaving strategy. Existing or recently deactivated gas stations are privileged
791
locations for this purpose and many of them have available space and unused fuel
792
storage tanks. Furthermore, flow batteries also provide the possibility of taking
793
advantage of the availability of empty fuel storage tanks.
794
The present work details a preliminary project of a Vanadium Redox Flow Battery
795
of first generation (G1) to be used in gas stations for supplying electric energy for two
796
CHAdeMo chargers (50 kW each) working simultaneously. The VRFB is charged for
797
12 h during off-peak power demand (at night). The same cell stack is used for charging
798
and discharging the liquid electrolytes. This preliminary project was conceived using
799
commercially available system components.
800
A method for storing the liquid electrolytes of VRFBs in rubber tanks (installed
801
inside the fuel storage tanks normally used in gas stations) has been proposed. This will
802
prevent corrosion of the fuel tanks, which are normally made of steel, while allowing
803
the storage of both liquid electrolytes (anode and cathode) in the same fuel tank without
804
mixing. Furthermore, the flexibility of the rubber enables the use of large rubber tanks
805
that can still be inserted through the manhole entry of these fuel tanks.
806
The preliminary project was assessed in terms of voltage, current, power and
807
efficiency (both with and without pumping losses). An efficiency around 92%
808
(including pumping losses) has been predicted when using the VRFB system to fast
809
charge 26 EVs per day. Nevertheless, a more detailed assessment will require the
810
manufacture and testing of a prototype. Although specific input parameters have been
811
used, the methodology proposed in this work is sufficiently detailed to allow the
812
assessment of diverse configurations.
813
A cost analysis of the preliminary project was also performed in terms of Net
814
Present Value (NPV) for 20 years (the life time considered for the system) and the
815
Payback Time. It has been concluded that, for the input parameters considered and for a
816
Minimum Acceptable Rate of Return (MARR) of 5%, the project is economically
817
viable, and the investment is recovered in 9.5 years with a NPV of 109.9 kâ‚Ź. However,
818
the sensitivity analysis clearly shows the fragility of the obtained values, which should
819
be looked with caution given the initial stage of the project. The sensitivity analysis
820
illustrated that slight variations in the input conditions might substantially affect the
821
viability analysis. It is particularly important to recognize the potential for technology
822
development and even reach economies of scales that would make the project much
823
more attractive in the short term. However, the viability largely depends on the
824
electricity market operating conditions, namely electricity time-differentiated tariffs and
825
adequate regulatory conditions for the development of this business model supported on
826
free electricity market trading. Future work should then address both technology
827
development and regulatory and market environment as key factors for the commercial
828
success of the project. Additionally, issues related to the impacts of these projects on
829
the management of the electrical power grid, and their contribution for facilitating the
830
incorporation of intermittent renewable energy sources (such as wind power and solar
831
photovoltaic), with the benefits of reducing fossil fuel dependency and associated
832
emissions must also be further explored.
833
In the midterm, if the energy density of flow batteries substantially increases, the
834
philosophy proposed in the present work will be easily adapted in order to charge the
835
Electric Vehicles by substituting their discharged liquid electrolytes by charged
836
electrolytes, instead of indirectly charging the vehicle electrically via a fast charging
837
station. This would eliminate one of the major current disadvantages of EVs, which
838
consists on their long charging times. The time required to charge an EV would then be
839
similar to the time required to supply a conventional fuel vehicle.
840 841 842
ACKNOWLEDGEMENTS The authors would like to thank Petrotec S.A. for the support given to the present
843
work. This project was funded by Project MOBI-MPP (MIT-Pt/EDAM-
844
SMS/0030/2008) supported by the MIT Portugal Program and FEDER funds through
845
the Programa Operacional Factores de Competitividade - COMPETE and National
846
Funds through FCT - Foundation for Science and Technology. Francisco P. Brito
847
benefited from post-doctoral grants SFRH/BPD/51048/2010 and
848
SFRH/BPD/89553/2012 supported by the MIT Portugal EDAM and FCT, respectively.
849
850
REFERENCES
851 852 853 854 855 856 857 858 859 860 861 862 863 864 865 866 867 868 869 870 871 872 873 874 875 876 877 878 879 880 881 882 883 884 885 886 887 888 889 890 891 892 893 894 895 896 897 898 899 900 901 902 903 904 905 906 907 908
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FIGURES
993 994
995
Fig. 1 – Example of a CHAdeMo fast charging station (62) (courtesy Petrotec)
996 997 998
(a) Load Leveling Energy Stored
Energy Supplied by the Storage System
Power
Energy Supplied by the Storage System
Power
Energy Stored
(b) Peak Shaving
Power Demanded by Loads
21
999 1000
1001
3
9 time (h)
15
Power Demanded by Loads
21
21
3
9 time (h)
15
Fig. 2 - Comparison between the processes of peak shaving (a) and load levelling (b)
21
Increase of Road Transport Energy Consumption (base year 1990)
3
2,5
2
1,5
1
EU (27 countries) Ireland Spain Portugal
Germany Greece Italy United Kingdom
0,5 1990
1002
1995
2000 Year
2005
2010
1003
Fig. 3 - Variation of road transport energy consumption between 1990 and 2011 in some
1004
countries of European Union (adapted from [38])
1005
1006 1007
1008
Fig. 4 - Operating principle of a Redox Flow Battery (RFB)
1009 1010
Fig. 5 - Typical charge/discharge cycle of a single cell (G1 technology) for a current
1011
density of 40 mA/cm2 (adapted from [56]).
1012
1013 1014
Fig. 6– Typical fuel tank used in gas stations (courtesy of Henriques & Henriques S.A.)
1015
[57].
1016
1017
1018
Fig. 7 - Scheme of rubber tanks for VRFBs (outline view of fuel tanks with support
1019
structure): (a) Two tank configuration; (b) Four tank configuration.
1020 vi ii
v o io
Power Grid
t
v o io
Power Converter t
Vanadium Redox
Power Converter t
Flow Batteries
Power Converter
Renewables
1021
Fig. 8 – Proposed system architecture.
1022
1023
1024 1025
Fig. 9 – Typical evolution of the charging power output of a Nissan Leaf, as monitored
1026
by Bai et al. [64].
1027 1028
Fig. 10 - Discharging process of a VRFB.
1029
1030 1031
Fig. 11 - Electrical resistance of the GFA6EA graphite felt electrodes of SGL GROUP
1032
as a function of the compression rate [66].
1033
1034 1035
1036
Fig. 12 - Charging process of a VRFB.
1037
Fig. 13 - Permeability of the graphite felt electrodes SGL GFA6EA [66].
1038
1039
80%
400 60% 350 40% 300 20%
250 200
(a)
350
80%
300 250
60%
200
40%
150
20% 100 50
0% 0
1040
100
200
300
100%
Current SOC
0% 0
400
(b)
Time (minutes)
SOC
450
400
100%
Discharging Current (A)
Voltage SOC
SOC
Discharging Voltage (V)
500
100
200
300
400
Time (minutes)
Fig. 14 - Discharging Voltage (a) and Current (b) cycles for VRFB system.
1041
1042
350
60%
300
40%
250
20%
0% 0
1044
(a)
200
400
SOC
80%
140
60% 120 40% 100
20%
80
0% 0
600
Time (minutes)
100% Current
80%
200
1043
160
(b)
200
400
600
Time (minutes)
Fig. 15 - Charging Voltage (a) and Current (b) cycles for the VRFB system.
SOC
400
100%
Charging Current (A)
Voltage SOC
SOC
Charging Voltage (V)
450
1045
80%
1200 60%
800
40%
400
20%
0 100
(a)
200
300
100% Flow rate SOC
80%
120
60% 80 40% 40
20%
0
0% 0
1046
SOC Flow rate (L/min)
Flow rate (L/min)
1600
160
SOC
100% Flow rate (L/min) SOC
0% 0
400
200
400
600
(b)
Time (minutes)
Time (minutes)
Fig. 16 - Variation of flow rate during discharging (a) and charging (b) cycles.
1047
1048
40
80%
30
60%
20
40%
10
20%
0 100
200
300
100%
16
80%
12
60%
8
40%
4
20%
0
0% 0
Pumping power SOC
0% 0
400
(b)
200
400
600
1049
(a)
1050
Fig. 17 - Variation of pumping power during discharging (a) and charging (b) cycles.
Time (minutes)
Time (minutes)
1051
96% 94,8%
94%
92%
93,8%
93,4%
91,7% Efficiency with pump
90% 2 cars 1052
Efficiency without pump
1 car
SOC
20
100%
Pumping power SOC
SOC Pumping power (kW)
Pumping power (kW)
50
1053
Fig. 18 - Efficiency comparison between 1 and 2 EVs charging simultaneously.
1054 Efficiency without pumping
Efficiency with pumping
750
Maximum current
600 93%
450 300
89%
Current (A)
Efficiency
97%
900
150
85%
0 125 150 175 200 225 250 275 300 325 350 375 400
1055
Number of cells
1056
Fig. 19 - Variation of efficiency and maximum current as a function of the number of cells.
1057
99%
Efficiency
95%
250 200
91%
150
87%
100 83% 50
79% 75%
Current density (mA/cm2)
Efficiency without pumping Efficiency with pumping Maximum Current Density
0 0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1
Membrane Area (m2) 1058 1059
Fig. 20 - Variation of the efficiency and maximum current density as a function of membrane
1060
area.
1061
300
95%
250 200
90%
150 85%
100
80%
50
75%
Maximum current (A)
Efficiency
100%
Efficiency without pumping Efficiency with pumping
Maximum current
0 6
7
8
9
10
11
12
13
14
15
16
VRFB charging time (hours)
1062 1063
Fig. 21 - Variation of the efficiency and maximum current (during charge) as a function of
1064
VRFB charging time.
1065
VRFB efficiency with pumping
NPV
150 000 €
100 000 €
50 000 €
0€
1066
NPV Payback time (yearss)
60.0% 47 183 9.72
70.0% 73 103 9.10
80.0% 92 544 8.69
91.7% 109 906 8.35
95.0% 114 030 8.27
1067
Fig. 22 - NPV and Payback time as a function of VRFB efficiency with pumping (with 91.7%
1068
corresponding to the efficiency obtained by the analysis with 2 EVs in simultaneous charging).
1069
MARR 150 000 €
NPV
100 000 €
50 000 €
0€ 4%
6%
8%
10%
-50 000 €
1070 1071
5%
Fig. 23 – Net Present Value as a function of the Minimum Acceptable Rate of Return (MARR).
1072
Average number of EVs per day 150 000 €
NPV
100 000 € 50 000 € 0€
-50 000 €
1073 1074
1075
NPV Payback time (years)
18 -4 720 € 11.3
20 23 936 € 10.4
22 52 593 € 9.6
24 81 250 € 8.9
26 109 906 € 8.3
Fig. 24 - NPV and Payback time as a function of the average number of EVs charged per day.
System cost variation 300 000 €
NPV
250 000 € 200 000 € 150 000 € 100 000 € 50 000 €
0€ -50 000 €
1076
50% 60% 70% 80% 90% 100% 110% 120% 130% Série1 241 221 214 958 188 695 162 432 136 169 109 906 83 643 € 57 380 € 31 117 € Série2 4.5 5.4 6.1 6.9 7.6 8.3 9.0 9.7 10.4
1077
Fig. 25 - NPV and Payback time as a function of the change in the initial investment (100%
1078
means no change in cost).
1079
Influence of selling price (€/kWh) 250 000 €
NPV
200 000 € 150 000 € 100 000 € 50 000 € 0€ 0.30
1080 1081
1082 1083
0.35
0.40
0.45
0.50
-50 000 €
Fig. 26 - Influence of selling price on the Net Present Value
TABLES
1084 1085 1086
Table 1 - Compatibility of various types of rubber with sulphuric acid and vanadium oxides [60-62].
Natural Rubber Sulphuric acid C dilute (10%) Sulphuric acid B 25% Sulphuric acid B 25 – 50% Sulphuric acid 50 – 98% Sulphuric acid D 98% Vanadium Oxide Vanadium Pentoxide
EPDM Nitrile Neoprene Viton SBR
Silicone Teflon Butyl rubber rubber
B
C
B
A
C
D
B
A
A
-
-
C
-
-
A
A
A
-
-
B
-
-
A
A
A
-
-
A
-
-
-
A
C
D
D
A
D
D
D
C
D
A
B
A
D
D
A
-
D
A
B
A
D
D
A
-
1087 1088
A - Recommended
1089
effect
B - Minor to moderate negative effect
C - Moderate to severe negative
D - Not recommended
1090 1091
Table 2 - VRFB stack components selected for the analysis
1092
Membrane
Eletrodes
Bi-polar plates
Nafion 117
SGL GFA6EA [66]
SGL PPG86 [66]
Resistivity
-
15 Ωmm
1 Ωmm
Thickness
-
6 mm
3 mm
Compression ratio
-
20%
-
Resistance reduction
-
70%
-
0.1 Ωcm2
0.018 Ω
0.000297 Ω
250
500
249
Model
Electric Resistance Number of Elements 1093 1094
1095
1096 1097 1098
Table 3 - Input values used to simulate the VRFB system. Number of cells (N)
250
Cell equilibrium potentials (E+/ E-)
1.004 / -0.255 V
Energy density (E)
33 Wh/L
Volume of liquid stored (V)
14000 L
Dynamic viscosity of liquid electrolyte (Îź)
4.93x10-3 Pa.s
Density of liquid electrolyte (Ď )
1320 kg/m3
Membrane area (for each cell)
0.5 m2
Internal resistance (R)
4.897 mΊ
Efficiency of VRFB AC/DC charger (đ?œ‚đ??´đ??śâˆ’đ??ˇđ??ś )
95%
Efficiency of ChadeMo fast charger (ΡCh)
95%
Initial (maximum) State of Charge (SoCmax)
100%
Operating Temperature (T)
25 ÂşC
Vanadium Concentration
2 M/L
Number of EVs charging simultaneously
2
VRFB Charging time (tch)
12 h