Electrochemical

 genera/on  and  
storage  
Generality  
 A  list  
•  Primary  and  secondary  ba7eries  
•  Capacitors,  electroly/c  capacitors    and  
supercapacitors  or  EDL  capacitors;  hybrid  
capacitors  
•  Fuel  cells  and  hydrogen  gas  generators  
•  Hybrid  devices:  rechargeable  solid  or  liquid  
devices  (ba7eries  using  metals,  flow  ba7eries)  
•  Electrochemical  PV  cells  (Graetzel  cells)  
 A  classifica/on  
•  Ragone  plot:  what  is  that?  
•  A  correla/on  between  energy  density  and  power  density  of  
different  electrochemical  devices  

•  What  is  the  power  density  and  what  is  the  energy  density?  
•  Obtainable  energy    divided  /mes  the  weight  or  the  volume  of  
an  electrochemical  device,  specific  energy,  joules/kg  or  
joules/dm3  
•  wh/kg  or  wh/dm3  

•  Maximum  Power  divided  /mes  the  weight  or  the  volume  of  
an  electrochemical  device,  specific  power,  wa7s/kg  or  wa7s/
dm3  
A  classifica/on  
 Ragone  plot  
ELECTROCHEMICAL SYSTEMS 349

FIGURE 19.4 Dependence of the specific energy w with respect to mass on the specific dis-
charge power p for various heavy drain batteries; the straight lines correspond to different
times of full discharge τd: τd ! 100 h (a); 10 h (b); 1 h (c); 6 min (d ).
Ragone  plot  
Materials  for  electrochemical  
capacitors  
Patrice  Simon  &  Yury  Gogotsi  
Nature  Materials  7,  845  -­‐  854  
(2008)  
doi:10.1038/nmat2297  

If  a  supercapacitor  is  used  in  

an  electric  vehicle,  the  
specific  power  shows  how  
fast  one  can  go,  and  the  
specific  energy  shows  how  far  
one  can  go  on  a  single  charge.  
Times  shown  are  the  /me  
constants  of  the  devices,  
obtained  by  dividing  the  
energy  density  by  the  power.  
Ragone  plot  
 Some  basic  informa/ons:  should  
remain  in  your  mind  
•  Energy  density  fossil  fuels  or  hydrogen:  30-­‐50  
MJ/kg=  
•  Present  energy  density  ba7ery:  5-­‐10  MJ/kg  
•  Metal-­‐air  ba7ery  (theore/cal):800-­‐11.000  Wh/kg  
or  3-­‐40  MJ/kg  (ZnO  and  Li2O2  ba7eries)  
•  Hydrogen  produc/on  efficiency:  70-­‐80%  
•  Hydrogen  fuel-­‐cell  max  eff.  70-­‐80%  
•  Fossil  fuel  to  electricity  eff.:  30-­‐60%;  mean  italian  
value  43%  
 Electrochemical  and  thermal  engines  
•  Carnot  limit  ηcarnot  =  1  –  (Tc/Th)  
•  Courzon-­‐Albhorn  effec/ve    
•  ηendoreversible  =  1  –  √(Tc/Th)  
•  All  the  irreversibility  is  limited  to  heat  exchange;  the  engine  is  
essen/ally  reversible  
•  Electrochemical  engines  are  essen/ally  isothermal  
•  In  electrochemistry  Carnot  law  is  not  valid;  the  2  principle  is,  in  the  
form  of  overpoten/al  (ma7er,  charge  and  reactant  transport  and  
barrier  overpoten/al);  catalyser  may  help  to  reduce  barrier  
overpoten/al.  
•  It  may  be  applied  to  photoelectrochemical  engines  (Th  is  the  Sun  
temperature  and  Tc  is  the  Earth  temperature);  if  dissipa/on  
increase  the  local  temperature  efficiency    decreases  by  this  effect  
but  other  effects  are  complex  (electrolytes  solu/ons  increase  
conduc/vity  with  temperature  and  also  reac/on  rates  increase)  
 Storage  
•  Poten/al  energy  (dams)  
•  Chemical  energy  (gas,  metals  or  solu/ons  of  
electrolytes)  
•  Electrochemical  energy  (Ba7eries,  
SuperCapacitors)  
•  Mechanical  energy  (flywheels,  high  pressure  gas  
in  caves)  
•  Thermal  energy  (thermal  storage)  
•  Others  (electromagne/c)  
Ba7eries  
 y

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n Figure 1 | Revisiting the past. In 1899 a Belgian car, La jamais contente (top left), equipped with lead–
t- acid batteries, reached a speed of 30 metres per second (ref. 26). In the same year, at a car competition
It in Paris, the only petrol-driven car was disqualified for having unpractically high consumption. Inside
n the United States, between 1900 and 1920, the proportion of electrical cars produced fell from 60%
to 4% of the total. One century later, fully electrical cars, such as the Tesla roadster (bottom left), are
ss
coming back into the picture. Meanwhile, the first wireless communication took place in Pennsylvania
9 in 1920 (top right, after ref. 27). Nearly 100 years later, the latest mobile phones (bottom right) can
g- perform a wide range of functions.
t-
es maintaining the charge balance, and electrical neering but crucially on the chemicals the bat-
energy can be tapped by the external circuit. In tery contains. Hundreds of electrochemical
es secondary, or rechargeable, batteries, a larger couples were proposed during the nineteenth
al voltage applied in the opposite direction can and early twentieth centuries, the most nota-
e cause the battery to recharge. ble primary battery being Zn–MnO2, with
e The amount of electrical energy per mass lead–acid and Ni–Cd being the most common
c- or volume that a battery can deliver is a func- secondaries1.
al tion of the cell’s voltage and capacity, which The stored energy content of a battery can
 The  situa/on   FEATURE NEWS

ack the lithium

o two lithium POWERING UP
Portable rechargable batteries tend to hit an energy-
PREDICTED
MAXIMUMS
Estimated
possible
han one metal Actual
storage-per-weight limit. Lithium-ion technology has
um. All of that 1,000

Energy density (Wh kg–1)

gone through several phases and types, but is also 2017
t advantage for expected to reach a ceiling soon. JCESR* LITHIUM–
target OXYGEN
May prove
lithium and 400 impossible
the battery is LITHIUM-ION 800 to achieve†
Mobile phones, cameras,
ble Li–S com- laptops and many electric cars LITHIUM–
rolyte, degrad- NICKEL–METAL HYDRIDE
SULPHUR
May be closest
battery loses 300 AA batteries and some electric cars
600 to market
Energy density (Wh kg–1)

o prevent this, NICKEL–CADMIUM

MAGNESIUM-ION
le by advances Old AA batteries, emergency lighting
Cheaper than
lyte chemistry LEAD–ACID lithium, and ranks
Starter batteries for cars, and
phur electrode 200
back-up power supplies
even better on
400 energy per unit
and using spe- volume.
do not dissolve Tesla Li-ion car
Cairns predicts battery pack ADVANCED LI-ION
Industry's current
uld achieve an 100 200 target
Wh kg−1. Other
s, he says. *Joint Center for Energy
t the academic Storage Research
†Density doesn’t take into
mmercial suc- 0 0 account weight of air-filtering

w proportions 1980 1990 2000 2010 2020 equipment

olyte, which is
cent. The cathode was found to enable fast anion diffusion and The cell was first optimized in a Swagelok cell operating at 25 uC with
intercalation, affording charging times of around one minute with a PG foil cathode. The optimal ratio of AlCl3/[EMIm]Cl was found to
a current density of 4,000 mA g–1 (equivalent to 3,000 W kg–1), be ,1.3–1.5 (Extended Data Fig. 2a), affording a specific discharging

The
 unexpected
and to withstand more than 7,500 cycles without capacity decay.
Owing to the low-cost, low-flammability and three-electron redox
properties of aluminium (Al), rechargeable Al-based batteries could in
principle offer cost-effectiveness, high capacity and safety, which would
capacity of 60–66 mA h g21 (based on graphitic cathode mass) with a
Coulombic efficiency of 95–98%. Raman spectroscopy revealed that
with an AlCl3/[EMIm]Cl ratio of ,1.3, both AlCl42 and Al2Cl72 anions
were present (Extended Data Fig. 2b) at a ratio [AlCl42]/[Al2Cl72] < 2.33

a Battery discharging b 2.5

2.5

Voltage (V)
2.0
2.0 1.5
e–

Voltage (V)
e– 1.0
e– e– 1.5 0.5
0.0
Anode Cathode 1.0
360 365 370
Time (h)
(aluminium) (graphite)
Charging
0.5 Discharging
AlCl3/[EMIm]Cl
0.0
Ionic liquid 0 30 60 90 120 150
c Specific capacity (mA h g–1)
100 100

Specific capacity (mA h g–1)

Coulombic efficiency (%)

AlCl4– 80 80
60 60
40 40

– 20 Charging capacity 20
Al2Cl7 EMI+ Discharging capacity
0 0
– – – 0 50 100 150 200
Al + 7AlCl4 4Al2Cl7 + 3e Cn[AlCl4] + e– Cn + AlCl4–
Cycle number

Figure 1 | Rechargeable Al/graphite cell. a, Schematic drawing of the Al/ intercalated and de-intercalated between graphite layers during charge and
graphite cell during discharge, using the optimal composition of the AlCl3/ discharge reactions, respectively. b, Galvanostatic charge and discharge curves
[EMIm]Cl ionic liquid electrolyte. On the anode side, metallic Al and AlCl4– of an Al/pyrolytic graphite (PG) Swagelok cell at a current density of
were transformed into Al2Cl7– during discharging, and the reverse reaction 66 mA g21. Inset, charge and discharge cycles. c, Long-term stability test of an
took place during charging. On the cathode side, predominantly AlCl4– was Al/PG cell at 66 mA g21.
1
Department of Chemistry, Stanford University, Stanford, California 94305, USA. 2Green Energy and Environment Research Laboratories, Industrial Technology Research Institute, Hsinchu 31040, Taiwan.
3
School of Physics and Electronics, Hunan University, Changsha 410082, China. 4Department of Chemistry, National Taiwan Normal University, Taipei 11677, Taiwan. 5Institute of Atomic and Molecular
Sciences, Academia Sinica, Taipei 10617, Taiwan. 6Department of Chemical Engineering, National Taiwan University of Science and Technology, Taipei 10607, Taiwan.
*These authors contributed equally to this work.

0 0 M O N T H 2 0 1 5 | VO L 0 0 0 | N AT U R E | 1
©2015 Macmillan Publishers Limited. All rights reserved
 A  common  problem  

Figure 1.5 Effect of the solubility of the reaction products on electrode structure when the
discharging/charging mechanism occurs via the dissolved state.

in Fig. 1.4. If the product of the discharge is highly soluble, during discharge the
 Solubility  

Figure 1.6 Simplified charge and discharge mechanism of the nickel-hydroxide electrode
with simultaneous release and absorption of protons (Hþ ions) and incorporation of a small Figure 1.4 Reaction steps in the lead-acid battery. Double-lined arrows mark the charging
amount of potassium ions ðKþ Þ.
reaction.

a large surface area on the order of m2/g. The advantage of the low solubility is that
the products of the reaction are precipitated within the pores of the active material,
Oversizing  ba7eries  
close to the place of their origin, and the structure of the electrode remains nearly
Spongy  structures  
lead sulfate ðPbSO4 Þ causes precipitation of the formed new compound, as
illustrated for the lead-acid system in Fig. 1.4.
stable. Nevertheless, a gradual disintegration of the active material is observed after
a certain number of charge/discharge cycles.
During discharge, lead ions ðPb2þ Þ are dissolved at the negative electrode. A
A quite different course takes the reaction in the nickel-hydroxide electrode corresponding number of electrons is removed from the electrode as negative charge.
The solubility of the Pb2þ ions is, however, limited to about 10$6 mole=dm3 in the
 Intercala/on  

Figure 1.7 Charging/discharging of lithium-ion batteries. In the charged state, the carbon
electrode is filled with lithium. During discharge, lithium ions are intercalated into the oxide
(from Ref. 7).

Another reaction mechanism that in a certain aspect resembles to the above

one characterizes lithium-ion batteries (cf. Chapter 18). The course of the cell
reaction is illustrated in Fig. 1.7
In such a battery, a carbon electrode that forms layers and allows intercalation
of Li ions is combined with a positive electrode of a metal oxide that also intercalates
the small Liþ ions into a layered structure (mainly Lix CO2 , Lix NiO2 , or Lix Mn2 O4 ).
These positive electrodes intercalate the lithium when discharged, i.e. the
lithium-filled material characterizes the discharged state of the positive electrode,
and the Liþ ions compensate for a corresponding reduction of the metal ions
4þ # ð4#xÞþ
 Two  general  criteria  
•  1.  The  free  enthalpy  ΔG  should  be  large  to  
achieve  a  high  cell  voltage.  
•  2.  The  equivalent  weight  (mole  weight  per  
exchanged  electron)  of  the  reac/ng  
components  should  be  as  low  as  possible  to  
gain  a  high  energy  output  per  weight.  
 Hypothe/cal  ba7eries  
Table 1.7 Hypothetical electrode couples and their theoretical specific energy and cell
voltage on the basis of thermodynamic data.

Positive Negative electrode

electrode H2 Li Na Mg

F2 4100 Wh/kg 6270 Wh/kg 3588 Wh/kg 4690 Wh/kg

3.06 V 6.07 V 5.62 V 5.45 V
Cl2 1000 Wh/kg 2520 Wh/kg 1830 Wh/kg 1732 Wh/kg
1.36 V 3.99 V 3.99 V 3.08 V
Br2 354 Wh/kg 1116 Wh/kg 941 Wh/kg 755 Wh/kg
1.07 V 3.62 V 3.61 V 2.59 V

(Br2) in Table 1.7 and their combinations with lithium (Li), sodium (Na), and
magnesium (Mg). The halogens F2, Cl2, and Br2 are of similar chemical affinity for
these three negative electrode materials, but their mole weight is 19, 35.5, and 79.9 g/
mole, respectively. Thus the cell voltage for the corresponding combination is very
similar, but the specific energy is reduced in the ratio of the mole weight.
 Ba7ery  geometry  
•  Common  ba7eries  and  generally  all  the  
electrochemical  devices  have  a  very  well  
precise  geometry  and  structure;  the  plane-­‐  
symmetrical  or  the  cylinder-­‐like  symmetries  
are  the  only  two  shapes  of  electrochemical  
devices  (we  are  referring  here  to  the  
electrodes  shape);  why  this  happens?  
 A  poe/cal  answer  
'Beauty  is  truth,  truth  beauty,—that  is  all    
Ye  know  on  earth,  and  all  ye  need  to  
know.’  
 J.  Keats:  Ode  on  a  Grecian  Urn  
La  bellezza  matema<ca  è  una  qualità  
che  non  può  essere     definita,  non  più  
di  quanto  la  bellezza  possa  essere  
definita  per  l'arte,  ma  chi  studia  
matema<ca,  di  solito,  non  ha  
difficoltà  ad  apprezzarla.    
     P.A.M.  Dirac,  Public  lessons  
 A  physical  answer  
•  Suppose  the  following  4  condi/ons:  
•  Validity  of  Ohm  law  for  conductors  
•  Homogeneity  and  isotropy  of  the  electrical  
materials  
•  Surface  of  the  electrode  is  equipoten/al  
•  Uniformity  of  the  electric  poten/al  difference  
between  the  electrode  and  the  electrolyte  
 Faraday  approach  
•  Faraday  did  not  study  at  school;  he  was  
originally  a  technician;  Maxwell  developed  
the  mathema/cal  theory  of  Faraday  ideas  
 Electrochemical  device  

Equipoten/al  surfaces  are  con/nuous  lines,  while  the  broken  lines,  perpendicular  to  them  
are  the  current  lines.  
Electrodes  or  metallic  surfaces  are  equipoten/al  surfaces;    
while  the  insula/ng  boundaries  of  the    device  have  a  behaviour  similar  to  the  current  lines,  
because  as  it  happens  for  them  no  current  line  is  able  to  trespass  them,  exactly  as  it  
happens  for  the  surface  current  made  considering  a  line  and  the  current  lines  passing  
through  each  one  of  its  points.  
All  the  equipoten/al  surfaces  end  on  the  boundaries.    
 Subs/tu/on  rules  
•  The  electric  field  configura/on  is  not  changed  
subs/tu/ng  a  metal  surface  to  an  equipoten/al  
surface  
•  The  electric  field  configura/on  is  not  changed  
subs/tu/ng  to  each  “current  surface”  an  
insula/ng  material  surface  
•  Applying  these  rules  it  is  possible  to  build  
subsystems  which  are  equivalent  to  the  original  
one  or  in  which  the  equipoten/al  surfaces  and  
the  current  surfaces  have  been  “inverted”  
An  example  
 Another  example  
Insula/ng  boundaries  

Metallic  i.e.  equipoten/al  boundaries  

 Three  cases  
•  There  are  only  three  geometries  in  which  the  
intensity  of  the  electric  field  on  the  electrodes  is  
uniform  and  consequently  the  current  is  
homogeneous  on  all  the  surface  
•  In  all  other  cases  the  electric  field  is  not  uniform  
on  the  electrodes  and  the  current  is  not  
homogeneous;  this  corresponds  to  a  strong  
dissipa/on  effect  with  loss  of  efficiency  
•  For  this  reason  all  the  efficient  electrochemical  
devices  have  electrodes  which  are:    
 Three  cases  
•  Plane  parallel,  uniform  intensity  on  both  electrodes  
•  Cylindrical,  uniform  intensity  but  the  intensity  is  higher  
on  the  center  electrode  than  on  the  external  boundary  
•  Spherical,  which  is  not  used  because  of  the  prac/cal  
difficulty  to  manage  the  center  electrode  
•  The  first  two  cases  are  correct  if  the  electrodes  are  
infinite;  what  is  not  the  case  really,  so  there  are  
boundary  effects  on  the  boundaries  of  the  electrodes  
Three  cases  

Hemispherical  field  
 Boundary  effects  
248 N.IBL

(2)
1 - - - -....
----&---
+
----
---_
".............. _-/....... "'/
/

d'

1
flow
Figure 3. Electrolysis cell with plane parallel electrodes
embedded in isolating walls: - - -, current lines; =,
current tubes.

the electrode simulating the overpotential. (193) A number of authors used the
method of conformal mapping, (27-32,127) or Hankel transforms, the latter
applied mainly to the case of the disk. (130)
For simple geometries, analytical solutions can be given. Let us consider
two cases of particular importance in electrochemistry. Our first system is the
cell of Figure 3, containing two plane parallel electrodes embedded in isolating
walls with d and d' » I. This is an example of the application of the conformal
mapping methodY27) One obtains the following current distribution(34,127):
jx e cosh e/ K tanh2 e
j = [sinh2 e - sinh2 (2x' e/ t)]1/2
(7)

where e = 1TI/2h, h is the distance between the two electrodes, 1 the length
of the electrode, and x' the distance from the center of the electrode. The
Other  cases  

The  inclined  cathode  or  Hull  cell  

A  plate  in  a  cylindrical  environment  

A  folded  electrode  
 Other  cases  
242 N.IBL

Figure 1. Copper coating on a serrated profile showing the increased thickness at the peak. a,
protective layer; b, Cu deposit; c, substrate.

3. Main Types of Current and Potential Distributions

The main factors on which the current and potential distributions over
an electrode depend are: