dspace. u b .cz
Supe capaci o s: P ope ies and Applica ions
LIBICH, J.; MÁCA, J.; VONDRÁK, J.; ČECH, O.; SEDLAŘÍKOVÁ, M.
Jou nal o Ene gy S o age
2018, ol. 17 iss. 1, pp. 224-227
ISSN : 2352-152X
DOI: h p://dx.doi.o g/10.1016/j.es .2018.03.012
Accep ed manusc ip
© 2018. This manusc ip e sion is made a ailable unde he CC-BY-NC-ND 4.0 license
(h p://c ea i ecommons.o g/licenses/by-nc-nd/4.0/), doi: 10.1016/j.es .2018.03.012
Final e sion a ailable om
h ps://www.sciencedi ec .com/science/a icle/pii/S2352152X18301634
Supe capaci o s: P ope ies and Applica ions
Jiří Libich, Jose Máca, Jiří Vond ák, Ondřej Čech and Ma ie Sedlaříko á
Depa men o Elec ical and Elec onic Technology, Facul y o Elec ical Enginee ing and
Communica ion, B no Uni e si y o Technology, 616 00 B no, Czech Republic
Abs ac
Ene gy accumula ion and s o age is one o he mos impo an opics in ou imes. This pape p esen s
he opic o supe capaci o s (SC) as ene gy s o age de ices. Supe capaci o s ep esen he al e na i e
o common elec ochemical ba e ies, mainly o widely sp ead li hium-ion ba e ies. By physical
mechanism and ope a ion p inciple, supe capaci o s a e close o ba e ies han o capaci o s. Thei
p ope ies a e somewhe e be ween ba e ies and capaci o s. They a e able o quickly accommoda e
la ge amoun s o ene gy (smalle han in he case o ba e ies - lowe ene gy densi y om weigh and
olume poin o iew) and hei cha ging esponse is slowe han in he case o ce amic capaci o s. The
mos common ype o supe capaci o s is elec ical double laye capaci o (EDLC). O he ypes o
supe capaci o s a e li hium-ion hyb id supe capaci o s and pseudo-supe capaci o s. The EDLC ype is
using a dielec ic laye on he elec ode - elec oly e in e phase o s o age o he ene gy. I uses an
elec os a ic mechanism o ene gy s o age. The o he wo ypes o supe capaci o s ope a e wi h
elec ochemical edox eac ions and he ene gy is s o ed in chemical bonds o chemical ma e ials. This
pape p o ides a b ie in oduc ion o he supe capaci o ield o knowledge.
Keywo ds
Supe capaci o , Ene gy, S o age, Pseudo-supe capaci o , Hyb id-supe capaci o , Li hium
Highligh s
 Supe capaci o s ha e in e es ing p ope ies in ela ion o s o ing elec ic ene gy, as an
al e na i e o ba e ies.
 Supe capaci o s can handle e y high cu en a es.
 Supe capaci o s ha e low ene gy densi y o uni weigh and olume.
 The p ice pe uni o ene gy (kWh) is ex emely high.
 Co espondence au ho : Jiří Libich
e-mail add ess: [email p o ec ed]
Depa men o Elec ical and Elec onic Technology,
B no Uni e si y o Technology
1. In oduc ion
Limi ed sou ces o ossil uels along wi h
g owing popula ion and echnology
de elopmen pu he mankind in on o an
ene gy p oblem. Inc easing pollu ion o ces us
o hink abou ene gy and he app oach o
ene gy managemen . The e a e wo main ypes
o ene gy sou ces, ully con ollable powe
plan s (nuclea powe s a ions, incine a ion
plan s, ossil uels, biomass, geo he mal) and
enewable ene gy sou ces, which a e non-
dispa chable (wind and sola ene gy).
The wo ld human popula ion canno use only
enewable ene gy sou ces, a leas in he nea
u u e. The sha e o enewable ene gy among
o he ypes o ene gy sou ces in 2015 is shown
in Fig. 1. In he ideal case, enewable ene gy
should co e 100 % o wo ld ene gy
consump ion, bu i is only a heo e ical idea
ha is no possible o be achie ed. We should
howe e inc ease he p opo ion o enewable
ene gy sou ces in he wo ld ene gy p oduc ion
as as as possible.
Fig. 1 Es ima ed enewable ene gy sha e o global inal ene gy consump ion [1].
Ene gy om enewable ene gy sou ces needs
o be (due o i s non-dispa chabili y) s o ed and
used when needed. Ene gy s o age and
accumula ion is he key pa o enewable
ene gy sou ces u iliza ion. Use o ba e ies o
special hyd opowe plan s is he only way how
can we oday s o e he ene gy om enewable
ene gy sou ces. The e a e o he expe imen al
al e na i es - s o ing ene gy in supe conduc ing
magne ic ene gy s o age sys ems (SMES),
which s o e i in a magne ic ield c ea ed by he
low o cu en in a supe conduc ing coil ha
has been c yogenically cooled o a empe a u e
below i s supe conduc ing c i ical empe a u e.
The e a e also o he ene gy s o age sys ems
s ill in he phase o basic esea ch, so hey
canno be conside ed as egula ene gy s o age
sys ems. Ano he impo an s ep o dec easing
pollu ion and keeping sus ainable de elopmen
o popula ion is educing emissions p oduced
by combus ion engine ehicles and eplacing
hem wi h elec ic ehicles. Au onomy elec ic
ehicles, which do no ha e connec ion o he
elec ical g id, also need o s o e elec ic ene gy
in ba e ies. Using ba e ies, especially li hium-
ion ba e ies, is a widely discussed and
echnologically de eloped opic.
Supe capaci o s could be conside ed as an
al e na i e o con en ional ba e ies o elec ic
ehicles. This pape is ela ed o
supe capaci o s, i p o ides hei b ie
desc ip ion, ope a ion p inciples, ypes and
ecen de elopmen .
Elec ochemical capaci o s, also named
supe capaci o s o ul acapaci o s, a e elec ical
componen s ha a e able o s o e and
accommoda e ce ain amoun s o ene gy.
The de elopmen o supe capaci o s s a ed in
he 50s o he 20 h cen u y. Fi s expe imen s
s a ed be ween 50s and 70s and we e
conduc ed by US companies Gene al Elec ic
(GE) and S anda d Oil o Ohio (SOHIO).
These i s elec ochemical supe capaci o s
eached he capaci y a ound 1F. This ype o
supe capaci o s was pa en ed in 1971 by
SOHIO. The i s supe capaci o named “Gold
Cap” was eleased o he comme cial ma ke in
1982 by Panasonic and had high equi alen
se ies esis ance (ESR). In 1982, i s elec ic
double-laye capaci o (EDLC) supe capaci o
was de eloped o mili a y pu poses by he
Pinnacle Resea ch Ins i u e (PRI). This i s
EDLC supe capaci o al eady had a low ESR.
A e en yea s, in 1992, Maxwell Labo a o ies
in oduced o he comme cial ma ke a wide
ange o EDLC supe capaci o s wi h low ESR
named “Boos Cap” wi h nominal capaci y o 1
kF. Since 2007, he de elopmen o no el
hyb id-supe capaci o s ook place. This kind o
supe capaci o s should each highe nominal
ol age along wi h highe olume ic and
g a ime ic ene gy densi y han con en ional
EDLC supe capaci o s. Mos o oday’s
supe capaci o s ha e capaci y o e se e al
housands Fa ads and can p o ide cha ge-
discha ge cu en s in he ange om en hs o
hund ed hs o Ampe es. Thei main ad an age
om he applica ion poin o iew is ex emely
high cu en (in compa ison o ba e ies) ha
hey a e able o ope a e wi h. Thanks o his
cha ac e is ic p ope y, supe capaci o s ill he
oid gap among ene gy s o age de ices
be ween ba e ies (accumula o s) and common
capaci o s (see Fig. 2 below).
Fig. 2 Ragone cha : Powe densi y as a unc ion o ene gy densi y o a ious ene gy de ices [2].
Supe capaci o s a e used in applica ions, whe e
is he need o s o e o elease huge amoun o
ene gy in a e y sho ime. Nowadays, he
supe capaci o s a e used p ima ily in Hyb id
Elec ic Vehicles (HEV), Elec ic Vehicles
(EV) and Fuel Cell Vehicles (FCV) like
passenge ca s, ains, olleybuses. Ano he
a ea o supe capaci o s’ use a e elec onic
de ices as Unin e up ible Powe Supplies
(UPS) and ola ile memo y backups in PCs.
Thi d a ea o use a e ene gy ha es ing
sys ems, sola a ays o wind u bines, whe e
supe capaci o s play a supplemen a y ole nex
o con en ional ba e ies [1 -14].
Especially he applica ion o supe capaci o s in
au omo i e indus y b ings many ad an ages.
Supe capaci o s can be used o inc ease he
e iciency o hyb id elec ic ehicles in se e al
ways. Today’s hyb id ehicles ypically u n
o he engine comple ely when he ca s ops,
and hen e y e icien ly s a i again using
ene gy s o ed in supe capaci o s. The e a e
o e 600 housands HEVs ha use
supe capaci o s in hei s op-s a sys ems.
Some supe capaci o manu ac u e s designed
eplacemen s o con en ional ehicle ba e ies
using supe capaci o s connec ed ac oss a
smalle lead acid ba e y. The concep o hei
applica ion is in he momen s when he powe
demand peaks, such as s a ing a ca , and hey
dec ease he o e all ene gy consump ion om
he ba e ies. Ba e ies las much longe when
he discha ge is small and s eady.
Supe capaci o s in his “hyb id lead-acid
ba e y” con igu a ion essen ially smoo h ou
he ene gy demands on he ba e y.
2. Supe capaci o ca ego ies and ope a ion
p inciples
Supe conduc o s can be di ided in o h ee
basic ca ego ies acco ding o he ene gy s o age
p inciple. I should be no ed ha he
supe capaci o s belong in o he ca ego y o we
elec oly ic capaci o s using a liquid elec oly e
ha con ains ions (cha ged complexes) o
ensu e cha ge anspo . The i s ca ego y
includes Elec ic Double-Laye Capaci o s o
so-called EDLC Supe capaci o s. This ype o
supe capaci o is he mos common ype and
ep esen s majo i y on he comme cial ma ke .
The EDLC supe capaci o s use liquid
elec oly e. Mos o hese elec oly es use
ap o ic sol en s like p opylene ca bona e (PC),
die hyl ca bona e (DEC), dime hyl ca bona e
(DME) o e hylene ca bona e (EC), which
include dissol ed sal s like
e ae hylammonium e a luo obo a e
(TEABF4) o li hium hexa luo oa sena e
(LiAsF6). As elec oly es a e used
(expe imen ally) ionic liquids as
ie hylsul onium bis( i luo ome hylsul onyl)
imide o 1-e hyl-3-me hylimdazolium
hiocyana e and a wide ange o o he ionic
liquids. These EDLC supe capaci o s use
elec os a ic in e ac ion o accumula e ene gy
in Helmhol z double laye s on he phase
in e ace be ween he su ace o he elec odes
and he elec oly e. Double-laye capaci ance is
a ising om po en ial-dependence o he
su ace ene gy s o ed elec os a ically a he
in e ace o capaci o elec odes. In his ype o
supe capaci o s, he e is no elec on exchange
and no edox eac ion and he ene gy is s o ed
non- a adaically. The key poin o ob ain an
ex emely high capaci y is he la ge su ace o
he elec odes and he Helmhol z laye
hickness. EDLC supe capaci o s possess good
du abili y and cycleabili y in millions o cycles.
As an elec ode ma e ial o EDLC
supe capaci o s, ac i a ed ca bon (AC) is
widely used, whe e i s la ge speci ic su ace
a ea is ad an ageous.

Fig. 3 Diag am o he Helmhol z double laye on a liquid-solid (elec oly e-elec ode) in e ace.
A model o Helmhol z double laye is shown in
Fig. 3.
The second ca ego y ep esen s so-called
pseudo-supe capaci o s o a adaic
supe capaci o s. This kind o supe capaci o s is
used much less equen ly han EDLC
supe capaci o s and is comme cially o e ed
only by a ew companies. By ope a ion
p inciple, hey a e close o ba e ies han o
capaci o s. Pseudocapaci ance is a
phenomenon, whe e elec ode ma e ials
in e media e elec on ans e and unde go
edox eac ions. The pseudocapaci ance a ises
a he elec ode su aces, whe e a adaic
eac ions o igin, and he eac ions in ol ing he
passage o ene gy ac oss he double laye ,
simila o ba e y cha ging o discha ging, bu
capaci ance g ows due o he special ela ion
ha can be exp essed as he amoun o ene gy
accep ed (Δq) and he change o po en ial (ΔV),
so ha he de i a i e d(Δq)/d(ΔV) o dq/dV is
equi alen o he capaci ance C. Du ing cha ge
and discha ge, he e occu s a edox eac ion
(a ising om he bonds in he compounds) and
ene gy ans e be ween elec oly e and
elec ode. Ene gy is no s o ed in he
“dielec ic” laye , bu is ep esen ed by he
ene gy o molecule bonds. The disad an age o
hese sys ems is he p inciple i sel , because
du ing cha ging and discha ging, he elec odes
a e s essed and deg ade as e , compa ed o he
elec os a ic s o age p inciple. I is connec ed
wi h inc easing he in e nal esis ance o
supe capaci o s. Pseudosupe capaci o s ha e
bo h elec odes made by pseudocapaci i e
ma e ials like u henium oxide (RuO2) o
manganese dioxide (MnO2). The s abili y and
cycleabili y a e lowe han in he case o EDLC
supe capaci o s along wi h lowe cha ging
e iciency and longe ime esponse (lowe
discha ge a e).
The hi d, las ype o supe capaci o s, is called
hyb id supe capaci o s. I is he newes ype o
supe capaci o s. This mos ad anced
supe capaci o combines bo h p e ious
supe capaci o ypes, he EDLC and pseudo-
supe capaci o s. The main ad an age is highe
olume ic and g a ime ic ene gy densi y
along wi h he capabili y o p o ide high
cu en s. Due o a adaic eac ion ha occu s
on he nega i e elec ode, which is ypically
made om pseudocapaci i e elec ode
ma e ial, hyb id supe capaci o s possess highe
ene gy densi y. The posi i e elec ode is
ypically made om ac i a ed ca bon ha
s o es elec os a ic ene gy in he double laye
on he elec ode su ace. Thanks o he
elec os a ic in e ac ion be ween cha ge ca ie s
and elec ode su ace on posi i e elec ode
side, hyb id supe capaci o s can deli e high
cu en s. Hyb id supe capaci o s a e om he
cons uc ion and ope a ion poin o iew close
o li hium-ion ba e ies. Nowadays, he e a e no
hyb id supe capaci o s comme cially a ailable
on he ma ke , bu hey a e in es iga ed in
labo a o y condi ions. Table 1 summa izes and
compa es supe capaci o s wi h o he ypes o
elec ochemical ene gy sou ces [14-19, 21-33].
Tab. 1 Summa iza ion and compa ison o impo an a ibu es [1 - 16].
A ibu e
Supe capaci o (SC)
Li hium-ion
ba e y
EDLC SC
Pseudo SC
Hyb id SC
Cha ge ime [s]
1 – 10
1 – 10
100
600
Cycle li e
1 000 000
100 000
500 000
500
Cell ol age [V]
2.7
2.3-2.8
2.3-2.8
3.6
Speci ic ene gy
[Wh.kg-1]
3–5
10
180
250
Cos pe kWh
[USD]
~ 10 000
~ 10 000
*
~ 140
Ope a ing
empe a u e [°C]
-40 – 65
-40 – 65
-40– 65
-20 – 60
Sel discha ge pe
mon h [%]
60
60
*
4
Type o
elec oly e
Ap o ic o P o ic
P o ic
Ap o ic
Ap o ic
* Da a no a ailable
Elec oly es used in supe capaci o s can be
di ided in o wo g oups - ap o ic and p o ic
elec oly es (see Tab. 1 abo e). Each one has
di e en bene i s and limi a ions. P o ic
sol en s based on wa e a e mo e
en i onmen ally iendly, sa e and o e highe
conduc i i y. Ap o ic elec oly es inc ease he
wo king ol age window compa ed o ha o a
wa e soluble elec oly e, hence p oducing a
highe ene gy densi y. The mos widely used
p o ic elec oly e is po assium hyd oxide
(KOH) o sodium hyd oxide (NaOH) and
sul u ic acid (H2SO4) elec oly e. Among mos
widely used ap o ic elec oly es a e li hium
sal s li hium hexa luo ophospha e (LiPF6),
li hium pe chlo a e (LiClO4) and li hium
e a luo obo a e (LiBF4) dissol ed in a
mix u e o sol en s such as dime hyl ca bona e
(DMC), die hyl ca bona e (DEC) and e hylene
ca bona e (EC). The p o ic elec oly es possess
highe conduc i i y, hey exhibi highe i e
sa e y, lowe p ice and a e mo e
en i onmen ally iendly han he ap o ic ones.
On he o he side he p o ic sol en s possess,
signi ican ly na owe wo king po en ial
window.
3. Conclusions
Supe capaci o s ep esen an in e es ing
al e na i e o con en ional ba e ies. The e a e
new ypes o hyb id supe capaci o s based on
he es ablished li hium-ion echnology. These
hyb id li hium-ion supe capaci o s al eady ha e
a highe ene gy densi y. Today, hese hyb id
li hium-ion supe capaci o s can ind use in
applica ions, whe e only con en ional li hium-
ion ba e ies we e used so a . The use o
supe capaci o s in many applica ions was
limi ed by hei low ene gy densi y and high
p ice (SC $10 000 kWh, Li-ion $240 kWh).
New gene a ion o supe capaci o s possess a
simila ene gy and powe densi y (EDLC SC 6
Wh.kg-1 Li-ion 250 Wh.kg-1, Hyb id SC a ound
180 Wh.kg-1) as li hium-ion ba e ies and a e
able o deli e conside ably highe cu en s
han li hium-ion ba e ies [30].
As a ollow-up on his issue, we a e pe o ming
a se ies o expe imen s dealing wi h hyb id
li hium-ion supe capaci o s based on ou
expe ience in he ield o li hium-ion ba e ies,
especially he p e-li hia ion me hod, which is a
e y impo an elemen in he hyb id li hium-
ion supe capaci o echnology.
Acknowledgmen
This wo k was suppo ed by he p ojec o
he Cen e o Resea ch and U iliza ion o
Renewable Ene gy unde p ojec No. LO1210
– "Ene gy o Sus ainable De elopmen (EN-
PUR)" eg. No. 0398.
Re e ences
[1] Renewables Global S a us Repo (REN21),
h p://www. en21.ne /wpcon en /uploads/2
017/06/178399_GSR_2017_Full_Repo _0
621_Op .pd (access 17.11.2017), Global
S a us Repo (2015) 42.
[2] J. B. Goodenough, H. D. Ab una, M. V.
Buchanan, Repo o he Basic Ene gy
Sciences Wo kshop on Elec ical Ene gy
S o age (2007) 1-21, DOI: 10.2172/935429.
[3] L. Nèg e, B. Da os, P.L. Tabe na and P.
Simon, Jou nal o Elec ochem. Socie y,
162(5) (2015) A5037-A5040, DOI:
10.1149/2.0061505jes.
[4] P. D o ak, Ma e ials o Supe capaci o s -
disse a ion hesis, B no Uni e si y o
Technology, (2014) 82.
[5] J. Zhang, H. Wu, J. Wang, J. Shi, Z. Shi,
Elec ochimica Ac a, 182 (2015) 156-164.
[6] S. Zhang, Jou nal o Powe Sou ces, 343
(2017) 322-328.
[7] B. E. Conway, Elec ochemical
Supe capaci o s, Sp inge US, New Yo k,
1999.
[8] J. Mille , P. Simon, Jou nal o he
Elec ochemical Socie y, 17(1) (2008) 31-
32.
[9] K. Naoi, M. Mo i a, Jou nal o he
Elec ochemical Socie y, 17(1) (2008) 44-
48.
[10] A. Shukla, A. Bane jee, M. Ra ikuma and
A. Jalajakshi, Elec ochimica Ac a, 84
(2012) 165-173.
[11] Y. Zhang, H. Feng, X. Wu, L. Wang, A.
Zhang, T. Xia, H. Dong, X. Li and L.
Zhang, In e na ional Jou nal o Hyd ogen
Ene gy, 34 (2009) 4889-4899.
[12] G. Yu, X. Xie, L. Pan, Z. Bao and Y. Cui,
Nano Ene gy, 2 (2013) 213-234.
[13] Y.-P. Lin, N.-L. Wu, Jou nal o Powe
Sou ces, 196(2) (2011) 851-854.
[14] C. A bizzani, M. Mas agos ino and L.
Meneghello, Elec ochimica Ac a, 40
(1995), 2223-2228.
[15] C. Lei, F. Ma koulidis, Z. Ashi aka, C.
Lekakou, Elec ochimica Ac a, 92 (2013)
183-187.
[16] J. Dai, K. Fu, R. Palanisamy, A. Gong, G.
Pas el, R. Ko n eld, H. Zhu, M.
Sanghadasa, E. Bekya o a and L. Hu,
Jou nal o Ma e ials Chemis y A, 5 (2017)
15266-15272.
[17] J. Sun, Y. Huang, Y. N. S. Sea, Qi Xue, Z.
Wang, M. Zhu, H. Li, X. Tao, Ch. Zhi,
H. Hu, Ma e ials Today Ene gy, 5 (2017)
1-14.
[18] Y. Liu, X. Peng, Applied Ma e ials Today,
8 (2017) 104-115.
[19] A. E ekha , Ene gy S o age Ma e ials, 9
(2017) 47-69.
[20] M. Ce aolo, G. Lu zembe ge , D. Poli,
Jou nal o Ene gy S o age, 11 (2017) 211-
218.
[21] D. Qu, X. Feng, X. Wei, L. Guo, H. Cai, H.
Tang, Z. Xie, Applied Su ace Science, 413
(2017) 344-350.
[22] A. M. Elshahawy, C. Guan, X. Li, H.
Zhang, Y. Hu, H. Wu, S. J. Pennycook, J.
Wang, Nano Ene gy, 39 (2017) 162-171.
[23] S. Makino, R. Yamamo o, S. Sugimo o, W.
Sugimo o, Jou nal o Powe Sou ces, 326
(2016) 711-716.
[24] S. Kim, J. Lee, J. Soo Kang, K. Jo, S. Kim,
Y.-E. Sung, J. Yoon, Chemosphe e, 125
(2015) 50-56.
[25] S. S.Zhang, Jou nal o Powe Sou ces, 343
(2017) 322-328.
[26] J. Zhanga, Z. Shia, C. Wang,
Elec ochimica Ac a, 125 (2014) 22-28.
[27] J. Zhang, H. Wu, J. Wang, J. Shi, Z. Shi,
Elec ochimica Ac a, 182 (2015) 156-164.
[28] G. Gou din, P. H. Smi h, T. Jiang, T. N.
T an, D.Qu, Jou nal o he Elec oanaly ical
Chemis y, 688 (2013) 103-112.
[29] N. S. Hudak, A. D. Schlich ing, K.
Eisenbeise , Jou nal o Elec ochemical
Socie y, 164(4) (2017) A691-A700.
[30] R. A ias, D. Malka, A. Bo ens ein, O.
Hana, S. Luski and Do on Au bach, Jou nal
o Elec ochemical Socie y, 164(9) (2017)
A2231-A2237.
[31] Ba e y Uni e si y, h p://www.
h p://ba e yuni e si y.com (access
17.11.2017), A icle: BU-209, (2017).
[32] T. B oussea, D. Bélange , J. W. Long,
Jou nal o Elec ochem. Socie y, 162(5)
(2015) A5185-A5189, DOI:
10.1149/2.0201505jes.
[33] V. Sedlako a, J. Sikula, J. Majzne , P.
Sedlak, T. Kupa owi z, B. Bue gle , P.
Vasina, Jou nal o Powe Sou ces, 286
(2015) 58-65, DOI:
10.1016/j.jpowsou .2015.03.122.