Supercapacitors: Properties and applications

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. 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