A o es y was e-de i ed li hium ion capaci o : Sus ainable, high-powe
ene gy s o age
Jon Rod iguez-Rome o, Idoia Ruiz de La amendi
*
, Eide Goikolea
**
Depa amen o de Química O g´
anica e Ino g´
anica, Facul ad de Ciencia y Tecnología, Uni e sidad Del País Vasco (UPV/EHU), Ba io Sa iena S/n, 48940, Leioa, Spain
HIGHLIGHTS
•Li hium-ion capaci o using Pinus Radia a-de i ed biomass elec odes is p esen ed.
•Ha d ca bon anode achie es 112 mAh g⁻
1
a 10C wi hou expensi e addi i es.
•The sys em deli e s 105 Wh kg⁻
1
a 700 W kg⁻
1
and e ains 60 % capaci y a e 10,000 cycles.
•Biomass-based LIC o e s a sus ainable and cos -e ec i e ene gy s o age solu ion.
ARTICLE INFO
Keywo ds:
Li hium-ion capaci o
Ha d ca bon
Ac i a ed ca bon
Biomass-de i ed ca bon
ABSTRACT
In o de o ill he demand o e icien and sus ainable ene gy s o age, hyb id sys ems combining ba e ies and
supe capaci o s a e being explo ed. Li hium-ion capaci o s (LICs), which le e age ad ances in elec ical double-
laye capaci o s (EDLCs) and li hium-ion ba e ies (LIBs), a e pa icula ly p omising. In his s udy, we p esen a
LIC using elec odes de i ed om Pinus Radia a biomass. The nega i e elec ode, made o a ha d ca bon, achie es
high capaci y alues (up o 112 mAh g⁻
1
a 10C) wi hou complex doping p ocedu es, he use o expensi e
addi i es o complex p ocessing. The posi i e capaci i e elec ode u ilizes an ac i a ed ca bon de i ed om he
same ha d ca bon, which has a high speci ic su ace a ea o 2399 m
2
g
−1
. The p oposed sys em exhibi s an ene gy
densi y o up o 105 Wh kg⁻
1
a 700 W kg⁻
1
, e aining 60 % capaci y a e 10,000 cycles a 10C. By u ilizing
locally accessible biomass, his app oach o e s a cos -e ec i e and sus ainable al e na i e o con en ional LICs,
wi h u he op imiza ion po en ial. This esea ch highligh s he po en ial o biomass-de i ed ma e ials in
de eloping high-powe , eco- iendly, and a o dable ene gy s o age sys ems.
1. In oduc ion
The exponen ial ene gy demand in mode n socie y necessi a es sus-
ainable ene gy solu ions ha do no con ibu e o global wa ming, bu
he spo adic cha ac e o enewable enewable ene gies poses chal-
lenges o make he leap o a mo e sus ainable u u e [1]. Ene gy s o age
sys ems play a c ucial ole o b idge he gap be ween ene gy p oduc ion
and ene gy consump ion [2,3]. Today’s leading ene gy s o age sys ems
a e li hium-ion ba e ies (LIBs) and supe capaci o s (SCs). The di e -
ences in hese de ices lie in hei ope a ing mechanisms. While LICs a e
based on e e sible elec ochemical eac ions in he bulk o he ac i e
ma e ial, ypical SCs o m an elec ical double laye on he in e ace o
he elec odes by elec os a ic adso p ion o cha ges [4]. LICs enjoy a
wide po en ial window, p o ide high ene gies (150–200 Wh kg
−1
) and
p esen a e y low sel -discha ge a e [5]. SCs, on he o he hand, p o-
ide a high powe ou pu (5–15 kW kg
−1
) and compa ed o ba e ies,
hei cycle li e is o de s o magni ude longe . Ne e heless, each inds i s
limi a ion in he s eng h o he o he : LIBs su e om sluggish kine ics
in he Li
+
di usion ac oss elec ode ma e ials, and a much educed cycle
li e due o he deg ada ion o hei ma e ials du ing cycling [6,7]. SCs,
on he o he hand, p esen limi ed speci ic ene gy, due o hei ela i ely
low ope a ing ol age. In addi ion, hey sel -discha ge a e a sho
pe iod o disuse [8,9].
These p ope ies make hem complemen a y echnologies, wi h
ba e ies being p e e ed o high-ene gy applica ions, while SCs a e
needed when high powe and as cha ge/discha ges a e equi ed. The
* Co esponding au ho .
** Co esponding au ho .
E-mail add esses: [email p o ec ed] (I. Ruiz de La amendi), [email p o ec ed] (E. Goikolea).
Con en s lis s a ailable a ScienceDi ec
Jou nal o Powe Sou ces
jou nal homepage: www.else ie .com/loca e/jpowsou
h ps://doi.o g/10.1016/j.jpowsou .2024.235961
Recei ed 5 Sep embe 2024; Recei ed in e ised o m 15 No embe 2024; Accep ed 26 No embe 2024
Jou nal o Powe Sou ces 629 (2025) 235961
A ailable online 4 Decembe 2024
0378-7753/© 2024 The Au ho s. Published by Else ie B.V. This is an open access a icle unde he CC BY-NC license (
h p://c ea i ecommons.o g/licenses/by-
nc/4.0/ ).
sys em ha e ec i ely combines elec odes o hese wo echnologies is
known as a Li-ion capaci o (LIC), and has eme ged as a p omising
sou ce o high ene gy and high powe wi h a long cycle li e. Combining
he bene i s o bo h de ices opens doo s o applica ions ha we e p e-
iously only achie able by o e sized SCs and LIBs. In ac , some LICs
ha e al eady been comme cialized and p o en o be an a o dable op-
ion o s a iona y applica ions like windmills and elec omobili y ap-
plica ions such as ams and elec ic buses [10].
The selec ion o ac i e ma e ials and cell design signi ican ly impac s
he success o any hyb id de ice, allowing o ully exploi hei po en ial.
Among he ex ensi ely esea ched LIC con igu a ions, one combines a
ca bona e elec oly e and a LIB anode coupled wi h an elec ic double-
laye capaci o ype (EDLC- ype) posi i e elec ode. In his app oach,
Li
+
ions in e cala e/dein e cala e in he bulk o he anode ma e ial,
while he coun e ion o he elec oly e is adso bed/deso bed on he
su ace o he ac i a ed ca bon [11,12]. Since ion in e cala ion is a slow
p ocess compa ed o ion elec oso p ion, i is necessa y o de e mine a
co ec mass balance be ween he elec odes o help balance he kine ics
wi hin he sys em. O he wise, he ene gy and powe densi ies o he
asymme ic sys em could be comp omised [13].
LICs a e in ended o ill he ene gy- o-powe gap be ween ba e ies
and supe capaci o s, so excellen high powe pe o mance is expec ed.
Tha is why no all LIB anode ma e ials a e sui able o LICs. Con e -
sion/alloying anodes, such as me al ni ides/oxides/sul ides and Si/Sn
based ma e ials, o example, su e om low conduc i i y and a
no iceable olume change when cycling, which usually esul s in high
capaci ies bu poo pe o mances a high a es [14–16]. On he o he
hand, in e cala ion anodes, such as ca bonaceous ma e ials, Li
4
Ti
5
O
12
o
LTO and Nb
2
O
5
, show be e cycling s abili y and powe densi y
[17–19]. Al hough he la e a e a less a ac i e op ion as hei Li
+
in e cala ion/dein e cala ion po en ial is highe han ha o ca bona-
ceous ma e ials, esul ing in lowe ene gy and powe densi ies in a ull
cell. The e a e mul iple me hods o imp o ing he ma e ials’ conduc-
i i y, as well as o mi iga e olume wa ping. These s a egies include
he e oa om doping, in oducing la ice de ec s, nanos uc u ing he
ma e ial, o o ming composi es wi h mo e conduc i e ma e ials
[20–22]. Howe e , hese app oaches may no be as a ac i e o he
indus y due o hei complexi y o high cos [23]. On he o he hand,
ca bonaceous ma e ials o e an excellen op ion o his applica ion.
Thei s uc u al s abili y and low in e cala ion po en ial allow no only a
long cycle li e a high powe alues, bu also accep able ene gy densi ies
[24,25]. Fo ha eason dual ca bon - LICs (DC-LICs) ha e had a g ea
exposu e in his a ea. These hyb id sys ems ypically employ a nano-
s uc u ed ca bonaceous posi i e elec ode, and a ca bon-based ma e ial
capable o in e cala ing Li
+
as anode.
G aphi e is he ma ke leade o nega i e elec odes in bo h LICs and
LIBs. Howe e , i s excellen pe o mance is o e shadowed by i s limi ed
accessibili y [11]. G aphi e is classi ied as a c i ical aw ma e ial (CRM),
and can be ei he mined o syn hesized. Un o una ely, bo h p oduc ion
me hods ha e se e e en i onmen al impac s. The high empe a u es
needed o he syn hesis and he chemical eac ions in ol ed in he
pu i ica ion when mining con ibu e o ad e se e ec . Mo eo e , he
si ua ion is expec ed o wo sen because o he inc easing need o
g aphi e in he ene gy s o age indus y [10].
The mos popula al e na i es o g aphi e include ha d ca bons
(HCs), so ca bons (SCs), g aphene, ca bon nano ubes (CNTs), and
g aphdiyne. Ha d and so ca bons a e ypically de i ed om ca bon-
ich ma e ials h ough he mal py olysis. Due o he in e laye c oss-
linking o he p edecesso s, HCs a e mos ly composed o andomly
sca e ed, cu ed g aphi ic shee s ha a e incapable o es uc u ing
in o g aphi e, no e en a empe a u es as high as 3000 ◦C [26,27].
No ably, wi hin he minuscule g aphi e-like po ions o HCs, he diso -
de ed s uc u e pe mi s Li
+
inse ion on each side o he g aphene
shee s, po en ially esul ing in inc eased capaci y [28]. In con as , so
ca bons show g ea e c ys allini y, due o hei mo e semi-g aphi ic
egions. This s uc u e enables so ca bons o exhibi g ea e ionic
di usion a es [29]. Bo h HCs and so ca bons show a la ge in e laye
dis ance and inc eased in e ace su ace, ou pe o ming g aphi e in
e ms o cyclabili y and s abili y a high powe s. Consequen ly, hey a e
acknowledged as p omising anode ma e ials o u u e me al-ion sys-
ems [30,31]. Un o una ely, because o hei i egula s uc u e and
nume ous de ec s, hei elec ical conduc i i y emains lowe han ha
o g aphi e. S ill, one use ul app oach o ge o e his p oblem is p o-
ducing composi es employing low dimensional nanoca bons o
conduc i e polyme s [32,33].
Nanosized ca bons, including g aphene, CNTs, and g aphdiyne, a e
conside ed p omising anodic ma e ials o bo h LIBs and LICs because o
hei unique s uc u al, mechanical, and elec ical p ope ies [34–36].
While hese ma e ials o e ad an ages such as unable in e laye
spacing, hey also ace challenges ela ed o hei low olume ic ca-
paci y, high cos and complex syn hesis [37]. Some o hese
nano-ca bons possess high speci ic su ace a eas (SSAs), and hus, hey
ha e also been explo ed as posi i e capaci i e elec odes in LICs.
Howe e , ac i a ed ca bons (ACs) emain he mos popula choice due
o hei well-es ablished ab ica ion p ocess, low cos and high SSA [23].
Typically ACs a e ob ained om he chemical ac i a ion o a ca bona-
ceous p ecu so a high empe a u es, using ac i a ing agen s like KOH,
H
3
PO
4
, o H
2
O. In ou cu en s udy, he AC is de i ed om he same
biomass p ecu so used o ob ain he HC. Mos ypes o biomass a e
usually eadily a ailable, and when ca bonized, he p oduc ends o
e ain he mo phology and mic os uc u e o he sou ce ma e ial
[38–41]. In he s udy epo ed he e he biomass comes om a local
o es indus y in he no he n egion o Biscay, Spain. Speci ically, i
consis s o he ac ion o Pinus Radia a ha he company disca ds due o
i s small size (<6 cm), making i easily and con inuously ob ainable in
abundan quan i ies. This wo k aims o exploi his ma e ial o he
de elopmen o a high-ene gy, high-powe LIC, while main aining
accessibili y and p oduc ion cos -e ec i eness. To achie e his, he ull
cell was buil using elec ode ma e ials ha do no elay on he use o
expensi e addi i es, high py olysis empe a u es, o addi ional p epa-
a ion s eps.
2. Ma e ials and me hods
2.1. P epa a ion o ac i e ma e ials
The biomass used in his s udy o igina es om a local o es y
company, Bio e miak S.L., loca ed in he Basque Coun y, in he no h o
Spain. The aw ma e ial consis s o Pinus Radia a pa icles disca ded by
he company. The e o e, by epu posing his ma e ial, his esea ch adds
alue wi hou con ibu ing o de o es a ion.
The p epa a ion and i s py olysis o he sample was epo ed by J.
Sola e al. [42,43] The ini ial p epa a ion in ol ed sie ing he woody
biomass in o pa icles anging om 0.5 o 2 mm. Subsequen ly, he
py olysis was ca ied ou in a con inuous sc ew eac o , wi h ou
empe a u e zones: 300, 500, 700 and 700 ◦C (in ha o de ). This p o-
cess yielded a HC ha was used as he ac i e ma e ial o he nega i e
elec ode.
Fo he p epa a ion o he AC, a ubula u nace was used unde a N
2
low. The p e iously p epa ed HC se ed as he p ecu so , which was
py olyzed a 700 ◦C o 2 h, an hen mixed wi h KOH in a 1:4 mass a io.
The esul ing ca bon was washed wi h HCl and dis illed wa e , ollowed
by o e nigh d ying a 80 ◦C. Finally, he ma e ial was ball-milled using
a SPEX 8000D mixe /mill.
2.2. Ma e ials cha ac e iza ion
X- ay di ac ion (XRD) spec a o bo h ac i e ma e ials we e ob-
ained in a Panaly ical X’Pe PRO ins umen be ween 5 and 70◦θ wi h
Cu K
α
adia ion. The mo phology o bo h samples was also examined by
scanning elec on mic oscopy (SEM) employing a JEOL JSM-7000F. N
2
adso p ion/deso p ion measu emen s we e ca ied ou a 77 K on a
J. Rod iguez-Rome o e al.
Jou nal o Powe Sou ces 629 (2025) 235961
2
Quan ach ome Au oso bIQ, and es ima ed alues o he speci ic su ace
(SSA) o he samples we e calcula ed by applying he B unaue -Emme -
Telle heo y (BET). P io o analysis, degasi ica ion was pe o med a
200 ◦C o 12 h, unde a acuum o 10
−4
ba . Finally, Raman spec os-
copy was ca ied ou on bo h ca bons using a Renishaw inVia spec-
ome e wi h 514 nm A
+
lase , acqui ing 4 scans in he 1000 o 2000
cm
−1
ange.
2.3. Elec ochemical cha ac e iza ion
The elec ode composi ion ollowed a 8:1:1 mass a io o he ac i e
ma e ial ( he HC o he AC), Supe P C65 (ca bon black) and poly
( ynildi luo ide) (PVDF), espec i ely. Slu ies o each elec ode ype
we e p epa ed in N-me hyl py olidone (NMP) and cas on o coppe oil
( o HC) and aluminium oil ( o AC). A e d ying he lamina es o e -
nigh a 80 ◦C, hey we e cu in o 12.7 mm diame e ci cles. The elec-
ode mass loading anged om 1 o 3 mg pe elec ode.
The assembly o cells ook place in an a gon- illed glo e box
(MB aun) wi h a wa e and oxygen con en o less han 0.1 ppm. The
elec oly e solu ion used was 1 M LiPF
6
in a 1:1 ol mix u e o e hylene
ca bona e (EC) and dime hyl ca bona e (DMC) (Sol ionic).
The elec ochemical pe o mance es s o bo h HC and ull cells we e
ca ied ou in h ee-elec ode PAT-Cells (EL-Cell®). ACs we e es ed in
h ee elec ode Swagelok- ype cells wi h o e sized sel -s anding coun e
elec odes made om comme cial AC (No i DLC Supe 30, SSA 1600
m
2
g
−1
). Me allic li hium se ed as he e e ence elec ode, and po ous
glass mic o ibe discs (Wha man GF/A) we e used as sepa a o s.
Fo hal -cells, gal anos a ic cha ge/discha ges (GA) we e pe o med.
The AC was es ed a cu en densi ies o 0,1, 0,5, 1, 2, 5, 10, 15 and 20 A
g
AM
−1
be ween 2.0 and 4.2 V s. Li
+
/Li, while he HC was es ed a C/10,
C/5, C/2, C, 2C, 5C, 10C, 20C, 50C and 100C (C =372 mAh g
−1
) be-
ween 2.0 and 0.005 V. Addi ionally, cyclic ol amme y es s (CVs)
we e conduc ed a 5 mV s
−1
o explo e he maximum sa e cu o po-
en ial o he AC.
The inal HC//AC ull cell sys em was es ed wi h 1:1 and 1:2
(HC
ixed
:AC) mass a ios, pe o ming GAs a a ious C- a es (C/5, C/2, C,
2C, 5C, 10C, 20C and 50C) based on he ac i e ma e ial o he anode. To
assess long- e m s abili y, 10,000 GA cycles we e ca ied ou a 10C o
selec ed mass a ios. Each measu emen was epea ed mul iple imes o
ensu e accu a e pe o mance assessmen . Be o e any ull cell es ing, he
HC was p e-condi ioned wi h 5 cycles a C/10 s. me allic Li, ollowed by
es ing a 0.1 V. On he o he hand, he AC was ini ially cha ged om
open ci cui ol age (OCV) o 4.2 V s. Li
+
/Li.
3. Resul s and discussion
3.1. Physicochemical cha ac e iza ion o ac i e ma e ials
SEM images e eal dis inc mo phological di e ences be ween he
wo ca bons, as depic ed in Fig. 1. No able, he HC p esen s shapes ha
appea o s em om he e en ion o he mic os uc u e inhe en in he
ege al p ecu so . In addi ion, he chemical ac i a ion p ocess in-
oduces de ec s, c acks and mic opo es in he ca bon ma ix. In ac , in
he AC he e is no e idence o he p ima y s uc u es o he p ecu so ,
bu a he agglome a ed s uc u es o i egula ly shaped and sized
pa icles.
To gain a be e unde s anding o he po osi y and su ace a ea
changes, i was de e mined om N
2
gas adso p ion/deso p ion mea-
su emen s ha he BET SSA inc eased om 4.5 m
2
g
−1
in he HC o 2399
m
2
g
−1
in he AC (Fig. 2a, b). The ele a ed SSA obse ed in he AC is
consis en wi h he iso he m p o ile, which exhibi s a ype I shape spe-
ci ic o mic opo ous ma e ials, and he signi ican gas adso p ion a low
ela i e p essu es sugges s he p esence o an ex ensi e mic opo ous
s uc u e, as epo ed by o he au ho s [44–48]. The po e size dis i-
bu ion indica es a signi ican po osi y wi h sizes anging be ween 0.5
and 1 nm, calcula ed applying he 2D-NLDFT heo y o he AC iso he m
(inse in Fig. 2b).
In he XRD pa e ns o he wo ca bons (Fig. 2c, d) a p ominen b oad
maximum a ound 43◦co esponds o he (100) e lec ion (JCPDF No.
75–1621). This ea u e is common in low-g aphi ized and highly
diso de ed ca bons [24]. Addi ionally, he (002) e lec ion appea s as a
b oad peak a ~23◦, pa icula ly no iceable in he HC. This may be due
o he lowe c ys allini y o he AC sample a e he ac i a ion p ocess.
As o he Raman spec a (inse in Fig. 2c, d), bo h samples exhibi
he cha ac e is ic G (~1580 cm
−1
) and D (~1340 cm
−1
) bands o
g aphi e, which a e ela ed o he in-plane C-C ib a ions and o he
Fig. 1. SEM images o HC (a,c), and AC (b,d).
J. Rod iguez-Rome o e al.
Jou nal o Powe Sou ces 629 (2025) 235961
3
p esence o de ec s in g aphi ic laye s, espec i ely [49,50]. The in-
ensi y a io (I
D
/I
G
) o HC is 1.08, while o AC, i is 1.13. This
disc epancy indica es highe diso de in he ac i a ed sample, bu also
con i ms he p esence o g aphi ic ca bon e en a e ac i a ion.
3.2. Hal cell elec ochemical cha ac e iza ion
The hal -cell elec ochemical cha ac e iza ion is summa ized in
Fig. 3. P io o he GA cha ge/discha ge measu emen s on he AC, CV
Fig. 2. N
2
adso p ion/deso p ion iso he ms o HC (a) and AC (b). Po e size dis ibu ion o AC is shown as an inse in b). XRD and Raman plo s HC (c) and AC (d).
Fig. 3. a) CVs o AC unning in di e en windows om 2-4.2 V o 2–4.8 V a 5 mV s
−1
. b) P o iles o he GA cu es o HC unning om C/10 o 100C s me allic Li. c)
Capaci y compa ison o AC and HC a di e en cu en densi ies. d) Capaci y alues ex ac ed om he measu emen om b).
J. Rod iguez-Rome o e al.
Jou nal o Powe Sou ces 629 (2025) 235961
4
measu emen s we e pe o med o de e mine he uppe limi o i s
wo king po en ial window (Fig. 3a). Below 4.2 V he beha iou is pu ely
capaci i e, as can be deduced om he squa e shape o he eco ded
cu e. Howe e , ex ending he cycling window o 4.4 V e eals a small
bump be ween 3.0 and 4.0 V a p onounced de ia ion om he ec an-
gula shape in he uppe and lowe cu o ol ages. This de o ma ion
indica es edox ac i i y in he sys em, and i is u he accen ua ed by
widening he window up o 4.6 and 4.8 V. This is ypically associa ed
wi h elec oly e decomposi ion, commonly obse ed a po en ials
exceeding 4.2 V. A po en ials exceeding 4 V s. Li
+
/Li, sol en s such as
e hylene ca bona e (EC) and p opylene ca bona e (PC) oxidize o CO
2
and alkylene oxide de i a i es [51,52]. This eac ion can occu as a side
eac ion wi h he unc ional g oups o he ac i a ed ca bon and any
esidual mois u e apped wi hin he po es. Since hese i e e sible e-
ac ions a e conside ed pa asi ic, leading o gas e olu ion, po e-blocking
p oduc s, and o he pa asi ic eac ions, such as hyd ogen luo ide (HF)
gene a ion [53–55], he uppe cu -o ol age has been se o 4.2V s.
Li
+
/Li.
A e de ining he po en ial window o he AC be ween 2.0 and 4.2 V,
GAs we e pe o med o ob ain he capaci y alues shown in Fig. 3c. The
GA p o iles and he capaci ies a each C- a e (9 h cycle) o he HC hal -
cell es ing a e depic ed in Fig. 3b and Fig. 3d, espec i ely. Fig. 3b
shows ha he HC eco ded a sloping cu e p o ile in i s en i e po en ial
ange. The absence o a dis inc pla eau is common, especially in HCs
p oduced a lowe empe a u es. In ac , his ype o ma e ials enables
as ion/elec on ans e and exhibi s lowe pola isa ion a high cu -
en s, making hem p omising candida es o high- a e applica ions
[56]. While he mechanism behind Li s o age in HCs emains deba ed,
many au ho s associa e he sloping egion om he cu e wi h Li
in e cala ion and he pla eau wi h po e illing [57–62]. Fig. 3d also
highligh s he high i e e sibili y o he HC du ing ini ial cycles, wi h up
o 50 % capaci y loss in he i s cycle. This beha iou is ypical o HCs,
and is associa ed wi h g ow h o he solid elec oly e in e phase (SEI).
Ca bons wi h mo e de ec s, he e oa oms and unc ional g oups exhibi
highe ini ial i e e sibili y. In e es ingly, hese cha ac e is ics end o
p edomina e in ca bons syn hesized a lowe empe a u es, howe e ,
hey can also be bene icial and inc ease he e e sible capaci y, so hey
can be conside ed a double-edged swo d [63–65].
The mass a io o nega i e and posi i e elec odes is a c ucial aspec
when a emp ing o balance he kine ics o bo h elec odes. Es ima ing
he a ge cu en o he en i e cell ope a ion is impo an o de e mine
an op imum mass balance. As can be seen in Fig. 3c, a 7.5 A g
−1
bo h
elec odes show simila capaci y. A ha cu en densi y he discha ge
ime o he anode is 36 s while he discha ge ime o he AC alls be ween
26 and 53 s (a 5 and 10 A g
−1
, espec i ely). The e o e, o balance he
cha ges s o ed in each elec ode, and a he same ime ma ch he kine ics
o bo h, a 1:1 mass balance o he elec odes is es ima ed o be adequa e.
Howe e , a ull-cell u ilizing elec odes in a 1:2 mass a io (HC:AC) was
also buil o be e unde s and he e ec o he elec ode mass balance in
he sys em, especially a lowe cu en s, whe e an o e sized AC elec-
ode could help ma ch he capaci ies o he elec odes.
3.3. Full cell elec ochemical cha ac e iza ion
Fi s , he 1:1 HC//AC sys em was e alua ed be ween 1.5 and 4.2 V.
Since he anode is pa icula ly sensi i e o high cu en s, we decided o
es he hyb id ull cell a cu en a es co esponding o he C- a es o
he anode. Howe e , all capaci ies shown he ea e a e calcula ed wi h
he masses o bo h ac i e ma e ials. Fig. 4 shows ha unde hese con-
di ions he posi i e elec ode eaches po en ials o app oxima ely 4.5 V
s. Li
+
/Li, which could ad e sely impac he li e ime o he de ice due o
he elec oly e decomposi ion (see Fig. 3a). To add ess his issue, he
po en ial window was na owed o 1.5–4.0 V, a e which, in addi ion o
achie ing highe capaci ies a high a es he AC did no exceed he 4.2 V
po en ial alue.
In addi ion o educing he cell ol age, we also explo ed he s a egy
Fig. 4. ( op) Pe o mance o ull cells om C/10 o 100C (calcula ed wi h he anode). (Bo om): Elec ode window isualiza ion du ing he c- a e es ing.
J. Rod iguez-Rome o e al.
Jou nal o Powe Sou ces 629 (2025) 235961
5
o inc easing he AC mass loading up o a 1:2 a io. This inc eases he
capaci y o he elec ode p e en ing he AC om exceeding he sa e
po en ial limi se in Fig. 3a. This app oach na ow he cu -o po en ial
o 4.3 V s. Li
+
/Li, a sa e alue han ha ob ained wi h a 1:1 mass a io
a he same cell ol age. Al hough bo h s a egies could sac i ice ene gy
densi y -ei he by limi ing he po en ial window o by inc easing he
o al mass o he sys em- hey enhance he capaci y o he ini ial 1:1
1.5–4.2 V sys em, especially a medium/high a es. This op imiza ion
p ocess has acili a ed he obse a ion o he impac o he elec ode
mass- a io on he po en ial windows o each elec ode. The capaci i e
elec ode eached unsa e po en ial alues due o he applica ion o an
excessi e cell ol age, which was e ec i ely mi iga ed by inc easing he
mass o he AC. Con olling he AC po en ial window agains o e -
cha ging, ei he by educing he cell ol age o inc easing i s ela i e
mass, has helped o achie e highe capaci ies a highe cu en densi ies.
Compa ing he 1:1 1.5–4 V and 1:2 1.5–4.2 V sys ems, bo h achie ed
simila esul s, wi h he la e exhibi ing sligh ly highe capaci ies a low
a es. The esul s in e ms o powe and ene gy can be seen in he Ragone
plo om Fig. 5.
The 1:1 HC//AC sys em achie ed an ene gy densi y o 111 Wh kg
−1
a 51 W kg
−1
. In con as , he 1:2 sys em exhibi ed highe ene gies a his
low powe le els, eaching 124 Wh kg
−1
a 35 W kg
−1
. Howe e , a
highe a es he 1:1 sys em sligh ly ou pe o med i s coun e pa ,
deli e ing 52 Wh kg
−1
a 24.4 kW kg
−1
compa ed o 42 Wh kg
−1
a 33.3
kW kg
−1
. Bo h con e ged a ca. 6 kW kg
−1
main aining a simila pe -
o mance up o 75 Wh kg
−1
.
We also in es iga ed he long- e m beha iou o each sys em. Bo h
sys ems unde wen o 10,000 cycles a 10C ( ela i e o he anode). The
choice o his cu en was made based on he p o iles obse ed in Fig. 4.
A highe a es such as 50C and 100C he anode exceeded 0.0 V s Li
+
/
Li, aising conce ns abou li hium pla ing and dend i e o ma ion [62].
Mo eo e , he discha ge imes o 56 s o he 1:1 sys em and 90 s o he
1:2 sys em -bo h close o 1 min-, sugges ha hey can ope a e wi hin he
applica ion a ge egime o a LIC, i.e. b idging he gap be ween LIBs and
EDLCs.
Fig. 6 shows he capaci y e en ion ob ained in he cyclabili y es s.
The 1:1 cell ou pe o med i s coun e pa in e ms o capaci y e en ion
a e 10,000 cycles. The cell wi h a 1:1 mass balance e ained 70 % o i s
ini ial capaci y a e 5000 cycles and up o 60 % in 10,000. In con as ,
he cell wi h a highe ol age and a 1:2 mass a io did no pe o m as
well. This clea ly a ou s he i s sys em. No ably, he mos signi ican
di e ence occu ed in he i s 800 cycles, whe e he wo s -pe o ming
cell los 28 % o i s ini ial capaci y compa ed o 10 % o i s coun e -
pa . Subsequen ly, bo h sys ems showed ela i ely linea ends,
achie ing 50 % and 60 % o capaci y e en ion, espec i ely.
Rega ding he beha iou o each elec ode, nei he o he AC elec-
odes in he wo cells exceeded he po en ial o 4.3 V a any poin ,
sugges ing ha he e has been no disce nible elec oly e deg ada ion
linked o he capaci y dec ease. As he cycles p og ess, bo h sys ems
exhibi a shi in elec ode u iliza ion: less eliance on he posi i e
elec ode and inc eased use o he nega i e elec ode. Al hough his
endency is p esen in bo h sys ems, i is mo e no iceable in he 1:2 cell,
which also shows g ea e capaci y luc ua ions. The obse ed shi in he
1:2 sys em may be a ibu ed o he HC exceeding 0.0 V in i s ini ial
cycles, which may ha e ini ia ed an inc ease in Li pla ing, a loss o Li
+
om he elec oly e, and a subsequen g adual inaccessibili y o he
pa hway o ac i e si es [66]. This would also explain he p ema u e loss
o e en ion obse ed in he 1:2 sys em.
Ul ima elly, he aim o he ex in hand is o ha ness he eliablili y o
one unique local biomass sou ce as he mains ay o a dual-ca bon LIC.
The ini ial capaci y in he 1:1 cell we e 29 mAh g
−1
and 27 mAh g
−1
in i s 1:2 homologue. Gi en hei simila ini ial capaci y, and he su-
pe io capaci y e en ion o he 1:1 sys em, i is concluded ha he 1:1
1.5–4.0 V sys em is he mos p omising among he p oposed con igu-
a ions. In essence, he ul ima e goal o he ex in hand is o p esen a
speci ic biomass sou ce as he undamen al co ne s one o he de el-
opmen o a dual ca bon LIC. Lines ha e been d awn owa ds he pa h o
a compe i i e comple e cell s ill lea ing oom o u he explo a ion o
ully comp ehend he deg ada ion mechanisms o each elec ode unde
di e en mass balances.
4. Conclusions
In summa y, a Li-ion capaci o (LIC) was success ully de eloped
using a ha d ca bon (HC) elec ode and an ac i a ed ca bon (AC) elec-
ode bo h p epa ed om he same eadily a ailable biomass sou ce.
This s udy p io i ised an ene ge ically e icien elec ode p epa a ion,
a oiding cos ly and unsus ainable p ocesses. The e o e, he syn hesis
empe a u es did no exceed 700 ◦C, and he use o expensi e addi i es
was e ained. The esul ing ma e ials exhibi excellen quali ies o a
high a e capabili y de ice. Speci ically, HC elec odes achie ed 112
mAh g
−1
a 10C, while AC elec odes achie ed 71 mAh g
−1
a 10 A g
−1
.
Fo he ull cell, he cell ension and elec ode mass a ios we e s udied
o op imise he pe o mance o each elec ode and p e en issues like
li hium pla ing o elec oly e decomposi ion. The bes pe o ming ull
cell used 1:1 mass a io and ope a ed in a cell ol age o 1.5–4.0 V. This
sys em achie ed ene gy densi y alues o 111 Wh kg
−1
a 51 W kg
−1
and
52 Wh kg
−1
a 24.4 kW kg
−1
. Fu he mo e, i demons a ed a capaci y
e en ion o 70 % a e 5000 cycles and 60 % a e 10,000 cycles a 10C
(calcula ed ela i e o he anode). This s udy con ibu es o add essing
he cu en limi a ions o ene gy s o age sys ems om a sus ainable and
cos -e ec i e pe spec i e, opening up possibili ies o high-powe
echnologies.
CRediT au ho ship con ibu ion s a emen
Jon Rod iguez-Rome o: W i ing – o iginal d a , In es iga ion,
Fo mal analysis, Da a cu a ion. Idoia Ruiz de La amendi: W i ing –
e iew & edi ing, Supe ision, Me hodology, Funding acquisi ion. Eide
Goikolea: W i ing – e iew & edi ing, Supe ision, Me hodology,
Funding acquisi ion, Concep ualiza ion.
Funding sou ces
This wo k was suppo ed by Gobie no Vasco/Eusko Jau la i za
(p ojec IT1546-22) and p ojec PID2023-151153OB-I00 unded by
MICIU/AEI/10.13039/501100011033/FEDER, UE and p ojec
Fig. 5. Ragone plo o he wo selec ed inal sys ems.
J. Rod iguez-Rome o e al.
Jou nal o Powe Sou ces 629 (2025) 235961
6
TED2021-131517B-C21/AEI/10.13039/501100011033/Uni´
on
Eu opea Nex Gene a ionEU/PRTR, unded by MCIN/AEI/10.13039/
501100011033 and by he “Eu opean Union Nex Gene a ionEU/PRTR”.
Decla a ion o compe ing in e es
The au ho s decla e ha hey ha e no known compe ing inancial
in e es s o pe sonal ela ionships ha could ha e appea ed o in luence
he wo k epo ed in his pape .
Da a a ailabili y
Da a will be made a ailable on eques .
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