Lignin in storage and renewable energy applications: A review

José Luis Espinoza-Acosta, Patricia I. Torres-Chávez, Jorge L. Olmedo-Martínez, Alejandro Vega-Rios, Sergio Flores-Gallardo and E. Armando
Zaragoza-Contreras
Citation: Journal of Energy Chemistry 27, 1422 (2018); doi: 10.1016/j.jechem.2018.02.015

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 Journal of Energy Chemistry 27 (2018) 1422–1438

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Journal of Energy Chemistry

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journal-of-energy-chemistry/
journal homepage: www.elsevier.com/locate/jechem

Review

Lignin in storage and renewable energy applications: A review

José Luis Espinoza-Acosta a,∗, Patricia I. Torres-Chávez b, Jorge L. Olmedo-Martínez a,
Alejandro Vega-Rios a, Sergio Flores-Gallardo a, E. Armando Zaragoza-Contreras a
a
Department of Engineering and Materials Chemistry, Centro de Investigación en Materiales Avanzados, Miguel de Cervantes #120, Complejo Industrial
Chihuahua, Chihuahua, México
b
Departamento de Investigación y Posgrado en Alimentos (DIPA), Universidad de Sonora, Hermosillo, Sonora, México

a r t i c l e i n f o a b s t r a c t

Article history: Lignin is a cheap, abundant and non-toxic group of complex phenolic polymers obtained in large amounts
Received 27 October 2017 from the papermaking and cellulosic biofuel industries. Although the application of lignin has been ex-
Revised 30 January 2018
plored in these and several more industries, there are limited applications of lignin in the energy industry.
Accepted 17 February 2018
However, numerous research revealed a great interest in the exploration of this renewable biopolymer in
Available online 2 March 2018
storage energy devices. Some of these applications include the use of lignin as an expander for lead–acid
Keywords: batteries, electrodes for primary and rechargeable batteries, electrodes for electronic double layer capac-
Lignin itors and electrochemical pseudocapacitors, and to feed different types of fuel cells. The use of lignin in
Batteries energy storage devices improves not only the performance of these devices but also decreases the price
Lithium-ion batteries and toxicity, contributing to obtaining greener energy devices. Based on the above, this review provides
Supercapacitors an overview of the main research work related to the use of lignin as a renewable component, suitable
Solar cells
to replace some synthetic and toxic compounds used in the fabrication of energy storage devices with
Fuel cells
particular emphasis on batteries, advanced supercapacitors, and solar and fuel cells.
© 2018 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published
by Elsevier B.V. and Science Press. All rights reserved.

José Luis Espinoza-Acosta received his Ph.D. degree in
Food Science and Technology at Department of Food Re-
search & Graduate Program (DIPA), University of Sonora,
Mexico, in 2015. Currently, he is conducting a research
as a postdoctoral fellow at Research Center for Advanced
Materials (CIMAV-CONACYT). His research interests fo-
cuses in the extraction, characterization, and application
of lignins isolated from different sources, the develop-
ment of lignin-starch composites, and the synthesis of
conducting polymers-lignin composites for application in
high-performance supercapacitors.
Jorge L. Olmedo-Martínez received his M.Sc. degree in
Materials Science at Research Center for Advanced Mate-
rials (CIMAV-CONACYT), Mexico, in 2016. He is currently
a Ph.D. student at the University of the Basque Country,
Spain. His subjects of interest include the study of solid
polymer electrolytes for lithium batteries, and the devel-
opment of advanced dye-sensitized solar cells.

Patricia I. Torres-Chávez is a Senior Researcher and full-
time professor in Food Science and Technology at the De-
partment of Food Research & Graduate Program, Univer-
sity of Sonora (DIPA-UNISON), Mexico. Dr. Torres received
her Ph.D. degree in Food Science at Research Center
for Food Development (CIAD-CONACYT), Mexico, in 20 0 0.
Her research interests mainly focuses on the study of car-
bohydrates functionality and proteins in cereals and the
application of lignin extracted from agricultural wastes.
Alejandro Vega-Rios received his D.Sc. degree in Chem-
istry at Technological Institute of Tijuana (Graduate Cen-
ter & Chemistry Research), Mexico, in 2011. He made a
postdoctoral stay at Research Center for Advanced Materi-
als, (CIMAV-CONACYT), Mexico in 2012. In 2013, he began
working at CIMAV as a Senior Researcher and full-time
professor. His research interests included synthesis, char-
acterization and modification of polymeric materials, de-
sign and synthesis of conjugated polymers, and synthesis
of modified cellulose nanocrystals with RAFT agents.

∗
Corresponding author.
E-mail address: jose.espinoza@cimav.edu.mx (J.L. Espinoza-Acosta).

https://doi.org/10.1016/j.jechem.2018.02.015
2095-4956/© 2018 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.

Downloaded to IP: 192.168.0.213 On: 2019-10-16 09:25:02 http://engine.scichina.com/doi/10.1016/j.jechem.2018.02.015

 J.L. Espinoza-Acosta et al. / Journal of Energy Chemistry 27 (2018) 1422–1438
Sergio G. Flores-Gallardo received his D.Sc. degree in
Polymers at Research Center in Applied Chemistry (CIQA-
CONACYT), Mexico, in 2003. He is the head of Engineer-
ing and Chemistry of Materials Department at Research
Center for Advanced Materials, (CIMAV-CONACYT). His re-
search focuses on the polymers processing and, in partic-
ular, on additive manufacturing such as nanocomposites,
multifunctional polymers as chain extenders, 3D printing.
E. Armando Zaragoza-Contreras received his D.Sc. de-
gree in Polymers at Research Center in Applied Chemistry
(CIQA-CONACYT), Mexico, in 1999. He is currently a Se-
nior Researcher at Research Center for Advanced Materi-
als (CIMAV-CONACYT), Mexico. His subjects of interest in-
clude conducting polymers, chemical sensors, polymers in
dispersed media, and nanocomposites.
1. Introduction
Nowadays, the environmental problems, the reduction of fossil
fuel sources, and the severe environmental safety policies are forc-
ing the industry to be sustainable. In the energy industry, there is a
great interest in developing more efficient energy storage devices
using renewable raw materials [1]. Over the past decade, impor-
tant research directed to improve the field of energy storage de-
vices and renewable energy devices using alternative materials was
performed. Iota-carrageenan [2], cellulose [3], and lignin [4] are
considered suitable natural polymers for the development and im-
provement of energy devices because they are inexpensive and
highly abundant. Particularly lignin has gained interest because it
is a non-toxic aromatic polymer obtained in large amounts (up to
50 million tons per year) as a by-product from the industrial pro-
cessing of cellulose pulp and the production of cellulosic fuels [5].
This lignin acquires both a name and chemical properties based
on their extraction method. Over three decades, the applications
of several types of lignin have been explored outside the pulp and
paper industry, for example, as an additive for concrete [6], feed
additives [7], and phenolic resins [8,9]. In the last two decades,
the design and fabrication of lignin advanced composites, in com-
bination with other organic and inorganic polymers, have been the
focus of much research [10,11]. More recently, the biological activ-
ity of lignins (e.g., antioxidant and biological activity) from differ-
ent sources has been studied [12–15], which, under certain circum-
stances, were more efficient than some synthetic antioxidants [16].
In spite of a large number of possible applications reported in
the literature for lignin, in the energy storage field, its applica-
tion is still limited [17]. However, over the last few years, consid-
erable research has reported the exploration of several lignins as
an interesting component for applications in storage energy de-
vices. The first research reported the use of lignosulfonate (LS)
as an expander of lead–acid batteries for increasing their useful
life [18]. The incorporation of LS retards the reactions of charge
and discharge but increases the capacity of the negative plates.
In lithium batteries, some lignins have been used in the prepara-
tion of organic cathodes with promising results [19]. Besides, the
application of lignin as a natural binder for lithium-ion batter-
ies (LIBs), with the aim of replacing conventional binders which
are toxic to animals and humans, has been explored [20]. Many
composites based on conductive polymers doped with LS or al-
kali lignin have been investigated for application in electrochem-
ical capacitors [21]. The use of some lignins in the development
of organic solar cells [22] and fuel cells [23] have been also ex-
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1423
plored. Furthermore, lignin is considered as one of the most viable
“green” carbon precursors [24]. For this reason, several lignins are
being transformed into carbonaceous materials with well-defined
porous structure, such as activated carbon nanofibers and hierar-
chical porous carbons (HPCs) [25], which have been used in the
preparation of electrodes for LIBs and supercapacitors [26].
A large number of reviews about lignin, with different ap-
proaches, have been published, for example, the use of lignin and
its derivates with beneficial effects on the human health [27], the
antioxidant and antimutagenic activity of different lignins [28], the
elaboration and design of lignin-based biodegradable composites
[29], and the preparation of nanoparticle based-lignin and other
nanostructures with different applications [30]. The conversion and
depolymerization of lignin using thermochemical methods for ob-
taining valuable chemicals have also been reviewed [31–33]. In the
energy storage energy field, the role of lignin as electrode and
binder for batteries has been brefly reviewed [34,35]. However, al-
though there is considerable research related to the use of lignin in
the development of energy devices, a review devoted to this spe-
cific topic has not been published yet. For the reasons as aforemen-
tioned, this review provides an overview of most relevant advances
concerning the use of lignin in the fields of energy storage devices
and solar cells.
2. Background of lignin
Plants are composed of cellulose, hemicellulose, lignin, and mi-
nority compounds. Lignin comprises 20–30% of the plants solid
weight, where the remaining 70–80% are cellulose and hemicel-
luloses. In plant tissues, lignin is not available as an independent
polymer. Instead, it is covalently bound to the polysaccharides cell
wall such as cellulose and hemicellulose. The separation of lignin
from the rest of the cell wall components includes the rupture of
natural lignin using different separation methods. The literature re-
ports that lignin is an amorphous and highly branched polypheno-
lic polymer, composed of three main units, p-coumaryl, coniferyl,
and sinapyl alcohol, jointly called monolignols [36]. The lignin
polymer network is obtained by the radical random coupling of
the monolignols. In the lignin molecule, the aromatic constituents
of the three main monolignols are p-hydroxyphenyl (H), guaiacyl
(G), and syringyl (S) units, which have a different methoxylation
degree on the aromatic ring (Fig. 1). The proportion of H, G, and
S units is highly variable according to the plant type [37]. For ex-
ample, G units are abundant in gymnosperms, GS units constitute
hardwood, while the grasses contain the three monolignols HGS-
units [38]. The main interunit linkages in the lignin structure are
condensed bonds (β –O–4, α –O–4, β –β ) and uncondensed bonds
(β –5, β –1, 5–5) [39].
2.1. Lignins isolation processes
There are many isolation processes reported to separate lignin
from the other polymers contained in the biomass [41]. The sul-
fate and the sulfite processes are the dominant isolation, produc-
ing more than 90% of the industrial lignin. In these processes,
kraft lignin and lignosulfonates are obtained as a by-product of the
wood processing. In the sulfate process, kraft lignin is separated
from the rest of the components under strongly alkaline condi-
tions [42] breaking the lignin into smaller chains, making it sol-
uble in water and alkali solutions. The use of sulfur compounds,
such as sodium sulfide, produces lignin with hydrophobic aliphatic
thiol groups (Table 1). In the sulfite pulping process, lignosulfonate
is obtained in a similar way to the kraft lignin but the alkaline
medium is replaced with an acidic one. LS contains sulfur but in
the form of sulfonate groups (SO3 − ). A simplified chemical struc-
ture of various lignin is shown in Fig. 2.
1424 J.L. Espinoza-Acosta et al. / Journal of Energy Chemistry 27 (2018) 1422–1438

Fig. 1. Precursors (a) and common interunit linkages of lignin (b) (From Ref. [40]).

Table 1. Physicochemical properties of lignin used in energy storage devices.

Kraft Lignosulfonate Organosolv Ref.

Status Industrial Industrial Laboratory/Pilot [40]

Extraction conditions Sodium hydroxide and sodium Sulfur dioxide (Na, Ca or Mg as Alcohols, mixtures of alcohols, organic [43]
sulfide, pH 13–14, 170 °C, 1–2 h counter ion), 120–180 °C, 1–5 h acids and mixtures of organic acid and
water, HCl as catalyst, 80–120 °C, 1–4 h
Separation methods Precipitation (pH change) Ultrafiltration Precipitation (addition of non-solvent) [44,45]
Dissolved air flotation
Molecular weight × 1.0–5.0 20–50 0.5–4.0 [46]
103 (g mol−1 )
Polydispersity 2.5–3.5 6.0–8.0 1.5–4.0 [47]
Impurities (%) Sulfur 1.0–3.0 Sulfur 3.0–8.0 Carbohydrate and ash < 10 [48]
Solubility Alkali and some organic Water Organic solvents [48]
solvents

Fig. 2. Simplified chemical structure of sulfur-containing and sulfur-free lignin. Organosolv and soda lignin from Ref. [40].

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 J.L. Espinoza-Acosta et al. / Journal of Energy Chemistry 27 (2018) 1422–1438
Fig. 3. Annual worldwide production of kraft lignin, lignosulfonate and sulfur-free lignins and their potential applications.
There are other processes to isolate organosolv lignin, soda
lignin, and ionic liquid lignin, produced in pilot plants and labo-
ratory scale. These lignins are obtained using acid solutions or al-
cohols (organosolv lignin), strong alkaline conditions (soda lignin),
and salts in a liquid state (ionic liquids) [42]. These lignins are ob-
tained through the chemical pulping of non-wood material species.
Organosolv and soda lignins, for example, are considered the
purest lignins because they are sulfur-free and contain a low im-
purities amount, therefore, these lignin structures are considered
the closest to the structure in the natural form. However, neither
organosolv nor soda lignin has gained sufficient importance to be
used on a commercial scale, although organosolv lignin is under
important research to increase its applications.
Regarding its applications, LS is the most explored lignin, fol-
lowed by kraft lignin and sulfur-free lignins (Fig. 3). The LS anti-
flocculant properties make this type of lignin more interesting than
the other ones for applications in energy storage devices. Lignosul-
fonates are amphiphilic molecules, that possess hydrophobic and
hydrophilic parts, exhibiting high water solubility. For example, in
lead–acid batteries the hydrophilic SO3 − anions, for instance, are
absorbed on the lead particles surface, resulting in an increase of
the repulsion potential, which prevents the particles from coalesc-
ing or sintering [49].
3. Batteries
3.1. Lead–acid battery
A lead–acid battery is a kind of rechargeable cell commonly
used as a cars power source [50]. To improve the charge-
acceptance and the general performance of the lead–acid batteries,
the use of an expander is essential [51,52]. An expander is an
additive added to the negative paste of a lead–acid battery to
increase its efficiency, cycle life, cold-cracking ability (CCA), and
durability through numerous charge and discharge cycles [52].
Carbon [53], barium sulfate [54], and various types of lignins
[18] are the most common components in the formulation of
expanders for lead–acid batteries. Chemically modified lignins,
modified or unmodified LS (so-called “organic expanders”), and
lignin derivates such as quinones have been under research for
several years because these derivatives are cheap and abundant,
and influence positively the lead–acid batteries performance. Com-
mercially, there are several organic additives used as the expander
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1425
of the negative paste of lead–acid batteries, for example, Vanis-
perse A, Maracell XC, Lignotech, Krafplex, and Indulin AT, which
are partially desulfonated, oxidized, or purified lignosulfonates and
modified kraft lignins. However, the influence of the incorporation
of these and other lignins (commercial and non-commercial) as
expander on the performance of negative electrodes in lead–acid
batteries have been the subject of numerous studies. These studies
have been focused on obtaining a relation between the chemical
composition of the lignin or lignosulfonate and the performance
of lead–acid batteries. So far, a correlation between the effect of
functional groups present in LS on the electrochemical, physic-
ochemical, and crystallization process that occur in the negative
plates of lead–acid batteries has been difficult to determine.
The lignins and derivates are a complex substance that contains
many functional groups (carbonyl, methoxyl, thiol, phenolic and
aliphatic hydroxyls, and sulfonate). These numerous functional
groups are occupying various positions in the expander structure,
which implies that the expander influences in different ways the
performance of the negative plates on the lead–acid batteries.
According to Ritchie, the order of functional groups that impart a
beneficial effect on the negative plate characteristics is: hydroxyl
phenolic > sulfonate > carboxyl > ketonic > aldehyde [55]. Reactions
between phenolic groups and antimony, tin, and calcium ions
influence the lead–acid batteries efficiency due to the formation
of organometallic compounds. Pavlov et al. [56] determined the
efficiency of eight LS families in the general performance of
lead–acid batteries negative plates. They report that, in addition to
the functional groups, the molecular weight and the lignin purity
are important properties that improved the efficiency of lead–acid
batteries. Myrvold and Pavlov [57] stated that the lignin molecular
weight and solubility are important factors that improved the
lead–acid battery cycle life. Regarding molecular weight, LS with
high molecular weight can be adsorbed onto lead or lead oxide
substrates, while LS with low molecular weight tends to form
lead–LS complexes that stay in solution [56]. This promotes the
dissolution–precipitation mechanism for the lead to lead sulfate
transformation. These results were in agreement with the report
of Francia et al. [58], which also mentioned that the formation
of lead–LS complexes influence the growth of large lead sulfate
crystals.
Generally, the lead–acid batteries application falls into three
major categories: (a) starting and lighting ignition SLI (automo-
tive), (b) motive power, and (c) standby power. As a fact, a high
1426 J.L. Espinoza-Acosta et al. / Journal of Energy Chemistry 27 (2018) 1422–1438
Fig. 4. EC-AFM images of electrode surface observed before and after potenstiostatic oxidation (Modified from Ref. [61]).
percentage of LS is used in the formulation of expanders for au-
tomotive application, while in industrial batteries, a small percent-
age of LS is employed [49]. The high percentage of LS in automo-
tive plates is necessary to produce the high cold-cranking ability
(CCA). CCA is defined as the ability of a battery to start a vehicle
under cold temperatures. Following a life test for automotive stor-
age batteries (SAEJ240 with slight modifications), Boden [49] eval-
uated the effect of the type and concentration of LS on the CCA of
lead–acid batteries negative plates. The results of the test showed
that LS type-A was the best LS increasing the CCA at low concen-
trations (0.5 wt%), however, the CCA decline at concentrations up
to 0.75 wt%.
The reactions that occur in lead–acid batteries have been stud-
ied using electrochemical techniques such as charge/discharge test,
while the morphological changes occurring on the electrode sur-
face have been analyzed using advanced microscopy (scanning
electron microscopy and atomic force microscopy). The observa-
tion of the reactions achieved on lead electrodes during oxidation
and reduction has only been possible using electrochemical atomic
force microscopy (EC-AFM) [59,60]. Ban et al. [61] reported the use
of EC-AFM to know the effects exerted by the lignin incorporation
on the electrodes surface of lead–acid batteries. From the results,
they observed that the negative electrode surface shows a uniform
distribution of lead–acid crystals because of the incorporation of
lignin after potenstiostatic oxidation (Fig. 4).
A model to explain the lignin effect on the lead electrode was
developed (Fig. 5d–g). Without lignin, the lead sulfate crystals were
dispersed irregularly. The drawing (a–c) represents the lead ions
dissolution in the electrolyte without lignin during oxidation. The
drawing (d) illustrates the lignin initial effect. When absorbed on
the electrode, the lignin acts to remove the obstructive layer from
the electrode surface by a reduction or solvent effect. Drawing (e)
shows the initial dissolution of lead ions when the oxidation po-
tential is applied. Finally, the drawing (e–g) illustrates the adsorbed
lignin second effect (transfer of the lead ions); where the lead
ions diffuse from their dissolution sites to further locations on the
lignin molecules.
Based on this model, Buqa et al. [84] concluded that lignin acts
as a cleaner to remove the obstructive layer from the electrode sur-
face by a reduction or solvent effect; however, a detailed reaction
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between the lead oxide and lignin was not elucidated. In addition,
it was emphasized that the above-mentioned effects of lignin are
useful only when the additives amount is suitable for the electrode
area. If too much lignin is added, it suppresses the lead ions disso-
lution because the lignin adsorption area becomes too wide or its
adsorption layer becomes too thick.
Otherwise, Hirai et al. [62] combined cyclic voltammetry (CV),
EC-AFM, and rotating ring-disk electrode (RRDE) to investigate the
LS concentration effect on the electrochemical reactions of nega-
tive lead electrodes in 1 M, 3 M, and 7 M H2 SO4 solutions. As a CV
resul, two cathodic peaks were observed when a low LS concen-
tration was added. This effect was attributed to the LS sulfonation
when it is in contact with the sulfuric acid solution; therefore, im-
proving their electroactive response. Recently, the growth of PbSO4 ,
in the sodium LS presence added in the electrolyte, was studied
using SEM and transmission X-ray microscopy (TXM) [63]. The LS
effect to H2 SO4 was reflected in the average size and PbSO4 crys-
tals growth rate. Without LS (Fig. 6), the number and average size
of the PbSO4 crystals increased because of a progressive nucleation
and growth mechanism, where new crystals are continually form-
ing, and pre-existing crystals are continually growing. In contrast,
the PbSO4 crystals number increases while the size distribution re-
mains relatively the same. This trajectory in morphology indicates
that lignin retards the crystal growth.
The LS influence as an expander on lead–acid batteries is com-
plicated. There is a complex interplay between the expander prop-
erties and their performance. As reported, the molecular weight,
the solubility, the purity, and the presence of many functional
groups in lignin seem to be important characteristics to produce
positive effects on the final lead–acid batteries performance. Based
on the literature review, it can be concluded that the use of LS as
organic expander has various positive effects on the lead–acid bat-
teries performance. The LS addition in the negative paste controls
the size and distribution of lead sulfate crystals and controls the
conversion rate of lead to lead sulfate oxidation during discharge.
A panel of experts in lead–acid batteries answered several ques-
tions about lead–acid technology and performance. The answers
and questions were published in a paper titled "Manufacturing and
operational issues with lead–acid batteries." This paper dedicated a
wide section to the functions of LS in negative-plate [64]. Besides,
 J.L. Espinoza-Acosta et al. / Journal of Energy Chemistry 27 (2018) 1422–1438
Fig. 5. Model of lignin effect on the lead electrode during oxidation (From Ref. [61]).
the book titled “Lead–acid Battery Technologies Fundamentals, Mate-
rials, and Applications” presents a considerable amount of informa-
tion about the use of LS as an expander in negative-active materi-
als [52].
3.2. Primary lithium batteries
Primary lithium batteries (single-use or disposable) (PBLs) have
been long used for power supplies in numerous applications be-
cause of their excellent performance. The typical PLB contain
inorganic-compounds based cathode, an electrolyte, and lithium-
based anode. The PLBs are characterized by having some limita-
tions of the component base such as non-renewability, toxicity, and
high cost. Numerous studies related to PLBs have been focused on
the search and creation of electrochemical systems using low-cost
and environmentally friendly materials. Organic electroactive ma-
terials containing chemically active C = O groups have been under
extensive investigation because of the electroactive redox proper-
ties. In this sense, lignin has been investigated for this purpose
because it is a highly available, renewable, and low-cost material
which also contains C = O groups.
Klason lignins extracted from sunflower husk [65] and buck-
wheat husk [19] has been studied to the development of low-
cost cathode-active material for PLB. These studies emphasized
that these lignins contain heterogeneous morphology on the lignin
particles surface and it facilitates the Li+ ions diffusion during
the lithium battery operation. Milling treatment (manual and auto
milling) has been applied to reduce the lignin particle size. A di-
rect relationship between lignin particle size and the cell discharge
parameters were reported. Also, the content of oxygen-containing
groups present in lignin has been directly associated with the spe-
cific capacity of lithium/lignin cells [66]. According to the liter-
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1427
ature, the electrochemical reaction mechanisms in Li/lignin cells
have been proposed using cyclic voltammetry and galvanostatic
discharge/discharge test. These reactions have been represented
with the help of various equations: interaction between Li+ ions
and lignin carbonyl groups (Eq. (1)), O–H groups reduction (Eq.
(2)), the interaction between Li+ ions and C–O–C groups (Eq. (3)).
Finally, the mechanisms of Li+ ions interaction and ether groups
have been widely using aprotic dipolar organic solvents [67,68].
(1)
2C6 – C3 – OH + 2Li+ + 2e− → 2C6 – C3 – O – Li + H2 (2)
C6 – C3 – O – R + 2Li+ + 2e− → C6 – C3 – O – Li + R– Li, (3)
Where (C6 –C3 ) is the lignin phenylpropane structural unit, R
(C6 –C3 ); CH3 .
On the other hand, the lignin hydrolysis (HL) has also been
investigated for application as energy storage material. HL shows
also interesting physical properties such as micro- and macropores
on its surface and a high percentage of oxygen content, which are
suitable for application as a cathode material for PLB [66,69]. The
electrochemical properties of organic cathodes based on HL (up
to 50%) were investigated and the possible electrochemical reac-
tions occurring in the Li/HL system were reported on the basis of
the products composition analysis. The probable lithium interac-
tion with HL was simplified in the below equation:
6nLi + (C10 H11 O3 ) → 3nLi2 O + (C10 H11 )n (4)
where n is the number of polymer units.
1428 J.L. Espinoza-Acosta et al. / Journal of Energy Chemistry 27 (2018) 1422–1438

Fig. 6. Crystal size distribution for PbSO4 grown on Pb in 4.6 M H2 SO4 without and with 26 ppm of sodium lignosulfonate: (a) TXM experiment, (b) separate experiment on
electroplated Pb. Time in the figure is in reference to the start of OCV (Adapted from Ref. [63]).

This reaction on a cathode can be represented as that of lithium
ions with HL ether groups (Eq. (5)):
(5)
It is well known that both chemical and electrochemical re-
actions between Li and organic electrolyte solvent occurre very
slowly. Thus, the probability of the interactions between lithium
ions and hydrolysis lignin ether groups is not high. According to
the literature, the electrochemical reaction between Li and car-
bonyl groups of HL is most probably because lignin contains 20
carbonyl groups per 100 phenylpropane structure units. More de-
tailed knowledge of all the reactions that occur in the cathode-
based lignins is complicated because lignin contains many func-
tional groups (phenol, carboxyl, hydroxyl, carbonyl, alcohol, benzyl,
aldehyde, and methoxyl groups).
Klason lignin and hydrolysed lignin are characterized by pos-
sessing a moderate specific electronic conductivity of 10–11 S cm–1 .
It is a common disadvantage against several electroactive materi-
als. Moreover, electroconductive additives as carbon black are ap-
plied to prepare lignin cathodes to ensure the electroconductiv-
ity. However, in the formation of lignin-based cathode material,
smaller amounts of electroconductive additive are necessary com-
pared with Li/fluorocarbon systems. Opra et al. [70] reported the
optimization of the cathodes fabrication processes for PLB based
on hydrolytic lignin. According to their results, 6 wt% of the binder
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and up to 25% of conductive additive were the optimal concentra-
tions to obtain the best values of specific capacity in the battery.
As a date, the drying temperature at 280 °C produced the oxidation
of some oxygen-containing functional groups present in hydrolytic
lignin and partial binder destruction and increased the battery dis-
charge capacity by 30%.
Primary lithium batteries based on different lignin as cathode
materials have been developed and the possible interaction mech-
anisms occurring in the system Li/lignin have been analyzed by
advanced electrochemical techniques. The results of these research
demonstrate the potential of many types of lignin-based batteries
to be used as low-rate power sources. However, the great chemical
complexity and problems that surround lignin hinder the commer-
cial scaling.
3.3. Lithium-ion batteries
Lithium-ion batteries (LIBs) are a kind of rechargeable batter-
ies having high energy density used in many commercial elec-
tronic devices [71,72]. Opposite to primary lithium batteries, LIBs
can be charged and discharged many times, being able to store a
large amount of energy in a relatively small volume. Thus, LIBs are
becoming a common replacement for lithium-based primary bat-
teries because they offer high energy density, lightweight design,
and longer lifespan [73]. However, the long manufacturing time
and high cost are two big constraints to fabricate such batteries.
The cathode, the anode, and the electrolyte comprise around 60%
of the LIB cost. For example, the activated carbon (AC) used in
the anode manufacture of conventional LIBs has a price of $15/kg.
 J.L. Espinoza-Acosta et al. / Journal of Energy Chemistry 27 (2018) 1422–1438 1429

Fig. 7. (a) Schematic diagram of the formation process of LHPC, (b) galvanostatic charge–discharge (GCD) cycling performance of LC and LHPC at different current densities,
(c) GCD LC and LHPC at 200 mAh g–1 , and (d) GCD LHPC at 500 mAh g–1 (Adapted from Ref. [76]).

Besides, Badi et al. [74] mentioned that the LIBs specific energy
LIBs is limited because AC contains little space to release and stor-
age lithium ions reversibly. The lignin conversion into activated
carbon was reported by Suhas et al. [75] although in this review
details of the applications of these based-lignin activated carbons
were not suggested.
A strategy to decrease the LIBs cost and to increase the ef-
ficiency is the use carbon from renewable sources with specific
morphologies, which allows easy transport of lithium ions. In this
sense, 3D hierarchical porous carbon, carbon nanofibers, and car-
bon fibers mats (CF mats) have been prepared using lignin as
a raw material. 3D lignin hierarchical porous carbon (LHPC) pre-
pared using KOH as a template and activating agent acting simul-
taneously in the calcination process were applied as the electrode
for LIBs [76]. The LHPC showed a higher theoretical capacity than
graphite and carbonized lignin in bulk. These 3D LHPC has a high
specific surface area and its specific porous structure allows an
easy pathway for the lithium ions adsorption–desorption in the

Fig. 8. FE-SEM images of electrospun nanofibers (a,c,e) and CNFs with 0, 30% and 50% of alkali lignin (b,d,f). Initial charge and discharge of carbon nanofibers (g), and charge
capacities for 50 cycles (h) (Adapted from Ref. [77]).
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1430 J.L. Espinoza-Acosta et al. / Journal of Energy Chemistry 27 (2018) 1422–1438

battery charge–discharge (Fig. 7). Tenhaeff et al. [4] developed an performance. Also, the lignin/PVA membrane was comparatively
anode for LIBs using CF mats from Alcell lignin as the active ma- thicker than the commercial separator (Fig. 9).
terial and current collector; these interconnected lignin CF mats
had specific charge capacities, comparable with typical graphite
4. Supercapacitors
used in anodes of LIBs. These results are promising for the anodes
development for LIBs without using binders or additional active
Recently, supercapacitors (also known as electrochemical
materials.
capacitors) have received considerable attention because the ad-
Research has also been focused on the preparation of carbon
vantages that this present compared to batteries, such as high
nanofibers (CNFs) from lignin and polymers such as polyacryloni-
power density, fast charge/discharge capability, and long durability.
trile (PAN) [77–79] and polyethylene oxide (PEO) [1] for application
Supercapacitors are generally categorized as electronic double
as an electrode for LIBs. PAN is the most common material used in
layer capacitors (EDLC) and pseudocapacitors (also known as
the anodes fabrication for rechargeable LIBs. The substitution of a
redox capacitors) base on the energy storage mechanism [90].
percent of PAN for lignin implies a lower production cost of anodes
EDLC store energy physically through the charge accumulation at
for LIBs. The CNFs manufacture from PAN and kraft lignin blends
the electrode–electrolyte interface, while pseudocapacitors store
(PL) was reported by Choi et al. [77]. Thinner CNFs were obtained
energy as a result of Faradaic redox reactions involving the charge
by replacing 50 wt% of PAN for kraft lignin. The CNFs capacity re-
passage across the double layer during charging and discharging
tention was ∼150 mAh g–1 and the CNFs retention capacity was in
[91]. High-surface-area (porous) carbon materials such as activated
function of the charge/discharge rate (Fig. 8). Thus, these studies
carbon, mesoporous carbon, and graphene have been commonly
suggest that lignin is a suitable low-cost substitute for PAN as a
used in EDLC [92]. However, in most cases, the mesoporous
precursor for carbon electrodes.
carbon preparation involves complex synthetic procedures, while
Binders and conductive materials are necessary components in
graphene can be obtained in the laboratory after harsh chemical
the electrodes fabrication for LIBs. Despite the importance of both
treatments but this increase the final cost. Activated carbon de-
binder and conductive materials, these components increase the
rived from renewable and abundant sources can be obtained by
LIBs cost manufacture. Binders are necessary to hold the active ma-
sustainable processes at low cost [93]. Several types of lignin have
terial particles together and in contact with the collectors. The con-
been identified as the most viable carbon precursors, because of
ventional binder materials used in commercial LIBs are typically
high carbon content (∼60 wt%) [94] and low cost [24]. Lignin-
a combination of polyvinylidene fluoride (PVDF) and N-methyl-2-
derived porous carbon, such as HPCs and electrospun fibers are
pyrrolidone (NMP) as the solvent. Nevertheless, PVDF has three
being used for the preparation of electrodes for EDLCs (Fig. 10).
disadvantages: (1) is expensive, (2) is not easy to recycle, and (3)
For example, HPCs from lignin have been prepared by template-
deteriorates rapidly [80]. A study by Maleki et al. [20] demon-
assisted routes or combined templating/activation methods. Some
strated that reactions between PVDF and lithium could cause self-
soft templates include the use of polyethylene oxide (PEO) [95],
heating and thermal runaway. Meanwhile, NPM is environmentally
poly-(methyl methacrylate) [96], and Pluronic surfactant [97].
harmful and toxic to animals and humans. The high cost, exother-
Meanwhile, zeolites have been used as a hard template [98,99].
mal reactions, and toxicity of the actual binders have made neces-
Usually, physical and chemical activating agents such as CO2 ,
sary the development of alternative binders using eco-friendly and
KOH, and NaOH solutions are applied to obtain porous carbon
economically viable precursors.
with a high specific surface area [24]. Electrospun porous carbon
There are many reports about the use of alternative
fibers or CF mats from lignin are also being tested as a possible
binders such as modified cellulose [81], poly(acrylamide-co-
replacement of traditional carbonaceous materials used in the
diallyldimethylammonium chloride) [82], polyacrylic acid [83] and
EDLCs electrode. In the next sections, we are summarizing the
mixtures of styrene-butadiene-rubber/modified cellulose [84]. The
recent progress in the preparation and application of HPCs and
use of lignin as a binder is relatively new, Lu et al. [85] reported
electrospun fibers from lignin as an electrode for EDLCs.
the preparation of negative and positive electrodes for LIBs using
lignin as a binder. Before electrode fabrication, the lignin was
subjected to a leaching pretreatment to remove small fractions 4.1. Porous carbon-based on lignin for EDLC
and improve its stability in the electrolyte. More uniform lignin
fractions with enhanced chain flexibility, which makes the lignin HPC has been identified as one of the most viable porous car-
more elastic binder were obtained after leaching. Despite the bonaceous materials for advanced supercapacitors because it pos-
good results of reversible capacitance, further work is still needed sesses micro–, meso–and macropores [100]. The multimodal poros-
to obtain less fragile electrodes. Contrarily, Chen et al. [86] ob- ity in the HPC structure improves the performance of supercapac-
tained a binder-free negative electrode for LIBs from pyrolyzed itors [101]. For example, the presence of macro- and mesopores
lignin and silicon nanoparticles. They developed a procedure to facilitate a rapid ion transport, allowing a short ion-transport path-
obtain uniform interconnected core-shell electrodes base Si/C way, while micropores are electroactive sites to store energy. Zhang
directly on the current collector without the need of binder and et al. [102] found that an excessive carbonization, the activation
conductive carbon. These electrodes exhibited high specific capac- temperature, and the KOH–HPC ratio have a great influence on
itance comparable with electrodes of silicon nanoparticles [87,88]. the specific capacitance of HPC from lignin. Carbonization tempera-
The low quantity addition of PEO in the mixture of pyrolyzed ture up to 500 °C destroys unstable pores making the carbon more
lignin and silicon, produced a binder-free matrix with excellent compact, while high activation temperature up to 800 °C reduced
electronic conductivity, and adhesion, eliminating the neces- the specific capacitance as a result of an accelerated activation. An
sity to use conventional binders such as PVDF. Recently, Uddin increase in the specific capacitance was only possible when the
et al. [89] published a simple water-based method to fabricate KOH–HPC ratio does not surpass 4:1.
lignin/PVA membranes with applications as a separator of LIBs. Porous activated carbonaceous materials from lignin, modified
Lignin/PVA membranes showed high porosity, wettability, and by N-rich pyrrole with cheese-like morphology, were reported by
thermal stability, as well as good compatibility with different Wang et al. [103], these cheese-like materials showed high spe-
electrolytes. Compared with Celgard (a commercial separator), cific surface area (> 200 m2 g–1 ) which is desirable for EDLCs.
the lignin/PVA membranes have a low cost, simple preparation, The high specific surface area and the porous morphology of this
improved safety and compatibility, and better electrochemical carbon provide electrodes for EDLCs with good capacitance and
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 J.L. Espinoza-Acosta et al. / Journal of Energy Chemistry 27 (2018) 1422–1438 1431

Fig. 9. (a) SEM images of lignin/PVA membrane, (b) Celgard separator (10 kX and 20 kX magnification) and (c) photograph of lignin/PVA membrane and Celgard separator
before and after thermal exposure at 150 °C for 1 h (Adapted from Ref. [89]).

Fig. 10. (a) SEM image of carbon lignin-based fiber mats and (b) SEM image of hierarchical porous carbon activated (HPCs) lignin-based for EDLC.

excellent cycle stability after 10 0 0 cycles, even better than similar
electrode materials reported recently.
Lignin porous carbon-based templates, with well-ordered pore
structure, have been obtained by liquid phase impregnation and
chemical vapor deposition [98,99,104]. The synthesis of lignin-
based carbon templates, commonly involves four steps: (1) the ze-
olites are added to a lignin solution, (2) the mixture lignin/zeolite
is dried and carbonized, (3) the zeolite is removed using acid or
basic solutions, and (4) the obtained carbon templates are rinsed
with distilled water and dried. Ruiz-Rosas et al. [98] obtained HPC
from Alcell lignin using two different zeolites as a hard template.
Among the most important findings were that the mesopore vol-
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ume and the mean mesopore size were dependent on the zeolite
type, while the microporosity was related to the carbon source se-
lected as raw material and the carbonization temperature. HPC fab-
ricated using β and Y zeolites as templates were prepared to pre-
pare electrodes for asymmetric supercapacitors [104]. The HPC ob-
tained showed connected and developed porosity with similar mi-
cropore size but different mesoporous size. The porosity size and
distribution depended on the template. The HPC based-lignin elec-
trodes surpass the energy density and rate performance than sym-
metric devices using commercial activated carbon. An asymmetric
configuration in the fabrication of the supercapacitor improves its
stability, allowing the capacitor to operate safely at 1.4 V.
1432 J.L. Espinoza-Acosta et al. / Journal of Energy Chemistry 27 (2018) 1422–1438
Lignin mixtures with nitrogen (N) compounds such as urea
or lignin with a residual content of proteins have been con-
verted to interconnect HPC. The nitrogen incorporation in lignin-
based porous carbon had a positive effect on the conductivity and
good surface wettability with the electrolyte ions. The study of
the chemical states of N showed the presence of pyridinic-N and
quaternary-N in lignin-based porous carbon [103]. The obtained re-
sults are in agreement with previous works which mention that N
introduction in the porous carbon improves its conductivity and
enhances the capacitance of supercapacitors [105].
Soft and hard templates are a good option for the synthe-
sis of porous carbonaceous materials for supercapacitors. How-
ever, the use of templates increases the complexity and cost of
the carbonaceous material. Also in some cases, an appropriate re-
moval of the template residues conveys the use of extra chem-
ical compounds. Chang et al. [26] took advantage of the lignin
excellent solubility in a sodium hydroxide solution to avoid us-
ing additional extra chemical compounds in the HPC fabrica-
tion process. They found that the low sodium hydroxide con-
centrations created micropores with a size smaller than 1 nm
and mesopores/macropores below to 200 nm. As an effect of a
high concentration of sodium hydroxide, micropores enlarge to
mesopores, while mesopores collapse to macropores. According to
the HPC electrochemical performance, cycling voltammetry curves
present a rectangle shape at 100 mV s–1 , which is slightly lost at
200 mV s–1 . Jeon et al. [106] obtained high-surface-area porous car-
bon without the use of a template or activating agents. This was
possible using lignin with low molecular weight (Mw from 10 0 0 to
2600 g mol–1 ) through direct carbonization. During the carboniza-
tion, the oxygen-containing functional groups present in this lignin
generate CO2 and H2 O which act as internal activating agents. Also,
the end groups, high chain mobility, and high free volume of low
molecular weight lignin allowed the lignin carbonization easily. As
an electrode for supercapacitors, the lignin with lower molecular
weight and high surface area exhibited high energy density and
good capacity of retention.
4.2. Lignin-based carbon fibers for EDLC
Lignin-based carbon fibers have been utilized directly as an
electrode for supercapacitors in the binders absence. In some cases,
lignin has been combined with support polymers such as polyvinyl
alcohol (PVA) [107] and polyethylene glycol (PEG) [108] to facili-
tate the electrospinning. Ago et al. [107] obtained high surface area
free-standing electrospun mats from lignin/PVA solutions. The use
of PVA in a low amount (25%) allowed obtaining flexible and free-
standing carbon networks with a high surface area (20 0 0 m2 g–1 ).
As the electrode, the use of these free-standing fibers showed ex-
cellent specific double layer capacitance and maintained their ca-
pacity up to 83% over 1500 cycles (Fig. 11). This unique perfor-
mance was attributed to a microphase separation between lignin
and PVA; it produced wide pore distribution in the mesopore range
of the carbon fibers.
You et al. [109] fabricated lignin-based activated carbon fibers
(ACFs) using different types of electrospinning techniques and dif-
ferent types of lignins. These carbon fibers were tested as an elec-
trode for EDLC and internal tandem electric double-layer capacitors
(IT-EDLCs). One important finding, reported in this work, was the
reduction of thermostabilization time in the lignin-based carbon
fibers to only 3 h using hexamethylenetetramine (hexamine) in a
mixture of solvents (acetic acid/carbon tetrachloride 8/2). Addition-
ally, the incorporation of hexamine increased the surface area and
the fibers porosity. These porous were generated as a result of the
unsolved carbon tetrachloride, which was quickly evaporated from
the spinning dope during the electrospinning coagulation process.
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The fibers porous morphology was maintained even in carboniza-
tion and stream activation processes.
Recently, You et al. [108] prepared electrodes for application in
EDLC based on polyethylene glycol (PEG) and soda lignin (SL) by
dry electrospinning. These fibers showed a smaller diameter than
PEG fibers obtained by dry and melt spinning. The fibers were
thermostabilized through a high heating rate but in a short time.
Moreover, the ACFs/SL electrodes had an impedance and specific
capacitance of 4.5  and 55.6 F g–1 , respectively, these values were
higher than in PEG-ACFs electrodes. With the purpose of fabricat-
ing EDLCs, with a wide potential window and a high energy den-
sity, You et al. [110] reported the use of thick ACFs prepared from
polyethylene glycol lignin (PEGL) as an electrode for IT-EDLCs. Elec-
trodes for IT-EDLCs were internally laminated and connected in se-
ries, in parallel, and in a series/parallel combination. The results
indicated that the combination of connections was more efficient
than that of a single cell. In IT-EDLCs the potential window was
expanded by the connection in series, and the capacitance was in-
creased by connection in parallel.
The binderless porous carbon development from lignin, by di-
rect routes such as electrospinning, has received more and more
attention. The use of electrospinning permit to obtain carbon elec-
trodes with improved stability, and at the same time, it helps to
reduce the time of fabrication and the environmental and eco-
nomic impacts. In this sense, mechanically flexible electrodes from
carbon based-lignin without the binders addition have been pro-
duced using electrospinning. The fabrication of binderless fibrous
carbon electrodes (from lignin-ethanol solutions) with the use
of electrospinning was reported recently [111]. As an electrode
for supercapacitors, lignin carbon fibers only lost about 10% of
their initial power after an exhaustible charge–discharge test. Sim-
ilarly, Lai et al. [112] fabricated binder-free electrodes form al-
kali lignin/PVA mixtures. From the mixtures prepared, the sam-
ple with 70/30 mass ratio of lignin/PVA showed higher specific
surface area, higher gravimetric capacitance, and higher stability
after 60 0 0 cycles of charge/discharge. According to various re-
ports, lignin-based carbon fiber electrode materials with nano-
size and well-defined porous could allow the advanced superca-
pacitors creation, even without the addition of binders or con-
ductivity promoters. These lignin-based electrodes for supercapac-
itors have demonstrated even better gravimetric capacitance, spe-
cific surface area, and stability than some electrodes obtained from
non-renewable resources.
4.3. Electrochemical pseudocapacitors
In pseudocapacitors, transition metal oxides (RuO2 , Fe3 O4 ,
and MnO2 ) and conducting polymers such as polyaniline (PANI),
polypyrrole (PPy), poly(3-4-ethylenedioxythiphene) (PEDOT), and
polythiophene are materials used in redox capacitor electrodes.
Metal oxides yield high capacitance values; however, the cost,
material scarcity, and processing variability limit their applicabil-
ity to large-scale systems. On the other hand, conducting poly-
mers have been widely used as electrode materials due to their
important properties, which include high conductivity, low-cost,
and relatively easy synthesis. Nonetheless, conducting polymers
present two drawbacks: (1) inferior rate capability than metal ox-
ides and (2) poor cycling stability when they are subjected to
charge/discharge test for a long time [113]. To increase the per-
formance of electrochemical supercapacitors electrodes conducting
polymer/sulfonated lignin composites have been extensively inves-
tigated. The lignosulfonate incorporation effects on the conduct-
ing polymers properties and their performance as an electrode for
electrochemical pseudocapacitor are shown in Table 2.
Several reports allude that the synergic combination of the CPs
and lignin can surpass the electrochemical performance of the CPs
 J.L. Espinoza-Acosta et al. / Journal of Energy Chemistry 27 (2018) 1422–1438
Fig. 11. (a) SEM images of electrospun lignin-based fiber mats after carbonization (900 °C 1 h), (b) photograph of a flexible carbon mats after carbonization, and (c) cycling
stability of carbon mat and powder electrode (scan rate at 10 mV s–1 ) (Adapted from Ref. [107]).
Table 2. Effect of the incorporation of LS on the properties of conducting poly-
mer/LS composites.
LS act as Enhanced property
Conducting Dopant Conductivity
polymers/LS
composites
Surfactant Solubility
Template Thermal stability
Morphology modulator Charge storage ability
Specific capacitance
Cycling stability
Redox electroactivity
alone. Milczarek and Inganäs [114] reported that an interpenetrat-
ing polymer network between PPy and lignin exhibited excellent
charge storage ability due to the lignin and PPy synergic combina-
tion. CP/lignin composites (PANI/LS, PEDOT/LS, and PPy/LS) can be
synthesized easily using chemical polymerization or electrochemi-
cal polymerization. The macromolecular assembly of this compos-
ites has been able to overcome the CPs electrochemical perfor-
mance alone. Milczarek and Inganäs [114] reported that an inter-
penetrating polymer network between PPy and lignin exhibited
excellent charge storage ability due to the lignin and PPy syn-
ergic combination. Additionally, the changes in the morphology
and chemical properties of CPs can be obtained using LS very
low amounts. For example, composites with ratio 9:1 aniline/LS
showed enhanced conductivity and thermal stability than the pure
PANI [115]. The SO3 – groups present in the aliphatic chains of
LS are considered to be responsible for acting as CPs dopant
[116–121]. Also, the LS incorporation during the PANI synthesis
helps to obtain more extended chains of PANI, leading to an in-
creased conjugation length. Thus enhancing the conductivity of
PANI owing to the charge carriers free motion [119]. Shao and co-
workers also found that the LS-PANI conductivity at room temper-
ature increases when LS was incorporated at a certain mass frac-
tion, but an LS excess produced a stack of single-strand LS chains,
leading to the electrical conductivity reduction.
Quinone groups present in lignin and lignosulfonates can be
used as electron and proton storage and exchange during redox cy-
cling (Fig. 12). The lignin aromatic methoxy groups are converted
to hydroxyl groups during the initial voltammetric cycles [122]. Al-
though a large variation of the electrochemical activity between LS
obtained from different sources have been observed, the incorpo-
ration of additional dopants such as anthraquinone sulfonate (AQS)
in PPy/LS composites, increases, even more, the charge storage ca-
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1433
pacity of CPs [21]. In this case, both anionic dopant (LS and AQS)
carrier quinones.
The use of other lignin types, such as alkali lignin (AL), has
been less common for this purpose; however, it is reported that
LS is continuously declining in availability while AL accounts for
∼98% of the world pulp production [123]. Even though the al-
kali lignin high worldwide production, the low solubility of this
lignin type in inorganic acids limits its use in electrical energy stor-
age. Inorganic acids are typically used to prepare conductive poly-
mer films, which provide electron transport to the redox groups in
lignin in mixed polymer films. Using this strategy, Leguizamon et
al. [123] reported that PPy/AL electrodes increased 30% its capaci-
tance compared with electrodes containing similar compositions of
LS, and 56% higher than PPy electrodes. Additionally, a correlation
between the lignin phenolic content and the electrochemical prop-
erties was found, using alkali lignin fractions that were separated
based on the molecular weight and aromatic content.
Admassie et al. [124] studied the electrochemical and charge
storage properties of several subtropical lignins in biopolymer elec-
trodes (alkali lignin/PPy composites) and correlated them with
the chemical variations of these lignins monomeric units. By us-
ing nuclear magnetic resonance spectroscopy (NMR), it was found
that the sinapyl to guaiacyl (S/G) ratio increased considerably
both the specific capacitance and charge capacity. Besides, the
quinones generated on S-units contributed more to charge stor-
age in the biopolymer electrodes. This left supposing that lignins
with more S-units allow improving more the charge storage. Rebis
et al. [125] reported homopolymers and copolymers of syringol (S)
and guaiacol (G) as well-defined lignin model compounds. Then,
these synthetic monolignols were used to polymerize synthetic-
lignins via polycondensation with formaldehyde. Additionally, hy-
droquinone (HQ) was introduced to the synthetic-lignin to extend
the redox potential window. Subsequently, the composites were in-
corporated into the electroconducting matrix of single-walled car-
bon nanotubes (SWNT) and polypyrrole (PPy). The electrochemical
evaluation of this composites revealed that composites with PPy
carrying S, G, and HQ showed better performance than has pre-
viously been obtained with lignin derivatives. Moreover, a lower
amount of electronic conductor (20 wt% of SWNT) was adequate
to perform efficient electron communication between redox active
quinones and the electrode surface.
On another hand, ternary structured composites graphene
oxide/polyaniline/lignosulfonate (GO/PANI/LS), cotton/LS/PPy,
polypyrrole/phosphomolybdic acid/LS (PPy/HMA/LS), and has been
synthesized and tested as the electrode for an electrochemical
supercapacitor (Table 3). In this system, the LS acted as both
1434 J.L. Espinoza-Acosta et al. / Journal of Energy Chemistry 27 (2018) 1422–1438

Fig. 12. (a) CVs of PANI, and PANI/LS. (b) Illustrative schematic of lignin structure along with the redox processes occurring between hydroquinone/quinone (QH2 /Q) (Adapted
from Ref. [122,123]).

Table 3. Specific capacity values of electrodes for electrochemical pseudocapacitors based on conducting polymers/lignin and ternary structured lignin composites.

Composites Electrolyte Rate (A g–1 ) Specific capacitance (F g–1 ) Cycle numbers Capacity after cycles (%) Ref.

PANI/LS 1.0 M H2 SO4 10 377.2 10 0 0 0 74.3 [122]

PEDOT/LS 0.1 M HClO4 water: acetonitrile 9:1 mixed solvent 1.0–16 170.4 10 0 0 83 [116]
PPy/AL 0.5 H2 SO4 0.5–0.125 mA g–1 444 – – [123]
PPy/LS 0.5 H2 SO4 0.5–0.125 mA g–1 312 – – [123]
PPy/LS 0.1 M HNO3 1.0 480 20 0 0 54 [124]
PANI/GO/LS 6.0 M KOH 0.5 266 10 0 0 103 [126]
PPy/HMA/ LS 0.1 M HNO3 1.0 682 20 0 0 70 [124]
Cotton/LS/ PPy 2.0 M aqueous solution NaCl 0.1 304 300 76 [127]

surfactant and morphological controlling agent of PANI, while
PANI/LS carbon spheres acted as spacers that prevent graphene
nanosheets from aggregation. Accordingly, this spacer provided
high specific surface area and channels for electrolyte ions to
reach, playing an important role in improving the electrochemical
properties of PANI/LS composite. For example, flexible superca-
pacitor electrodes obtained using cotton/LS/PPy were used for
supercapacitors as both the electrode and the current collector,
which showed a specific capacitance of 304 F g–1 and conductivity
of 3.03 S cm–1 under the optimized conditions. These results
demonstrated that is possible obtaining flexible electrodes for
wearable supercapacitors using raw materials, less toxic and
compatible with the human body than those currently used [127].
5. Solar cells
Solar cells are defined as devices capable of converting energy
from the sun into electrical energy. The use of lignin and lignophe-
nols in combination with conducting polymers (CP) has been re-
ported for the development of alternative photosensitizers of dye-
sensitized solar cells (DSSCs) and polymer solar cells (PSCs) [128].
In this area, water-soluble PEDOT/LS and PEDOT/AL composites
have been studied as a material for hole transport in PSCs. The re-
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sults of this studies showed that the content of phenolic hydroxyl
groups from the lignin contributed to the PSC power conversion ef-
ficiency [129]. Polystyrene sulfonic acid (PSS) is the most common
dopant of PEDOT in photovoltaic applications. Wu et al. [130] syn-
thesize grafted sulfonated–acetone–formaldehyde lignin (GSL) for
the use as dopant and dispersant of PEDOT. The efficiency of PE-
DOT/GLS composites was compared with PEDOT/PSS. PEDOT/GSL
showed higher efficiency than PEDOT/PSS. These results were at-
tributed to small particle size and better dispersion of PEDOT/GSL;
this can facilitate the charge transport improving the PSC electric
conductivity.
DSSCs have attracted considerable attention since the photo-
chemical cells breakthrough with porous nanocrystalline titanium
dioxide (TiO2 ) with ruthenium complexes as the photosensitizers
[131]. Some types of lignins have been studied as a photoanode
working with TiO2 to improve the electrode absorption (Table 4).
Before the application in DSSC, the lignin must be chemically
modified to act as a photosensitizer. Aoyagi and Funaoka [135] re-
ported the use of some lignophenols as the photosensitizer ob-
tained from modified lignins. They found that p-cresol, catechol,
resorcinol, and pyrogallol show strong interactions on the TiO2 sur-
face. These lignophenols were more stable than lignin because of
the benzyl groups position blocked with OH groups. This DSSC
 J.L. Espinoza-Acosta et al. / Journal of Energy Chemistry 27 (2018) 1422–1438
Fig. 13. Lignin and its derivates in dye-sensitized solar cell (DSSC) applications. (a) ACFS-Pt layer, (b) modified lignophenols as photosensitized, and (c) TiO2 /BCP (Adapted
from Ref. [133]).
Table 4. Applications of lignin and derivatives in solar cells.
Applications Type of cells Efficiency (%)
Lignophenol Photosensitizer DSSC 0.11
Lignophenol Photosensitizer DSSC 3.61
TiO2 /BCP Photoanode DSSC 5.4
ECNFs–Pt Counter electrode DSSC 6.94
Alkali lignin Hole extract layer PSC 14.94
LS Hole extract layer PSC 5.19
efficiency was 0.11%. Aoyagi et al. [132] developed DSSC using
lignophenols, which were directly synthesized on the mesoporous
TiO2 electrode. The light to electricity conversion in a sandwich
type cell was 3.61%, while in the single cell made of TiO2 was
0.81%. These results were influenced by the lignophenols molec-
ular weight and the chemical structure.
Also, lignin-based porous carbon has been another pathway to
develop organic solar cells. Chou et al. [133] reported efficiencies
of 5.4% using electrodes based on TiO2 /bamboo-charcoal-powder
particles (BCP) in a DSSC. Ma et al. [134] achieved an efficiency of
6.94% using electrospun carbon nanofiber composites derived from
alkali lignin. The aim of the preparation of these composites was
the reduction of DSSC cost, using renewable and eco-friendly poly-
mers. Fig. 13 shows a schematic illustration of the specific sites
where lignin or lignin derivatives have been collocated in a DSSC.
6. Fuel cells
A fuel cell is a device which produces electricity through chem-
ical reactions between a fuel and an oxidant. For several years fuel
cells have been under development for applications in transport
and portable appliances. At least 11 different types of fuel cells can
be found in the literature [136]. However, because this field of in-
vestigation is vast, in this review we only focus on fuel cell types
which reported the use of lignin; for example, direct methanol fuel
cell (DMFC), biophotofuel cell (BPFC), microbial fuel cell (MFC), di-
rect carbon fuel cell (DCFC), and solar-induced hybrid fuel cell (SI-
HFC).
Commonly, the primary materials for DMFC are sulfonated
polymers such as sulfonated polystyrene and sulfonated polysul-
fone (PSF). Sulfonic acid groups form ionic micro-channels where
the protons are transported together with solvating water [137].
Under this context, LS contains sulfonic acid groups which can act
as a proton transport media. LS has been used for the prepara-
tion of homogeneous PSF-LS membranes incorporating LS into a
PSF network [138]. The LS presence influences the membrane mor-
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1435
Ref.
[22]
[132]
[133]
[134]
[130]
[129]
Fig. 14. Direct carbon fuel cell (DCFC) using lignin as fuel (From Ref. [140]).
phology making wider pores because of the LS dispersing proper-
ties. The proton ability in the PSF-LS membrane was attributed to
the LS polyionic structure. Porous LS membranes with high poros-
ity and high dimensional stability in water with better properties
that Nafion 117 have been applied in DMFC [23].
Furthermore, BPFC is being utilized to photodecompose lig-
nocellulosic wastes, while recovering electrical energy for such
wastes. Nemoto et al. [139] reported that lignin derivates are ca-
pable of being photodecomposed in BPFC, generating electrical
power. Lima et al. [140] utilized for the first time LS and KL as a
fuel through the direct conversion into electricity using DCFC with-
out preceding carbonization. Both lignins were blended with com-
mercial activated carbon and their structure was modified by a pH
adjustment. In this way, lignin serves as both electrode and fuel
(Fig. 14). A maximum power density of 25 mW cm−2 was achieved
by the cell composed by LS + AC for a fuel operated at 560 °C. De-
spite the good results of a maximum power density, these authors
stated that many adjustments and improvements of the DCFC re-
main for further investigation.
Many research groups are interested in converting lignocellu-
losic biomass into monomeric components to produce electricity
using microbial technologies [141]. Nonetheless, producing electric-
ity directly from lignin using microbial technologies is a challenge.
1436 J.L. Espinoza-Acosta et al. / Journal of Energy Chemistry 27 (2018) 1422–1438
Table 5. The processing required to use lignin in fuel cells.
Lignin Processing
LS Dissolving in DMF
No identifying Solubilization
LS and KL Carbonization to biochar
No identifying Degradation to small molecules
No identifying Gasification of lignin to syngas
Recently, Shewa et al. [142] reported the use of photocatalytic pre-
treated LS to produce electricity in a single chamber microbial fuel
cell (SCMFC). Using pretreated LS to feed SCMFC under specific
conditions, the authors achieved to obtain, respectively, a maxi-
mum current and power density normalized to the cathode area of
868 mA m–2 and 248 mW m–2 . These research results are a start-
ing point for further studies based on the use of microbial fuel cell
system and LS as a substrate to produce clean energy.
Until today, the lignin use in almost all fuel cell system re-
quires of external processing to convert the lignin to suitable fuel
(Table 5). An alternative fuel cell system which uses lignin without
external chemical processing was reported by Zhao and Zhu [143].
To achieve this, the authors reported the use of phosphomolybdic
acid (PMo12 ) as electron and proton carrier in the anode of a direct
biomass fuel cell (DBFC). Under specific conditions, the power den-
sity was 560 times higher than that of phenol-fueled MFCs. When
the cathode reaction was catalyzed by PMo12 , the current density
was 5 mW cm–2 . Previously, Liu et al. [144] obtained a current den-
sity of 0.75 mW cm–2 using polyoxometalates as the charge carrier
and photocatalyst in a solar-induced hybrid fuel cell.
These results are promising because they demonstrated the
possibility of using industrial lignin to generate clean energy at
low temperature and, in some cases, avoiding the external process-
ing use. However, more research is needed, because compared to
commercial PEMFC, the fuel cells reported in the research referred
above still need to be further optimized to increase the power out-
put. Because, until now, PEMFC cannot be used to convert lignin
into energy, because the cleavage of C–C bonds in these types of
fuel cells is a significant challenge.
7. Conclusions and perspectives
This review covers the recent advances in supercapacitors, bat-
teries, and solar and fuel cells based on lignin or lignin blends
with organic and inorganic compounds. The selection of articles
cited reflects a research combination dedicated to the knowledge
generation, methodologies, and strategies for using lignin in the
energy storage field. In recent years, the research related to the
use of various lignins for the energy storage devices development
has increased enormously. The early research of this topic was fo-
cused on improving the performance of lead–acid batteries. Mainly
lignosulfonates and modified lignins were investigated for almost
two decades, resulting in the use of lignosulfonates as organic ex-
panders for lead–acid batteries under different commercial names.
Lignin is a multipurpose complex polymer, which can be the
starting material for the development and performance improve-
ment of energy storage devices. Lignin is a green raw material to
obtain other materials or it can be used in applications that require
greater complexity. In this sense, porous activated carbon lignin-
based with distinct morphologies (fibers, nanospheres, or 3D hi-
erarchical morphologies) have been reported and applied as elec-
trodes for primary lithium batteries, lithium ion batteries, or dou-
ble layer capacitors. Nevertheless, the research reported to obtain
lignin-based activated carbon gives importance to the methodolo-
gies used to obtain the carbonaceous material. Information on eco-
nomic aspects related to comparecosts of lignin and lignin-based
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Application Fuel cell Ref.
Membrane DMFC [23,138]
Fuel BPFC [139]
Fuel DCFC [140]
Fuel MFC [145]
Fuel SOFC [146,147]
activated carbon with other materials are limited or not are read-
ily available in the literature.
Regarding conducting polymer/lignosulfonate blends, the prop-
erties such as conductivity, thermal stability, solubility, and me-
chanical properties are notably enhanced when lignosulfonate is
added. These conducting polymer/lignosulfonate composites have
been applied as pseudocapacitor electrodes with better perfor-
mance than electrodes previously obtained using only conduct-
ing polymers. For solar cells, lignin/conducting polymer compos-
ites and lignin/conducting polymer derivatives have been used as
a photosensitizer, hole conductive layer, and counter electrode in
carbon substitution. Although the studies in this area are very lim-
ited, possibly due to the complexity that each lignin type presents
and the large time amount needed to modify the lignin. Finally,
for fuel cell applications, there is still much to investigate and im-
prove, because, the lignin must be necessarily modified by chemi-
cal, thermal, or biological procedures, and only a few investigations
have achieved the direct use of lignin without external processing
to produce energy.
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