DOI: 10.1002/cssc.

201((w ill be com pleted by the editorial staff))

Lignin-Derived Carbon Materials

Sabornie Chatterjee, Tomonori Saito

Dedication ((optional))

Lignin is a highly abundant source of renew able carbon that can be consider ed as a valuable sustainable source of biobased
mater ials. By application specific pretreatments and manufacturing method, lignin can be converted to a variety of value adde d
carbon materials. How ever, the physical and chemical heterogenitites in lignin complicate its use as a feedstock. In this rev iew ,
lignin manufacturing process, effects of pretreatments and manufacturing methods on the properties of lignin, properties and
applications of various lignin der ived carbon mater ials such as carbon fibers, carbon mats, activated carbons, carbon films; a re
discussed.

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 [Link]

1. Introduction

Lignin, the largest biomass source w ith aromatic pr operty and

a carbon content above 60%, can b e considered as the most
attractive sustainable precursor for carbonaceous mater ials. 1-
7
The use of lignin for the production of bio-based commodity
has minimum environmental effects. Additonally, this energy 2. Chemical compositions and physical
feedstock does not belong to the human food chain. Lignin properties of lignin
constitutes of the major component of cell w alls of vascular
plants, w hich gives plants neutr al res istance against chemical Lignin is an amorphous complex biopoly mer w ith
or microbial attack and protects plants from other heterogeneous aromatic structure, der ived mainly f rom p-
environmental stresses.4 The amount of lignin differs among coumaryl, coniferyl and sinapyl alcohols. 2, 4 These alcohols or
plant types. Generally, in w oody plants, the amount of lignin monolignols for m lignin monomer ic units p-hydroxypheny l ( H),
is 15-40% of the plant w eight, w hereas in her bs, the amount guaiacyl (G) and syringyl (S) respectively (Figure 1). 2 -3, 16 In
of lignin is less than 15%.1 The estimated natural production lignin macromolecule, these monomeric units are linked by
of lignin on earth is in the range of 5-36 X 108 tons annually.5 variety of carbon-oxygen and carbon-carbon bonds such as
8
The annual production of commercial lignin is more than 70  -O-4, 5-5, 4- O-5,  - and so on w here the  -O-4 is the most
million tons.9 Most commercial lignins are produced as side common one (Figure 2).1, 4, 26
products in paper and pulping industries and in bio-
refineries.7, 9
In recent years, a great deal of research has focused on
the development of lignin derived carbon fibers, activated
carbons, and many other carbonaceous materials. 3, 9-1 4 Lignin
is also used in commercial applications such as concrete OMe MeO OMe
additives, ther moplastic materials. 5, 1 5 How ever, the use of
OH OH OH
lignin in different products other than as inexpensive fuel is
still very limited due to lignin’s heterogeneous molecular p-hydroxyphenyl (H) guaiacyl (G) syringyl (S)
weight, functionality and ther mal properties that vary w ith
source and isolation process of lignin.1-2, 16-19 Figure 1. Structural units of lignin
In this review , synthesis, properties and applications of
variety of lignin derived carbon materials such as carbon
fibers, carbon mats, activated carbons, carbon films , etc. are
discussed. In addition, lignin manufacturing process, effects
of pretreatments and manufacturing methods on the
properties of lignin materials are also discussed. There are
several review papers on lignin composite mater ials. 1, 20-21 A
few review s also present that are themed on a carbon
mater ials derived from lignin.22-24 How ever, only a very
limited literature ( mostly book chapters) on lignin der ived
carbon mater ials are available that cover variety of lignin
carbon materials.25 This review is designed to cover most of
lignin based carbon materials and provide design guides for
future carbonaceous materials from lignin. Figure 2. Common chemical bonds in lignin

The molecular w eight and compos ition of any particular

lignin type largely depend on the plant source and
environmental and developmental factors. Properties of lignin
also highly depend on the extraction procedure. Plant lignins
[a] Dr. T. Saito can be divided mainly in three classes, commonly called
Chemical Sciences Division softw ood, hardw ood and grass lignins. 4 Softw ood contains
Oak Ridge National Laboratory
higher amount of lignin than hardw ood, w hile grasses contain
Oak Ridge TN 37831-6210, USA
E-mail: saitot@[Link] the least amount of lignin. The typical S/G r atios in hardw ood
[b] Supporting information for this article is available on the WWW and softw ood lignins are 2:1 and 1:2-1:3, respectively.27
under [Link] delete if not Lignins from grasses have S/G ratio about 1:1-1:2.27 Lignins
appropriate))
from softw oods and grasses contain large amount of p-
hydroxyphenyl ( H) unit. The additional methoxy groups on the
aromatic ring of syringyl ( S) unit prevent for mation of 5-5 or
dibenzodioxocin linkages. For this reason, the formation of
linear structures in softw ood lignin is less favorable than
hardw ood lignin, w here syringyl (S) unit is present in excess. 1,
4, 26, 28

2
 The majority of lignin is an amorphous ther moplastic enzymes, w hich hydrolyze cellulose and produce lignin. The
poly mer and has a glass transition temperature ( Tg) in the produced lignin is then further purified.
melt- processeble temperature range at 50- 150 °C. Several The second method of lignin isolation uses chemical
other lignins possess Tg higher than 150 °C and a few reagents to isolate lignin from carbohydrates. Based on the
reported cases even indicates higher value of Tg than the reagents used, lignins generated in this process can be
degradation temperature depending on the lignin isolation broadly divided into tw o types, 1) sulfur containing lignins
and processing method.5, 29 For example, one study reports such as kraft lignin and, 2) non-sulfur containing lignins such
that the Tg of native hardw ood lignin is betw een 65 and 85 C as soda lignin and organosolv lignins. 28 It should be noted
while that of softw ood lignin is betw een 90 and 105 C. 18 In that sulfur-containing lignins are mor e commercially available
another example from our ow n previous study, solvent- worldw ide than the non-sulfur lignins. Some chemical pulping
extracted hardw ood lignin show ed Tg 108 C5 w hile Tg of processes are briefly described in the follow ing section.
softw ood Kraft lignin w as 153 C.29

3. Lignin extraction from various sources

Extraction of pure lignin from plant sources has several

challenges.2 The challenges in isolating lignin from plants are
primar ily associated w ith the complex structure of the cell w all
and the interactions of its components. 19 In addition, lignin
condensation and oxidation reactions occur dur ing var ious
isolation procedures, w hich makes the process complicated.
Due to the highly linked structures of lignin and Scheme 1. Dif f erent Pretreatment methods used in lignin isolation
carbohydrates in plant materials, it is impossible to isolate
pure lignin w ithout any chemical mediated cleavages. 20 3.1. Acid sulfite process
Isolation of lignin from plants can generally be pursued in tw o
ways.21 In the first case, carbohydrate is hydrolyzed using In this process, salts of sulfurous acid are used as reagents
enzymes and dissolved aw ay from lignin, w hich is obtained which add sulfonic acid gr oups to the lignin backbone. This
as an insoluble mater ial. In the second case, chemicals are process makes the lignin w ater-soluble. The degraded lignin
used to dissolve lignin to separ ate from the cellulose fiber is dissolved out from carbohydrates and forms a dark pulp.
and the process produces the spent liquor know n as the
black liquor containing lignin. The second method is more 3.2. Alkaline kraft process
often implemented commercially.
The first method typically involves a pre-treatment of In kraft process, lignin is treated w ith a solution of sodium
the feedstock because enzy matic hydrolysis cannot be hydroxide and sodium sulfide at r elatively high temperature
directly applied to w oody biomass. Pretreatments are used to (170C). During the treatments, ether linkages are cleaved,
break the bonds betw een lignin and carbohydrates in the which consequently increases the number of phenolic
biomass. A variety of pretreatment methods such as bal l hydroxyl groups. This tr eatment also breaks lignin and
milling, mechanical, acid treatments, alkali treatments, decreases its molecular w eight. Further, thiol groups are
hydrogen peroxide treatment, or enzy matic hydrolysis are incorporated int o lignin in this process. Due to the presence
used to separate carbohydrates and lignin (Scheme 1). 4, 16, 25 of alkaline medium in the treatment, the phenolic gr oups on
All pretreatments decrease the s ize of biomass and lignin get ionized w hich in turn dissolves the lignin in w ater
disassemble its physical structure to be amenable to its post and forms a dark pulp.
treatments. In most cases, these pretreatments also alter the
chemical structure of lignin. Lignin carbohydrate bonds are [Link] process
more stable than various bonds in lignin. Therefore, for
example, the use of acid treatment to obtain lignin results not In case of organosolv process, pulping f eedstoc k in organic
only in extensive cleavage of lignin carbohydrate bonds, but solvents w ith acidic or basic catalysts produces lignin. This
also cleavage of certain amounts of lignin-lignin ether bonds. process is more env ironment ly friendly than kraft or sulfite
In the case of acid pretreatments, lignin undergoes process because in this case, solvents can be recovered and
depoly merization through the cleavage of  -O-4 and other reused. This method efficiently fractionates biomass into
bonds. At the same time, electrophilic attacks of side chain lignin, cellulosic fibers, and hemicellulosic sugars.
carbonium ions to aromatic r ings occur, w hich form a new set
of carbon-carbon bonds. This bond for mation reverses the [Link] pulping
depoly merizations of lignin and generates new condensed
phases in the lignin matrix. On the other hand, a decrease in A soda pulping is mainly used for non-w ood fibers such as
the acidity of the solvent to avoid degradation of lignin grass, straw , sugarcane bagasse, etc. that have relatively
structures results in lignin w ith a high amount of open and more accessible structures w ith low lignin content.
carbohydrates. Mechanical pretreatments also alter lignin’s The feedstock is digested at around 160 C w ith an aqueous
chemical structure by increasing the amount of carbonyl and solution of sodium hydroxide. In this case, lignin
phenolic-OH groups and cleaving the  -O-4 linkages.4, 16, 25 depoly merization occurs by the cleavage of  -O-4 bonds,
After pretreatment, the resulting biomass is treated w ith which first starts in phenolic units and then continues in non-

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phenolic units at a later phase of lignin degradation. These

reactions generate free phenolic groups, w hich under alkaline
conditions ionize and facilitate dissolution of lignins in the
alkaline solvent.
In later steps, different methods such as extraction and
precipitation w ith diff erent solvents are used to collect lignin
from the lignin solution. Lignin is also collected using acid or
enzymatic hydrolysis. This hydrolysis method w orks better
and gives high yield of lignin in the case of softw ood kraft
pulp. 4, 16, 25
It should be noted that, most of these methods w ere
initially developed w ith a goal to achieve high quality cellulose
w ith great yields and thus less attention has been given to the
production of pure lignin w ith native structure. Almost all
extraction processes change the structure of the isolated
lignin, making it difficult to produce homogeneous pure lignins Figure 3. Composition of the produced straw lignin
for industrial applications. products 30

4. Effects of manufacturing processes on Table 1. Molecular w eight of lignin products obtained using
properties of lignin SEC.30

Lignin’s molecular w eight, physical and chemical properties Lignin type Mw Mw/Mn
largely depend on the source and the isolation methods of (g/mol)
the lignin. The combined impact of the pretreatment method Alcell Organosolv lignin 2390 2.9
Straw Organosolv lignin 8680 5.1
and the extraction procedure on the properties of lignin is
Soda lignin 8000 4.8
dominant over the effect of the lignin source. Different Aquasolv lignin 2600 3.1
researchers reported the effect of extraction procedure on Dioxane extracted Aquasolv solid lignin 7080 4.0
lignin’s molecular w eight. Wör meyer et al. studied an effect of
different pretreatment methods on the properties of rye straw Sun et al. studied the effect of extraction procedures on
lignin.30 They studied straw and Alcell organosolv lignin, soda the molecular w eight of w heat straw lignin. 31 In this study,
pulp lignin, and three Aquasolv lignins (obtained by a alkali lignins, ball- milled lignins, enzy me lignins and
organosolve lignins w ere prepared and molecular w eights of
combination of ther mal hydrolysis and enzy matic hydrolysis
these lignins w ere studied by SEC. The result show ed the
procedures) such as Aquasolv liquid (AL), Aquasolv solid alkali lignin, milled lignin, enzy me lignin and organosolv lignin
(AS) and dioxane extracted Aquasolv solid ( DAS) along w ith were composed of low er molecular w eight lignin fragments.
liquid hot w ater processed (LHW) (obtained by hydrother mal The MW of enzymatic lignin, ball- milled lignin, organosolv
process) lignins. They found the LHW and the DAS lignin lignin and alkali lignin w ere 2020, 1890, 1640 and 1400 g/mol,
contained the highest amount of acid insoluble lignin or solid respectively, w hich corresponded to the reducing contents of
associated polysaccharides in the isolated lignin fractions.
lignin follow ed in descending order by the soda, the
In another study, Toledano et al. explored the influence
organosolv, the AL and the AS lignins ( Figure 3). of extraction treatment on the olive tree pr uning lignin
Car bohydrate content w as high in both straw organosolv (7% structure.32 In this case, organosolv treatment, alkali
w/w) and AS (13.2%) lignins that makes the AS lignin less treatment and autohydrolysis treatment w ere performed to
suitable for various material applications. When molecular isolate lignin. Different processes produced lignin w ith varying
weights of all lignins using Size Exclus ion Chromatography concentration (g/L) such as organosolv lignin (55.5), auto-
(SEC) w ere compared, straw organosolv lignin w as found to hydrolysis lignin (0.59), alkali treated lignin (31.8) w ith purity
of 65.8%, 26.9% and 4.5% respectively. Autohydrolysis lignin
have the highest w eight-average molecular w eights ( Mw)
was found to have the low est Mw, w hile Organosolv lignin had
follow ed by the soda lignin, DAS and AL lignins (Table 1). the highest molecular w eight ( Table 2). Additionally,
The ther mal stability of these lignins by autohydrolysis lignin and organoosolv lignin w ere found to
ther mogravimetric analysis ( TGA) show ed comparable have higher contents of hydroxyl groups. Alkali treated lignin
degradation w ith increase of temperature ( Figure 4a), contained low er hydroxyl group content but high carboxyl
how ever, Tmds ( Temperature of maximum decomposition) of group indicating alkali treatment promoted oxidation reactions.
these lignins are varied. Interestingly, the AS lignin, DAS High carboxyl content can be related to more degradation in
lignin and LHW lignin’s solid residue based samples have lignin structure. Or ganos lv lignin w as found to have the
higher Tmds ( Figure 4b) than corresponding liquid fraction low est carboxyl group content.
based products. Also, solid residue based lignin samples In a recent w ork, Saito et al. prepared the high molecular
show ed different w eight loss trend than the liquid fraction weight lignin fraction via for maldehyde crosslinking, 5, 29 w hile
based samples. LHW lignin w as found to loose less w eight as-received lignin contained a significant amount of low
than other straw based lignin and degraded only at high molecular w eight fraction. The crosslinked high molecular
temperature. In a comparison study, Tmds of S lignin, DAS weight fraction of lignin show ed a much higher Tg than that of
lignin and LHW lignin w ere found to surpass the Tmd of as-received lignin.
novolac resin. These studies clearly show ed that the
pretreatment affects on the ther mal stability of the produced
lignin.

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 based solvent extracted lignin to a softw ood kraft lignin, the
yield of MeOH insoluble lignin increased to 50% 29 due to the
increased amount of high molecular w eight and MeOH
insoluble fraction in the softw ood Kraft lignin.
In the study of methanol fractionation of softw ood Kraft
lignin,29 the MeOH insoluble lignin show ed much higher Tg
(211 °C) than as-received lignin (153 °C) due to the removal
of a low molecular w eight (LMW) fraction, w hich appeared at
higher retention time in DMF SEC w ithout LiBr (Figure 5a),
while MeOH soluble lignin show ed an increased LMW
fraction and a low er Tg (117 °C) compared to the as-received
lignin (Table 3). The difference of Tg over the range of roughly
100 °C from the same batch of the sample is quite s ignificant
and no other conventional poly mers possess this kind of
characteristic. More importantly, the trend of these Tg values
agreed very w ell w ith the Fox equation using the LMW area
(a)
from RI peaks in SEC ( Figure 5a) converting to the w eight
fraction (Figure 5b), w hich indicates that the LMW lignin
oligomer fraction contributes to low ering its Tg, and the
estimated Tg of LMW fraction from the Fox equation w as -
89 °C. The Fox-equation-der ived Tg value of oligomeric lignin
was so low that it justified the plasticization effect by the LMW
lignin fraction. The capability to tailor the Tg of lignin is
extremely important for its processing in applications such as
carbon fiber precursors because it directly correlates to the
melt- processing temperature or the stabilization conditions
prior to carbonization.
The amount of LMW fraction also correlated w ell w ith
the char yield through a linear regression (Figure 5b), i.e. an
increase in the LMW fraction decreased its char y ield ( Table
3). High char yield of MeOH insoluble lignin is advantageous
for using lignin as a carbon precursor. Although the lignin
peak from SEC data from neat DMF most likely represents
both s ingle lignin molecules and lignin aggregates in DMF,
the data correlated very w ell w ith other physical properties
and the resulting significantly high PDI r ather represents
(b) heterogeneities existing in lignin sample. Single, monomodal
Figure 4. (a) TGA of Alcell organosolv lignin, straw peaks of these lignin samples obtained in the case of DMF
organosolv lignin, soda lignin and aquasolv liquid lignin.30 (b) SEC w ith LiBr (Table 3) indicates that the size of lignin
TGA of aquasolv solid lignin, dioxane extracted aquasolv corresponds to a single distribution, but combined results of
solid lignin and liquid hot w ater processed lignin. 30 DMF SEC both w ith and w ithout LiBr suggested that the
chemical structure and compositions among as -received,
Table 2. Functional group contents and Mw, Mn and MeOH insoluble, and MeOH soluble lignins are s ignificantly
polydispersity ( Mw/Mn) of alkali lignin (AL), hydrolysis altered. It should be noted that researchers tend to report low
lignin(HL) and organossolv lignin (OL). 32 lignin molecular w eight w ith single monomodal distribution,
similar to the data from RI detector in DMF SEC w ith LiBr in
Functional Alkali treated Hydrolysis Organosolv this study, how ever, absolute molecular w eight from light
Groups lignin lignin lignin scattering detector w as significantly higher and
Hydroxyl 2.62 ± 0.05 10.12± 0.18 9.81± 0.04 concentionally reported narrow er PDI does not reflect
Carbonyl 0.12±0.01 0.53± 0.01 0.24±0.01 property of lignin.
Carboxyl 6.57± 0.07 7.15±0.12 4.03± 0.08
Molecular Weight (g/mol)
Mw 10,900 3660 12,900
Mn 4930 2120 2250
Mw/Mn 2.21 1.73 5.74

The key for the successful synthesis of lignin-based

ther moplastic copoly mers in these studies w as the utilization
of the high molecular w eight lignin fraction to produce an
efficient connection betw een the hard segment (i.e. lignin)
and the soft segment. The initial study 5 not only show ed
effectiveness of the formaldehyde crosslinking but also the
increase of lignin molecular w eight and Tg by methanol Figure 5. (a) SEC curves of As-received Lignin ( ),
(MeOH) fractionation. The effect of metha nol fractionation MeOH Insoluble Lignin ( ), and MeOH Soluble Lignin
w as further investigated in the most recent article. 29 ( ), (b) The linear regression of char yield and 1/Tg as a
Solvent fractionation to increase molecular w eight and function of LMW fraction from the SEC curve. 29
Tg is a more facile approach than performing a formaldeyde
crosslinking reaction; how ever, the initial study on MeOH
fractionation of hardw ood-based solvent extracted lignin
show ed very small isolated yield of MeOH insoluble lignin
(17%).533 Sw itching to the lignin source from a hardw ood-

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 [Link]

Table 3. Tg obtained from DSC, thermal degradation 6. Lignin-derived carbon materials

properties obtained from TGA, and molecular w eight of lignin
via MeOH fractionation29
[Link] carbon fibers

Resi Car bon fibers are high perfor mance mater ials w ith
dual salient properties of high stiffness, great tensile strengths,
Mn[b1]
Tg wt % Mn[a] PDI [ PDI [b Mw[b2] elevated temperature tolerance, low thermal expansion,
a] [g/mo 1]
[°C] at [g/mol]
l]
[g/mol] lightw eight, high flexibility, and high fatigue r esistance. 3, 10 -12,
1000 14-15, 22, 37-40
°C
These properties make carbon f ibers important
component in advanced compos ites for a variety of industries,
As-
receiv e including aerospace, civil engineering, automotive and w ind
d lignin 153 41 10,000 110 2,360 3.05 96,100 pow er applications. Many of these enhanced material
properties can be correlated to the or ientation of graphite
layers, w hich are mostly aligned parallel to the long axis of
MeOH the fiber. The properties of carbon fibers largely depend on
insolub 443,00
le
211 47
0
3.5 6,520 2.28 188,000 the precursor mater ials. Currently, carbon fibers are mainly
lignin manufactured from polyacrylonitrile ( PA N) precursor and to a
small extent from mesophase pitches, w hich make carbon
fibers expensive due to the high volatile price of the
MeOH petroleum based feedstoc k and corresponding pr ocessing
soluble 117 32 3,800 129 1,590 1.90 86,600 expenses.22, 39 Thus, there is a huge demand for a low cost
lignin
carbon fiber precursor material, w hich can be converted to
[a] decent quality carbon fiber.
DMF SEC w ithout LiBr, Determined from refractive index
detector
[b1]
DMF SEC w ith LiBr, Determined from refractive index
detector
[b2]
DMF SEC w ith LiBr, Determined from light scattering
detector

These molecular w eight analyses in conjunction w ith Tg

and char yield data r aise a good question to the research
field about w hat properties researchers measure for lignin
samples in SEC analysis, e.g., monomodal distribution might
not mean much due to the heterogeneity of lignin samples.
This study also investigated the chemical composition and
LMW-containing MeOH soluble lignin revealed higher
contents of aliphatic carbon and guaiacyl grou ps and a low er
content of aliphatic hydroxyl groups, w hich corresponded to
low ering its Tg and char yield. Schem e 2. Flow chart for the commercial production of lignin.

Lignin is a non-petroleum-based alternative carbon fiber

5. Lignin production: from tree to carbon precursor, w hich is renew able and abundant. Lignin as a
material precursor precursor for carbon fiber production has been studied for
more than 50 years. A detailed history of past and current
Lignin is a good precursor for graphitic structures research on lignin based carbon fiber are discussed in a 2013
because of its highly ar omatic structural contents. Based on review paper.22 Thus, this artic le w ill mention only a few
the precursor type, carbon materials can be divided broadly research milestones of lignin carbon fiber research.
in three types, graphite type, diamond type, and amorphous Otani et al. reported methods of making lignin based
type. Lignin-derived carbon can be considered as an carbon fibers by melt spinning and dry spinning of lignins in
amorphous carbon w ith domains of microcrystalline graphit e, 1966.4 1 He also patented a process to manufacture carbon
w hich are randomly stacked w ith a turbostratic structure. 34-35 fibers from lignin in 1969. Lignin based carbon fibers w ere
Lignin-derived carbon mater ial manufacturing first made commercially by Nippon Kayaku Co. 2 2, 39 The
processes typically involve several steps (Scheme 2). 36 At process involved carbonization of dried fibers made from
first, trees (or other plants) are harvested in different fields lignin dissolved in an alkali solution w ith polyvinyl alcohol
depending on the types. At one point of tree’s lifecycle, it is which w as added as a plasticizer. Sudo and co-w orkers
collected and transported to a chip mill for conversion to show ed that lignin could be converted into a molten viscous
wood chip to use as a feedstock by either a bio-refinery or mater ial w ith suitable properties for thermal spinning by
pulp or paper mill. At the bio-refinery, lignin is dissolved aw ay hydrocracking, phenolation, or hydrogenolysis follow ed by
from cellulose into blac k liquor and ethanol is produced from heat treatment on vacuum.13, 42 They described a process for
the cellulose present in the w ood chips. At the pulp mill, l ignin the production of carbon fiber from hardw ood lignin in w hich
is also dissolved aw ay from cellulose into blac k liquor and the steam explosion technology w as used to isolate lignin from
cellulose is used for the productions of paper and chemicals. birch w ood. In this process, the steam-exploded lignin w as
Finally, in both cases, the lignin is collected from the black hydrogenated using a Raney Nickel catalyst to low er its
liquor by precipitation. The obtained lignin is then w ashed softening point to 110 C and modify the lignin to improve
and dr ied. The dried lignin is pac ked either in pow der or pellet melt spinninability. Comparing the chemical structure of the
forms w hich are then used in variety of applications. precursor to the crude lignin, it w as found that precursor
contained significantly less amount of aliphatic functional
groups than the original starting material. Lignin carbon fibers
made in this process w as found to have diameter
approximately 7.6 m w ith tensile strength of 0.660 GPa. The

6
fibers had modest mechanical properties w ith moderate Table 6. Spinning temperature and Tg of pyrolytic, Alcell and
tensile strength. Uraki et al. w orked on the pr oduction of kraft lignins 44
carbon fibers from birchw ood derived organosolv lignin
obtained by aqueous acetic ac id pulping. 43 The fiber w as Lignin Spinning temperature Tg Mw
made by melt-spinning the clean and dr ied lignin. The (°C) (°C) (PDI)
produced carbon fibers w ith a 14  1 m diameter show ed Zone 1 Zone 2
tensile strength of about 0.035 GPa and modulus of about Kraft 170 202 131 1256
39.1 GPa. (2.2)
Kadla et al. reported pr eparation of carbon fibers from Alcell 130 158 77 790
various lignins.12, 14, 44 In their study, w hen Alcell lignin, (2.5)
hardw ood kraft lignin and softw ood kraft lignin w ere Pyrolytic 105 125 70 702
compared as lignin fiber precursor, it w as found that the (2.3)
softw ood kraft lignin could not be spun into lignin fiber,
charring occurred before melting. On the other hand, both Kubo reported the application of a variety of lignin –
Alcell and hardw ood kraft lignin w ere found to be melt- synthetic poly mer blends as precursor material for the
spinnable to make lignin fiber. Alcell lignin show ed low er production of carbon fiber. Fibers made from unmodified
spinning temperature than the hardw ood kraft lignin ( Table hardw ood kraft and organosolv lignin w ere found to be
4.). Kadla investigated the applicability of lignin– [Link] use of blends of lignin and synthetic poly mers such
polyethelene oxide ( PEO) blends as precursors for the as poly (ethylene terephth alate) ( PET), PEO and
production of carbon fibers. In this w ork, a blend of polypropy lene ( PP) w as found to reduce the brittleness and
commercially available unmodified kraft hardw ood lignin and show ed improved tenacity (Table 7).
polyethylene oxide ( PEO) w as used to make moderate
strength carbon fibers by ther mal spinning follow ed by Tabel 7. Mecahnical Properties of hardw ood kr aft lignin,
carbonization (Table 5). Use of PEO facilitated the fiber hardw ood kraft and PEO blend and Alcell lignin 14
spinninability but did not significantly alter the properties of
the fiber. In another w ork, this group made carbon fibers from Lignin Diameter Tensile- Modulus
bio-oil der ived pyrolytic lignin by ther mal spinning follow ed by (µm) strength (GPa)
carbonization. Pyrolytic lignin show ed melt spinnability at a (MPa)
low er temperature than other technical lignins ( Table 6). Hardw ood 46±8 605 41
Fibers generated in this process w ere found to have hollow Kraft
structures and these fibers w ere prone to fiber-fiber fusion
during ther mal stabilization probably due to low softening
Hardw ood 47±5 332 57
temperature.
kraft/ poly
propylene
Table 4. Spinning temperatures of lignin/polyethylene oxide
95/5
(PEO fiber) blends 14

Lignin/ PEO blend Hardw ood kraft Alcell lignin Hardw ood 31±5 669 84
lignin (°C) kraft/ poly
(°C) ethylene
100/ 0 195-228 138-165 terephthalate
95/ 5 189-198 153-172 95/5
87.5/ 12.5 191-200 138-172
75/ 25 150-182 120-157 In recent years, considerable research effort has
contributed to the production of carbon fiber from lignin at the
Oak Ridge Natio nal Laboratory ( ORNL). Baker et. al. at
ORNL investigated lignin and its blends as low -cost, high-
Tabel 5. Mecahnical Properties of carbon fibers from production volume feedstock for carbon fiber. They found
hardw ood kraft lignin, hardw ood kraft and PEO blend and difficulties in the melt spinning of as-received hardw ood kraft
Alcell lignin14 lignin, w here the melt spinning of organic-solvent-w ashed
hardw ood kraft lignin w as easily perfor med. 22 The carbon
Lignin Diameter Tensile- Modulus fibers obtained in this process show ed tensile strength of
(µm) strength (GPa) 0.517 GPa and also the yield of carbon fibers from starting
(MPa) lignin w as only moderate. Baker also w orked w ith Alcell lignin.
Hardw ood 46±8 422±80 40±11 They found that the increase of Tg and softening temperature
Kraft (Ts ) of Alcell lignin by use of a ther mal pretreatment could
enhance the tensile strength and yield of Alcell lignin der ived
carbon fiber. The tensile strength and obtained yield of
Hardw ood 46±3 396±47 38±5 ther mally pretreated lignin carbon fiber w ere 0.710 GPa and
kraft/ PEO 41%, r espectively, w hereas the original untreated lignin
(100K) 95/5 carbon fiber had tensile strength and yield of 0.338 GPa and
31%, respectively.
Hardw ood 63±7 339±53 33±53 At present, lignin carbon fibers w ith average tensile
kraft/ PEO strength as high as 1.07 GPa w ith moduli of 82.7 GPa can be
(600K) 95/5 prepared from modified lignin.22, 4 5 Synthesis of such higher
Alcell 31±3 388±123 40±14 performance lignin carbon fibers requires highly pure lignin
w ith tuned properties. Especially, contamination had a major
effect on the properties of carbon fibers. Based on their
research, the ORNL team described a general specification
of lignin for the production of carbon fiber (Table 8).

7
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Table 8. ORNL specification for lignin feedstock to be used susceptibility. Thus, in general, ther mo-stabilization is
as carbon fiber precursor.10, 37 performed in different stages w ith different heating rate. An
Specification Value example of such heating profile is first heating the lignin from
Lignin Content 99 (w eight %) room temperature to about 105 ºC at a rate of 1 ºC/min. 10
Ash Content < 0.1 (w eight %) The lignin fiber is then held at 105 ºC for 1 h to remove
Volatile Material Content <5% (at 250°C) (w eight %) moisture in the sample. Next, the lignin fiber is heated from
Particulate Matter Removal of all particulate 105 º C to 200 º C at a rate of 0.25 ºC/min. In the last step, the
matter > 1 µm in diameter lignin fiber sample is held at 200 º C for 24 h to further oxidize
and cross-link the lignin and raise Tg value. During ther mo-
Based on the precursor mater ials, tw o types of lignin stabilization, the oxygen content of the various lignins
carbon fibers are made, 1) carbon fibers from unmodified increases to a maximum and then decreased w ith increasing
lignin w here no additive is used, 2) carbon fibers from a blend temperature.12, 15 The slow er heating rate favors reactions
of lignin and additive, w hich are coextruded. In this review , that increase oxygen content at low temperatures and
the manufacturing process from unmodified lignin der ived decrease oxygen at higher temperature. At temperature
carbon fiber w ill be discussed as an example. The process to below 250C w ith a slow er heating rate, oxidation of lignin
produce carbon fiber from purified lignin can be divided into dominates. Due to the presence of oxygen in this stage,
three steps (Scheme 3); i) carbon fiber precursor spinning, ii) reactions such as autooxidation, variety of rearrangements
ther mal stabilization, and iii) carbonization. The process and radical coupling reactions occur in lignin, w hich
requires highly pure lignin to produce good quality carbon generates functional groups such as carbonyl groups on
fiber. Also, the lignin should have a narrow molecular w eight lignin. At this stage, breaking of aliphatic side chains,
distribution,22 w hich more likely mean requiring less methoxy groups, and -O-4 bonds occur. Thus, the relative
heterogeneous batch of lignin than actually narrow PDI as amount of aryl ether structures in lignin significantly
discussed in above section. This property facilitates an even decreases after thermo stabilization. At temperature above
increase in molecular w eight of the entire fiber dur ing the 250C, dehydration reaction, condensation, cross-linking and
ther mal stabilization that results in a more unifor mly elimination reactions dominate, w here w ater, CO and CO2
structured carbon fiber during carbonization. In some cases , are released from lignin through the for mation of keto, ester
lignin is w ashed and dried under vacuum prior to spinning and anhydride linkages.12
and ther mally pr etreated under vacuum for about 1h to It should be noted, the chemistries of ther mo
remove any volatile. stabilization of lignin and pitch based carbon fibers are quite
different.12, 15 In the lignin-based systems, slight w eight loss
occurrs during ther mal spinning and stabilization. These yield
losses are accompanied by an increase in molecular w eight,
which is the result of condensations and dehydrations in the
lignin macromolecule. In contrary, in case of pitch based fiber,
increase of w eight occurs during oxidative stabilization.
Dur ing the ther mo stabilization, alkyl components of pitch are
oxidized before dehydr ogenation and cyclization r eaction,
which increases the w eight. Lignin due to the presence of
oxidized side-chain, dur ing ther mo stabilization, undergoes
Schem e 3. Preparation of carbon fibers from lignin.
condensation reaction and releases w ater and consequently
6.1.1. Melt-spinning looses w eight.

The majority of lignin melts and flow s upon heating if Tg 6.1.3. Carbonization
is low enough.10 The spinning temperature is related to its Tg,
Ts , and molten viscosity of the lignin sample. For a material After the ther mo-stabilization pr ocess, the lignin fiber is
having low melting viscosity, a low spinning temperatur e is carbonized by heating the samples to 1000 ºC or higher. The
required. The ther mal spinning temperatur e of lignin should purpose of carbonization is to eliminate all elements except
be w ell below its decomposition or cross-linking carbon and graphitize the structure. Thus, in this step, the
temperature.10, 12, 22, 38 Thus, the spinning temperatures of majority of w eight loss occurs. With the increase of
different lignins vary w ith the lignin’s property. For example, carbonization temperature, the extent of oxygen-containing
the spinning temperatur e of Alcell lignin is 138-165 ºC functional groups such as carbonyl, carboxyl, methoxy
whereas; hardw ood kraft lignin required a temperature range groups decreases and a significant increase of aryl and
of 195-228 ºC.10 In both cases, these temperatures ar e low er condensed acyl carbons occurs. 10 These changes make the
than their corresponding ther mal decompos ition temperatures, carbon fiber more hydrophobic. To prevent lignin combustion
170 and 268 ºC, respectively. or any carbon fiber precursor combustion, this process
requires oxygen free atmosphere. Thus, carbonization
6.1.2. Therm o-stabilization process is generally carried out in Argon or Nitrogen
atmosphere w here a heating rate of 3-5 ºC/min is used in a
In the manufacturing of carbon fiber from lignin fiber, a batch mode and multiple processes at different temperature
ther mo-stabilization is used to make lignin fibers stable in a continuous mode. Similarly to the ther mo-stabilization,
tow ards high temperature, w hich prevents the fiber fusion the heating rate in carbonization has a major effect on the
during the carbonization step. 10, 12, 14-15 During ther mo- structure of the carbon fiber. In some cases, it w as found that
stabilization, lignin is cross-linnked to raise lignin softening slow heating rates resulted in highly br ittle and porous carbon
temperature. Reactions occurring during ther mo-stabilization fiber, w hile rapid heating rate pr oduced carbon fiber w ith less
step increase the Tg , changing the ther moplastic property of brittleness and more stable fiber structur e. Car bonization
lignin to ther mosetting. This transfor mation of ther moplasicity process changes the surface and porosity of carbon fibers to
to ther mosetting properties is necessary for lignin fibers to a large extent by releasing volatile components w hich in turn
maintain a fiber for m and prevents from softening and generates imperfections and defects on the surface of the
deformation during the carbonization step. fiber. SEM images of lignin based carbon fibers at different
The rate of heating of lignin fibers during ther mo- stages of preparation are show n in the Figure 6.11
stabilization has a profound effect on fiber stability and fusion

8
 standing lignin-derived carbon fiber mat based electrodes
exhibited comparable electrochemical perfor mance to
commercial carbon-based anodes at a fraction of the
mater ials and processing costs. The tentative estimated costs
of lignin carbon fibers are $3/lb for monolithic, electrically
interconnected, self -supporting mats. This value is
significantly low er than the price of battery grade graphite
(a) (b) pow der ($12/lb for unprocessed battery grade graphite).
The compos itional and electrochemical character ization
show ed that carbonized lignin had a disordered nano-
crystalline microstructure. The carbonized mats cycle
reversibly in conventional aprotic organic electrolytes w ith
Coulombic efficiencies over 99.9%. Moreover, lignin carbon
fibers carbonized at 2000 °C can cycle reversibly in 1M LiPF 6
in propy lene carbonate, w hile irreversible lithium insertion
(c) (d) and extraction w as observed in more disordered LCFs ,
carbonized at 1000 °C w ith the s mallest nanoscal e graphitic
domains.

(e) (f)

Figure 6. SEM images of a,b) lignin fibers extruded from

organic solvent extracted kraft hardw ood lignin; c,d) oxidized
lignin fiber at a heating rate of (c) 0.05°C/min and (d) (a)
0.025°C/min show ing different degrees of fusion; e,f) carbon
fiber, carbonized to 1000°C at 2°C/min after stabilization at a
heating rate of 0.05°C/min.11

6.2. Carbon fiber m ats

Lignin can be utilized as a sustainable precursor for

fabricating free-standing carbon fiber mats. One of the (b) (c)
attractive applications of the car bon fiber mats is utilization as
high performance electrode mater ials for lithium ion batteries. Figure 7. a) Fused lignin carbon fiber mats after
Current carbon materials like battery-grade graphites have carbonization.; b,c) SEM images of lignin carbon fibers mats
high pr oduction costs and they provide limited storage w ith different degrees of fusion and density.35
capacities. Lignin-based carbon fiber mats could be used as
an alternative to the battery-grade graphite. Microstructures Chatter jee et al. reported the synthesis of organosolv
of these carbons can be controlled by incorporating different lignin based microstructured carbon mater ials w ith a unique
functional groups in lignins.3, 6 Us e of carbon fiber mats as carbon mesostructur e and graphite-like electrical properties.3
electrode materials has several advantages: 1) lignin-based These materials show ed similar performance to conventional
carbon can form highly porous free-standing fibrous mats that anode mater ials in Li- ion or Na- ion batteries. In this w ork,
can be directly used as electrode materials w ithout adding lignin based fibrous materials w ere synthesized using a
any binder or current collector agent, w hich not only reduces combination of chemical modifications and carbon fiber
the complexity and processing time of a battery but also processing techniques. Lignin w as modified by incorporating
reduces the cost. 2) Anodes made from battery -grade different ester groups, w hich resulted in highly compatible
graphite are highly sensitive to electrolyte solutions, w hich w ith melt processing and conversion into active battery
can promote exfoliation and for mation of an unstable solid electrodes. Modified lignins w ere subsequently converted to
electrolyte interface (SEI) resulting in loss of capacity and microstructured carbons using the carbon fiber pr ocessing
failure.46 Due to highly porous structures, lignin fiber mats are technique consisting melt-extrusions, stabilizations, and low
more stable tow ards electrolytes than battery grade graphi te temperature carbonization in a nitrogen atmosphere. The
and 3) the electrochemical performance of the carbon fiber applied chemical modification and subsequent ther mo-
mats can be further tuned by chemical or physical mechanical conversion methods w ere effective in preserving
modifications such as doping. the heter ogeneous structure present in the lignin, w hich are
Recently Tenhaef f et al. r eported a use of such lignin- nanoscale crystalline domains that w ere linked to the
derived stable free-standing porous carbon fiber mats as enhanced electrochemical performance. SEM analysis of
anodic materials.35 In this w ork, fibrous three dimens ional carbon mater ials show ed fibers had a hollow center and a
lignin- derived carbon mats ar e produced from solvent microporous surface morphology ( Figure 8). BET surface
extracted lignin using a combination of forced air driven melt area measur ements of these fibers show ed the most of the
processing and ther mal conversion methods ( Figure 7). The fibers had surface areas similar to commercial graphitic
conversion of lignin mat produced by melt processing to an carbon ( Table 9). Thus, combined w ith a fused carbon fiber-
electrically connected monolithic mat is conducted by ther mal based anode architecture, these mater ials could promote
stabilization and carbonization. In this process, controlling the short diffusion paths for lithium ions, w hile mitigating aging
temperature is crucial as that influences the extent of fiber- processes, w hich w ould result in charge loss or irreversible
fiber fusion and mat density. The fused fiber mat structure is capacity. When the conductivities of carbon fiber samples
essential for eliminating the binder and current collector were assessed by resistivity measurements, this carbon
components from the electrode materials. The resulting free-

9
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a
mater ial show ed resistivity comparable to the typical values Standard deviations in each case is specified inside
for graphite. parentheses 3
In a recent w ork, Wang et al. reported the use of lignin-
derived fused eletro-spun carbon fibrous mats as high
performance anode materials for lithium ion batteries. 6 In this 6.3. Activated carbons
work, a nitr ogen- doped free-standing fused lignin fiber mat
was made from organosolv lignin-polyethylene oxide (90:10)
blend by electro-spinning follow ed by carbonization and
Activated carbons are highly porous materials w ith large
ther mal annealing in the presence of urea. The fused carbon
internal surface area. They can be effectively used as
fibers w ithout nitrogen doping exhibited high specific capacity
adsorbents in a w ide range of applications such as gas
up to 445 mAh/g at a current density of 30 mA/g and good
separation, catalyst support, filtration systems, and others. 23,
cyclic stability at different current rates. After thermal 25, 47
Due to lignin’s high carbon content and functionalized
annealing in the presence of urea, the charge capacity w as
phenolic structure, it can be considered as one of ideal
further improved to as high as 576 mAh/g and still maintained
precursors for activated carbons. Properties of activated
a good capacity of about 200 mAh/g even at a high current
carbons largely depend on quantity and nature of pores
rate of 2000 mA/g.
present in it. Pores can be divided into micropores ( pore
diameter below 2 nm), mesopores (por e diameter betw een 2-
50 nm), and macropores (pore diameter larger than 50 nm). 48
Porosity of activated carbon depends on the types of surface
functional groups present on the precursor and method of
activation. Lignin content of the feedstoc k controls the yield of
the char and corresponding activated carbon yield. The
microstructure of char and activated carbons also depends
on the lignin and cellulose contents of the biomass source.
According to the study of Gergova et al. , lignin-der ived char
had mor e total pore volume and higher BET surface area
compared to cellulose-based char.49 On the other hand, lignin
(a) chars had low reactivity than cellulosic chars and thus, it w as
easier to activate chars w ith high cellulos ic contents. It w as
also found that, activation of lignin produces mostly
micropores, w hile activation of cellulose produces a mixture
of pore size.
Traditionally, activated carbons can be div ided into tw o
types: pow dered activated carbon ( PA C) and granular
activated car bon ( GA C).47 Pow dered activated carbon ( PA C)
contains fine particles w ith less than 0.2 mm diameter and
thus, presents a large external surface area and relatively
small diffusional resistance. These properties of PA C result in
a very high adsorption capacity. On the other hand, granular
activated carbon ( GAC) has larger particle size of about 5
(b) mm in diameter, w ith s maller external surface area and
Figure 8. SEM images of a) carbon fiber made from phthalic adsorption capacity relative to PA C. How ever, GA C is more
anhydride modified lignin and b) microscale porosity of stable tow ards continuous contact processes.
phthalic anhydride modified lignin.3 Activated carbons are mainly prepared by physical and
chemical activations (Scheme 4).23, 25 In both cases, the
Table 9. BET surface areas and pore volumes of unmodified yields of the char depends on the lignin content of the starting
and modified lignins after oxidation and carbonization. a mater ial. In the physical activation, starting material is
carbonized and then the resulting char is activated using
Carbon BET Adsorbed carbon diox ide or steam. An application of a long activation
type Surface pore time produced carbons w ith relatively high microporosity and
area volume w ide micropore size distribution. In one case, w hen the
(m2 /g) (cm3/g) starting mater ial w as activated at 850 °C for 20 h in CO2, the
Phthalic 32.7230 0.0133 process produced activated carbons w ith surface area 1853
Anhydride (1.5566) (0.0009) m2/g w ith a micropore volume of 0.57 c m3/g. On the other
modified hand, the increase in the carbonization temperature only
generated moderate changes in the BET surface area and
Acetic 37.4293 0.0151 micropore volume of the carbon.
anhydride (1.2133) (0.0006) In the chemical activation, lignin is first activated by
modified impregnating different chemical reagents such as zinc
chloride (ZnCl2), phosphoric acid ( H3 PO 4) and then lignin is
Succinic 15.3236 0.0077
carbonized. During activation, the release of different
anhydride (1.8268) (0.0008)
substances from lignin generates pores on the surface and
modified
results in high surface area and poros ity in the produced
Maleic 6.3865 0.0018 carbon. In chemical activation, the ratio of lignin to
Anhydride (1.2363) (0.0007) impreganating r eagent and the activation temperature are
modified tw o most important parameters. Hayashi et al. studied the
effect of different parameters of the chemical activation on
Unmodified 8.1976 0.0042 the pr operties of the activated carbon. They reported that use
(0.7089) (0.003) of ZnCl2 as activating agents produced activated car bons w ith
surface area about 1000 m2/g. The surface area w as found
to be max imum w hen an impregnation ratio of lignin to ZnCl2

10
of 1:2.3, w as used. At a low temperature (generally <500 °C), The use of solvent extracted low er molecular w eight lignin
the surface area and microporos ity of the activated carbons fraction facilitated the controlling of the template synthesis of
increased w ith the increase in temperature. How ever, at a carbon. In this process, mesopor ous carbon w as synthesized
higher temperature ( >600°C), the surface area and by i) cross-linking lignin w ith for maldehyde using an acid or a
microporos ity of this mater ial decreased. At a high base catalyst in the presence of a surfactant ( Pluronic F127)
temperature, the carbon structure shrank and that in turn and ii) treating precross-linked lignin w ith ( Pluronic F127)
decreased the surface area and pore volume of the material. under acidic conditions. The portion of the surfactant reacted
Interestingly, w hen alkali metal compounds w ere used as w ith the hydroxyl groups of lignin and formed a miscible part
activating agents, activated carbons w ere found to have low while the other portion did not inter act and formed an miscible
surface area w hen the carbonization temperature w as below domain at the core of the resin. The product w as
500 °C. These compounds w ere found most effective above subsequently pyrolysed, w hich removed the surfactant and
800 °C in generating high surface area mostly due to the pore carbonized the mater ial simultaneously. When no activation
enlar gement. Authors noted that above 800 °C, the excess was used, mesoporous carbons made in this process w ere
enlar gement caused merging of pores, resulting in an found to have BET surface areas in the r ange of 205-418 m2
increase in mesopores and a decrease of micropore volume, /g.52 (Table 10) The synthesized carbons also exhibited
and of surface area. Fierro et al. show ed that w hen H3 PO 4 characteristic mesopores at a volume 2-6 times than that of
was used as the activating agent, low impregnation ratios micropores. Further, Saha et al. show ed the surface areas of
promoted the creation of micropores. 50 The acid/lignin ratios these mater ials could be further increased by incorporating
equal to or higher than 1.0 s lightly affected the pore size an activation step.53 Thus, w hen surfactant template lignin
distribution. Increasing impregnation times reduce d the BET derived mesoporous carbon w as physically and chemically
surface area and the total pore volume. Moreover, activated w ith CO2 and KOH, both surface area and total pore
impregnation times also affected the pore size distribution of volume of the mesoporous carbon increased.
the activated carbons.

Schem e 5. Synthesis of mesoporous carbon from lignin. 52

Another important type of lignin activated carbon is

Schem e 4. Preperations of activated carbons 25 activated carbon fibers. This can be considered as the fiber
form of activated carbon.54 -55 Compared to pow dered
Gonzalez-Serrano et al. reported that all activated activated carbons, the activated carbon fiber has higher
carbons produced in the range 350–600 °C show ed fairly specific surface area and porosity. Due to a fibrous structure,
high values of micropore volume and its variation w as the the activated carbon fiber facilitates its use in variety of
same as that of surface area.51 How ever, the same behavior applications. This highly porous mater ial is made by
was also observed for the mesopore volume. It w as activating lignin carbon fibers. Shen et al. described that the
suggested that increasing the activation temperature and synthesis of activated carbon fibers w ith controllable pore
impregnation ratio leads to w idening of the pore size size w ere fabricated from alkali lignin.5 5 The material w as
distribution w ith a higher relative contribution of mesoporosity. made by melt-spinning of a synthesized lignin-phenol–
In recent years, the use of activated carbons in various formaldehyde resin follow ed by ther mo-stabilization and
applications such as energy storage systems is receiving carbonization. In this case, no separate activation step w as
significant attentions. How ever, use of porous carbon in these used. During the carbonization step, s mall molecules such as
systems requir es precise control over the type of porosity. water, formaldehydes released from the material generate
Narrow distributions of pores are favored due to the macropores.
increases in surface area of regular pore distr ibutions vs. Hu et al. reported the synthes is of sub- micrometer sized
broad distr ibutions of pores. How ever, activated carbon activated lignin carbon fibers from alkali lignin w here alkali
produced from lignin does not exhibit controlled metal hydroxides w ere used as activating agents. 54 In this
mesoporos ity; usually microporos ity (pore w idth <2 nm) case, an aqueous solution of alkali lignin and alkali metal
dominates in such products. Controlling pore s izes during hydroxide (<50% of lignin’s w eight) w as blended w ith
carbon synthesis is extremely difficult, primarily because as poly(ethy lene oxide) and electro-spun to for m a fiber mat,
the mass shrinks during pyrolysis, the pores collapse. Thus, which w as then simultaneously activated and carbonized by
in one such w ork, Saha et al. developed mesopor ous carbon heating upto 850 C. The activated carbon fibers made in this
from lignin using a surfactant-templated approach (Scheme process w ere found to have specific surface areas and pore
5).52-53 The w ork w as performed us ing methanol soluble volumes up to 1400 m2/g and 0.91 c m3 /g. When NaOH
fraction of kraft-processed hardw ood lignin and an ac id activation w as used, resulting carbon fiber materials show ed
catalyzed pre-cross-linked derivative of the hardw ood lignin. both mesoporosity and microporossity w ith a maximum

11
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surface area of 1440 m2 /g. When KOH w as used, carbon electrical measur ements revealed the sensitivity of lignin
mater ials w ere found to have mainly microporosity w ith a tow ards aniline. AFM analysis show ed a decrease in the film
maximum surface area of 1407 m2/g. surface roughness after exposure to aniline.

7. Outlook
Table 10. Pore textural character istics of lignin der ived
carbons a
Lignin is the major constituent of biomass. The U.S.
Renew able Fuels Standard ( RFS) mandated to produce 16
Entry Pr eperation BET Mesopore Total
(Surfactant specific volume pore billion gallons of lignocellulosic biofuels (primarily EtOH) by
content surface (cm3/g) volume 2022.5 7 This decision inevitably generate enor mous amount
w t. %) area (cm3/g) of lignin as a co-product of biofuel manufacture. This
(m2/g) remarkable level of lignin production and availability is a
rather exciting opportunity to develop valuable use of lignin in
LMC- HCHO/acid 418 0.34 0.50 various applications. An application of lignin based carbon
1 (105) mater ials that fulfill consumer needs and maximize the
environmental sustainability is rapidly developing. All the
LMC- HCHO/acid 205 0.13 0.20 potential use of lignin-derived carbon materials described
2 (210)
here show a promising development and some of the novel
mater ials might be on a consumer market in near future.
LMC- 222 0.15 0.22
3 HCHO/base How ever, it should also be noted that further intensive
(160) research is needed to foster understanding the basic
chemistry and processing technology of lignin more efficiently
LMC- HCHO/base 214 0.17 0.19 to provide improved properties, value, service life and utility,
4 (160) which can offer better r enew able carbon based products. The
fostered know ledge for manufacturing lignin-based carbon
LMC- Precrossed 208 0.24 0.28 mater ials should also contribute to many other valued-added
5 lignin/THF applications of lignin. Good usage of lignin w ill help to
(116) achieve a clean and sustainable society.

LMC- Precrossed 276 0.11 0.22

6 lignin/DMF
(116)
8. Acknowledgements
a
LMC = Lignin mesoporosus carbon, Here only a part of the
original table is show n52 This research w as sponsored by the Laboratory Directed
Research and Development Program of Oak Ridge National
6.4. Lignin Film Laboratory, managed by UT-Battelle, LLC, for the U. S.
Department of Energy.
Lignin is used to make thin films using the vacuum
ther mal evaporation technique ( PV D, physical vapor
deposition) in recent report.56 These films have possible
applications in surface coatings, composites and transducer
in sensing devices. The properties of these thin films such as
crystallinity, thickness, molecular arrangement influenced the
performance of the related devices. In the PV D technique, .
the organic materials are first vaporized from solid sources.
This vapor is then transported under vacuum. When this +Keyw ords: lignin • carbon materials • carbon fiber •
vapor comes in contact w ith the substrate, the vapor solidifies
activated carbon • carbon film
and for ms a thin film on the surface of the substrate w ithout
causing defects. The thic kness of the film typically varies
from nano to micrometers. 1. G. Gellerstedt and G. Henriksson, in Monomers,
Volpati et al. produced thin carbon films of 20-120 nm Polymers and Composites from Renewable
thickness from lignin using PV D method. The lignin used here Resources, eds. M. N. Belgacem and A. Gandini,
was extracted from sugar cane baggase using a modified Elsevier, Oxford, UK
organosolv process. The reported Mw, Mn and PDI of lignins Amsterdam, The Netherlands, 1998, ch. 9, pp. 201-224.
were 1970 g/mol, 1190 g/mol and 1.66, respectively. While 2. J. Zakzeski, P. C. A. Bruijnincx, A. L. Jongerius and
the lignin PV D films w ith 120 nm thic kness w as deposited B. M. Weckhuysen, Chemical Reviews, 2010, 110,
onto Au interdigitated electrode ( IDE) for dc and ac electrical 3552-3599.
characterization. A conductiv ity of 3.6 X 10 -10 S/m w as 3. S. Chatterjee, A. Clingenpeel, A. McKenna, O. Rios
deter mined from the current versus voltage dc measurement. and A. Johs, RSC Advances, 2014, 4, 4743-4753.
A dielectr ic constant of 8.0, Tan  of 3.9 X 10 -3, and 4. U. Riaz and S. M. Ashraf, in Lignin Properties and
conductivity of 1.75 X 10 -9 S/m w ere deter mined using Applications in Biotechnology and Bioenergy, ed. R.
impedance spectroscopy, at 1 KH z. Interestingly, these thin J. Paterson, MNova Science Publishers Inc., New
lignin films w ere found to react w ith vapors of aniline. When York, 1 edn., 2012, ch. 3, pp. 69-137.
the Au IDE coated w ith 120 nm lignin PV D film w as used as a
sensing unit by expos ing to aniline vapor, both DC and A C

12
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Receiv ed: ((will be f illed in by the editorial staf f ))

Published online: ((will be f illed in by the editorial staf f ))

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Entry for the Table of Contents (Please choose one layout)

Layout 1:

REVIEW
1. Introduction
2. Chemical composition and Sabornie Chatterjee, Tomonori Saito*
physical properties of lignin
3. Lignin extraction from Page No. 1 – Page No.13
various sources
3.1 Acid sulphite process Lignin-Derived Carbon Materials
3.2 Alkaline kraft process
3.3 Organosolv process
3.4 Soda pulping process
4. Effect of manufacturing
process on the properties of
lignin
5. Lignin production: from tree
to carbon material
precursors
6. Lignin derived carbon
materials
6.1 Structural carbon fibers ((Insert
6.1.1 Melt spinning
6.1.2 Thermo stabilization
6.1.3 Carbonization
6.2 Carbon fiber mats
6.3 Activated carbon
6.4 Lignin films
7. Outlook

15