Accepted Manuscript

Title: A review on cellulose and lignin based binders and

electrodes: Small steps towards a sustainable lithium ion
battery

Authors: Trupti C. Nirmale, Bharat B. Kale, Anjani J. Varma

PII: S0141-8130(17)30892-9
DOI: http://dx.doi.org/doi:10.1016/j.ijbiomac.2017.05.155
Reference: BIOMAC 7644

To appear in: International Journal of Biological Macromolecules

Received date: 10-3-2017

Revised date: 23-5-2017
Accepted date: 25-5-2017

Please cite this article as: Trupti C.Nirmale, Bharat B.Kale, Anjani J.Varma,
A review on cellulose and lignin based binders and electrodes: Small steps
towards a sustainable lithium ion battery, International Journal of Biological
Macromoleculeshttp://dx.doi.org/10.1016/j.ijbiomac.2017.05.155

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 1

A review on cellulose and lignin based binders and electrodes:

Small steps towards a sustainable lithium ion battery

Trupti C. Nirmalea , Bharat B. Kalea and Anjani J. Varmab,c*

a
Centre for Materials for Electronic Technology (C-MET), under DeitY, Panchawati,

Off Pashan Road, Pune 411008, India.

b
School of Chemical Sciences, Central University of Haryana , Mahendragarh, Haryana 123031,India.
c
Polymer Science & Engineering Division, CSIR-National Chemical Laboratory, Pune 411008, India.

Highlights:

1. Recent progress of green cellulose and lignin containing electrodes and binders for

lithium ion batteries has been reviewed.

2. The possibility of using environment friendly aqueous systems over non-aqueous

system arises by the use of cellulosic materials.

3. Role of lignin as both electrode and binder for lithium ion batteries has been discussed

for the first time.

4. CMC overcomes the mechanical issues with volume expansion with emerging anode

materials as silicon, MoS2, etc.

Abstract:

Lithium ion batteries (LIB) are the most promising energy storage systems for portable

electronics and future electric or hybrid-electric vehicles. However making them safer, cost

effective and environment friendly is the key challenge. In this regard, replacing petro-derived

materials by introducing renewable biomass derived cellulose derivatives and lignin based

materials into the battery system is a promising approach for the development of green

materials for LIB. These biomaterials introduce sustainability as well as improved safety in the
 2

final disposal of LIB batteries. In this review we introduce LIB materials technology in brief

and recent developments in electrodes and binders based on cellulose and their derivatives and

lignin for lithium ion batteries.

Corresponding Author at: School of Chemical Sciences, Central University of Haryana, Mahendragarh, Haryana

123031,India.

E-Mail address : anjanikumar@cuh.ac.in

Keywords: Cellulose; Binder; Lithium ion battery; Carboxymethylcellulose; Silicon anode;

Lignin.

1. Introduction:

Technological revolution has spectacularly changed human life. However this

monumental effect of science results in huge emission of carbon dioxide causing global climate

change with potentially disastrous consequences for mankind if remedial measures are not

taken with a sense of urgency. Utilization of fossil fuels as energy source is expected to rise as

the world population continues to grow. The availability of the limited amounts of fossil fuels

is a serious worry, and alternate sources of energy are continually being researched. Energy

can be obtained and converted from different sources, but future energy economy needs to be

not only cost effective and sustainable but also be amenable to appropriate storage for use on

demand. One such most promising storage technologies is the Lithium ion battery (LIB).

Lithium-ion batteries have been used in high-end electronics like mobile phones and computer

laptops, and new researches towards hybrid electric motor vehicles is a promising application

that can contribute substantially to lower emissions of ozone depleting gases [1]. Hence, the

development of high energy density, safe, cheap and easily recyclable lithium-ion battery has

become an urgent requirement. The issue of safety also includes the eventual safe disposal of

the battery after its active life is over and in this context; use of renewable and/or biodegradable

materials to replace non-degradable hydrocarbon based materials in battery components is an

 3

attractive strategy. Considerable efforts have been taken to develop new electrode and

electrolyte materials to make greener batteries, for which use of bio-sourced polymers such as

cellulose derivatives and lignin are very promising. However, very little attention has been

devoted towards other battery components like binders, current collectors, battery body

material, etc.

Most of the lithium ion batteries still rely on traditional electrode architectures i.e., a

mixture of electrode active materials, polymeric binders and electroconductive additives on

current collectors. To achieve high power and energy density LIBs, selection of suitable

electrode materials is crucial. Electrode materials should provide high capacity, good cycling

life and easy diffusion of lithium ions. Widely used cathode materials include layered lithium

transition metal oxides (LiMO2, M = Co, Ni, Mn). However, in general LiMO2 suffers from

structural instability, safety issues and high cost. In this respect, lithium metal phosphates

LiMPO4 (M = transition metal) emerged as promising cathode materials for applications in

rechargeable LIBs. As far as the anode is concerned, graphite is the predominant material. To

improve the theoretical current capacity numerous Li-alloys and few elements like Si, Sn, Al,

Sb and P have been extensively investigated. However, the large volume change during cycling

and the deterioration of the performances due to stresses generated in electrodes are the major

limitations. Therefore additional research efforts are still necessary to develop low cost high

quality LIB electrodes. Recently, materials derived from abundant, low cost cellulose and

lignin sources have shown good cycle life and higher capacity, which is discussed here in detail.

These advantages are in additional to the safer environmental disposal features that would

result by the incorporation of natural polymers into the ubiquitous LIB.

Recent studies have shown that electrode stability and irreversible capacity losses are

strongly dependent on binder properties. Thus, binders play a crucial role in electrode

processing [2]. Additionally, recent papers highlight the fact that the choice of binder is also
 4

important in stabilizing the charge-discharge cycling performance of electrodes for lithium ion

batteries so that they can resist large volume changes [3,4]. Binders are materials made up of

one or more polymers which are electrochemically inactive but have the ability to provide

mechanical support to electrode active materials [5]. The binder maintains mechanical integrity

between electrode active particles and current collector of the composite electrode. There are

several other important characteristics that a good binder must possess, namely, it must be able

to withstand dimensional changes during charging-discharging cycles, it should be

electrochemically and chemically stable, and small amount of binder should be enough to

maintain low energy density of battery. As the binders are mixed with electrode active material

and conducting additives in a proper solvent to make a slurry, good solubility and homogeneity

of slurries at room temperature is crucial. Polyvinylidene difluoride (PVDF) is the traditional

binder for both the negative and positive electrodes and current collectors for commercial LIBs,

because of its good electrochemical stability and excellent binding strength with electrode

materials [6]. However, since it is insoluble in water, it requires organic solvents like N-

Methyl-2-pyrolidone (NMP) for processing. Organic solvents are costly, flammable, volatile

and cause environment pollution, and replacing them with benign water is a goal of new studies

in many research laboratories such as ours. Further, PVDF is highly unstable in presence of

lithium salts, costly and has safe disposal issues [7, 8]. Indeed, most fluorinated polymers can

easily deteriorate during the charging-discharging cycling performance of batteries due to the

formation of stable LiF after reaction with lithium metal or lithiated graphite [9]. In addition

the reaction between Li and PVDF is exothermic and can cause self heating and thermal

runaway reactions [10]. Thus, a large amount of effort has been devoted to finding a substitute

for PVDF binder which is both environment friendly as well as cost-effective for use in lithium

ion batteries. In this context, renewable resource derived cellulose derivatives like

carboxymethylcellulose (CMC) play a very important role as they are water soluble, cheap,
 5

environment friendly and can avoid disposal issues. In this review, we present recent advances

in the development of cellulose based electrodes and binders in lithium ion batteries. A part of

the review also looks at the role of lignin as an electrode and binder, as lignin is a by-product

in the extraction of cellulose from biomass.

2. Principle of Lithium ion battery:

A battery is just an energy tank which stores chemical energy and converts it directly

into electrical energy for power its variety of gadgets. Electricity cannot be stored directly

(except electrolytic capacitors or superconducting coils), hence it is essential to develop an

indirect form of storage. Batteries have proved to be most convenient option for electricity

storage since they can be manufactured in wide range of sizes and capacities, have the ability

to supply electrical power instantly, are portable, and provide options of even being used in

series. All batteries contain three basic components as, a negative electrode (anode), a positive

electrode (cathode) and an electrolyte. The electrolyte is a pure ionic conductor (electron

insulator) that separates anode and cathode from each other and allows ions to flow between

them. Due to difference in chemical potential at electrodes, when they are connected to an

external device, electrons spontaneously flow from anode to cathode, while ions are transported

through the electrolyte, maintaining the charge balance. Batteries can be classified as primary

(non-rechargeable) which utilize the chemicals once and discharge and others are secondary

(rechargeable) which can be recharged and used again. In rechargeable batteries a larger

voltage is applied in the opposite direction, which can recharge the battery [11, 12].

Lithium ion batteries utilize lithium intercalation compound as the positive and

negative electrode materials. The lithium ions rock back and forth between the positive and

negative electrodes when the cell is being charged and discharged [13]. The positive electrode

material is typically a metal oxide such as lithium cobalt oxide (LiCoO2) or lithium manganese
 6

oxide (LiMn2O4) [14,15]. The negative electrode material is typically a graphitic carbon [16].

These materials are coated onto the metal foil current collector (aluminium for the cathode and

copper for the anode) with a binder, typically a fluorinated polymer such as polyvinylidene

fluoride (PVDF) and an electronic conductivity enhancer, like a high-surface-area carbon

black. In most LIBs, the electrolyte is liquid, made of lithium salt dissolved into an organic

solvent and the positive and negative electrodes are electrically isolated by a separator film

made up of microporous polyethylene or polypropylene polymers. An intense research is being

carried out for safe and high performing alternatives for liquid electrolytes like ionic liquids,

ceramics and polymeric solid electrolytes [17,18]. When a Li-ion cell is charged or discharged

lithium ions are de-intercalated or intercalated from electrodes and travel through electrolyte

from one to another electrode, while the compensating electrons simultaneously travel in the

external circuit and are accepted by the host to balance the reaction [19]. The data on commonly

used constituents of LIBs are presented in Table 1.

Billions of lithium-ion cells produced are based on non-sustainable synthetic materials

which are also a concern for safe disposal of the LIB after active use. The presence of

combustible material and oxidizing agent, internal short-circuits, thermal instability carries the

risk of fires or explosions. Improvements in the battery materials like electrodes, binders and

electrolyte composition could make the chemistry safer. Hence, for future needs of mankind

designing green and sustainable battery systems is most essential. In this regard, cellulose based

battery system has the potential to fulfil all these expectations, which will result in an

improvement in battery capacity, safety and sustainability.

Table 1: Commonly used constituents of lithium ion batteries

Components Material
Active anode LiTi4O5, TiO2, Carbonaceous materials (Hard carbon, CNTs, Graphene),
material Silicon, Germanium, Tin, Antimony, Metal oxides (Fe2O3, Co3O4, MnxOy,
 7

CuO, NiO, Cr2O3, RuO2, MoO2, MoO3, etc.), Metal phosphides/ sulphides/
nitrides, lithium metal, nano TM oxides, metal-organic framework, etc.

Active cathode Lithium TM oxides LiMO2 (M=Co,Ni,Mn,Cr), Lithium TM Phosphates

material (M=Fe,Co,Mn),V2O5, LiV3O8, Li(NixMnyCoz)O2, TM silicates Li2MSiO4
(M = Mn,Fe,Co,Ni),TM fluorosulphates (LiFeSO4F), metal organic
frameworks, etc.

Electrolyte Organic-based liquid electrolytes (Organic carbonates EC,DMC,PC,DEC,

etc.), Solid polymer electrolytes (PEO,PMMA,PVDF-HFP etc.), Gel
polymer electrolytes(liquid electrolytes incorporated in
polymers),Composite polymer electrolytes, Ionic liquids, Glass
electrolytes (Li2O.SeO2.B2O3, Li2S.P2S5, LixPOyNz,etc.), Ceramics (La1/3-
xLi3xTaO3,Li1.3Ti1.7Al0.3(PO4)3,

Li1.4 Ti1.6Y0.4(PO4)3, Li9Bi2Cl3,Li3InBr6, etc.)

Separator Polyethylene(PE), polypropylene(PP), PE-PP, High density polyethylene

(HDPE), PE/PP/PE, etc.

Binder Polymers as polyvinylidene fluoride ( PVDF), Polytetrafluoroethylene

(PTFE), polyvinyl alcohol (PVA), Carboxymethyl cellulose (CMC),
Styrene butadiene rubber (SBR), etc.

Conductive Carbon black, graphite, graphene, Carbon nanotubes, Conductive

additives polymers, etc.

Collectors For Cathode: Aluminium, nickel, Ag, Au, Pt, alloys, graphene etc.
For Anode: Copper, Nickel etc.

Sealing material Aluminium plastic, aluminium, stainless steel, polymers (PDMS, PP, etc.)

3. Cellulose based binders:

 8

The binders used in LIBs have significant influence on the overall product performance.

In recent years, Eco-friendly and low cost polymer materials like cellulose are being explored

intensively for this purpose. Cellulose is a renewable and biodegradable polymer and is the

most abundant material available on planet earth. Cellulose fibers contain a dense hydrogen

bond network consisting of microfibrils and fibrils which eventually lead to a structural

polymer insoluble in both water and common organic solvents. Substitution of hydroxyl groups

leads to soluble derivatives like ethyl cellulose (EC), cellulose acetate (CA), sodium

carboxymethyl cellulose (CMC), etc. and can be processed as binder material in LIBs. Further,

nanofibers of cellulose are known to form new lightweight composite materials, and these can

also be considered as binders.

3.1. Carboxymethyl Cellulose (CMC):

OCH2COONa

O OH
O HO
O
HO O
OH O n
OCH2COONa

Fig.1. General chemical structure of Carboxymethyl cellulose (CMC)

Carboxymethyl cellulose is a cellulose derivative with carboxymethyl groups bound to some

of the hydroxyl groups of the cellulose as shown in Fig. 1. It’s commonly used salt sodium

carboxymethylcellulose (CMC) is an anionic and water soluble polymer with varying

applications in many diverse industries [20]. CMC has received extensive attention as a binder

material for LIB as an alternative to currently used PVDF, because it is a sustainable material

and also facilitates processing in water. Indeed, CMC is already a component of some

commercial LIBs. Further it is significantly less expensive as compared to PVDF. Since CMC
 9

is a biodegradable polymer, at the end of the battery life, the electrodes can be removed and

the remaining part containing CMC, electrode active material, etc can be more safely buried in

soil. Once electrode material is extracted, the active electrode material can be easily recovered

by pyrolysis of the binder [21]. CMC is non reactive towards electrolytes but can form chemical

bonds with active substances. Therefore it is commonly used as binder for both electrodes in

lithium ion battery [22]. It has a strong shear-thinning behavior that adjusts the slurry rheology

[23]. CMC has a small elongation at break (<8%) hence it is very stiff [24,25] which is a

desirable property for binders.

Many factors like structural characteristics of CMC (degree of substitution (DS),

counter ion, molecular weight), the amount added, electrode porosity and pH of the paste have

considerable effects on CMC performance as binder. Mazouzi et al. [26] concluded that

reversible specific capacity of electrodes with pH=3 is more than that of the electrodes with

pH=7. The pH value of slurry can be always maintained at about 3 by using buffered solutions.

It was observed that at pH=3, CMC can form strong covalent bonds with Si surface, so that the

stability of the electrode structure can be enhanced and the cycling performance of electrodes

can be improved. Hoehgatterer et al. [27] have compared the electrochemical properties of Si/C

electrodes for two kinds of CMC with degree of substitution DS > 0.8 and DS > 1.2. DS is the

average number of carboxymethyl groups substituted per monomer unit, ranging from 0 to 3.

They noted that the cycling performance for CMC electrode with high DS and higher molecular

weight is superior to that for CMC electrode with low DS, since CMC with a larger molecular

weight can simultaneously connect many Si particles together, which makes the electrode

structure more stable and improves the cycle performance. In conclusion, they observed that

the formation of a covalent chemical bond between the binder and the active masses is the

major prerequisite for effective binding and improved cycling stability. In lithium-ion batteries,

CMC was first applied as an aqueous binder in graphite anode materials.

 10

Drofenik et al [28] tested different types of cellulose like carboxymethylcellulose

(CMC), ethyl cellulose (EC), methylcellulose (MC) and hydroxyethylcellulose (HEC), as

potential binding materials in graphitic anodes for lithium ion batteries. These cellulose

derivatives were mixed with graphite and then deposited on copper substrate and pressed at

1000 kPa. It is shown that a minimum content of a cellulose which gives suitable anode

properties is about 2 wt.%, which is less than in the case of conventional polymeric binders (5-

10 wt.%). Also the presence of CMC does not affect the intercalation and deintercalation of

Li+ in the graphite layer or the formation of solid electrolyte interface (SEI) film during the

charge-discharge process, so it is an excellent binder for lithium ion batteries. Among all

cellulose types, CMC has shown the lowest irreversible loss, which may have happened

because CMC dissolves much more easily in water as it contains groups which can be ionized

in solution. It was observed that CMC tends to form networks and at a sufficiently high content,

the cellulose networks probably become continuous in the whole bulk material, which holds

the anode together. At contents smaller than about 1-2 wt. %, certain parts of the anode become

detached from the rest of electrode due to material dilatation. The conclusion drawn was that

the CMC affects neither the intercalation-deintercalation nor the passivation processes. Buqa

et al [29] studied styrene butadiene block copolymer (SBR) and carboxymethylcellulose either

alone or in combination as binders for negative electrodes. The cycling performance of lithium-

based half cells showed that they have a similar bonding ability and nearly same cycleability

as conventional PVDF. Unfortunately, the addition of SBR was found to decrease the

conductivity which would limit the rate capability of the electrode. Another disadvantage with

using SBR alone was that mechanical stability of electrode after some cycles was not

satisfactory. When mixed with CMC, mechanical stability improved significantly. The

combination of SBR and CMC gave good stability to nano silicon/graphite electrode using 1-

2% SBR with 1-2% Na-CMC as binder, equivalent to an identical electrode containing 10%
 11

PVDF binder. They also noted that SBR and CMC content should be less than 5-6%, as larger

content leads to barrier formation.

Chou et al [30] prepared a tin nanoparticle/polypyrrole composite in which CMC was

added as binder. The electrochemical results showed that capacity retention and rate capability

are much better with CMC than traditional PVDF. It was observed that CMC can prevent

formation of cracks in electrodes caused by the large volume changes during charge-discharge

processes. Moreover, anode slurry containing the CMC-based binder exhibits improved

dispersibility and strong adhesive force. CMC based cathode materials for lithium ion battery

was investigated by Klopsch et al. [31], results obtained showed that CMC operates well at

very high voltages (4.8 V). Compared to the PVDF binder, the CMC-based electrode shows an

improved cycling stability and a very promising rate capability. However, considering the truth

that the presence of ppm level of water can deteriorate the overall cell performance, processing

this material in aqueous environments presents the risk of losing some capacity.

These days LiCoO2 is increasingly being replaced with LiFePO4 as cathode due to

environment friendly nature of the latter. Only few groups have reported or studied CMC as a

binder for LiFePO4 cathodes. Guerfi et al. [32] used CMC as a binder with an elastomer for

LiFePO4 cathode materials. The electrochemical performance shows lower irreversible

capacity losses with cathodes using CMC as a binder. The use of CMC allows the preparation

of an electrode with higher compactness with respect to PVDF [33]. Another group observed

that LiFePO4 slightly changes upon aging when it is brought into contact with water, which

can be seen by a growth of a Li3PO4 layer of a few nanometers at the grain surface in HRTEM

(high resolution transmission electron microscopy) image [34]. In order to avoid structural

modification of LiFePO4 fast processing techniques are needed with CMC slurries, like drying

at 170oC. Care has to be taken to prevent condensation of water, as this residual moisture affects

the performance of the battery. This process along with CMC can avoid roll pressing. In other
 12

words, use of CMC allows the use of water based slurries and a simpler, less expensive post-

coating treatment for electrodes.

Qiu and group [23] used carboxymethyl cellulose (CMC-Li) for LiFePO4 electrode.

Figure 2 shows the scanning electron microscope (SEM) images of CMC-Li (Fig. 2a) and

LiFePO4 electrodes prepared by different binders after 200 cycles (Fig. 2b-f). As shown in

SEM images the electrode containing CMC displays a more homogeneous surface with smaller

size particles and a more uniform distribution, while electrode containing PVDF appear less

homogeneous and with a higher number of bigger aggregate particles. The higher compactness

and no serious aggregation of particles of the electrodes containing CMC avoids or reduces

post-preparation treatment and the immersion process of electrolyte becomes better. Moreover,

authors noted the existence of “black holes” in the surface of electrode slice and the crystal

structure present inside, which may benefit extraction and insertion efficiency of lithium ions

between anode and cathode. Also it fasten the time for lithium ions extraction and insertion,

increasing the ionic and electronic conductive efficiency. CMC-Li can ionize to obtain lithium

ions, which could increase the contents of freely moving lithium ions in lithium ion battery and

shorten the diffusion pathway to cathode particle surface. It improves conductive efficiency of

CMC and allows a very broad range of potential applications [25,35,36]. Li et al. [37] found

that CMC can also be used as the binder for the high voltage (up to 4.8 V) cathode material

like Li2MnO3-LiMO2 (M = Ni, Mn, or Co). Wang et al.[38] reported CMC as a binder in the

high voltage (5 V) LiNi0.4Mn1.6O4 cathode with theoretical capacity being nearly 146 mAhg-1

and low self-discharge (~10%).

 13

Fig. 2. SEM images of LiFePO4 electrode materials with different binders at the end of the

200th cycles charge-discharge. a) Digital pictures of CMC-Li, b) PVDF as binder, c) CMC as

binder, d-f) CMC-Li as binder. Reprinted from [23]. Copyright 2010 by Elsevier.

The impact of the structure and properties of binders such as PVDF, CMC and Polyvinyl

alcohol (PVA) on the electrochemical properties of spherical graphite anodes for Li-ion

batteries was investigated, and it was observed that the surface of electrodes showed a higher

homogeneity level with water based CMC and PVA [39]. The surface of the electrodes with

CMC and PVA was much higher than that of electrodes with PVDF. The structure of polymer

binders and their ability to swell in liquid electrolytes influenced the mechanical properties of

graphite electrodes. Satisfactory adhesion was observed for water based binders CMC and

PVA. In case of PVDF-based electrodes, after 10 cycles, the electrode mass drops drastically.

This happens because the electrode mass separates from the current collector as PVDF is prone

to swell in a liquid electrolyte, which results in decreasing adhesion. A hypothesis proposed

was that the acetylene black and CMC binder may act as a conductive bridge between the

adjacent graphite spheres because of the capillary effect of the binder solution [40].

It has also been reported that the high rate capability of spinel lithium titanate Li4Ti5O12

electrodes using CMC as binder is much better than PVDF. The Li4Ti5O12 electrodes with CMC
 14

showed the highest specific capacity at 62 mAhg-1 at 40 C, whereas those using PVDF as binder

showed a capacity of only 25 mAhg-1. The charge curves of electrodes using PVDF as binder

start to show sloping from 20 C, whereas those using CMC as binder still show a flat plateau,

even at 40 C. This highlights the kinetic difference present between the two binders.

Electrochemical impedance studies indicates that the electrodes with CMC and PVDF as binder

showed same lithium diffusion coefficient, but the electrode with CMC had a much lower

charge transfer resistance, a lower activation energy, and a lower diffusion activation energy

than the electrode with PVDF as binder [41].

There are few non-traditional or emerging electrode materials like molybdenum

disulfide (MoS2), organic electrodes and silicon for lithium ion batteries, where CMC works

as a potential binder. MoS2 has received much attention because it can accommodate lithium

ions at lower potential and hence it can be used as anode paired with a suitable high voltage

(>4 V) lithiated cathode. Yet the bare MoS2 still suffers from electrochemical instability and

poor cyclic performance, which can be resolved by using CMC [42]. CMC exhibits a strong

interaction between conversion anodes and facilitates the reaction processes by overcoming the

mechanical issues associated with the huge volume expansion, which makes it more stable than

PVDF. They proved that the combination of MoS2 and CMC binder could successfully

overcome the effect of volume change and improve the electrochemical performance with

excellent cycling stability and rate capability. Organic based electrode sheets suffer from non

uniform distributions of the binder and graphite. This could happen because of slow

evaporation rate of NMP solvent and longer drying time of organic based slurry. The flow of

NMP solvent causes the migration of the binder to the top surface of an electrode sheet leading

to non-uniformity. However, water based SBR/CMC binder shows better uniformity compared

to PVDF [43]. CMC can also be a promising alternative as a binder for Lithium sulfur battery

electrodes, where PEO (polyethylene oxide) and PVDF are commonly used binders currently
 15

[44,45,46]. CMC plays a vital role for silicon electrode which we have discussed in the next

section.

Wanjie Zhang and his group [47] summarized some polymer binders for sodium ion

batteries. Here they mentioned the application of Na-CMC binder for hard carbon electrode in

Na ion battery, which is an emerging field. The decomposition of electrolyte on hard carbon

during the initial cycle was sufficiently suppressed by Na-CMC binder. An amorphous

phosphorus composite electrode with carbon was developed and shown to deliver a high

capacity of 1764 mAh/g at a current density of 250 mA/g using CMC as binder [48]. The

presence of water during processing, limitations with flexibility and electronic conduction in

active material particle-CMC composite films requires further study and understanding of

reaction mechanism to develop this binder. However, considering advantages, it is clear that

the introduction of CMC as a binder for electrodes could be an important step for the

development of the preparation of electrode materials and the development of greener and cost

effective lithium ion batteries.

3.2. Natural cellulose and nanocellulose:

As mentioned earlier, there are obvious advantages to the use of cellulose and

nanocellulose in LIBs, but their lack of solubility in common solvents and water had limited

their use. However, inexpensive ionic liquids have been developed which are able to dissolve

cellulose. S.S.Jeong et al. [49] dissolved cellulose into ionic liquid 1-ethyl-3-methyl

imidazolium acetate (EMIMAc) and then coated it on typical battery current collectors. Ionic

liquid was recycled by a phase inversion process by using water as the co-solvent. It showed a

specific capacity of 123 mAhg-1 of LiFePO4 at room temperature. A rapid and reliable

technique for large scale production of self-standing electrodes for LIB exploiting the use of

microfibrillated cellulose as binder and water as solvent has also been demonstrated [50]. Paper

hand-sheets soaked in a standard liquid electrolyte solution have been used as separator
 16

between electrodes. The characteristics are similar to traditional PVDF binder and the battery

remained stable over prolonged cycling, indicating that the cellulose fibers did not affect the

cycling stability.

Nanocelluloses usually combine both properties of cellulose and nanoscale materials.

Microfibrillated cellulose (MFC) nanoparticles as binders for the manufacturing of self-

standing and flexible electrodes using a straightforward water evaporation process were

developed [51]. An aqueous slurry was prepared by mixing synthetic graphite and MFC in the

solid phase and then was poured into a Teflon mould to obtain porous graphite/MFC film after

evaporation of the water. Microfibrillated cellulose formed a nanostructured web-like network

around graphite platelets to provide graphite anode a highly porous structure, excellent

flexibility and good cycling performances. MFC/polypyrrole (ppy) composite paper for use as

electrodes in energy storage devices has also been proposed [52]. The composite papers

obtained by coating MFC with PPy, using in situ chemical polymerization and filtration of the

suspension of the coated fibers were used to prepare self standing electrically conducting

composite paper. MFC was dissolved in water and then the solution was mixed with a pyrrole

solution in water, oxidizing solution and then HCl. The reaction between the oxidant solution

and the MFC dispersion gives layer of polypyrrole on the cellulose fibers, which was poured

on filter paper in a Buchner funnel employing reduced pressure and allowed to dry in air. This

easy processing can make large scale production more environmental friendly. Another

formulation used cellulose fibers as binder for the preparation of LiFePO4/Carbon

black/Cellulose fibers cathodes by using simple filtration process. The obtained paper-cathodes

showed very good mechanical properties, with Young’s modulus as high as 100 MPa,

discharge capacity values up to 110 mAh g-1 and very good cycling performances, comparable

with conventional polymer-bonded LiFePO4 cathodes [53].

 17

Flexible paper electrodes using low amount of TEMPO-oxidized cellulose (carboxy

celluloses) nanofibrils as a binder has recently been reported [54]. Typically electrode films

made up of binder PVDF have poor mechanical properties, while CMC is an extremely stiff

and brittle polymer and which can also form a continuous matrix around electrode active

materials which limits their application in flexible devices [55,56]. In this respect TEMPO

oxidized cellulose nanofibrils have proven to be much better as they show good mechanical

properties and can also be used in water based processes. However, the water trapped inside

CNF (cellulose nanofibrils) structure may affect the Li ion battery performance. To overcome

this they reduced the binder content to only 4wt%, which is very low compared to traditional

flexible electrodes which use 10-33% binder. Such a low amount leads to low moisture content

and also increases the capacity of the battery. Drying the electrodes for 1h in a vacuum at 110oC

produces good cycling stability for lithium ion batteries. Alberto Varzi and group [57] used

natural cellulose as binder for electrochemical double layer capacitors (EDLC) by employing

high voltage ionic liquid electrolytes. Cellulose with ionic liquids or nano-cellulose derivatives

has proven to be an excellent choice to make flexible batteries where CMC has some

limitations. Also they don’t involve chemical processing as like preparation of CMC from

cellulose.

4. Chitosan as binder:

Chitosan is a linear polysaccharide composed of randomly distributed β-(1-4)-linked D-

glucosamine (deacetylated unit) and N-acetyl-D-glucosamine (acetylated unit)(Fig. 3). The

presence of amino and hydroxyl functions, its large scale potential availability has given it

unique status amongst sustainable polysaccharides.

 18

OH

O NH2
O HO
O
HO O
NH2 O n
OH
Fig. 3. General chemical structure of chitosan

It has been used as an electrolyte for LIB but has not been explored as binder for electrodes

[58]. Recently, Chao Chen et al. [59] introduced chitosan as a polymer binder for Si anode.

Chitosan is a cross-linkable polymer which can interconnect with Si through hydrogen bonding

between amino groups of chitosan and hydroxyl groups of the Si surface. They used cross-

linked chitosan with glutaraldehyde through the amino groups to form a 3D network. This

limits the large movement of Si particles and provides much better cycle stability for Si based

anodes. Thus chitosan is a potential material for LIB binder and should be explored further.

5. Lignin as binder:

Lignin is a component of lignocellulosic biomass material, with a predominantly

aromatic architecture (Fig. 7). It is a structural material which adds strength and rigidity to cell

walls. Lignin has high carbon content of approximately 60 wt % and is readily available in

large amounts from the paper and pulp industry. Thus lignin has emerged as an interesting raw

material for the preparation of chemicals and carbon materials in LIBs due to its low price, and

properties such as low density, high hardness and resistance to heat, chemicals, friction, and

humidity [60]. Lignin has been used to prepare anode material for LIB, however it has not so

much explored as a binder material for LIB.

Huiran Lu and his group [10] reported the use of lignin as a binder material for both

LiFePO4 and graphite electrodes. Lignin was dissolved in acetone with 5% PEG to improve its

elasticity to electrodes. To this LiFePO4 or graphite along with super porous carbon and water
 19

were added to prepare electrodes. Obtained electrodes were pressed to decrease the porosity of

electrodes and increase the contact between the particles. It was observed that leaching of lignin

prior to preparing the electrodes is necessary to remove low molecular weight soluble fractions

of lignin. Such electrodes have shown relatively high specific capacity and good stability as

binder to enhance electrode performance.

In a potential study a high performance and durable silicon nanoparticle anode was

developed in which the conventional binder and conductive additives were replaced by lignin

[61]. The composite electrode showed an excellent electrochemical performance with an initial

discharge capacity of up to 3086 mAhg-1 and retaining 2378 mAhg-1 after 100 cycles at 1 Ag-
1
. In this study, lignin was treated at 600°C, as at this temperature lignin was sufficiently

carbonized and the resulting structure provided excellent electron conductivity while

maintaining some of its polymeric flexibility and simultaneously allowing the composite to

fully utilize silicon capacity and accommodate volume expansion. In conclusion, lignin has a

huge scope to develop renewable, cost effective, environment friendly and high performance

binder for LIBs.

6. Binder for Si anode:

Silicon is the most promising anode material for next generation lithium ion batteries

due to its high theoretical lithium storage capacity. The main challenge in its application here

is its significant volume changes during lithium insertion and extraction. Hence, particular

attention was given to the development of polymeric binders, as they can bind the Si-active

materials of electrodes to maintain electrode integrity. Binders prevent electrical contact loss

between Si-particles to accommodate severe volume changes during cycling. Recent progress

in the area of polymeric binders for Si anodes in cells has recently been published [26,62]. A

binder like CMC can resist the volume changes of Si based anodes. By varying the levels of
 20

carboxymethyl substitution on CMC, the adhesion of active material to current collector and

dispersion of the electrode slurry can be controlled [63]. Different mechanisms for Si particles

and CMC have been proposed (Fig. 4). Among them a weak hydrogen bond formation between

CMC binder and Si is more favorable than the covalent bond between carboxyl group of CMC

and hydroxyl group of the SiOx oxide layer covering the Si nanoparticles [64,65]. Moreover

the hydrogen bonding between carboxyl groups in CMC and hydroxyl groups on Si surface

may exhibit self-healing behaviour that would be favourable to the long-term cycling stability

[66]. A chemical bond between the binder and the active masses could lead to long-lasting

reversibility of lithium uptake/release for Si-C-composite anodes. It was observed that

hydroxyethyl cellulose through such bonding significantly improves cyclability, but to a lesser

extent than CMC [27].

The linear chain nature of polymer binders limits their multi-point interaction with Si

particles. To overcome this sodium polyacrylate-grafted-carboxymethylcellulose (NaPAA-g-

CMC) polymeric binder was developed for Si anodes. The NaPAA-g-CMC binders with

branched structure is believed to present multi-point interaction with Si surface, resulting in

enhanced binding ability with Si particles as well as with the copper (Cu) current collectors.

NaPAA-g-CMC builds a stable solid electrolyte interface (SEI) layer on Si surface and

improves cycling performance compared to linear polymer binders. The moduli of PAA and

CMC did not change when exposed to solvents like diethyl carbonate. However, the stiffness

of PVDF was found to significantly decrease on contact with diethyl carbonate. Most likely

this happens because of carboxylic groups (both -COOH and –COONa) present on CMC.

Hydrogen bonding of carboxylic groups on CMC with hydroxy groups on Si surface and -

COONa group together with SEI protect the Si –C interface from degradation upon solvent

interaction [67].
 21

Fig.4. Proposed mechanisms of the CMC binder with Si nanoparticles: A: covalent bond

formation, B: hydrogen bond formation. Reprinted from [64]. Copyright 2011 by Elsevier.

Repeated expansion/shrinkage of Si particles can destroy the dense CMC binder structure and

crack the SEI film. In order to avoid the deformation of the CMC binder during cycling, a

porous CMC scaffold structure as binder for Si anodes was developed [68]. The pores present

in scaffold allow the Si particles to expand without deformation of the anode structure which

ultimately improve cycle stability and rate capability. CMC scaffold electrodes were prepared

by using two different techniques like (i) Slurry spray technique: It consist of 52 wt% Si-nano

particles, 12 wt% carbon black, 36 wt% CMC in water as solvent. The slurry was sprayed onto

the heated copper foil, and water evaporated instantly upon contact with the copper foil, thus a

porous scaffold electrode was formed. (ii) Carbon coated Si nano-particles that were obtained

via emulsion polymerization followed by carbonization. Carbon coating enhances the

electronic conductivity of the Si nano-particles and stabilizes the SEI film. These Si nano-
 22

particle electrodes with CMC scaffold binder structure showed high energy density, power

density and excellent cycle stability. It was concluded that the cohesive strength between the

binder and active particles is a crucial factor. Despite tremendous amount of work on Si

electrodes, it is still early to expect its commercialization. The optimization of all parameters

especially binders, to raise the performance of Si electrodes has not yet been accomplished.

Cellulose and lignin based renewable and low cost binders with improved structures and

properties can certainly be used advantageously in new age LIBs.

6. Cellulose and lignin based electrodes:

Electrodes in any battery system must be both good electronic conductor and ionic

conductor. Currently commercially available batteries contain expensive and hazardous

materials, hence economical and eco-friendly electrodes based on biopolymers like cellulose

and lignin are necessary for sustainable LIBs.

6.1. Cellulose as electrodes:

Cellulose has been developed as both an anode and cathode in LIBs using different

processing techniques. A simple paper making technique was used by [69] to construct eco-

friendly electrodes. Filtration of aqueous slurries containing graphite or LiFePO4 particles and

cellulose fibers on a buchner funnel produced an easy to handle and flexible electrodes. These

electrodes are free of visible sheet formation defects and showed good electrochemical

performances. The same group introduced CMC as a wet-end additive to improve paper sheet

dry strength and uniformity [70]. Such cellulose based anodes showed excellent tensile

properties and cycling performance. Thermally carbonized rice paper in nitrogen atmosphere

was used to prepare three-dimensionally porous carbon films, which were used as both a free-

standing active anode material and as current collector of a cathode for LIB [71]. The rate and

cycling performances of both these electrodes were found to be better than the traditional
 23

electrodes due to the three-dimensionally porous structure of carbon. A battery with

approximately 250 µm thickness was developed by using nano-fibrillated cellulose (NFC). In

such a flexible battery, NFC served both as an electrode binder material and separator, and

demonstrated good reversible specific capacities even for prolonged cycling [72].

A new concept of heterolayered, one dimensional nanobuilding block mat battery based

on cellulose nanofibrils (CNF) and single walled carbon nanotube (SWNT) netted electrode

active materials architecture was reported [73]. Here CNF acted as a separator membrane

which played a critical role in securing the tightly interlocked electrode-separator interface.

Thermally stable CNF separator improved the thermal tolerance of the LIB and also avoided

harmful side reactions. The only concern with CNF was that slightly larger water content was

observed in the h-nanomat cell than the conventional cell. The major challenge in fabricating

cellulose composites was the insolubility of cellulose in most common solvents. Interestingly,

a room temperature ionic liquid (RTIL) which dissolved cellulose permitted its use as an

electrolyte in LIBs or supercapacitors [74].

A wide range of hard carbons were produced by Kierzek and group [75] by

carbonization of powder cellulose and assessed as potential anode material of LIB. It was

observed that increased temperature resulted in little change in the chemical composition and

structural ordering of resultant carbons but considerably decreased porosity with lowering of

the reversible and irreversible capacities. It was observed that bacterial cellulose (BC) formed

three-dimensional (3D) conductive porous network and exhibited excellent electrochemical

performance like specific capacity of over 857.6 mAh g−1 after 100 cycles at 100 mA g−1. Its

hierarchical micropore mesopore structure and high surface area enhanced the contact area of

the electrode–electrolyte. Further, it decreased the diffusion resistance of lithium ions, to

provide a solid and continuous pathway for electron transport [76]. A 3D carbonaceous aerogel

was derived from biomass bacterial cellulose and introduced as a flexible framework for iron
 24

oxides anode in LIB. It resisted volume changes of Fe2O3 during the electrochemical cycling,

resulting in much higher specific capacity and longer cycle life when compared with its

crystalline counterpart [77]. A composite of cellulose nanofiber and carbon nanotube was used

to make lightweight flexible paper electrodes, where CNF serves simultaneously as building

skeleton and a binder [78]. Table 2 presents data on recent studies on cellulose based electrodes

for LIBs. It is clear that since the past decade there is an increasing demand to use sustainable

and environment friendly natural materials like cellulose in high volume LIBs and this trend

will continue.

Table 2: Recent cellulose based electrodes for LIBs reported in literature

Refe Electrode preparation Cellulose form Spacific Current Remarks

renc technique capacity Rate
es (mAh g )-1

Papermaking technique Cellulose fibers 90 1C Free of visible shut

[69] (water based filtration) formation defects
Papermaking technique Cellulose fibers 100/150 1C Improve strength and
[70] (water based filtration) uniformity of
papersheets
Sintering/coating/ Commercial 100 1C Three dimensionally
[71] rice paper porous carbon film
Lamination
formation
Papermaking technique Nanofibrillated 101 1C Single structured
[72] cellulose (NFC) battery with all
renewable components
[73] Vacuum assisted Cellulose 185 C/2 Heterolayered, 1D
infiltration process nanofibrils nanobuilding block mat
(CNF) battery based on
separator/electrode
assembly (SEA)
[74] Coating Nanoporous 110 1C Unchanged cellulose
cellulose paper dissolved in RTILs as
electrode binder
 25

6.2. Lignin as electrodes:

Most of the lignin produced is consumed as a fuel in the pulp–paper industry for

production of energy and chemical reactant, and only the 2% is actually being commercialized.

Development of lignin for value added products has many benefits for the environment as well

as for the economy. Lignin is a carbon rich complex network of phenolic monolignol units

(Fig. 7) producing a high carbon yield after pyrolysis treatment [79,80]. The network of

aromatic rings in lignin tends to form graphite-like domains, while linear branches are lost as

small molecules containing various hydrocarbons [81]. A good electrochemical performance

can be achieved using lignin based composites to prepare carbon-based materials for LIBs [82].

Fig. 5. Different thermostabilization stages of lignin

Lignin carbon fibers can be prepared from hardwood or softwood lignin precursors, but

chemistry of the precursor has little impact on carbon structure. Despite their limited

crystallinity, the carbon fibers exhibit resistivity comparable to typical values for graphite [83].

The thermostabilization stages i.e. from temperatures below 250°C to above 900°C explained

in fig. 5. It was observed that the isotropic nature of the lignin carbon fibers provides a good

interface for Li insertion and also accommodate the insertion-induced stresses [84]. Popova et

al.[85] studied the nature of carbon-graphite material produced from lignin and kinetics of
 26

intercalation of lithium ions through their matrix for LIB. It was observed that it surpasses other

graphite materials with high specific energy content 720 WhKg-1.

Recent studies demonstrate that lignin-derived carbons are promising materials for

lithium ion as well as sodium ion batteries due to their uniquely disordered microstructures.

Anode materials derived from solvent extracted lignin using scalable melt processing resulted

in electrically interconnected three-dimensional architectures (Fig. 6). The resulting free-

standing electrodes showed carbonized lignin has a disordered nano-crystalline microstructure

and can be used for both high-power and high-energy applications [81]. Here the carbon

framework functioned as the current collector, carbon additives and binders all in one, and thus

eliminated the extra mass and expense of inactive materials in conventional designs. Further

electroactive quinone functionalities from lignin can be oxidized and reduced during cycling

[86]. A variety of advanced carbon materials such as activated carbons, carbon fibers,

templated carbons, high ordered carbons from lignin were developed by thermochemical

processes. Fusion of carbon fibers and low-melting-point polymer additives exhibited much

lower electrical resistance as well as good electrochemical performance [60].

Fig. 6. Scanning electron images of varying levels of fiber–fiber fusion in lignin based carbon

fibers mats, indicating that fusion and mat densities can be controlled through the fabrication

process. Reprinted with permission [81]. Copyright 2014 by Wiley.

 27

Unfortunately, lignin carbon fibers have inferior flexibilities properties resulting in unstable

rate capacity and poor cycling performance [83]. Recent studies demonstrated that doping of

heteroatoms like nitrogen improved the stability and capacitance of the materials [87]. Nitrogen

doped free standing fused carbon fibrous mat from lignin: polyethylene oxide (90:10) blend

via electrospinning followed by carbonization and thermal annealing in the presence of urea

were also fabricated [88]. Such doping with nitrogen improved both specific capacity and

electrochemical conductivity of LIB electrode. With increased amount of lignin, rate and cycle

performances of carbon nanofibers also improve [89]. Nitrogen and oxygen containing carbon

micro/nanospheres (CPAN and CPNA) were prepared by direct pyrolysis of

lignosulfonate/polyaniline and lignosulfonate/poly(N-ethylaniline) composite spheres at

temperature of 700oC [82]. The ethyl substituent affected the composite structures and their

carbon spheres because of the steric and electronic effects of the alkyl substituents. CPAN

nanospheres possessed higher surface areas, more micropores & mesopores, and more nitrogen

and oygen containing functional groups. Hence, CPAN nanospheres displayed better

electrochemical performance and have potential application as an anode.

Generally lignin-based colloidal spheres suffer from spherical structure destruction

during the pyrolysis process. It was observed that nitrogen doping in lignin derived carbon

nanospheres generated high surface area. Further they improved their specific capacity upto

225 mAhg−1 at a current density of 60 mAg−1 after 50 cycle along with first coulombic

efficiency up to 66.4%. Also direct pyrolysis of alkali lignin at different temperature develops

hard carbon materials with high graphitization degree [90]. Careful selection of processing

conditions provided control over the surface area, the porosity, the volume fraction and size of

crystalline domains and other structural factors [91]. Electrospun carbon nanofiber (ECNF)

mats prepared by electro-spinning an aqueous mixture demonstrated high performance as free-

standing binder-free electrode materials for supercapacitors. It was revealed that with the
 28

higher amount of lignin in the precursor nanofibers, the resulting ECNFs would have the

smaller average pore size, larger pore volume and higher specific surface area [92]. Recently,

lignin has also been blended with pitch as the precursor for efficient sodium ion batteries [93].

These interesting results show that utilization of biomass derived lignin to synthesize

components like electrode and binder for LIB provides a green sustainable option for

converting inexpensive industrial lignin into value added materials.

OCH3
Lignin O
HO OH

HO O
OH
OH OH
OCH3
OCH3 O
H3CO HO
O O
O
HO O
H3CO OH
OCH3
HO OCH3 O
O
O HO OH
Lignin
HO
H3CO
H3CO O
OCH3
H3CO OH OH
Lignin O

Fig. 7. General chemical structure of Lignin. (Adapted from ref. [94])

7. Conclusion:

The rapidly developing technological revolution needs a better sustainable energy

storage system to store produced energy. Lithium ion battery is one of such most promising

and fastest growing storage system in the market. Also implementation of LIBs in hybrid

electric vehicles and portable electronic devices will create a high demand for safe, economic

and eco-friendly materials. In this context, abundant, renewable and water processable natural

polymers like cellulose, lignin and their derivatives are very useful. The purpose of this review

was to view the recent trends in applications of cellulose and lignin in the field of lithium ion

batteries as important components of a battery i.e. electrode and binder. It is clear from the
 29

research that cellulose derivatives like CMC, nanocellulose, etc. are efficient binders for not

only widely used carbon and metal oxide electrodes but also for emerging electrodes like

silicon and MoS2. Light weight, low cost and easily recyclable electrodes can be prepared by

using cellulose will make flexible and portable lithium ion batteries. Lignin has recently been

introduced as binder and electrodes in LIBs and more research is required to get a better

understanding. Thus there is huge scope to use cellulose and lignin based electrodes to develop

cost effective and sustainable batteries as well as flexible, light weight and easily recyclable

portable electronics.

<ACKNW>Acknowledgements:

TCN thanks to CSIR/UGC, New Delhi for Senior Research Fellowship. TCN also thanks C-

MET and NCL, Pune for support.

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