Department of Mechanical and Manufacturing Engineering
Faculty of Engineering
EMM 5977
Independent Study

Lecturer: Assoc. Prof. Ir. Dr. Nor Mariah Adam

Name Lai Jee Inn
Matrik No. GS 42146

INDIVIDUAL ASSIGNMENT

Review on How to Improve the Efficiency of the Rechargeable Batteries-Lithium Batteries
Lai Jee Inn GS42146
ABSTRACT

Batteries are playing important role in our life especially in this high technology era. Laptop, mobile phone, camera and otherwise are using battery to make it to function. In order to improve the efficiency the batteries, several methods are discussed in this paper. INTRODUCTION
In this advanced technology era, batteries have been commonly used by the consumers. We use them in different fields like cars, mobile phone, laptop and other else. (Hiroki Kitamura, 2012).Batteries is divided into two main groups which are primary and secondary batteries. (Clean Up Australia, 2009)

Primary batteries are the batteries that normally use in dairy life such as remote control, clock but for this kind of batteries is a non rechargeable battery which means that we only can use it for one time and will be throw away after used. This kind of batteries is actually converting the chemical energy to electrical energy and they are normally known as the alkaline batteries. Secondary batteries are batteries that can be rechargeable and recycle after it cannot be recharge. This batteries mostly use for our mobile phone, laptop and other. Although these two kinds of batteries have it own advantages and disadvantages but consumers still using them. As we know that the materials inside the batteries is harmful and toxicity. Therefore, consumers started to require more advance batteries which have long life span and more environmental friendly.

An electrolyte is a medium that allow the ions to flow in between the cathode and anode. There are three different kinds of electrolytes which are solid, liquid and gel. The most common electrolytes was liquid, this kind of electrolytes have bring a problem to the consumer which is leakage. In a battery, there is a pair of electrode which we know as cathode and anode. Therefore many researchers have come out a solution to improve the efficient of the battery such as improvement in the electrolytes and electrodes.

Problem Statement
Batteries have been widely used by the consumer and the consumers have been started request for a better performance battery which has long life span and safe to be use. Many researchers have been carried out to overcome the problem.

Research on biodegradable electrolytes such as solid polymer electrolyte (SPE) have been carried out by many researches since it’s allow the fabrication safer battery such as no leakage, low self-discharge in the batteries rechargeable and simple to be prepare (Lakshi & Chandra, 2002; Pandey et al, 1998). Some of the researchers find out that the SPE are safer to be use when compare to the liquid state polymer electrolyte due to the solid state biopolymer are more environmental friendly and more electrochemical stability (Biswal & Singal, 2004). In 2012, Chai and Isa have stated that the solid biopolymer electrolytes is more safe and no leakage when compare to the liquid state biopolymer. Besides, these kinds of electrolytes are easy to be prepared, no leakage and have a good ionic conductivity between the cathode and anode (Samsudin, 2012).

Energy Storage Devices
A high efficiency of energy storage devices would have medium to store the energy at off-peak times where will reduce the need for overall generation from power plants during peak time and help to lower the cost as well as green house gas emission (Xu et al.,2015).
There is much kind of energy storage devices such as batteries, fuel cell, and capacitor and so on but the rechargeable batteries had surpassed the others at the present time (Xu et al., 2015).

Energy storage devices like lithium ion batteries have been widely discovery by the researchers as the material that used is not harmful as the lead-acid and nickel-cadmium batteries where it would not bring negative effect to the health and environment (Jeong et al., 2012; Han et al., 2015).

Electrolytes
There are three types of electrolyte which are solid, liquid and gel. The function of the electrolytes is to allow the ion to transport through anode to cathode during charge and discharge (Chai & Isa, 2012)

The liquid electrolytes are commonly used in the commercially battery. However, due to the liquid type of electrolyte having some problems likes leakage and reaction with electrodes and poor electrochemical stability makes it less desirable in electrochemical devices (Idris et al., 2009). Therefore, new type of solid polymer electrolytes has created new opportunities in order to overcome the disadvantages of liquid electrolytes. The first reported solid polymer electrolyte (SPE) was in 1973 which was more suitable compared to the liquid electrolytes (Nadzri et al., 2011; Syzdek et al., 2009). This is because of its excellent mechanical and thermal stability and high ionic conductivity and it has been used in the development of the thin batteries and other electrochemical devices with flexibility design (Samsudin et al., 2012; Kadir et al., 2010). In addition, the SPE also have some advantages like good compatibility with electrodes, no leakage, and low self-discharge and easy to process (Yahya et al., 2006, Kadir et al., 2010; Ahmad & Isa,2012 ; Shukur et al.,2013 ; Sheha, 2009; Bhargav et al., 2009). According to Nadzri and Isa (2011), SPE shows a lot of excellent properties and it can be functioning as an electrolyte in many devices like rechargeable battery and fuel cell (Nadzri & Isa, 2011).

The next new technology-proton batteries have brought a better performance, long life span and large capacities. Besides that, there was no harmful material used it the proton battery which mean that it a biodegradable materials was used. A biopolymer electrolyte (BEs) was used for proton cell (Chai et al., 2013).

Polyethylene oxide (PEO) an alkali salt compounds were used as solid electrolyte materials for the solid state Li-ion batteries. The pure PEO electrolyte has propensity to form crystalline phases at room temperature when at low ionic conductivity, x10-6.

The Application of Polymer/Biopolymer Electrolytes
There are several research that used polymer and biopolymer in the application such as fuel cells (Smitha et al., 2005), solar cells (Liang et al., 2014), battery (Mohamed et al., 2000; Telli et al., 2012) and capacitors (Hashmi, 2000).

According to Smitha et al. (2005), the polymer electrolyte membrane fuel cells (PEMFCs) had acquired as this electrolyte are suited to the application of fuel cells. They also stated that the major requirements of fuel cell membranes are high proton conductivity, low methanol/water permeability, good mechanical and thermal stability and moderate price.

For solid- state battery, the liquid electrolyte in the conventional systems is defeated by the polymer electrolyte-based batteries which cause it to develop strongly. From the aspect of the anode, cathode and electrolyte, the manufacturing of the proton batteries are low cost and the lamination of the electrolyte that will allows the solid-state modular battery fabrication to be in many different sizes and shapes for example rectangular, spirally wound and Z-folder geometries (Mohamed et al., 2000). Telli et al. (2012) have developed a solid state protonic cell based on Zn/MnO2 electrode. In their work, they presented a system that are more stable over a wide potential range for the electrolyte comparable to the homologous liquid electrolytes and cause less electrode corrosion. They also manage to reduce the corrosion that cause by the liquid leakage.

Meanwhile, the electrical double layer capacitors (EDLCS) are a capacitor that consists of blocking electrodes which are carbon and other similar material. Also in EDLCS uses the carbon electrodes that has a large surface. The different forms of carbon in the large surface area electrodes and the liquid and polymeric electrolyte are used is develop in several EDLCS (Hashmi, 2000).

At year 2000, Mohamed et al. reported the electrochemical supercapacitor’s development has gained an interest due to the application in electronic, medical and electrical devices. The electrochemical supercapacitors are uses a material that is the polymer electrolyte most importantly the reason would be its good properties for example during the charged-discharged, the quick doping-dedoping, the huge charge density, the simple chemical/electrochemical synthesis and the inexpensive besides the noble metal oxides.

In the separator, cell of the separator uses a variety and classes of material where multiple requirements of different types of system are fulfil. Commonly, it acts as the electrical insulation between the positive and negative electrodes. There are a few requirements that the separator’s material needed to fulfil for example strong mechanical spacing between the electrode, electronic insulation, reasonable cast and etc (Othman et al., 2000).

The electrical energy’s renewable sources as the polymer solar cell (PSCs) serves due to many advantages for example the inexpensive fabrication and the simple process on a flexible substrate. The concept of introducing the bulk-heterojunction (BHJ) has momentously enhanced the PSC’s performance as the BHJ is an active layer. The active layer is the material of the electron donor and acceptor is mixed in a solution and it was sandwich between the two electrodes as it is cast into the thin film. For single cells, the state-of-the–art PSC’s power-conversion efficiency over 9% and in recent published research 10% for the tandem cells (Liang et al., 2014).

2.3 Electrodes
Negative electrode
H+
H+
H+
Electrolyte
Positive electrode

Figure 2.3: Ions Flow between the Electrodes

Rechargeable cells are designed to have two electrodes. Electrodes are dividing to two parts there are cathode and anode .The anode is the negative electrode and the cathode is the positive electrode. When electrochemical reaction occurs in the cell, oxidation will happen in the anode which will gives the electrons to the external circuit. However, the cathode will accepts the electrons from the external circuit and reduction will occur at this time (Pandey et al., 1998; Bansod et al., 2007; Braun et al., 2012).

Some of the researchers stated that to obtain rechargeable cells need a suitable reversible cathode and anode half-cell reaction (Tiwari, 2004, Braun et al., 2012). The structures of the cathode are playing an important role in charge and discharge characterises in a cell via intercalation and deintercalation. Therefore intercalating layered materials like MnO2, PbO2 and V2O5 are used in the cathode (Malankar, 2009). Among the present rechargeable battery, the zinc–manganese dioxide cells have certain advantages like high energy content, good in specific power and energy and it is low in cost and it also a low polluting electrode material that widely used in the primary cells (Minakshi &Ionescu, 2010). In order to enhance the performance of the cell, some researchers had tried to improve the performance of electrode by adding a binder, conductive agent and active materials (Kitamura et al, 2012, Lee & Oh, 2013, Ponrouch & Palacín, 2011).

Manganese Oxide
Manganese oxide is regarded as an environmental friendly material and it is cheap and common material and is an attractive material used for the positive electrode in the primary batteries, lithium ion batteries and act as a catalyst in sensors, solar cells (Thapa et al., 2014, Sheha, 2009, Wang et al., 2013, Yano et al., 2012). However, this material has not commonly used in secondary battery due to it would form oxygen gas in the electrolysis during the charging reaction:
4OH-→ 2H2O + O2+4e-

And it change to Mn3O4 simultaneously with reduction reaction as follow:
MnO2+ H2O +e-→MnOOH+OH-
MnOOH+e-→MnOOH-
2MnOOH+MnOOH-→Mn3O4+H2O+OH-

This is the formula that formed during the discharge reaction of MnO2 in a electrochemical reaction:
MnO2+ H2O +e-→MnOOH+OH-
Besides that, MnO2 is attractive materials that used in cathode as this material has good energy compatibility in reversible electrochemical system (Rusi & Majid, 2013) and it is a good reduction agent who can reduce the hydrogen peroxide and oxygen. (Minakshi & Ionescu, 2010 ; Yano et al., 2013).

Conductive Agent
A conductive agent like acetylene black and ketjen black are usually introduced due to its have large specific surface area, strong corrosion resistance and low cost-effective. As these materials can improve the capacity, charge and discharge speed as well as the cycle life of the batteries (Panjaitan et al., 2012; Kuroda et al., 2003; Rao et al., 2012 Tang et al., 2010). However, the conductive agent will affects the energy density and power in electrode. Therefore a polymer binder is used to overcome the problem of the cell’s performance (Panjaitan et al., 2012).
Binder
Binder are playing important role in electrode preparation due to its maintenances on the physical structure of electrode (Courtel et al.,2011).
Binder is a non-active electrochemically material that use to improve the adhesion of electrodes and the current collector therefore it have a significant influence on the electrode performance in such away it also enhanced the performance of the battery such as energy density, safety and stability (Lee & Oh, 2013; Rao et al., 2012). Therefore, the poly (vinylidenefluoride), PVdF is mostly used as the binder for the fabrication of electrode due to its good electrochemical stability (Fu et al., 2014,; Xu et al., 2013; Mancini et al., 2012; Kitamur et al., 2012; Choi et al., 2002).

Unfortunately, Lee et al stated that the cell performance might be affected by the slurry preparation during the mixing sequence for the solid mixture of electrode material and conductive agent is dispersed in a solution of polymeric binder or solvent. In order to allow the conductive agent to disperse homogeneously into other substance such as binder, therefore the n-methyl-2-pyrrolidone (NMP) is use as a dispersing agent (Bauer & Nötzel, 2013). According to Lee et al. (2010), Bitsch et al. (2014) and Bauer et al. (2013) reported that to consist a better cycle performance for observation, the slurry is prepared by adding the solution which known as dispersing agent in first followed by the binders in sequence into the premixed solid ingredients which are electrode material and carbon additive as compared to that prepared by adding the solution at once.
Binders such as styrene-butadiene rubber (SBR), sodium carboxymethyl cellulose (NaCMC) and combinations of both were studied with silicon and have proved in improving the capacity retention.(Courtel et al.,2011)

Carboxyl Methyl Cellulose (CMC)
CMC is important industry polymers which have a wide range of application in drug reduction, detergent, food production and oil well drilling operation (Biswal & Singal, 2004). CMC is a derivative of cellulose that is colourless, odourless. Among all the polysaccharides, CMC is a non-toxic and easily available which can obtained naturally from surrounding exhibiting environmental friendly and widely present in the wood and others plant therefore CMC is very cheap (Samsudin et al., 2012; Nadzri et al.,2011;Wang et al. ,2009). The CMC will become water soluble due to chemical reaction of its hydroxyl group with hydrophilic side chain then it has a number of sodium carboxyl methyl groups (CH2COONa) (Huang et al., 2003). Figure 2.1 show the structure of the CMC. As the CMC shows promising potential to react as polymer host in proton conducting electrolytes thus it can be a good film forming property with high mechanical strength and can be a transparent film (Chai et al., 2013; Ahmad & Isa., 2012; Nadzri et al., 2011;Kim et al.,2011; Courtel et al.,2011;Wang et al., 2009).

Figure 1: Structure of CMC

Energy Density
Role of a binder is the improvement the energy density of battery during the preparation of the electrode. Also the binder required a large repeated dimensional change of the electrode during the cycling of the cell. An active material was mix with the small amount of binder to improve the energy density of the negative electrode for the Li-ion batteries (Buqa et al., 2006).

Energy density also knows as mass density which can be defined as the nominal battery energy per unit volume, sometimes referred as the volumetric energy density. Usually it measure how much of the energy of the battery contain in its weight or volume (MIT Electric Vehicle Team, 2008 & Simpson, 2011). According to Braun, 2012 stated that the energy density was the product of battery voltage and its capacity.

The Open-Circuit Voltage (OCV)

According to Snihir et al. (2006), OCV of the cell or battery is defined as the equilibrium state of voltage of the cell when there are no current flow in or out from the battery/cell. The open-circuit voltage (OCV) of the battery is important characteristic parameters that refer to the battery’s inertial status and plays a role in many portions of battery technology, such as electrode material mechanism analysis, battery performance or the estimation state and working process management. Additionally, the OCV is used as an important judge basis for cell balancing strategy technology. Thus, an accurate determination of the OCV is requested to enable management of the battery in its optimal state.

Figure 2: Open Circuit Voltage for Proton Battery during 24 Hour

Shukur et al, (2013) has study on the proton conducting electrolyte based on plasticized chitosan-PEO blend and application in electrochemical devices. In their work, the average potential of the cells found were almost constant at (1.66 ± 0.02) V. From the study, they suggested the electrochemical reactions that probably took place at the anode: Zn Zn2+ + 2e- ; Eo = 0.76 whereas the reaction that formed at cathode: MnO2 + 2e- + 4H+ Mn2+ + 2H2O; Eo = 1.22 V and the overall reaction: Zn + MnO2 + 4H+ Zn2+ +Mn2+ +2H2O and the overall energy, Eo= 1:9

Power Density
Power density is a measure of the rate at which energy can be inserted into or extracted from a cell. There are a relationship between power density and energy density. The unit for power density is Watt/kg where unit for energy density is (Watt x hour)/kg. From here can clearer see that the different between them are the time.

The conducting agent likes acetylene black would affect the energy density and the power density of the cell. Nagata & Chikusa (2014) stated that the thickness of the positive side’s electrode will affected the power density of the cell, beside that authors also stated that the surface area of the conducting agent have a great influence on the cell performance.

DISCUSSION
According to the previous, to improve the efficiency of the battery such as Li-ion ,Zn-air; there are several methods can be taken such as adding the binder and active materials or by mixing both of the materials during the preparation of electrodes. Besides that the thickness of the negative electrodes will affect the performance of the batteries where resulting in different charge –discharge curves, capacities per unit volume and cyclic performance (Nakazawa et al., 2007). In addition, the researchers also try to figure out some new materials like CMC to substitute the PvdF and NMP here both of this material are toxic compare to CMC. Other that this, improve of batteries efficiency can be happen after adding plasticizer into the electrolyte where can improve the ionic conductivity of the electrolyte (Shukur et al., 2013).However, the performance of the batteries might be affected by the temperature.

CONCLUSION
Rechargeable batteries are widely used .Several methods were used to improve the performance of the batteries as well as improve the materials to a “green “materials which bring less effect to our health and environment.

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