Chapter 2

Review of Related Literature and Studies

A. Related Literature

In order to protect the grain of rice during its growing season, the coat around the grain called

rice husk or rice hull is formed out of hard materials including silica and lignin. Chemically, rice

husk possesses 86.94% silicon dioxide, 0.2% aluminum oxide, 0.1% iron oxide, 0.3 – 2.25%

calcium oxide, 0.2 – 0.6% magnesium oxide, 0.1 -0.8% sodium oxide, and 2.15 – 2.30%

potassium oxide.[1] On a dry basis, rice husk is proximately composed of 15% fixed carbon,

67% volatile matter, and 18% ash. Out of proximate analysis, the compounds were partitioned

based on the chemical properties into six categories such as moisture, ash, crude protein, crude

lipid, crude fiber, and nitrogen-free extracts (digestible carbohydrates). Using the ultimate

analysis, the verified composition of rice husk is 40% carbon, 5% hydrogen, 34.8% oxygen,

0.1% sulfur, 19.5% ash, and high heating value (HHV) of 14.8 MJ/kg. The main component of

the ash is silicon oxide with trace amounts of Al2O3, Fe2O3, CaO, MgO, K2O, and Na2O. Both

physical and chemical properties of rice husk ash are contingent on the components of the

combustion process, such as combustion type, feeding type, temperature, residence time, and

availability of oxygen (aerobic or anaerobic).[2]

There are types of rice husk including silicon rice husk and carbonized rice husk. Silicon rice

husk came upon with regards to its process. During the life cycle, the rice plant absorbs silica in

the form of silicic acid from the soil, wherein this silica accumulates the cellulose micro

compartments round and naturally exists in the form of nano particles. Nano particles do not

permit microorganisms to enter the seed however, these particles allow air and other gases to go
in and come out. Thus, rice husk is a natural source of nano structured silica and also its

derivatives. Furthermore, silica nano particles can also be processed directly from rice husks.

Ultimately, silica obtained in this way is relatively pure and accounts for as much as 20% of the

dry weight of the Rice husk. [3]

On the other hand, the other type of rice husk called carbonized rice husk (CHR) is known

for being a good soil fertilizer and conditioner for the reason that it contains Phosphorous (P),

Potassium (K), Calcium (Ca), Magnesium (Mg), and micronutrients which is essential in

growing crops. CRH also nurture good bacteria and it serves as houses for microorganisms.[4]

CRH is produced out of the incomplete or partial burning or by thermal decomposition. Thermal

processes are necessary to apply for rice husk processing, which includes combustion,

gasification, and pyrolysis. After rice milling, rice husk is collected with regards to the required

moisture content of about 14–15% for further pretreatment or processing. Mechanical

pretreatment, pyrolysis, gasification, and the gas refinery is a combined system for processing

biomass and known as the newest technology for biofuel conversion from biomass which is also

has been observed in the UK recently. Pretreatment such as mechanical, physical, and chemical

means could be used to solve barriers to energy conversion from rice husk. Bioprocessing can

also use in pretreatment or the combination of these processes. Energy products that can produce

out of rice husk are heat, electricity, and biofuel (solid or liquid). In addition, heat generated from

this could be used for house heating and cooking, industrial boilers, drying, and even generating

electricity. [5]

Rice husk has a great impact on the society and environment due to its benefits. For instance,

its ash can be used in the cement and steel industries that help to minimize the need for importing

these materials. Another advantage of rice husk is that it contributes a great help to the society
and even in the environment as the source of energy. Basically, it produces electricity and aids to

dispose of agricultural waste and use it for a new one.[6] There are manifold benefits of rice husk

as a source of electricity. One of these is Husk Power comes from rice husk which is one of the

ways to avoid generating electricity from fossil fuels. The Husk Power System is also affordable

to those people in rural places and cost-effective which can provide reliable electricity in rural

population. For power transmission, bamboo posts can be utilized effectively as support for the

transmission of wires. Using rice husk to produce electricity is also a way to give opportunities

for employment since pre-experienced technicians can be trained locally to operate the plant

once units are set up. Project Implementing Agency (PIA) can partner with Clean Development

Mechanism (CDM) program so that Power Plant can sell carbon credits for the emission

decreased by the plants. Mini plant has a great impact in terms of electricity production. Each of

it with 32KW can serve 400-450 households using 4-5 nos. of 15W of CFL and also 8-10 small

business establishments. [7] In addition a steam which is a byproduct of power generation is used

for paddy drying applications, and as a result, it will also help to increase local incomes and to

reduce the need to import fossil fuels. [6] Carbonized Rice Husk (CRH), one of the types of rice

husk, also helps in farming wherein, it will allow the soil to preserve the moisture much longer.

CRH also produce tillers abundantly in rice grown fields and capable to bear more grains. [7]

However, according to DOST, the known environmental contaminants called carcinogenic dioxin

and furans, predominantly comes from burning of agricultural wastes. It is an uncontrolled open

burning and the highest source of carcinogenic dioxin and furans that are emitted during the

combustion process. In the same way, the post-harvest burning is a threat not just to the

environment but also to the health of the farmers. It is said that there are also records of various
cases of road accidents because of the smoke from burning rice straw alongside the roads which

caused poor visibility to people. [8]

Supercapacitors, also referred to as double-layer capacitors or ultracapacitors, are

electronic devices used for storing electrical charge of large amounts. It is designed with

combined properties of battery and capacitor in one device. Supercapacitor can store greater

power density (10 3 e 10 6 W kg À 1) and lower energy density (1 e 10 W h kg À 1) than

batteries. [9]

There are three types of supercapacitors namely electric double-layer capacitors (ELDC),

pseudocapacitors, and hybrid capacitors. The EDLC is composed of graphene, carbon nanotubes

(CNT), carbide-derived carbon (CDC), activated carbons, and carbon aerogels. It is composed of

carbon materials because these materials have been tested and found suitable for energy storage

systems that are better resources to develop supercapacitors. Another type of supercapacitor,

pseudocapacitors have chemical reaction at the electrode which store energy by capacitive

charging of double layers of electrode and by Faradaic reactions where energy is stored

electrochemically. The third type of supercacitor is the hybrid capacitor. Hybrid capacitors are

made by combining the properties of EDLC with pseudocapacitors that lessen the disadvantages

made when the two are not joint. It can deliver about 4 Wh/kg energy density. [10]

Having an excellent charge-discharge cycle service, supercapacitors are being used in

many applications. Peak output assist, auxiliary backup power supply, battery load reduction, and

storage element are some. Supercapacitors are used to supplement the supply of electricity in

situations where a momentary burst of energy is needed. It can also be used to backup power
source when main power is interrupted and in cases where battery voltage becomes unstable.

[11]

B. Related Studies

Rice rusk as precursors to produce activated carbon, used as catalyst carriers, adsorbent to

adsorb metal ions and organic molecules. A low cost, high specific surface area activated carbon

with microporous and mesoporous ranges using rice husk as the raw material. Examined the

activation of temperature in a specific surface area, pore structure, morphology and thermal

stability of the activated carbon samples have been examined. The activated carbons were

prepared through the following procedure of removal of dirt and other contaminants, oven-

drying with a specific temperature, ground and sieved. Carbonized under nitrogen flow then it

was impregnated with NaOH and dried again. Heated under a nitrogen atmosphere at a specific

flow rate, raised to a predetermined temperature at a heating rate. Finally, the activated product

was grounded and neutralized by an HCI solution and washed several times with hot distilled

water at a constant ph then dried under vacuum and stored in the desiccator. The AC was

characterized and evaluated for potential application as supercapacitor electrode material. Thus,

improved gravimetric of AC when using as an active material in the supercapacitor, from the

high activation temperature resulted in a high specific area, high mesopore contribution and high

total basic group. [12]

Nanoporous activated carbon derived from rice husk for high performance capacitor.

RH's in electrochemical energy storage, having the major contents of cellulose, hemicelluloses,

lignin, inorganic silica and carbon element. The chemicals are of analytical reagent without
further purification, washed thoroughly with distilled water and boiled with HCl solution for 2

hours for the termination of metallic oxide within the sample. Hydrochloric acid treated rice

husks were annealed in a tube furnace at 550 degrees Celsius for 4 hours under N2. The product

was washed with water for repetitions and then dried at 100°C. Without KOH activation during

the heating process, activation of carbon was done. Precarbonized rice husk have been activated

it with KOH. Nanoporous carbon was produced from rice husk by carbonizing, followed by

alkali hydroxide activation. The nanoporous carbon has an average pore size of 2.2 nm. Excellent

rate performance when density increased to 20 times. The nanoporous carbon electrode from

RHs exhibits good long-term cycle life and the capacitance remains more than 90% after 10,000

cycles as it suggests as promising application as SC electrode. Samples were characterized by

SEM, X-ray diffraction. Brunnauer Emmet- Teller (BET) was used to measure the specific

surface area of the sample, it is a method with an automated chemisorptions/physisorption

surface area analyzer at 77K. The amount of nitrogen adsorbed at a relative pressure around 0.97

was used in order to obtain the single point total pore volume. The Density functional theory

(DFT) method was used to determine the size distribution from the adsorption branches of the

isotherms and lastly FT-IR spectrum. [13]

Direct carbonization of rice husk to prepare porous carbon for supercapacitor

applications. Rice husk based carbon was the product of direct carbonization method, is of low

cost due to the absence of activation, RHPC with higher specific surface area was prepared from

RHC by removing SiO2. RHPC exhibits high specific capacitance and good rate capability.

Thorough in a tube furnace without the inlet of N2, the RHC possesses specific capacitance,

specific surface area and possesses relatively high pore volume. Self- activation of rice husk is

by H2O, carbonization process produced CO2. Rice Husk carbon was further treated b alkali
etching to prepare a porous carbon. Due to the removal of SiO2 RHC, RHPC exhibits higher

specific surface area and specific capacitance than RHC.[14]

Rice Brans are carbonized in N2 atmosphere at 3 degrees Celsius min-1 up to 850

degrees Celsius for 1 hour. The product was grounded to powder, washed with 1 M HCl solution

and distilled water. Finally, the products were dried at 120º for 12. Synthesized honeycomb-like

3D porous carbon structure synthesis possess intrinsic natural pore channels framework structure

provides interconnected ion channels facilitate contact between ion and material that is

attributable to good intrinsic electronic conductivity properties of material. Also fast ion channels

and short diffusion distance to facilitate ion transport or decreasing the electric resistance. The

RBC-4 with an ultrahigh specific surface area with well-balanced mesoporosity and optimized

controlled DSP which can provide rich sites for adsorbing ions, resulting in large capacitance.

The RBC-4 was used for supercapacitor electrode material, and a stable cycle life over 10,000

cycle. Potassium (KOH) and hydrochloric acid (HCI) are used for analytical grade.[15]

The application of high surface area activated carbon obtained from rice husks as a

supercapacitor electrode. The AC was free from Lewis acid sites, making the electrical double

layer capacitance as the main charge storage mechanism. With cylic voltammetry, galvanostatic,

charge-discharge and electrochemical impedance spectroscopy the three sample of AC with

different surface areas were studied electrochemically. All of the AC samples exhibited good

electrochemical performance comparing to supercapacitor electrode. The maximum specific

capacitance of 147 F g-1 was obtained by the AC sample with the surface area of 2696 m2 g-1

which was prepared at an activation temperature of 850ºC. Low resistivity of AC sample and the

fast frequency response of the supercapacitor electrode was revealed by the detailed impedance

studies. [16]
 An investigation to ameliorate the performance of supercapacitors cells accompanied by

nanocomposite electrodes was made. The electrodes were composed of activated carbon (AC),

four types of multi-wall nanotubes (MWNTs) and pair alternative polymer binders, Polyvinyl

alcohol (PVA) or Polyvinylidene fluoride (PVDF). The concoction of electrode involves stages

of mixing and distribution of AC powder, carbon nanotubes and coatings which requires for the

present of aluminum substrate that serve as a current collector. Electrochemical double layer

capacitor (EDLC) types were utilized among all devices which incorporates four layers of tissue

paper as separator. After the formation of the electrode structure, a multi-channel

potentiostat/galvanostat/impedance analyser were used to evaluate the cell performance. The

supercapacitor cell undergo Cyclic Voltammetry (CV) at different scan rates from 0.01 V/s to 1

V/s, Charge-Discharge at a constant current steps (2 mA) and Electrochemical Impedance

Spectroscopy (EIS) with frequency range from 10 MHz to 1 MHz. AC-based supercapacitor is

accustomed with 0.15%w/w MWNT content and 30 μm roll coated, nanocomposite electrodes

which yield superior energy and power and energy densities while the cells was submerge in the

electrolyte.[17]

Direct carbonization method was used to prepare rice husk-based carbon (RHC). The RHC

was prepared through direct combustion of rice husk in a funnel furnace without the inlet of

nitrogen gas. RHC have the capability of relatively high pore volume, specific surface area and

capacitance. RHC’s high specific surface area was due to the self activation of rice husk by

water, carbon dioxide produced in the method. The rice husk-derived carbon was facilitated with

alkali etching in order to assemble a porous carbon which was referred to as RHPC. RHPC

produced more high specific surface area and specif capicitance than RHC. [18]
 C. Synthesis

Using the fluidized bed reactor, activated carbons from rice husk were prepared and

carbonized. Different activating agents were used to achieve the BET surface area of the samples

ranging from 540 to 3060 m2/g. Sodium or potassium carbonates were utilized for the results in

the BET surface area as far as 1400 m2/g. Samples with higher BET surface area (up to 3060

m2/g), was produced by sodium or potassium hydroxides. Carbons textural peculiarities were

studied through the result of adsorption of nitrogen at 77 K and of carbon dioxide at 273 K.

Utilized as the electrolyte with the use of home-made three-electrode electrochemical glass cell,

the cyclic voltammetry and chronopotentiometry in galvanostatic mode in 1 M H2SO4 were

used to examine the porous carbon samples as active materials for supercapacitors. With regards

to the samples with the highest surface area, the carbons gravimetric capacitance is linearly

proportional to the BET surface area wherein, at discharge current density of 0.2 and 1 A/g, it

reaches 230 and 196 F/g.[19]

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