Scientific & Technological Perspective: Future of Energy Storage With

Graphene Oxide (GO)

Paper Presentation By

Radhey Shyam Meena

InInternational Conference On

Advanced in Power Generation From Renewable Energy Sources

APGRES 2015, June 15-16, 2015Rajasthan Technical University Kota

Inside the Presentation

Application of Graphene Oxide

Meaning of Energy Storage & Its Technology

Advances in Synthesis of Graphene Oxide

Future Outlook & Conclusion

Reference

Graphite, Graphite Oxide, Graphene Oxide

Why We Present....Beauty of GO

Graphite

• Graphite is a crystalline form of carbon, a semimetal, a native element mineral, and one of the allotropes of carbon along with diamond. Graphite is the most stable form of carbon under standard conditions.

• Graphite may be considered the highest grade of coal,it is difficult to ignite.

• Graphite has a layered, planar structure. In each layer, the carbon atoms are arranged in a honeycomb lattice with separation of 0.142 nm, and the distance between planes is 0.335 nm

• Graphite occurs in metamorphic rocks as a result of the reduction of sedimentary carbon compounds during metamorphism. It also occurs in igneous rocks and in meteorites.

• Minerals associated with graphite include quartz, calcite, micas and tourmaline.

Applications of Natural & Synthetic Graphite

• Refractories• Batteries• Steelmaking• Lubricants• Brake lining• Foundry Facings• Others

• Scientific Research• Electrodes• Powder and Scrap• Neutron Moderator• Carbon Fiber Reinforced

Plastics• Radar Absorbent Materials

Graphite oxide

• Graphite oxide, an oxidized form of graphite was first discovered by Benjamin in 1859.

Graphene Oxide • Graphite oxide consists of several stacked Graphene layers that have been decorated with oxygen containing functional groups, such as hydroxy, epoxy, and carboxylic acids.

• Complete exfoliation of graphite oxide gives rise to Graphene oxide (GO), which is a single Graphene sheet factionalized with oxygen containing functional groups.

• Graphene is a 2D “ flat-mat ” consisting of a honeycomb-like structure of carbon atoms with sp2 bonding character for each carbon.

• It exhibits excellent electrical conductivity and mechanical strength, and can be synthesized in a number of ways.

Advances in Synthesis of Graphene Oxide

• Modified Hummers’ Method

• Tour’s Method

Hummer's Method

• A water free mixture of concentrated sulfuric acid (H2SO4), sodium nitrate (NaNO3), and potassium permanganate(KMnO4) was prepared and maintained below 45 °C to oxidize graphite for 2 h.

• A mixture of concentrated H2SO4 , K2S2O8 , and P2O5 at 80 °C for several hours. The pretreated mixture was diluted, filtered, washed, and dried after which oxidation using Hummers’ method was applied.

• The degree of oxidation and overall yield of GO has been extensively improved by this method in comparison to other method

Schematic diagram of the modified Hummers’ method for GO preparation

Tour’s Method

• To improve the modified Hummers’ method in the overall degree of GO oxidation as well as minimize the generation of hazardous gases. (NO2 , N2O4 , or ClO2)

• Replacement of sodium nitrate (NaNO3) with an increased amount of potassium permanganate for the oxidation reaction.

• In addition, phosphoric acid in a 9:1 mixture of H2SO4 /H3PO4 was introduced into the reaction flask.

A comparison of procedures and yield of the starting material left over after oxidation using different approaches.

Two chemical oxidation techniques have been used to convert graphite into GO:

• (i) potassium chlorate with conc. nitric acid and

• (ii) potassium permanganate with conc. sulfuric acid and optionally phosphoric acid.

• most commonly used oxidation agents are KMnO4 and H2SO4 . The reactivity of MnO4

− can only be activated in acidic solution, and is described using the following equations

Currently, graphene is one of the hottest materials and it can be applied for various energy storage and sensors devices.preparation methods available for graphene

• Micromechanical exfoliation,• Chemical vapor deposition, • epitaxial growth, • arc discharge method,• intercalation methods in

graphite, • unzipping of CNTs• electrochemical and

chemical method.

• Each method have its own advantageous and

disadvantages. Among all of these methods, chemical method is the efficient and profitable method for the production of bulk quantity of graphene towards

applications in electrochemical sensors and energy storage devices. and environmentally friendly.

Meaning of Energy Storage & Its Technology

• Energy storage is accomplished by devices or physical media that store energy to perform useful processes at a later time.

• Energy storage involves converting energy from forms that are difficult to store (electricity, kinetic energy, etc.) to more conveniently or economically storable forms. (A windup clock stores potential energy, rechargeable battery,hydroelectric dam, etc.)

• Storing energy allows humans to balance the supply and demand of energy. Energy storage systems in commercial use today can be broadly categorized as mechanical, electrical, chemical, biological and thermal.

Storage Methods

• Mechanical storage• Hydroelectricity• Thermal storage• Electrochemical

• Rechargeable battery- (lead –acid, nickel cadmium

(NiCd), nickel metal hydride (NiMH),

lithiumion (Liion), and lithium ion polymer.)

• Flow battery• Supercapacitors• UltraBattery

Electrical methods

• Capacitor• Electromagnetic storage

Applications

• Applications of GO/RGO in Energy Storage

High surface area, good electrical conductivity andlarge-scale processability, RGO has been widelyused as electrode materials in supercapacitorsand lithium-ion batteries.

Improved batteries with faster charge rates and greater capacity

GO/RGOs as Supercapacitors and/orUltracapacitors

• Supercapacitors are devices that are capable of storing energy and releasing it within a short time interval with a high power capability and large current density. They also present a high charge propagation, small size and ultra-long cycling life.

• Therefore, it has been proven that supercapacitors can act as perfect complements for batteries, and their joined performances are considered to be promising power supplies for many applications such as ecofriendly automobiles, artificial organs, portable electronics, etc.

• Electrochemical Double-Layer Capacitors (EDLC), pseudo-capacitors

• high surface area, good electrical conductivity, and large electrode porosity for high ion diffusion.

• GO not only acts as a separator, but also functions as an electrolyte, which allows the devices to function as a supercapacitor without adding any external electrolytes.

GO/RGO Application in Lithium Ion Batteries

• The most widely used electrode materials in LIBs are lithium cobalt oxide (LiCoO2) and graphite.

• The role of RGOs in LIB is usually as a supporting matrix for the active anode and/or cathode materials, and may sometimes contain engineered nanostructures to facilitate lithium ion diffusion and prevent volume expansion

Different structure of RGOs in LIB anode materials

Water Purification

• Around 1.1 billion people all over the world lack access to clean water and about 1.6 million people die every year because of diseases caused by polluted water

• coating of GO onto coarse sand surfaces followed by 150 ° C annealing resulted in a “super sand” material that can adsorb mercuric ions and rhodamine B dyes from contaminated water more effi ciently than the pristine sand

• GO can remove radionuclides from water

Biological Applications of GO

• GO in pristine form can form highly stable suspensions in water. Various functional groups on its surface enable its modifi cation to make it soluble in other biological systems too.

• GO-based drug delivery and bio-imaging systems.

• Multimodality contrast enhancement in photoluminescence imaging and MRI has been reported using fl uorinated GO.

• Use of GO functionalized with iron oxide nanoparticles for in vivo imaging and photothermal therapy for cancer treatment has been also demonstrated

Beauty Of GO• Graphene transistors could

make smaller, faster electronic chips.

• Graphene sheet is a million times thinner than a human hair.

• Graphene is 200 times more resistant to breakage than steel.

• In a computer, the hottest spots – microprocessors for the most – reach temperatures that range between 55 and 115°C (160 to 240 ° F). By applying a layer of graphene

• Carrier mobility was roughly 30 times greater than that of

conventional zinc oxidebased contact layers.

• Used in photovoltaic cells, electric vehicle batteries, and data centers processors.

• Graphene is more conductive than copper, perfectly transparent, and totally flexible.

• Generates 30 times more power per volume unit than the thinnest solar cells known (made either of gallium arsenide, silicon, or indium selenide) which are one micron thick, and whose performance near 30 %.

• Graphene and molybdenum layers disulfide performance could theoretically reach 10%.

• capable of conferring considerable strength to ordinary materials

• Possible to charge a smartphone in less than ten minutes.

• A graphene battery powering an electric car. boasts performance which is incommensurate with the most efficient lithiumion battery: it is 100 to 1000 times more powerful and three to four times denser.

• Future electric vehicles equipped with ultrareliable capacitors instead of expensive and heavy batteries.

Future Outlook & Conclusion

• It is a material that offers flexibility and tunability for a wide range of applications and more importantly, its synthesis can be easily scaled up to industrial scales.

• Advances in research have also been devoted to characterizing the nature and role of different functional groups attached to GO and how their density, functionality, and position (on the edge or basal plane) affect the intrinsic optical, electronic/ionic, and chemical properties.

• Chemists are going to play a key role in developing more refi ned synthesis techniques that will allow for tuning the band structure of GO for desired applications in flexible optoelectronics, energy storage, and bio-sensing.

REFERENCES

• Daniela C. Marcano, Dmitry V. Kosynkin, Jacob M. Berlin, Alexander Sinitskii, Zhengzong Sun, Alexander Slesarev, Lawrence B. Alemany, Wei Lu, and James M. Tour. Improved Synthesis of Graphene Oxide. ACS Nano 2010 4 (8), 4806-4814

• Cote, L. J., Cruz-Silva, R. & Huang, J. Flash reduction and patterning of graphite oxide and its polymer composite. J. Am. Chem. Soc. 131, 11027–11032 (2009).

• El-Kady, MF. et al. Scalable fabrication of high-power graphene micro-supercapacitors for flexible and on-chip energy storage. Nat. Commun. 4:1475 doi: 10.1038/ncomms2446 (2013).

• William S. Hummers Jr. and Richard E. Offeman. Preparation of Graphitic Oxide. Journal of the American Chemical Society 1958 80 (6), 1339-1339 DOI: 10.1021/ja01539a017

• [14] The royal socity of chemistry and Dept. Of elctrochemistry webpage from iits.• [16]A. Nourai, R. Sastry, and T. Walker, “A vision & strategy for deployment of energy

storage in electric utilities, ” in Proc. IEEE Power Energy Soc. Gen. Meet., Minneapolis, MN, Jul. 2010.

• [17] L. Guo, Y. Zhang, and C. S. Wang, “A new battery energy storage system control method based on SOC and variable filter time constant, ” in Innovative Smart Grid Technologies (ISGT), 2012 IEEE PES, Jan. 2012, pp. 1 –7.

Thanks to all......Special Thanks goes to

(APGRES-15,Coordinator, RTU-K) &

(EED, SBCET-J), Tagore Group Kcity

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