Description:FORM 2
THE PATENTS ACT, 1970
(39 of 1970)
&
The Patent Rules, 2003
COMPLETE SPECIFICATION
(See sections 10 & rule 13)
1. TITLE OF THE INVENTION
A PROCESS OF PREPARING PURE PHASE HIGH PERFORMANCE ANODE MATERIAL FROM SUGARCANE BAGASSE AND TUNING THE INTERPLANAR SPACING OF BIOMASS DERIVED HARD CARBON FOR Na-ION BATTERY APPLICATIONS
2. APPLICANT (S)
NAME NATIONALITY ADDRESS
INDIGENOUS ENERGY STORAGE TECHNOLOGIES PVT. LTD. IN I-10, 2nd Floor, Tides Business Incubator, IIT Roorkee, Roorkee-247667, Uttarakhand, India.
3. PREAMBLE TO THE DESCRIPTION
COMPLETE SPECIFICATION

The following specification particularly describes the invention and the manner in which it is to be performed.

FIELD OF INVENTION:
[001] The present invention relates to the field of metal ion battery. The present invention in particular relates to a process of preparing pure phase high performance anode material from sugarcane bagasse for rechargeable metal-ion batteries and tuning the interplanar spacing of biomass derived hard carbon.
DESCRIPTION OF THE RELATED ART:
[002] Sugarcane bagasse is one of the most abundant agricultural waste produced globally. The sugarcane byproduct bagasse estimated nearly 75 – 90 million tons per year in India. The major challenge is to dispose this huge amount of agriculture waste. However, the waste biomass contains fiber, pentosans, pitch and lignin could be converted into some valuable products in the field of biofuels, pulp and paper, biochemical and energy storage. All these areas require different kind of high purity carbon used for different purposes. Energy storage systems, being one of the most emerging field in the present scenario of emission free transportation, require graphite, soft carbon and hard carbon for one of its main components. From their commercialization in 90’s Li-ion batteries become the main energy storage system used for diverse applications such as portable electronics, small and large appliances, power tools and electrical storage systems. Considering the high price and low lithium reserves Li-ion batteries needs to be replaced with cheaper and more earth abundant energy storage system.
[003] Sodium shows similar properties with lithium and best suited to be use in place of lithium due to its resourceful abundance and low cost. Graphite is commonly used anode material in Li-ion batteries. Unfortunately, sodium could not be inserted into the graphite layers having larger size than lithium ions. Therefore, other anode materials need to search for sodium ion batteries. Thanks to the disordered and amorphous nature of hard carbon suitable for Na-ion insertion. Hard carbon is non graphitizable and disordered carbonaceous material adopted house of card structure model to store the sodium ions. The storage mechanism for hard carbon materials is different form the graphite as it mainly stores the sodium ion through four type mechanisms, first is intercalation filling, second is adsorption ? intercalation and third is adsorption filling and fourth is three stage model. The advantage of low cost precursors, low voltage plateaus and high capacity (>300 mAh g-1) of hard carbon giving edge to other material to be used as anode material for sodium ion batteries. Hard carbon can be prepared from a number of agriculture based bio-waste precursors such as rice straw, coconut shells, canola crop, jut fiber, peanut shells, cotton stalk, rice husk, sugarcane bagasse, banana peel, apple peel, and mango peel. Out of many available agricultures based bio-waste precursors sugarcane bagasse produced ~ 300 MT globally annually. India followed by brazil in sugarcane bagasse production with ~ 75 ? 90 MT annually. Reasonably, Sugarcane bagasse could be used as a potential precursor for developing hard carbon anode materials for safe, environmental benign and long life sodium ion batteries. Unluckily, low initial coulombic efficiency and poor cycling during charging and discharging leads to a significant reduction of energy density for SIBs.
[004] A substantial work has been done to improve the electrochemical performance of hard carbon to meet the standard require for practical application.
[005] Reference may be made to the following:
[006] IN Publication No. 201921007799 relates to the method formation of a Solid Electrolyte Interface Layer (SEI) on the surface of the anode electrode to prevent the irreversible loss of the capacity of the counter electrode. It basically includes designing sodium-ion battery; a positive electrode, cathode, which is comprising of a NASICON family member (Na3V2(PO4)3, in short NVP) and a negative electrode anode (Hard carbon).
[007] The present invention is a process of preparing high performance anode material from sugarcane bagasse via tuning its interplanar spacing for rechargeable metal-ion batteries.
[008] IN Publication No. 202111001722 relates to the synthesis of Rice Straw derived pure-phase high performance anode material (hard carbon) for Sodium-ion batteries (SIBs). Rice Straw derived pure-phase hard carbon material has been synthesized as a high performance anode material for Sodium-ion batteries (SIBs). In this invention (Claim 1 step d & step f) the grinded material is first socked in HCl and then HF. These two steps cannot be reversed as it affects the pure phase formation as well as the energy storage performance of the synthesized final hard carbon. Just after these two steps, the acid treated vacuum dried biomass material is pyrolyzed at high temperature.
[009] In the present invention, unlike the above invention related to rice straw, the dried sugarcane bagasse was first converted into biochar following step heating in the inert environment at the temperature in the range from 250 to 750°C (Claim 1 step d). After that this biochar material is first socked in HF (step 1) and then HCl (step 2) at 20 to 100°C for 1h to 48h. Unlike the above invention related to rice straw, these two steps are reversible and do not affect the pure phase formation as well as the energy storage performance of the synthesized final hard carbon material. After these two steps, the acid treated vacuum dried prepared biochar material is pyrolyzed at high temperature.
[010] Unlike the case of previous invention related to rice straw derived hard carbon, in the present invention pure phase of sugarcane bagasse derived hard carbon can be achieved just after HF treatment but the high performance is obtained only after including the step of HCl treatment. In the present invention, in comparison to the individual HCl and HF treatments of the biochar, for the same concentrations of these acids, best performance of the sugarcane bagasse derived hard carbon is achieved when both the HCl and HF treatments of the biochar are performed one after another. Here, HCl plays important role in improving the interplanar spacing and hence the energy storage performance of the biomass derived hard carbon.
[011] IN Publication No. 202327000612 relates to a serviceable energy storage device, such as a capacitor, ultra capacitor or super capacitor, includes electrodes made from activated carbon produced from a low-cost source, such as thermal coal or another low-cost feedstock. This invention is related to the development of a serviceable energy storage device, such as a capacitor, ultra capacitor, or super capacitor, includes electrodes made from activated carbon produced from a low-cost source, such as thermal coal or another low-cost feedstock. The activated carbon is manufactured with a pore sizing selected in accordance with the electrolyte such that an electrode material pore configuration matches an ion coupling size of the electrolyte.
[012] Present invention is related to the process of preparing high performance anode material (hard carbon) from sugarcane bagasse for rechargeable metal-ion batteries.
[013] Publication No. CN107887638 relates to a sodium ion total battery with super long cycle life and excellent low temperature performance. The invention discloses the preparation of a sodium ion battery designed using Se/G as a negative electrode and Na3V2(PO4)2O2F as a positive electrode. According to claim this battery showed long cycle life and excellent low temperature performance. Here, the negative electrode material Se/G was prepared by dispersing the commercial selenium powder in 2-6 mg mL-1 graphene oxide solution according to the mass ratio of 1-10:1, disperse evenly, and freeze-dry for 10-60 h to obtain a mixed material of selenium and graphene oxide, heat up to 400-600 ?, and calcined for 2-10 h.
[014] The present invention is totally different from this and related to the process of preparing high performance negative electrode (anode) material/ hard carbon from sugarcane bagasse for rechargeable metal-ion batteries. The Hard carbon material is quite different from the electrode material Se/G.
[015] Publication No. CN107240715 relates to a simple negative electrode handling method for improving the voltage and efficiency of a sodium ion total battery and a product, and belongs to the technical field of sodium ion batteries. The invention disclosed a simple negative (anode) electrode handling method for improving the voltage and efficiency of a sodium ion total battery and belongs to the technical field of sodium ion batteries. Here a negative electrode sheet was prepared by mixing the negative electrode material, conductive agent, and adhesive to the solvent. The obtained black viscous negative electrode slurry was applied on the current collector, and after drying the negative plate/electrode was obtained. After this the prepared negative electrode sheet was pre-sodiumized by contact method to increase the voltage and efficiency of a sodium ion full battery. In this process first the prepared negative electrode sheet was put into a suitable container under an inert gas environment, add an appropriate amount of electrolyte in the container, press the metal sodium sheet on the negative electrode sheet, apply a pressure of 25 kg/cm2~50 kg/cm2, and press it Stand still for 5-30 minutes under an inert gas environment, and remove the negative electrode sheet after the pre-sodiumization is completed, and we get the pre-sodiumized negative electrode sheet.
[016] Present invention is related to the process of preparing high performance negative electrode (anode) material/ hard carbon from sugarcane bagasse for rechargeable metal-ion batteries.
[017] Publication No. US2003135989 relates to a method to reduce the initial irreversible capacity in an alkali metal-based electrochemical cell, and thus the necessity for the presence of additional alkali metal source material in the cell comprising one or more preliminary reactions performed by either electrochemical or chemical means. The invention discloses a method to reduce the initial irreversible capacity in an alkali metal-based electrochemical cell, and thus the requirement of an additional alkali metal source material in the cell comprising one or more preliminary reactions performed by either electrochemical or chemical means. This invention claimed that the properties of such alkali metal battery negative electrodes can be substantially improved by performing one or more preliminary reactions, i.e. pre-treatment(s), or initial charging-discharging cycle or cycles, of the negative electrode prior to the final assembly of the battery.
[018] The present invention is related to the process of preparing high performance negative electrode (anode) material/ hard carbon from sugarcane bagasse for rechargeable metal-ion batteries.
[019] Publication No. CN115020643 relates to a preparation method thereof and application of the biomass-based hard carbon in a sodium-ion battery. The method comprises the following steps: carrying out mechanical ball milling, vibration milling or swelling pretreatment on biomass, and then carbonizing and cracking the pretreated biomass material in an inert atmosphere to obtain the biomass-derived hard carbon with high percentage of closed area. The invention describes the use of biomasses such as bamboo, bagasse, wheat straw, wood, and derivatives thereof as raw materials for preparing hard carbon. The process of making hard carbon involves mechanical ball milling, vibration milling or swelling pretreatment on biomass, and then carbonizing and cracking the pretreated biomass material in an inert atmosphere to obtain the biomass-derived hard carbon.
[020] The present invention is used to prepare hard carbon from sugarcane bagasse for rechargeable metal-ion batteries does not involves mechanical ball milling, vibration milling etc.
[021] Publication No. CN109659144 relates to a method for preparing a high-voltage water system supercapacitor electrode material by using bagasse. A porous carbon material doped with multiple atoms is prepared by taking waste bagasse as a carbon source and ZnCl2 as an activating agent through a high-temperature carbonization one-step method. The invention discloses a method for preparing a high-voltage water system supercapacitor electrode material by using bagasse. A porous carbon material doped with multiple atoms is prepared by taking waste bagasse as a carbon source and ZnCl2 as an activating agent through a high-temperature (800 °C) carbonization one-step method. The obtained product was washed with 0.5 M HCl to remove Zn2+ and impurities, then washed with distilled water to pH = 7 and then vacuum dried at 100 °C. The prepared carbon material is used as an electrode material for designing a symmetrical supercapacitor, which can be operated at 1.8 V ultra-high voltage window at low current density in an aqueous electrolyte sodium sulfate (Na2SO4).
[022] The present invention is the process of preparing high performance negative electrode (anode) material/ hard carbon from sugarcane bagasse for rechargeable metal-ion batteries.
[023] Publication No. CN108059144 relates to hard carbon prepared from biomass waste bagasse as well as a preparation method of the harden carbon and an application of the harden carbon using as a negative electrode material of sodium ion batteries and potassium ion batteries. The invention discloses hard carbon prepared from biomass waste bagasse as well as a preparation method of the harden carbon and an application of the harden carbon using as a negative electrode material of sodium ion batteries and potassium ion batteries. For the preparation of biomass waste bagasse derived hard carbon material, first waste bagasse is ball milled to obtain bagasse powder with a particle size of less than 37 µm and then carbonize in steps in a tube furnace at 800-1600°C for 1-6 hours with heating rate of 1-10°C/min under an inert atmosphere.
[024] The present invention is related to the process of preparing high performance negative electrode (anode) material/ hard carbon from sugarcane bagasse for rechargeable metal-ion batteries. The invention describes the effect of acid treatment on the interplanar spacing of the synthesized hard carbon material and hence the Na+ storage performance of the material.
[025] Publication No. CN101767784 relates to the preparation method of sugarcane bagasse derived mesoporous carbon electrode material for an ionic liquid super capacitor. For the preparation of sugarcane bagasse derived mesoporous carbon electrode material, first waste bagasse is dried cut into fragments with a certain length then the bagasse fragments are soaked in the solution with 10-90wt percent of activating agent, which is one of zinc chloride, sodium hydroxide and phosphoric acid for 2-72 hours, and then filtration is carried out to obtain the wet bagasse. The wet bagasse is dried at 100 °C then arranged in a quartz tube and is activated by microwaves under N2 protection. The activated product is cooled, washed and dried to obtain the mesoporous carbon electrode material.
[026] The present invention is related to the process of preparing high performance negative electrode hard carbon material from sugarcane bagasse for rechargeable Na-ion batteries. The invention describes the effect of acid treatment on the interplanar spacing of the synthesized hard carbon material and hence the Na+ storage performance of the material.
[027] Publication No. CN110931781 relates to the preparation method of biomass carbon/sodium ferric fluorophosphate composite as a positive electrode material (cathode) for lithium-ion battery. For the preparation of biomass carbon/sodium ferric fluorophosphate composite, first biomass is soaked in a sodiumhydroxide solution with the mass percent concentration of 5%; preparing a carbon source, carrying out ball milling on ferrous oxalate, sodium fluoride, ammonium dihydrogen phosphate, sodium acetate and the carbon source in absolute ethyl alcohol by using a ball milling method to prepare rheological phase slurry, and calcining the rheological phase slurry by using an in-situ pyrolysis method to prepare the biomass carbon/sodium ferric fluorophosphate composite material. The obtained final composite material is used as a positive electrode material (cathode) for lithium-ion battery.
[028] The present invention is related to the process of preparing high performance hard carbon a negative electrode (anode) material from sugarcane bagasse for rechargeable Na-ion batteries. The invention describes the effect of acid treatment on the interplanar spacing of the synthesized hard carbon material and hence the Na+ storage performance of the material.
[029] Publication No. CN106629661 relates to a process for preparing carbon nanospheres from bagasse. The process comprises following steps; first sugarcane bagasse is put into a solvent, so that cellulose and hemicelluloses in the bagasse are dissolved in the solvent then solvent is filtered to obtain filter liquid which is fed into the hydrothermal reactor to perform hydrothermal reaction. Low molecular weight sugar in the bagasse is dissolved out then the obtained low molecular weight sugar solution is used for preparing carbon spheres by the hydrothermal method. The cheap raw material of the waste biomass is used as a carbon source for preparing the carbon spheres, so that the production cost of the carbon spheres is reduced and the effect of changing waste into resources is achieved.
[030] The present invention is related to the process of preparing high performance hard carbon a negative electrode (anode) material from sugarcane bagasse for rechargeable Na-ion batteries. The invention describes the effect of acid treatment on the interplanar spacing of the synthesized hard carbon material and hence the Na+ storage performance of the material.
[031] Publication No. CN112707386 relates to a preparation method of a waste biomass derived graphene material, which comprises the following steps of: washing biomass waste, drying the biomass waste for the first time, pulverizing the biomass waste, screening to obtain biomass waste powder, uniformly mixing the biomass waste powder with a catalyst solution, and drying for the second time to obtain a precursor mixture; carrying out low-temperature carbonization treatment on the obtained precursor mixture in an inert atmosphere; after low-temperature carbonization treatment, transferring the precursor mixture into a sintering furnace, and sintering the precursor mixture in an argon atmosphere or under a low-vacuum condition; and sequentially washing with an acidic solution and water to remove the catalyst, filtering, and drying to obtain the waste biomass derived graphene material. The invention discloses a preparation method of a waste biomass derived graphene material.
[032] The present invention is related to the process of preparing high performance hard carbon a negative electrode (anode) material from sugarcane bagasse for rechargeable Na-ion batteries.
[033] Publication No. CN104528720 relates to the preparation method of a multistage porous carbon material. In the preparation method a carbon source (biomass, monosaccharide, disaccharide or polysaccharide of which the cellulose content is more than 20%) is blended with an activators (anyone from ammonium oxalate, potassium oxalate, potassium hydrogen oxalate, potassium tetroxalate, sodium oxalate, sodium hydrogen oxalate, sodium tetroxalate, sodium hydrogen carbonate or potassium hydrogen carbonate) and performing two-step carbonization; a low-temperature carbonization (200-400 °C) and high-temperature carbonization (800-1200 °C). After treatment the obtain material is multistage porous carbon material rich in macropore.
[034] The present invention is related to the process of preparing high performance hard carbon a negative electrode (anode) material from sugarcane bagasse for rechargeable Na-ion batteries. The invention describes the effect of acid treatment on the interplanar spacing of the synthesized hard carbon material and hence the Na+ storage performance of the material.
[035] Publication No. CN114639809 relates discloses a composite hard carbon negative electrode material, a preparation method and application, and relates to the technical field of sodium ion batteries. For preparing the composite hard carbon negative electrode material, the biomass raw material is heated and calcined in a protective gas atmosphere cooled to room temperature naturally then mixed with the catalyst, heated and calcined under a protective gas atmosphere and cooled to room temperature naturally to obtain a catalytic pyrolysis product. The catalytic pyrolysis product is etched, cleaned and dried to obtain a purified composite hard carbon negative electrode material.
[036] The present invention the process of preparing high performance hard carbon a negative electrode (anode) material from sugarcane bagasse for rechargeable Na-ion batteries. The invention describes the effect of acid treatment on the interplanar spacing of the synthesized hard carbon material and hence the Na+ storage performance of the material.
[037] Reference may be made to an article entitled “Carbonaceous anodes derived from sugarcane bagasse for sodium-ion batteries” by Rath, Purna Chandra; Patra, Jagabandhu; Huang, Hao-Tzu; Bresser, Dominic; Wu, Tzi-Yi; Chang, Jeng-Kuei; ChemSusChem 12(10); March 2019 talks about the effects of pyrolysis temperature on the material characteristics and electrochemical properties of sugarcane bagasse derived hard carbon negative electrode material. For preparing the sugarcane bagasse derived hard carbon negative electrode material, the raw material (sugarcane bagasse-SB) was collected, cleaned with deionized water, and dried in an oven for three days. Afterward, the dried SB was ground and repeatedly washed with deionized water. After being dried at 110?°C for 12 h, the powder was treated at various pyrolysis temperatures (750, 850, 950, and 1050?°C) for 6 h under an argon atmosphere. A heating rate of 5?°C?min-1 was used. A-HC was synthesized in a similar manner for comparison.
[038] The present invention relates to the process of preparing high performance negative electrode hard carbon material from sugarcane bagasse for rechargeable Na-ion batteries. The invention describes the effect of acid treatment on the interplanar spacing of the synthesized hard carbon material and hence the Na+ storage performance of the material.
[039] Publication no. WO2022153326A1 talks about the synthesis of Rice Straw derived pure-phase high performance anode material (hard carbon) for Sodium-ion batteries (SIBs). In the above invention (Claim 1 step d & step f) the grinded material is first socked in HCl and then HF. These two steps cannot be reversed as it affects the pure phase formation as well as the energy storage performance of the synthesized final hard carbon. Just after these two steps, the acid treated vacuum dried biomass material is pyrolyzed at high temperature.
[040] In the present invention, unlike the above invention related to rice straw, the dried sugarcane bagasse was first converted into biochar following step heating in the inert environment at the temperature in the range from 250 to 750°C (Claim 1 step d). After that this biochar material is first socked in HF (step 1) and then HCl (step 2) at 20 to 100°C for 1h to 48h. Unlike the above invention related to rice straw, these two steps are reversible and do not affect the pure phase formation as well as the energy storage performance of the synthesized final hard carbon material. After these two steps, the acid treated vacuum dried prepared biochar material is pyrolyzed at high temperature.
[041] Unlike the case of previous invention related to rice straw derived hard carbon, in the present invention pure phase of sugarcane bagasse derived hard carbon can be achieved just after HF treatment but the high performance is obtained only after including the step of HCl treatment. In the present invention, in comparison to the individual HCl and HF treatments of the biochar, for the same concentrations of these acids, best performance of the sugarcane bagasse derived hard carbon is achieved when both the HCl and HF treatments of the biochar are performed one after another. Here, HCl plays important role in improving the interplanar spacing and hence the energy storage performance of the biomass derived hard carbon.
[042] Publication No. CN105762372A talk about the preparation of microbial fuel cell anode electrodes from agricultural wastes. This invention describes a process to synthesize porous carbon based microbial fuel cell anode electrodes from useless bean dregs/agricultural waste. The obtained bean dregs were carbonized at 400 °C and continues reaction 30 min at this temperature, and heating rate is 10 °C /min, and nitrogen flow rate controls for 600ml/min. The material after carbonization was soaked for 6h with dilute hydrochloric acid (5w%) and hydrofluoric acid (3w%), and wash extremely neutral each time. The obtained material moves to nickel with potassium hydroxide mixed grinding Crucible, activates under nitrogen atmosphere, and activation condition is: at 700-900 DEG C react 1-2h, material with the mass ratio of KOH is 1:2-1:6.
[043] The present invention describes the procedure to synthesize pure phase hard carbon (anode material) using sugarcane bagasse for Sodium ion battery (SIB) applications. In the previous research, inventors said nothing about the molarity of the used acids (HCl and HF) their importance and their role in improving the energy storage performance of the final obtained sugarcane bagasse derived hard carbon material. The previous research used the KOH treatment process for activating the carbon to increase its surface area while hard carbon doesn’t require such activation to be used as anode material in Sodium ion batteries. The activated carbon, which being a high surface area material has totally different applications than hard carbon (a low surface area material). The present invention describes the effect of acid treatment on the interplanar spacing of the synthesized hard carbon material and hence the Na+ storage performance of the material.
[044] Thus, it has been observed by many groups that quasi-graphite structure with the d-interlayer spacing smaller than 0.37 nm is inexpedient for the intercalation of Na+ as Na-graphite compounds with high Na contents are not thermodynamically stable and only the sloping region behavior would be observed. Therefore, wider interlayer distance is suggested to be crucial for the high-capacity Na+ insertion in the hard carbon material. The interplanar spacing is found proportional to the plateau potential which implies that plateau potential is very much vital to design a battery of specific potential and thereby integration for pack design.
[045] In order to overcome above listed prior art, the present invention aims to provide anode material from sugarcane bagasse for and its method of preparation for rechargeable metal-ion batteries and a process of tuning the interplanar spacing of biomass derived hard carbon which increases capacity for Na-ion battery. Present invention is related to the process of preparing high performance anode material from sugarcane bagasse via tuning its interplanar spacing for rechargeable metal-ion batteries.
OBJECTS OF THE INVENTION:
[046] The principal object of the present invention is to provide pure phase high-performance anode material from sugarcane bagasse for and its method of preparation thereof.
[047] Another object of the present invention is to provide pure phase hard carbon material synthesized from sugarcane bagasse as high performance and stable anode material for rechargeable metal-ion batteries.
[048] Still another object of the present invention is to provides low cost, high yield, high performance, and stable electrode (anode) material for rechargeable metal-ion batteries.
[049] Yet another object of the present invention is to provide a process of tuning the interplanar spacing of biomass derived hard carbon and its impact on plateau capacity for Na-ion battery.
SUMMARY OF THE INVENTION:
[050] The present invention relates to a pure phase high-performance anode material rechargeable metal-ion batteries from sugarcane bagasse for and its method of preparation thereof. The invention provides low cost, high yield, high performance, and stable electrode (anode) material for rechargeable metal-ion batteries. The pure phase hard carbon material is synthesized from sugarcane bagasse as high performance and stable anode material for Sodium ion batteries (SIBs). The invention also provides a process of tuning the interplanar spacing of biomass derived hard carbon and its impact on plateau capacity for Na-ion battery.
BREIF DESCRIPTION OF THE INVENTION
[051] It is to be noted, however, that the appended drawings illustrate only typical embodiments of this invention and are therefore not to be considered for limiting of its scope, for the invention may admit to other equally effective embodiments.
[052] Figure 1 shows XRD pattern of SBPC, SBPHC, SBPFC, and SBPHFC samples.
[053] Figure 2 shows specific capacity vs voltage plot for SBPC, SBPHC, SBPFC, and SBPHFC at 0.1 C in a potential range of 0.005-1.0 V (vs. Na/Na+) (1 C=250 mA/g).
DETAILED DESCRIPTION OF THE INVENTION:
[054] The present invention provides a pure phase high-performance anode material from sugarcane bagasse for and its method of preparation thereof. The invention also provides a process of tuning the interplanar spacing of biomass derived pure phase hard carbon and its impact on plateau capacity for Na-ion battery.
[055] Synthesis of Sugarcane Bagasse Derived Hard Carbon
[056] Sugarcane bagasse received locally from the village near Roorkee town. It was dried under Sun then cut into small pieces followed by washing thoroughly in distilled water. The washed material was then dried in an air oven at a temperature in the range of 50 °C to 100 °C. The dried sugarcane bagasse precursor grinded into small pieces mesh size between 100 to 500 microns. The grinded precursor was then preheated in an Argon gas environment at the temperature of 450°C for 5h. The preheated sample, say SBP in short, was subjected to different sets of experiments given below;
[057] The invention will be more fully understood from the following examples. These examples are to be constructed as illustrative of the invention and not limitative thereof:
[058] Example 1) Certain amount of SBP sample was soaked in 3.5 M molar concentration of the HCl solution at 25 °C for 1h to 48h then washed thoroughly with D.I. water till pH reached to 7 and dried in a vacuum oven at 100 °C and the sample is SBPH.
[059] Example 2) Certain amount of SBP sample was soaked in 1.0 M molar concentration of the HF solution at 25 °C for 1h to 48h then washed thoroughly with D.I. water till pH reached to 7 and dried in a vacuum oven at 100 °C and the sample is SBPF.
[060] Example 3) Certain amount of SBP sample was soaked in 3.5 M molar concentration of the HCl solution 1.0 M molar concentration of the HF solution at 25 °C for 1h to 48h then washed thoroughly with D.I. water till pH reached to 7 and dried in a vacuum oven at 100 °C and the sample is SBPHF.
[061] Now all the samples SBP, SBPH, SBPF, and SBPHF were pyrolyzed at certain temperature under Ar environment for 0.5 h to 12 h and the final obtained samples are labelled as SBPC, SBPHC, SBPFC, and SBPHFC, respectively.
[062] The non-destructive characterization techniques X-Ray Diffractometer (XRD, Rigaku SmartLab SE using CuKa 1.5406 Å radiation)) was utilized to know the crystal structures of the synthesized sugarcane bagasse derived hard carbon. Figure 1 demonstrates the X-Ray Diffraction (XRD) patterns of the sugarcane bagasse derived hard carbon samples SBP, SBPH, SBPF, and SBPHF. All The XRD patterns consists of some amorphous peaks at 2? angles of 22.86o, 43.7o, and 79.4o which are ascribed to the (002), (100), and (110) peaks of hard carbon, respectively. The XRD patterns of SBP and SBPH demonstrate the presence of some impurity peaks belong to SiC. However, no impurity peaks are observed in the XRD patterns of SBPFC, and SBPHFC samples (pure phase). The presence of broadened peaks (hump) in all the XRD patterns suggest the presence of defects/disorderedness in the carbon structure of the synthesized sample. The d-interlayer spacing of all the samples were calculated using Bragg equation (1) given below
2d sin??? ?=n? (1)
[063] where d, ?, n, and ?, respectively, represent the interlayer spacing, Bragg angle, a positive integer, and the wavelength of the X-ray used.
[064] The interlayer spacing (d-value) of SBPHC, SBPFC, and SBPHFC are found to be increased 3.096%, 3.25%, and 4.071% with respect to that of sample SBPC.
[065] Electrode Preparation and Cell Assembly (Sodium ion battery):
[066] In order to investigate the sodium-ion storage performance of the sugarcane bagasse derived hard carbon, electrodes were prepared via uniformly mixing the hard carbon powder with acetylene black (Timcal) and water soluble sodium Carboxy-methyl-cellulose (CMC) (Sigma Aldrich) binder in a weight ratio of 80:10:10. This mixture was stirred for 12 h and the obtained ink like homogeneous slurry was uniformly coated onto the Al foil via doctor blade technique, and dried at 80 ºC in an air oven for 12h. After that, coated Al foil was passed through the calendaring machine to improve the adhesion of active materials to the Al foil. Then for the 2016-type coin cells fabrication, the electrodes were cut into a diameter of 16 mm from the coated Al foil, having mass loading of 2-2.5 mg cm-2. These electrodes were dried at 70 °C for 6 h and then transferred to an argon-filled glove box (M-Brawn, Germany) maintaining the content of H2O and O2 less than 0.5 ppm in the box. The Na cells (CR2016) were assembled in an argon-filled glove box using Sodium metal (Sigma Aldrich), 1.0 M NaClO4 in EC: DEC (1:1 v/v) (Sigma Aldrich), and glass fiber filter (Macflow) as a counter electrode, electrolyte solution and separator, respectively. For cell fabrication, first working electrode was positioned at the center of the coin/cup to form the positive terminal of the cell then a glass fiber filter, which is permeable to the Na-ions but impermeable to material particles and electrons, was placed over it. After that a circular piece of Na-metal (~16 mm diameter) was centrally placed on the separator followed by a steel spring. This forms the negative terminal of the cell. Finally, this arrangement was mechanically pressed using crimping machine (MTI corp.) to form half Na-cell.
[067] Electrochemical characterization (Sodium ion battery):-
[068] The galvanostatic charge-discharge cycling (GCD) analysis of the designed cell were performed at ~25 ºC using battery analyzer (MTI Corp. USA, BST8-WA in the voltage range of 0.005-1.0 V at current rate of 25 mA g-1.
[069] The energy storage performance of sugarcane bagasse derived hard carbon electrodes were examined in Na cells and the results are shown in Figure 2. Table 1 shows the initial reversible 1st charge capacity values (mAhg-1) for the hard carbon electrodes in Na cells.
Table 1.
Sample Acidic Concentration d-value (Å) 1st Charge Capacity
(mAhg-1)
SBPC 0 3.7660 273
SBPHC MHCl = 3.5 3.8826 279
SBPFC MHF = 1.5 3.8884 285
SBPHFC MHCl = 3.5 & MHF = 1.5 3.9193 314
[070] All the hard carbon samples SBP, SBPH, SBPF, and SBPHF are pyrolyzed at the same temperature and exhibit the initial reversible capacities of 273 mAh g-1, 279 mAh g-1, 285 mAh g-1, and 314 mAh g-1, respectively, as shown in Table 1. The hard carbon sample SBPHF delivered the highest initial reversible capacity of 314 mAh g-1 justifying the processed condition of synthesized HC from sugarcane bagasse derived hard carbon as a prospective negative electrode material for sodium ion batteries.
[071] Thus, the invention provides pure phase, low cost, high yield, high performance, and stable electrode (anode) material for rechargeable metal-ion batteries. The pure phase hard carbon material synthesized from sugarcane bagasse has high performance and stable anode material for Sodium ion batteries (SIBs).
[072] Numerous modifications and adaptations of the system of the present invention will be apparent to those skilled in the art, and thus it is intended by the appended claims to cover all such modifications and adaptations which fall within the true spirit and scope of this invention.
REFERENCES
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, Claims:WE CLAIM:
1. A process of preparing pure phase high performance anode material from sugarcane bagasse for rechargeable metal-ion batteries and tuning the interplanar spacing of biomass derived hard carbon include following steps-
a. drying the bagasse in an air oven at a temperature in the range of 50oC to 100oC.
b. grinding the dried bagasse precursor into small pieces mesh size between 100 to 500 microns followed by washing thoroughly in distilled water.
c. the washed material was then dried in an air oven at a temperature in the range of 50oC to 100oC.
d. the dried bagasse precursor material obtained was preheated following step heating in the inert environment at the temperature in the range from 250 to 750 °C.
e. the obtained material from step d was grinded then soaked in a hydrofluoric acid (HF) solution at a temperature between 20 to 100 °C for 1h to 48h to remove the Si impurity from the treated sample, wherein the molar concentration (M) of the acidic solution was taken in the range = 0.1 and = 10.0 M.
f. the obtained material from step e was washed thoroughly with distilled water till pH become neutral then dried overnight in a vacuum oven at a temperature between 60 to 100 °C.
g. the obtained material from step f then soaked in a hydrochloric acid (HCl) solution at a temperature between 20 to 100°C for 1h to 48h. This acidic treatment significantly increases the interplanar spacing (d value) of the obtained hard carbon material which is beneficial for improving the plateau capacity as well as reversible capacity of the material, wherein the molar concentration (M) of the acidic solution was in the range = 0.0 and = 8.0 M.
h. the obtained material from step i is washed with distilled water until pH become ~7 and then dried in a vacuum oven overnight at the temperature between 60 to 100 °C.
i. the materials obtained as per step d, step f, and step h are subjected to high temperature pyrolysis process involving intermittent heating/cooling profile under controlled-environment in the temperature range of 800 °C to 1650 °C for 0.5 h to 12 h.
2. The process of preparing pure phase high performance anode material from bagasse as claimed in claim 1 wherein the rechargeable metal-ion batteries are sodium ion battery, potassium ion battery, magnesium ion battery, zinc ion battery, or calcium ion battery.
3. The process of preparing pure phase high performance anode material from bagasse as claimed in claim 1 wherein alone HF treatment in step (e) is found to be more effective than alone HCl treatment of the material obtained in step (d). However, both the two treatment steps one after another i.e., step (e) followed by step (i) or vice versa, significantly increases the interplanar spacing (d value) and thus found beneficial for improving the energy storage performance of the sugarcane bagasse derived anode material.
4. The process of preparing pure phase high performance anode material from bagasse as claimed in claim 1 wherein the method can be applied to any type of biomass for tunning the interplanar spacing and preparing high performance anode material for rechargeable metal-ion batteries.
5. The process of preparing pure phase high performance anode material from bagasse as claimed in claim 1 wherein the inert environment consists of Argon (Ar) or nitrogen (N2), and or N2/Ar + H2 mixture.
6. The process of preparing pure phase high performance anode material from bagasse as claimed in claim 1 wherein the highest initial reversible capacity of synthesized material is 314 mAh g-1 in sodium ion battery.