Study on the synthesis process of silicon nanomaterials to fabricate anode orient application for li - Ion batteries

The samples of rGO, nano Si, nano Si @ rGO powder fabricated by the above methods are finely ground in an agate mortar or planetary grinding device. The active materials, conductive carbon black, and polyvinylidene fluoride (PVDF) were mixed together in a weight ratio of 8:1:1. Thus, the prepared mixture was further diluted by N-methyl pyrrolidinone (NMP) to form the slurry, which was then spread onto the copper foil and freeze-dried for 12 hours

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no Si@rGO materials 3.3.2.1. EDX pattern of nano Si@rGO: Figure 3.51. EDX pattern of nano composite Si@rGO. 90 The results showed that, after reduction, the Si and C content in Si@rGO samples was 71.28 %, 20.85 % respectively. This result is the average value at many different measurement points to ensure relatively quantitative when using EDX data. The result is in accordance with the above calculations and analysis of the Si@rGO component above. Thus, nano Si@rGO material is proportional to the mass of Si:rGO  0.7:0.3. 3.3.2.2. Crystal structure The crystal structure of the synthesized product was analyzed by XRD method. Figure 3.52 shows the XRD pattern of the sample. The diffraction pattern of the composite is in good agreement with the cubic Si (JCPDS card No. 27-1402). The diffraction peaks at 2 = 28,5o, 47,3o and 56,1o can be attributed to the Si (111), (220) and (311) structure, respectively. The characteristic diffraction peak of graphite at 26.4 o didn’t appear, revealing that Si nanoparticles deposited on the graphene surface could efficiently suppress the stacking of reduced graphene layers, thus, in this case, no graphite-like layered structure formed again. Figure 3.52. XRD pattern of nano composite Si@rGO. 91 3.3.2.3. Morphological analysis Figure 3.53. SEM (a), TEM (b) images of nano composite Si@rGO. From the SEM image, no apparent morphological difference can also be inferred between two processes after GO reduction. Thus, the process itself doesn’t affect the intrinsic properties of both materials. From the TEM image, the formed rGO sheets were wrapped around silicon nanoparticles, without affecting the size of silicon nanoparticles. Figure 3.54 schematically shows the process to synthesize the nano Si@rGO materials. Figure 3.54: Schematic for synthesis process of nano composite Si@rGO [103]. a b 92 Consequently, the nano Si@rGO material was used as a slurry mixture for LIB testing. 3.4. Application of rGO, nano Si and nano Si@rGO materials for fabrication LIB’s anode. 3.4.1. Experimental fabrication anode material combination The samples of rGO, nano Si, nano Si @ rGO powder fabricated by the above methods are finely ground in an agate mortar or planetary grinding device. The active materials, conductive carbon black, and polyvinylidene fluoride (PVDF) were mixed together in a weight ratio of 8:1:1. Thus, the prepared mixture was further diluted by N-methyl pyrrolidinone (NMP) to form the slurry, which was then spread onto the copper foil and freeze-dried for 12 hours. Figure 3.55. Compound slurry of nano composite Si@rGO/cacbon/PVDF + NMP. Figure 3.56. LIB’s anode with a 11 mm diameter. 93 Figure 3.57. Material structure of anode/cacbon/PVDF.  Morphological analysis of anode material combination Role of each component in anode material combination: - rGO, nano Si, nano Si@rGO: is a material capable of reversing the accumulation of Li + ions, affecting the electrochemical properties of LIB, but it is not highly conductive. Among these 3 materials, we can arrange the increasing conductivity in the following order: nano Si <nano Si@rGO <rGO. - Carbon SUP-P: is a material that increases the electrical conductivity of the electrode. Figure 3.58: SEM image and EDX pattern of carbon superP. - Poly-vinyl-difluoride (PVDF): is the adhesive material used commonly in LIB. It has high purity, good solubility in NMP solvent (N-methyl pyrrolidinone), has mechanical strength, acid resistance, does not participate in the electrochemical reaction of LIB however it has poor thermal stability and very poor electrical Electrolyte Anode electrode material PVDF + SUP-P arbon Li + Li + Li + Li + Li + i + Li + i + Li + LiLi + Copper foil 94 conductivity. Previous studies [63], [88], [96], [98] show that the ratio of active substances, conductive additives and adhesive polymers (PVDF) plays an important role in properties. conductivity and exchange Li + of composite materials. If the rate of polymer binding is missing, it will affect the mechanical properties, causing the surface of the electrode to crack, and if the rate of polymer binding is too high, it will interfere with the conductive and exchange processes Li + of composites. Figure 3.59. SEM image of the anode/cacbon/PVDF material. Observing the SEM image of the anode material combination in Figure 3.59, we can see that the surface is quite smooth, the adhesive polymer layer has covered a thin layer on inorganic material particles. 3.4.2. The electrochemical characteristics of LIB 3.4.2.1. Investigation of electrochemical characteristics of LIB with anode fabricated on rGO basis rGO-based electrodes are prepared as described in Chapter 2. Electrodes and cells are prepared in an argon-filled glove box with the working electrode as an rGO- based electrode, the counter and the reference electrode is Li metal. The electrochemical characteristics of the LIB sample are determined by cyclic voltammetry (CV) and galvanostatic charge-discharge (GC) measurements. a. Cyclic voltammetry (CV) LIB with anode fabricated on rGO basis was analyzed by cyclic voltammetry method with a scan rate of 0.1mV/s in the range of 0-2 V. Electrochemical characteristics of cyclic voltammetry were shown in Figure 3.60. 95 Figure 3.60. Cyclic voltammetry curves of LIB with anode fabricated on rGO basis of the first two cycles at a scan rate of 0.1 mV/s in the voltage range of 0.0-2.0 V. The CV results show that the rGO anode material can be charged near 0 V, corresponding to the published documents on this material. The peak at 1.6 V of the first cycle shows the formation of the SEI layer on the electrode surface, as a result of the reaction of Li metal with LiPF6 salt and the organic component in the electrolyte. The reaction equations occur at the electrodes during charge-discharge of LIB with the anode fabricated on rGO basis: + Cathode: Li  Li+ + e. + Anode: C + xLi + + xe  LixC b. Galvanostatic charge-discharge (GC) The discharge-charge characteristic of the battery was assessed by galvanostatic charge-discharge (GC) measurements with a constant current density of 0.1C (C = 372 mAh/g which is the theoretical specific capacity of carbon). The result is shown in Figure 3.61. With anode fabricated on rGO basis, LIB can only work for 35 cycles with capacitance reduced from 320 mAh/g to 220 mAh/g. From the 36th cycle, the specific capacity of the material decreases very quickly, down to 30 mAh/g in the 100th cycle. Especially in the first cycle, the charging capacity is very high, reaching 1875 mAh/g (the first square black point on Figure 3.61), however, the 96 discharge capacity is only 345 mAh/g (the first circle red point in Figure 3.61), resulting in very low Coloumbic performance (the first blue triangle point in Figure 3.61). This is evident in the charging process of the first cycle, the formation of the SEI layer is very pronounced on the surface of carbon materials, similar to the results of CV analysis in Figure 3.60 with characteristic chip at 1.6 V. Coulomb of the remaining cycles is also very low, at about 75 % until the 35th cycle. This proves the discharge-charge process of the anode material has a low level of reversibility Figure 3.61. Cycling performance of LIB with anode fabricated on rGO basis under the current rate 0.1C (37.2 mA/g) in the voltage range of 0.0-2.0 V, 100 cycles. Figure 3.62. The rate capability of LIB with anode fabricated on rGO basis at the current rates from 37.2 mA/g to 18.600 A/g, 110 cycles. 97 In another analysis, the results of the discharge and loading capacities at different current densities for the anode from rGO are shown in Figure 3.62. The current density starts from 0.1C (37.2 mA/g) with the LIB sample analyzed CV, increasing gradually every 10 cycles, to 50C (18600 mA/g), as shown in Figure 3.62. The results show that the anode can work at very high current densities, but the capacity is very low. At low current density (0.1C; 0.2C; 0.5C), the capacity of the anode is not stable, which indicates that the ejection-charge process is inefficient. However, after discharge-charge at high current density, the anode was reassessed at a current density of 0.1C. The results of discharge-charge after 100 cycles show that the anode works quite stable with the capacity unchanged compared to before evaluation. This suggests that it is possible for rGO anode materials to be discharge - charge at high current density before being able to work stably at low current density. It can be concluded that rGO anode material does not meet the capacity requirements but can operate at a very high current density. This is explained by the very high electrical conductivity of the rGO material. 3.4.2.2. Investigation of electrochemical characteristics of LIB with anode fabricated on nano Si basis Nano Si-based electrodes are prepared as described in Chapter 2. Electrodes and cells are prepared in an argon-filled glove box with the working electrode as an nano Si-based electrode, the counter and the reference electrode is Li metal. The electrochemical characteristics of the LIB sample are determined by cyclic voltammetry (CV) and galvanostatic charge-discharge (GC) measurements. a. Cyclic voltammetry (CV) The electrochemical characteristics of CV analysis showed that in the first cycle, the charging potential of Si anode at ~100 mV shows that the Si material used as anode has a crystal structure because the crystalline Si reacts with Li + at this potential (while amorphous Si is ~200 mV). This result once again proves that Si nanomaterials obtained from the reaction of nano SiO2 and Mg have a crystal 98 structure. The charging process (insert Li + ion) is finished with Si nanomaterials resulting in crystal Li15Si4 compound. The discharge process (extract Li + ion) starts at ~200 mV, indicating that Li + begins to exit the Li15Si4 compound. The apparent discharge at 300–400 mV shows the presence of two materials at this time: Li15Si4 crystalline and Si amorphous form, a result of the process of Li + coming out of the compound Li15Si4 crystals [94], [103]. Figure 3.63. Cyclic voltammetry curves of LIB with anode fabricated on nano Si basis of the first two cycles at a scan rate of 0.1 mV/s in the voltage range of 0.0-2.0 V. In the second cycle, the charging process starts at ~500 mV and there are two peaks distinct Li + ion inserts (lithiation) at ~200 mV and ~0 mV. This result shows that after the discharge process in the first cycle, Si material exists amorphous and after the charging process in the 2nd cycle there exists a crystal Li15Si4 compound, similar to the first cycle. The discharge process in the 2nd cycle is similar to the first cycle, with 2 peaks in the range of 300–400 mV [94], [103]. The results of the electrochemical properties of the Si electrode through CV analysis showed that only the charging process in the first cycle is different from the following cycles, due to the transition from crystalline Si material to the Li15Si4 compound. From the discharge process in the first cycle onwards, the electrochemical properties of the electrode do not change. 99 Figure 3.64. Galvanostatic discharge-charge profiles of LIB with anode fabricated on nano Si basis at the current rate of 0.05C in the voltage range of 0.0-1.5 V. b. Galvanostatic charge-discharge (GC) Figure 3.65. Cycling performance of LIB with anode fabricated on nano Si basis under the current rate 0.1C in the voltage range of 0.0-2.5 V, 35 cycles. The capacity of the nano-anode Si anode is assessed at the current density of 0.1C (C=4200 mA/g). The current density is calculated on the basis of Si’s specific capacity, which is a value of 4200 mAh/g in theory for the Li22Si5 compound. The lower the current density, the higher the value of the capacity of the anode, close to the theoretical value. With a current density of 420 mA/g, LIB with anode 100 fabricated on nano Si basis achieves the specific capacity of the adjacent anode 3000 mAh/g for the first 10 cycles. From cycle 11 onwards the capacity decreases, to 2250 mAh/g in the 35th cycle. After the 35th cycle, the capacity decreases markedly rapidly, indicating that the battery's ability to work is not guaranteed. This result corresponds to other claims about Si nanomaterials. The remarkable point here is that Coulombic efficiency is not high, reaching over 90 %, showing that the reversible charge-discharge process of Si anode is not satisfactory. This result can explain the working durability (number of charge-discharge cycles) reaching only 35 cycles. Thus, it can be concluded that the anode fabricated on rGO, nano Si basis do not have good charging and discharging effects when used separately. In the next study, these two materials are combined to be able to take advantage of the good conductive properties of the rGO material and the high capacity of Si nanomaterial. 3.4.2.3. Investigation of electrochemical characteristics of LIB with anode fabricated on nano Si@rGO basis Nano Si@rGO-based electrodes are prepared as described in Chapter 2. Electrodes and cells are prepared in an argon-filled glove box with the working electrode as an nano Si@rGO-based electrode, the counter and the reference electrode is Li metal. The electrochemical characteristics of the LIB sample are determined by cyclic voltammetry (CV) and galvanostatic charge-discharge (GC) measurements. a. Cyclic voltammetry (CV) Figure 3.66 shows the I-V correlation graph of CV analysis for the first 2 cycles, showing the electrochemical properties of anode fabricated on the nano Si@rGO basis. Compared to the CV characteristic of anode fabricated on the nano Si basis (Figure 3.63), there is not much difference. With the first cycle, due to the presence of rGO, the charging process starts at about 170 mV. From 100 mV is the charging process of crystalline Si nanomaterials, as shown above. At the end of the charging process, the voltage is reduced to 0 mV, which corresponds to the formation of Li15Si4 crystal and C6Li compounds. During the discharge (extract Li + ion) shows 2 poles at about 330 mV and 490 mV. This proves the coexistence of Li15Si4 crystal form and nano Si amorphous form. At the end of the discharge process in the first 101 cycle, the remaining silicon Si anode is amorphous and carbon (rGO). In the second cycle, the charging process started earlier, at a nearby 500 mV. This is the formation of the SEI (solid electrolyte interphase) layer on the anode surface (mainly nano- shaped amorphous Si) in parallel with the creation of the LixSiy compound. When the potential is reduced to 0 mV, the conversion of amorphous Si nanoparticles and rGO to Li15Si4 is completed in crystal form and C6Li compound, similar to the first cycle. The discharge process in the 2nd cycle is similar to the first cycle, and the following cycles (not shown in Figure 3.66). Figure 3.66. Cyclic voltammetry curves of LIB with anode fabricated on nano Si@rGO basis of the first two cycles at a scan rate of 0.1 mV/s in the voltage range of 0.0-2.0 V. b. Galvanostatic charge-discharge (GC) In parallel with the results of analysis by CV, LIB with anode fabricated on nano Si@rGO basis was assessed by galvanostatic analysis for the first 2 cycles. The result shows that the basic difference between the 2 cycles is in the charging process. In the first cycle, the charging process is lower than that in the second cycle, because the nanomaterial Si in the first cycle is crystalline. At the end of the discharge process, the first cycle onwards only exists in the amorphous form of Si. Therefore, the charging process will be the same from the second cycle. The point of attention here is for the discharge characteristic line, showing that the plateau segment at a potential of about 400 mV, corresponding to the CV characteristic 102 when exists concurrently substances Li15Si4 crystalline and nano Si amorphous form. At a current density of 0.05C, the anode specific capacity reaches > 3000 mAh/g. This is the overall value for the anode including nano Si and rGO. Figure 3.67. Galvanostatic discharge-charge profiles of LIB with anode fabricated on nano Si@rGO basis at the current rate of 0.05C in the voltage range of 0.0-2.5 V. Figure 3.68. Cycling performance of LIB with anode fabricated on nano Si@rGO basis under the current rate 1.5C in the voltage range of 0.0-2.5 V, 500 cycles. Figure 3.68 shows that the charge-discharge characteristic of the nano Si@rGO anode is performed at a current density of 1.5C. For the first cycle, specific capacity reaches > 1800 mAh/g and Coulombic efficiency reaches 98 %. These are very high values, comparable to Si nanowire materials in published studies. For the first 200 103 cycles, the anode's specific capacity holds at > 1200 mAh/g and keeping this value gives me 500 cycles. This value is comparable to the number of charge cycles of a commercially available LIB using the anode material of graphite. This result shows that the role of rGO material has a high conductivity, which helps to stabilize the charge-discharge of the battery. It can be explained by the nanocomposite structure, the graphene sheets surrounding and linking Si nanoparticles, making Si nanoparticles have a mutual connection, thus increasing the number of charge- discharge cycles. More explanation is needed here, the decrease in specific capacity and the low number of discharge cycles are due to the gradual reduction of the anode rate involved in the discharge process with physical and chemical causes. Physical causes are the fractures and flaking off the surface of the anode material. As a result, each part of the anode cannot continue to participate in the discharge and discharge of the battery. The chemical cause can be called anode of aging when the part of the whole electrode cannot reach the highest specific density after a certain number of discharge cycles. This result may be due to the formation of the SEI layer and the anode material gradually dissolving into the electrolyte solution. The result of charge-discharge at 1.5C current density also shows that Coulombic efficiency reaches 98 % from the 2nd cycle. It means that the reversible process (charge-discharge) has high efficiency. This result contributes to the working durability (number of charge-discharge cycles) of the anode. - The charge-discharge characteristic of the LIB at different current densities allows a better understanding of the anode charge-discharge characteristic when increasing the current density. The higher the current density means the lower the discharge time. This makes sense for the actual use of the anode, allowing it to be charged and discharged in a short time with high amperage. From the graph showing the charge-discharge characteristic of the LIB at different current densities, the capacity of the battery depends on the charge-discharge modes at different current densities. The LIB model has a very high specific capacity at current densities smaller than 1C, a specific capacity of over 3000 mAh/g in the discharge mode of 0.05C (C/20) (after 5 cycles of charge-discharge) and reaches specific capacity of approximately 2000 mAh/g at 1C (after 20 cycles of charge- discharge). At current density 2C, the specific capacity reaches 1320 mAh/g and 104 decreases to nearly 200 mAh/g At current density 5C (after 40 discharge cycles). This value is still greater than the specific density of a commercial anode on a graphite basis. After 45 cycles with changing current density, the half cell is re- discharge with a current density of 0.05C, showing that the specific capacity is equivalent to the current density 0.1C. This result makes sense for current commercial LIB to be charged in high-current density mode until they reach 80-90 % of the capacity, then the LIB is charged in low-current density mode to 100 % capacity. Figure 3.69. The rate capability of LIB with anode fabricated on Si@rGO basis at the different current rates in the voltage range of 0.0-2.5 V, 50 cycles. Table 3.7. The electrochemical characteristics of LIB with anode fabricated on rGO, nano Si and nano Si@rGO basis and previous publications. Anode materials Maximum theoretical capacity (mAh/g) Maximum current density Maximum number of charge- discharge cycles Coulombic efficiency rGO 372 50C (18600 mA/g) 100 75% Nano Si 2250 1C (3800 mA/g) 35 93% Si@rGO 1800 5C (13850 mA/g) 500 98% Nano Si [71] 2790 1C (4200 mA/g) 100 86% Si@rGO [103] 1600 2C (5540 mA/g) 100 56% 105 Thus, the results show that the Si@rGO nano-based anode has improved the durability and specific capacity, which can charge-discharge a higher current density than the anode from the Si nanomaterial. This result is due to the high electrical conductivity of the rGO material and the high specific gravity of nano nanomaterials. 3.5. Conclusion of chapter 3 - Selected the suitable conditions for the synthesis of nano-silica from rice husk: acid treatment concentration HCl: 10 %, acid treatment temperature: 90 °C, a treatment time: 2 hours, the ratio of rice husk/acid: 3 g rice husk/40 ml HCl 10 %, calcination temperature: 650 o C for 3 hours with a heating rate of 3 o C/min. The obtained silica nanoparticles have a size of 50-70 nm, amorphous phase structure, purity > 99%. - Determined the thermodynamic and kinetic parameters of synthesizing silica nano from rice husk: activation energy of synthesizing silica nano from rice husk, E * = 126.14 (kJ/mol) (FWO model); E * = 122.6 (kJ/mol) and the exponential factor in the Arrhenius equation is A = 1,033.10 10 (Kissinger model), thereby determining the reaction rate constant according to the Arrhenius equation: Determination of thermodynamic parameters of synthesis silica nanoparticles from rice husk from rice husk: ∆G* = 138,5  180,4 kJ/mol, ∆H* = 114,9  120,1 kJ/mol và ∆S* = -70,9  -61,5 J/mol.K. - Selected the suitable conditions for the synthesis of silicon nanoparticles from silica nanoparticles with the reducing agent magnesium: molar ratio of Mg/SiO2 is 2.1:1, calcination temperature at 800 o C for 2 hours with a heating rate of 5 o C/min. Silicon nanoparticles obtained with particle size from 30-50 nm, crystal phase structure, purity > 99%. Activation energy of silica reduction process with magnesium: E * = 308.34 (kJ/mol) (F-W-O model); E * = 314.13 (kJ/mol) and the exponential factor in the Arrhenius equation is A = 8.19.10 26 (Kissinger model). 106 - Synthesized rGO, nano Si@rGO and investigated the structure and morphology of rGO, nano Si@rGO materials. The C content in the rGO sample is 75.2 %; Si and C content in nano Si@rGO samples were 69.96 % and 31.04 %, respectively. - Successfully fabricated LIB with anode on rGO, nano Si and nano Si@rGO basis. The specific electrochemical characteristics are as follows: + LIB with anode on rGO basis: Maximum theoretical capacity 372 mAh/g; maximum current density 50C (18600 mAh/g); maximum number of charge- discharge cycles: 100 cycles; Coulombic efficiency: 75 %. + LIB with anode on nano Si basis: Maximum theoretical capacity 2250 mAh/g; maximum current density 1C (3800 mAh/g); maximum number of charge-discharge cycles: 35 cycles; Coulombic efficiency: 93 %. + LIB with anode on nano Si@rGO basis: Maximum theoretical capacity 1800 mAh/g; maximum current density 5C (13850 mAh/g); maximum number of charge- discharge cycles: 500 cycles; Coulombic efficiency: 98 %. 107 CONCLUSION 1. Selected the suitable conditions for the synthesis of nano-silica from the rice husk which is the acid treatment concentration HCl: 10 %, the acid treatment temperature 90 °C, the treatment time 2 hours, the ratio of the rice husk/acid 3 g rice husk/40 ml HCl 10 %, the calcination temperature 650 o C during 3 hours with the heating rate of 3 o C/min. The obtained silica nanoparticles have a size of 50-70 nm, the amorphous phase structure and the purity > 99%. 2. Determined the thermodynamic and kinetic parameters of synthesizing silica nano from the rice husk: the activation energy of synthesizing silica nano from the rice husk, E * = 126.14 (kJ/mol) (FWO model); E * = 122.6 (kJ/mol) and the exponential factor in the Arrhenius equation is A = 1,033.10 10 (Kissinger model), thereby determining the reaction rate constant according to the Arrhenius equation: Determination of thermodynamic parameters of synthesis silica nanoparticles from the rice husk: ∆G* = 138,5  180,4 kJ/mol, ∆H* = 114,9  120,1 kJ/mol và ∆S* = -70,9  -61,5 J/mol.K. 3. Selected the suitable conditions for the synthesis of silicon nanoparticles from silica nanoparticles with the reducing the agent magnesium: the molar ratio of Mg/SiO2 is 2.1:1, the calcination temperature at 800 o C during 2 hours with the heating rate of 5 o C/min. Silicon nanoparticles obtained with the particle size from 30-50 nm, crystal phase structure and the purity > 99%. The activation energy of silica reduction process with magnesium: E * = 308.34 (kJ/mol) (F-W-O model); E * = 314.13 (kJ/mol) and the exponential factor in the Arrhenius equation is A = 8.19.10 26 (Kissinger model). 4. Synthesized rGO, nano Si@rGO and investigated the structure and morphology of rGO, nano Si@rGO materials. The C content in the rGO sample is 75.2 %; Si and C content in nano Si@rGO samples were 69.96 % and 31.04 %, respectively. 5. Successfully fabricated LIB with the anode on rGO, nano Si and nano Si@rGO basis. The specific electrochemical characteristics are as follows: 108 + LIB with the anode on rGO basis: The maximum theoretical capacity 372 mAh/g; maximum current density 50C (18600 mAh/g); maximum number of charge- discharge cycles: 100 cycles; Coulombic efficiency: 75 %. + LIB with the anode on nano Si basis: The maximum theoretical capacity 2250 mAh/g; maximum current density 1C (3800 mAh/g); maximum number of charge- discharge cycles: 35 cycles; Coulombic efficiency: 93 %. + LIB with anode on nano Si@rGO basis: Maximum theoretical capacity 1800 mAh/g; maximum current density 5C (13850 mAh/g); maximum number of charge- discharge cycles: 500 cycles; Coulombic efficiency: 98 %. The contribution: 1. Determined the conditions to synthesis the silicon nanoparticles from the rice husk. 2. Fabricated an anode based on nano Si for the electrochemical characteristics such as the high specific capacity, the high current density and number of charge- discharge cycles, high Coulombic performance. Further research directions: 1. Further research on the thermodynamic and kinetic characteristics affecting the synthesis of silicon from nano-silica. 2. Further research on the anode fabrication processes based on the synthesis materials, which helps to optimize the anode fabrication process for LIB. 3. Further investigate the electrochemical characteristics of an anode made from rGO, nano Si and nano Si @ rGO to get more data about these batteries. 109 LIST OF PUBLICATIONS 1. Nguyen Van Thang, Nguyen Manh Tuong, Nguyen Tran Hung (2016), “Thermodynamic evaluation of synthesis of nanosilica from the rice husk”, Proceeding of The 5th Asian materials data symposium, Hanoi 11/2016, pp. 331- 340. 2. Nguyen Van Thang, Nguyen Manh Tuong, Nguyen Tran Hung (2017), “Silicon nanoparticles from the rice husk – thermodynamic evaluation and synthesis”, Vietnam journal of chemistry, 55(3e), pp. 176-182. 3. 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