nanomaterials Article
Synthesis of Lithium Metal Oxide Nanoparticles by Induction Thermal Plasmas Manabu Tanaka 1 , Takuya Kageyama 2 , Hirotaka Sone 2 , Shuhei Yoshida 3 , Daisuke Okamoto 2 and Takayuki Watanabe 1, * 1 2
3
*
Department of Chemical Engineering, Faculty of Engineering, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395, Japan; [email protected] Department of Chemical Systems and Engineering, Graduate School of Engineering, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395, Japan; [email protected] (T.K.); [email protected] (H.S.); [email protected] (D.O.) Chemical Engineering Course, School of Engineering, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395, Japan; [email protected] Correspondence: [email protected]; Tel./Fax: +81-92-802-2745
Academic Editors: Krasimir Vasilev and Melanie Ramiasa Received: 25 January 2016; Accepted: 29 March 2016; Published: 6 April 2016
Abstract: Lithium metal oxide nanoparticles were synthesized by induction thermal plasma. Four different systems—Li–Mn, Li–Cr, Li–Co, and Li–Ni—were compared to understand formation mechanism of Li–Me oxide nanoparticles in thermal plasma process. Analyses of X-ray diffractometry and electron microscopy showed that Li–Me oxide nanoparticles were successfully synthesized in Li–Mn, Li–Cr, and Li–Co systems. Spinel structured LiMn2 O4 with truncated octahedral shape was formed. Layer structured LiCrO2 or LiCoO2 nanoparticles with polyhedral shapes were also synthesized in Li–Cr or Li–Co systems. By contrast, Li–Ni oxide nanoparticles were not synthesized in the Li–Ni system. Nucleation temperatures of each metal in the considered system were evaluated. The relationship between the nucleation temperature and melting and boiling points suggests that the melting points of metal oxides have a strong influence on the formation of lithium metal oxide nanoparticles. A lower melting temperature leads to a longer reaction time, resulting in a higher fraction of the lithium metal oxide nanoparticles in the prepared nanoparticles. Keywords: thermal plasmas; lithium metal oxide; nanoparticle formation mechanism
1. Introduction Nanoparticles have become widely utilized due to their enhanced and unique properties relative to bulk materials. The preparation of nanoparticles can be classified into physical and chemical methods. The physical methods include mechanical milling [1,2], laser ablation [3–5], and other aerosol processes with energy sources to provide a high temperature. Among these methods, attractive material processing with thermal plasmas have been proposed for the nanoparticles production. This is because thermal plasmas offer unique advantages; high enthalpy to enhance reaction kinetics, high chemical reactivity, rapid quenching rate in the range of 103–6 K/s, and selectivity of atmosphere in accordance with the required chemical reactions. Thermal plasmas are capable of evaporating large amount of raw materials, even with high melting and boiling temperatures [6–9]. Furthermore, high-purity nanoparticles can be synthesized in an induction thermal plasma because thermal plasma can be generated in a plasma torch without internal electrodes [10,11]. These advantages of thermal plasmas have brought about advances in plasma chemistry and plasma processing [12–15]. Lithium metal oxides have attracted many researchers because of their unique properties as cathode for lithium-ion batteries [16–18], CO2 sorption material [19], and other magnetic, electrochemical materials. Layer structured LiCoO2 is widely employed as cathodes in commercial battery applications, Nanomaterials 2016, 6, 60; doi:10.3390/nano6040060
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Lithium metal oxides have attracted many researchers because of their unique properties as cathode for lithium-ion batteries [16–18], CO2 sorption material [19], and other magnetic, electrochemical Layer structured LiCoO2 is widely employed as cathodes in commercial Nanomaterials 2016, 6,materials. 60 2 of 9 battery applications, in spite of its toxicity and high cost. To solve the economic and environmental problems, alternatives of LiCoO2 have been intensively explored. One of the alternatives is spinelin spite of its toxicity and high cost. To solve the economic and environmental problems, alternatives structured LiMn2O4, which provides a promising high-voltage cathode material for lithium-ion of LiCoO2 have been intensively explored. One of the alternatives is spinel-structured LiMn2 O4 , which batteries owing to their high theoretical energy density, low cost, and eco-friendliness [18,20–22]. provides a promising high-voltage cathode material for lithium-ion batteries owing to their high LiNiO2 is also a candidate due to its excellent cycle life, with negligible capacity fading etc. [17,23]. theoretical energy density, low cost, and eco-friendliness [18,20–22]. LiNiO2 is also a candidate due to The liquid phase method is generally used in the synthesis of lithium metal oxide nanoparticles; its excellent cycle life, with negligible capacity fading etc. [17,23]. The liquid phase method is generally however, productivity of the nanoparticles in the liquid phase method is insufficient for industrial used in the synthesis of lithium metal oxide nanoparticles; however, productivity of the nanoparticles application. Therefore, the synthesis method of lithium oxide nanoparticles with a high productivity in the liquid phase method is insufficient for industrial application. Therefore, the synthesis method of is strongly demanded. lithium oxide nanoparticles with a high productivity is strongly demanded. Thermal plasmas are expected to be promising energy sources to fabricate nanoparticles at high Thermal plasmas are expected to be promising energy sources to fabricate nanoparticles at high productivity from micron-sized powder as raw materials. Here, one-step synthesis of lithium-metal productivity from micron-sized powder as raw materials. Here, one-step synthesis of lithium-metal oxide nanoparticles with induction thermal plasma is studied. The purpose of the present study is to oxide nanoparticles with induction thermal plasma is studied. The purpose of the present study synthesize the lithium metal oxide nanoparticles via the induction thermal plasma and to investigate is to synthesize the lithium metal oxide nanoparticles via the induction thermal plasma and to the formation mechanism of lithium-metal oxide nanoparticles. Different lithium metal systems—Li– investigate the formation mechanism of lithium-metal oxide nanoparticles. Different lithium metal Mn, Li–Cr, Li–Co, and Li–Ni—were compared to understand the formation mechanism. systems—Li–Mn, Li–Cr, Li–Co, and Li–Ni—were compared to understand the formation mechanism. 2. Results and Discussion 2. Results and Discussion 2.1. Experimental 2.1. Experimental Results Results Figure 11 shows shows X-ray X-ray diffraction diffraction spectra spectra of of the the prepared prepared nanoparticles nanoparticles by by the the induction induction thermal thermal Figure plasma in Li–Cr, and Li–Ni. In the of theofLi–Mn system, main plasma in different differentsystems—Li–Mn, systems—Li–Mn,Li–Co, Li–Co, Li–Cr, and Li–Ni. In case the case the Li–Mn system, diffraction peaks correspond to spinel-structured LiMn 2O4, while diffraction peaks of Mn3O4 are also main diffraction peaks correspond to spinel-structured LiMn2 O4 , while diffraction peaks of Mn3 O4 found. cases ofIn Li–Co LiCoO2 and LiCrO 2 were found as well as their are alsoInfound. casesand of Li–Cr, Li–Co layer-structured and Li–Cr, layer-structured LiCoO 2 and LiCrO2 were found oxides. In the Li–Ni case, Li 0.4Ni1.6O2 and unreacted Li2CO3 were confirmed. These results clearly as well as their oxides. In the Li–Ni case, Li0.4 Ni1.6 O2 and unreacted Li2 CO3 were confirmed. show the strong influence constituent metals onconstituent the formation of lithium oxide nanoparticles. These results clearly show of thethe strong influence of the metals on the formation of lithium Moreover, Figure 2 indicates composition of the prepared nanoparticles analyzed from X-ray oxide nanoparticles. Moreover, Figure 2 indicates composition of the prepared nanoparticles analyzed diffractometry (XRD) spectra. These compositions of the prepared nanoparticles were used to from X-ray diffractometry (XRD) spectra. These compositions of the prepared nanoparticles were used evaluate the ratio of metal that reacted with Li. Evaluated reaction ratio will be discussed in the to evaluate the ratio of metal that reacted with Li. Evaluated reaction ratio will be discussed in the following section. section. following LiMn2O4
Intensity [a.u.]
Li-Mn Li-Cr Li-Co
Mn3O4 LiCrO2 Cr2O3 LiCoO2 Li0.21Co0.79O Co3O4 Li0.4Ni1.6O2
Li-Ni
Li2CO3
10 20 30 40 50 60 70 80 90 2 [Degree] Figure (XRD) spectra of as-prepared nanoparticles by induction thermalthermal plasma Figure 1.1. X-ray X-raydiffractometry diffractometry (XRD) spectra of as-prepared nanoparticles by induction in different systems, Li–Mn, Li–Co, Li–Cr, and Li–Ni. plasma in different systems, Li–Mn, Li–Co, Li–Cr, and Li–Ni.
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Mole Fraction Fraction [%] [%] Mole
100 80 60
LiMn2O4 2 4
LiCrO2 2
LiCoO2 2
40 Li Co O Li0.21 Co0.79 O 0.21 0.79
Li Ni Li0.4 Ni1.6O O22 0.4 1.6
20 0
Mn Mn33O O44
Cr Cr22O O33
Co Co33O O44
Li Li22CO CO33
Mn
Cr
Co
Ni
Figure 2. Composition of prepared nanoparticles nanoparticles by induction induction thermal plasma plasma in different different systems, Figure Figure 2. 2. Composition Composition of of prepared prepared nanoparticles by by induction thermal thermal plasma in in different systems, systems, Li–Mn, Li–Co, Li–Cr, and Li–Ni. Li–Mn, Li–Mn, Li–Co, Li–Co, Li–Cr, Li–Cr, and and Li–Ni. Li–Ni.
Morphologies Morphologies and particle sizes of the the prepared prepared nanoparticles nanoparticles were were observed observed via via transmission transmission electron microscopy shows the representative TEM images and the (TEM). Figure 3 electron microscopy shows the representative TEM images and the particle particle size size distributions of the nanoparticles in different systems. Many spherical particles with 60 distributions of the nanoparticles in different systems. Many spherical particles with 60 nm nm in in mean mean diameter thethe Li–Ni system. In the of Li–Mn, Li–Co,Li–Co, and Li–Cr, of the particles diameter are areobserved observedinin Li–Ni system. In cases the cases of Li–Mn, and most Li–Cr, most of the with 50–80with nm in meannm diameters have polyhedral shapes including quadrangular, and particles 50–80 in mean diameters have polyhedral shapes includingpentagonal, quadrangular, hexagonal In particular, many particles many with aparticles hexagonal can be shape found can as shown in pentagonal,shapes. and hexagonal shapes. In particular, withshape a hexagonal be found Figure 3a.inHence, LiMn2 O4 isLiMn considered to have a to hexagonal shape because as shown Figurethe 3a. spinel-structured Hence, the spinel-structured 22O44 is considered have a hexagonal shape LiMn is a major product in the Li–Mn according to XRD results. because 22O44 is a major product in thesystem, Li–Mn system, according to XRD results. 2 O4LiMn
Figure 3.3. (a) Representative transmission electron microscopy (TEM) image and size 3.(a) (a)Representative Representative transmission electron microscopy (TEM)and image and particle size Figure transmission electron microscopy (TEM) image particle sizeparticle distribution distribution prepared induction thermal plasma in (b) in distribution of prepared nanoparticles nanoparticles bythermal induction thermal plasmasystem; in Li–Mn Li–Mn system; (b) that thatsystem; in Li– Li– of prepared of nanoparticles by inductionby plasma in Li–Mn (b)system; that in Li–Cr Cr system; (c) that in Li–Co system; (d) that in Li–Ni system. Cr system; (c) that in Li–Co system; (d) that in Li–Ni system. (c) that in Li–Co system; (d) that in Li–Ni system.
Scanning electron microscopy (SEM) observation was carried out to clarify morphology of Scanning electron microscopy (SEM) observation was carried out to clarify morphology of LiMn2O4 more specifically than TEM observation. Figure 4 shows the representative SEM image of LiMn22 O44 more specifically than TEM observation. Figure 4 shows the representative SEM image the prepared nanoparticles in the Li–Mn system. Many particles have truncated an octahedral shape
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as the shown in Figure 4. Previousinresearch on morphology of ferrite nanoparticles synthesized by the of prepared nanoparticles the Li–Mn system. Many particles have truncated an octahedral induction thermal plasma reported that the spinel-structured nanoparticles had a truncated shape as shown in Figure 4. Previous research on morphology of ferrite nanoparticles synthesized octahedral shapethermal [24]. The spinel-structured synthesized in thermalhad plasma have a by the induction plasma reported thatnanoparticles the spinel-structured nanoparticles a truncated truncated octahedral shape, although the stable structure of the spinel-structured particles are octahedral shape [24]. The spinel-structured nanoparticles synthesized in thermal plasma have a generally considered to be of an octahedral shape. The reason for this truncation is currently under truncated octahedral shape, although the stable structure of the spinel-structured particles are generally investigation. considered to be of an octahedral shape. The reason for this truncation is currently under investigation.
Figure 4. Representative Representativescanning scanningelectron electronmicroscopy microscopy (SEM) image of prepared nanoparticles in (SEM) image of prepared nanoparticles in Li– Li–Mn system. Mn system.
2.2. Nanoparticle Formation Mechanism
Homogeneous nucleation nucleationtemperatures temperatures of metals considered in the study present study were Homogeneous of metals considered in the present were estimated estimated based on theory nucleation theory non-dimensional considering non-dimensional surface tension [25]. The based on nucleation considering surface tension [25]. The homogeneous homogeneous rate J canasbe expressed as nucleation ratenucleation J can be expressed “ JJ
βijijnns22sSS 12 12
43 3 Θ 4Θ exp exp Θ ´ 2 2 27 plnSq 22π 27 ln S
c
˜
¸
(1) (1)
where where SS is is the the saturation saturation ratio ratio and and nnss is is the the equilibrium equilibrium saturation saturation monomer monomer concentration concentration at at temperature T. β is the collision frequency function. The dimensionless surface tension is given temperature T. β is the collision frequency function. The dimensionless surface tension is given by by following equation: thethe following equation: σs Θ“ 1 (2) kTs 1 (2) where σ is the surface tension and s1 is the monomer kT surface area. The surface tension and the saturation ratio have a dominant influence on determining the nucleation rate. Stable nuclei are where σ is the surface tension andnucleation s1 is the monomer surface surface and the ´3 ¨ s´The 1 . Hence, observed experimentally when the rate is over 1.0 cmarea. thetension corresponding saturation ratio have a dominant influence on determining the nucleation rate. Stable nuclei are value of the saturation ratio is defined as the critical saturation ratio. The detailed procedure to estimate −3·s−1. Hence, the corresponding value observed experimentally when the nucleation rate is over 1.0 cm the nucleation rate and corresponding nucleation temperature can be found in previous works [10,25]. of the saturation ratio is defined as the critical saturation ratio. The detailed procedure to estimate The relationship between the calculated nucleation temperature and the boiling and melting points the nucleation rate and corresponding nucleation temperature can be found in previous works is summarized in Figure 5. Because of the unknown properties of metal oxides, only melting[10,25]. point The relationship between the calculated nucleation temperature and the boiling and melting oxides are plotted for metal oxides. These temperatures indicate that the melting points of the oxides points is summarized in Figure 5. Because of ofpure the unknown properties of metalTherefore, oxides, only melting are higher than the nucleation temperatures metals in each Li–Me system. nucleation point oxides are plotted for metal oxides. These temperatures indicate that the melting points of the of metal oxides is considered to occur at first. Li oxide and metal vapors co-condense onto the nuclei oxides arethe higher than the nucleation temperatures of pure metals in each Li–Me system. Therefore, just after nucleation starts. nucleation of metal oxides is considered to occur at first. Li oxide and metal vapors co-condense onto the nuclei just after the nucleation starts.
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NiO Ni Co3O4
CrO2
Ni Co
Co3O4
Co
CrO2 Mn3O4
Mn2O3 MnO2
Li 0 0
Li
Melting point Nucleation temperature Boiling point Melting point
CoO Cr2O3 Cr MnO
Boiling point Cr2O3
Cr MnO
Mn3O4
Mn2O3 Mn
MnO2
Nucleation temperature
CoO NiO
Li2O
Mn
500
1000
500
1000
Li2O 1500
2000
Temperature [K] 1500 2000
2500
3000
3500
2500
3000
3500
Figure 5. Relationship between nucleation temperature and melting and boiling points of considered Temperature [K] metals 5. and metal oxides. Figure Relationship between nucleation temperature and melting and boiling points of considered Figure Relationship between nucleation temperature and melting and boiling points of considered metals 5. and metal oxides. The above mechanism metals and metal oxides. can be proposed as a common mechanism for all considered Li–Me
Ratio of Metal with Lithium Ratio of Reacted Metal Reacted with Lithium to Total to Metal Total [-] Metal [-]
systems the relationship between the temperature andconsidered the melting andsystems boiling The because above mechanism can be proposed as a nucleation common mechanism for all Li–Me The above mechanism can bethe proposed as a However, common mechanism forresults all considered Li–Me temperature of their oxides shows same trend. experimental show a different because the relationship between the nucleation temperature and the melting and boiling temperature systems because the relationship between the nucleation temperature andLi–Mn, the melting and boiling ratio of metal reactive with Li to total metal. In the cases of Li–Cr and high ratios the of their oxides shows the same trend. However, experimental results show a different ratio of of metal temperature of their oxides shows the same trend. However, experimental results show a different reactive metals obtained, low ratio was obtained in Li–Ni meltingmetals points reactive with Liwere to total metal. while In thea cases of Li–Cr and Li–Mn, high system. ratios ofThen, the reactive ratio of oxide metalin reactive with Li towere totalfocused metal. In the cases of Li–Crrate andofLi–Mn, high particles ratios of and the of each different system because the reaction metal oxide were obtained, while a low ratio was obtained in Li–Ni system. Then, melting points of each oxide in reactive metals were obtained, while a low ratio was obtained in Li–Ni system. Then, melting points the condensed wouldbecause drastically decreaserate after complete the growing different systemlithium were focused the reaction of metal oxidesolidification particles andofthe condensed of each oxide in different system were focused because the reaction rate of metal oxide particles and particles. lithium would drastically decrease after complete solidification of the growing particles. the condensed lithium would drastically after complete solidification the growing Figure 66 shows shows the relationship betweendecrease the lowest lowest melting temperature of metal metalofoxides oxides for each each Figure the relationship between the melting temperature of for particles. Li–Me system Li–Me system and and the the reaction reaction ratios. ratios. The Theresults resultssuggest suggestaalower lowermelting meltingpoint pointofofoxide oxideleads leadstotoa Figure 6 shows theThis relationship between the lowest melting temperature of metalthe oxides for each higher reaction ratio. can be explained by the different reaction time during nanoparticle a higher reaction ratio. This can be explained by the different reaction time during the nanoparticle Li–Me system and the reaction ratios. The results suggest a lower melting point of nanoparticles. oxide leads to A a formation process. ofof Li–Me oxide formation process. Figure Figure77summarizes summarizesthe theformation formationmechanism mechanism Li–Me oxide nanoparticles. higher reaction ratio. This can be explained by the different reaction time during the nanoparticle lower melting point of oxide leads to ato longer residence timetime of growing particles in a liquid-like state, A lower melting point of oxide leads a longer residence of growing particles in a liquid-like formation process. Figure 7 summarizes the formation mechanism of Li–Me oxide ananoparticles. A resulting in the longer reaction time with condensed lithium oxide. Consequently, higher reaction state, resulting in the longer reaction time with condensed lithium oxide. Consequently, a higher lower melting point of oxide leads to a longer residence time of growing particles in a liquid-like state, ratio canratio be obtained in the Li–Me system, in thatas of in Li–Mn and Li–Cr. OnLi–Cr. the other hand, a shorter reaction can be obtained in the Li–Meas system, that of Li–Mn and On the other hand, resulting in theof longer reactionparticles time with condensed lithium oxide. Consequently, a higher reaction residence time the growing in a liquid-like state leads to a shorter reaction time, resulting a shorter residence time of the growing particles in a liquid-like state leads to a shorter reaction time, ratio can be reaction obtained in theThese Li–Meresults system, as in that ofthe Li–Mn and Li–Cr. of On the other hand, aashorter in a lower suggest melting hasoxide strong resulting in a lower ratio. reaction ratio. These resultsthat suggest that thepoint melting metal point oxide of metal has residence time of the growing particles in a liquid-like state leads to a shorter reaction time, resulting influence on the reaction with lithium oxide. a strong influence on the reaction with lithium oxide. in a lower reaction ratio. These results suggest that the melting point of metal oxide has a strong influence on the reaction with lithium oxide. 0.6
0.5 0.6
Cr
0.4 0.5
Cr
0.3 0.4 0.2 0.3
Mn Co Mn Co
0.1 0.2 0.10500
Ni
1500 2000 Ni 2500 Temperature [K] 0 500 1000 1500 2000 2500 Figure Relationship between points [K]oxides Figure 6. 6. Relationship between lowest lowest melting meltingTemperature points of of metal metal oxides and and the the reaction reaction ratios ratios for for each each Li–Me system. Li–Me system. Figure 6. Relationship between lowest melting points of metal oxides and the reaction ratios for each Li–Me system. 1000
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Figure 7. 7. Conceptual Conceptual diagram diagram of of formation formation mechanism mechanism of of Li–Me Li–Me oxide oxide nanoparticles nanoparticles in in induction induction Figure thermal plasma. thermal plasma.
The above mechanism can explain the obtained results well, although this is still only a The above mechanism can explain the obtained results well, although this is still only a hypothesis. hypothesis. Further experimental and theoretical investigation will be required to understand the Further experimental and theoretical investigation will be required to understand the formation formation mechanism of complicated oxide nanoparticles in thermal plasmas. mechanism of complicated oxide nanoparticles in thermal plasmas. 3. Experimental 3. ExperimentalSection Section 3.1. Experimental Experimental Setup Setup and and Conditions Conditions 3.1. A schematic schematic illustration illustration of of the the experimental experimental setup setup for for Li–Me Li–Me oxide oxide nanoparticle nanoparticle fabrication fabrication is is A presented in in Figure Figure 8a. 8a. This This equipment equipment is is composed composed of of the the plasma the reaction chamber where where presented plasma torch, torch, the reaction chamber the nanoparticles 8b8b shows thethe enlarged illustration of the the nanoparticles are are synthesized, synthesized,and andthe thefilter filterunit. unit.Figure Figure shows enlarged illustration of plasma torch. HighHigh temperature plasma of more K was generated in the plasma by the plasma torch. temperature plasma of than more10,000 than 10,000 K was generated in thetorch plasma induction heating at 4 MHz. input power controlled at 20 kW. was Ar used forused the for carrier torch by induction heating at The 4 MHz. The inputwas power was controlled at Ar 20 kW. was the gas of the raw powder at 3 L/min and inner gas at 5 L/min. A mixture of argon and oxygen were used carrier gas of the raw powder at 3 L/min and inner gas at 5 L/min. A mixture of argon and oxygen for the plasma forming gasforming at 60 L/min. Mixture of LiMixture 2CO3 with diameter and metal or metal were used for the plasma gas at 60 L/min. of3.5 Li2μm COin 3 with 3.5 µm in diameter and oxide with 3–10 μm in mean diameter were injected from the powder by Arfeeder carrierbygas. metal or metal oxide with 3–10 µm in mean diameter were injected from feeder the powder Ar Different including Mn, Cr, Mn, Co, Cr, and compared to to investigate carrier gas.metals Different metals including Co,Ni andwere Ni were compared investigatethe the formation formation mechanism of of Li–Me Li–Me (Mn, (Mn, Cr, Cr, Co, Co, and andNi) Ni)nanoparticles. nanoparticles. The The composition composition ratio ratio of ofLi Li22CO CO33 to to metal metal mechanism was 0.5. The powder feed rate was fixed at 400 mg/min. These experimental conditions are listed in was 0.5. The powder feed rate was fixed at 400 mg/min. These experimental conditions are listed in Table 1. 1. Table Prepared nanoparticles were collected from the filter and the inner wall of the reaction chamber. Unevaporated raw materials were not confirmed according to SEM observation of the collected particles. This fact implies that the fed raw materials were completely evaporated in the high temperature region of the thermal plasma and converted into nanoparticles during the quenching process. Therefore, the mole fractions of the Li–Me oxides indicated in Figure 2 correspond to the yields of the Li–Me oxide in this nanoparticle fabrication process by the induction thermal plasma.
Figure 8. Schematic illustration of induction thermal plasma system for nanoparticles fabrication (a) and enlarged illustration of plasma torch (b).
for the plasma forming gas at 60 L/min. Mixture of Li2CO3 with 3.5 μm in diameter and metal or metal oxide with 3–10 μm in mean diameter were injected from the powder feeder by Ar carrier gas. Different metals including Mn, Cr, Co, and Ni were compared to investigate the formation mechanism of Li–Me (Mn, Cr, Co, and Ni) nanoparticles. The composition ratio of Li2CO3 to metal was 0.5. The powder feed rate was fixed at 400 mg/min. These experimental conditions are listed in Nanomaterials 2016, 6, 60 7 of 9 Table 1.
Figure 8. Schematic illustration of induction thermal plasma system for nanoparticles fabrication (a) and enlarged illustration illustration of of plasma plasma torch torch (b). (b). Table 1. Typical experimental conditions. Plasma Conditions Input power Frequency Pressure Sheath gas Inner gas Carrier gas Discharge time Feed rate
20 kW 4 MHz 101.3 kPa Ar: 57.5 L/min
O2 : 2.5 L/min Ar: 5 L/min Ar: 3 L/min 5 min 400 mg/min
Raw Materials System Raw powders Li/Me ratio
Li–Mn Li2 CO3 , MnO2
Li–Cr Li2 CO3 , Cr
Li–Co Li2 CO3 , Co
Li–Ni Li2 CO3 , Ni
0.5
3.2. Characterization of Prepared Nanoparticles The phase identification of the prepared nanoparticles was determined by X-ray diffractometry (XRD, Multiflex, Rigaku Co., Tokyo, Japan), operated with Cu Kα source (λ = 0.1541 nm). The diffraction data was collected using a continuous scan mode with a speed of 2 degree/min in the region of 10–90 degrees with a step size of 0.04 degrees. The accelerating voltage and applied current was 40 kV and 50 mA, respectively. The quantitative analysis of the composition of the prepared nanoparticles was conducted based on the whole-powder-pattern-decomposition (WPPD) method with the assumption that no amorphous particles were included in the prepared nanoparticles. The particle morphology and size distribution of the prepared nanoparticles were observed by TEM (JEM-2100HCKM, JEOL Ltd., Tokyo, Japan), operated at an accelerating voltage of 200 kV. The TEM specimens were prepared by dispersing the as-prepared nanoparticles in ethanol and placing a few drops of the dispersion on a carbon-grid. Furthermore, the 3D particle morphology was observed by field emission (FE)-SEM (SII TES+ Zeiss ULTRA55, Carl Zeiss, Oberkochen, Germany). 4. Conclusions Lithium metal oxide nanoparticles were synthesized in induction thermal plasma and formation mechanism was investigated. Obtained remarks are as follows:
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(a) Lithium metal oxide nanoparticles were synthesized in different Li–Me (Mn, Cr, Co, and Ni) systems. In the case of Li–Mn, Li–Cr, and Li–Co, lithium-metal oxide nanoparticles were successfully synthesized, while Li–Ni oxides were not synthesized in the Li–Ni system. (b) The spinel-structured LiMn2 O4 with a truncated octahedral shape was synthesized in Li–Mn system, although the stable shape of the spinel structure was an octahedral shape. (c) The relationship between nucleation temperature and boiling and melting points of the considered metals and their oxides suggests the following formation mechanism: Metal oxide starts to nucleate at first. Then, vapors of metal and lithium oxide co-condense on the metal nuclei with an oxidation reaction. (d) Melting point of metal oxides is an important factor in determining the final product of the Li–Me composite. A lower melting point of metal oxide leads to a longer reaction time, resulting in higher yields of the Li–Me composite. (e) Nanomaterial fabrication with induction thermal plasma enables the production of high-purity nanoparticles of Li–Me oxide at high productivity. Acknowledgments: The authors thank the Ultramicroscopy Research Center, Kyushu University for TEM and FE-SEM observation. The authors also thank the Center of Advanced Instrumental Analysis, Kyushu University for XRD analyses. Author Contributions: Manabu Tanaka, Hirotaka Sone and Takayuki Watanabe coordinated the study. Manabu Tanaka, Takuya Kageyama, Shuhei Yoshida and Daisuke Okamoto conducted the experiments. Takuya Kageyama, Hirotaka Sone and Shuhei Yoshida conducted analyses of the produced nanoparticles. Takuya Kageyama conducted the data analyses. Manabu Tanaka and Takayuki Watanabe prepared the manuscript. All authors read and approved the manuscript. Conflicts of Interest: The authors declare no conflict of interest.
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Liang, F.; Tanaka, M.; Watanabe, T. Measurement of anode surface temperature in carbon nanomaterial production by arc discharge method. Mater. Res. Bull. 2014, 60, 158–165. [CrossRef] Tanaka, M.; Watanabe, T. Enhanced vaporization from molten metal surface by argon-hydrogen arc plasma. Jpn. J. Appl. Phys. 2013, 52. [CrossRef] Xiao, X.; Wang, L.; Wang, D.; He, Q.; Peng, Q.; Li, Y. Hydrothermal synthesis of orthorhombic LiMnO2 nano-particles and LiMnO2 nanorods and comparison of their electrochemical performances. Nano. Res. 2009, 2, 923–930. [CrossRef] Kalyani, P.; Kalaiselvi, N. Various aspects of LiNiO2 chemistry: A review. Sci. Technol. Adv. Mater. 2005, 6, 689–703. [CrossRef] Curtis, C.J.; Wang, J.; Schulz, D.L. Preparation and characterization of LiMn2 O4 spinel nanoparticles as cathode materials in secondary Li batteries. J. Electrochem. Soc. 2004, 151, A590–A598. [CrossRef] Ida, J.; Lin, Y.S. Mechanism of high-temperature CO2 sorption on lithium zirconate. Environ. Sci. Technol. 2003, 37, 1999–2004. [CrossRef] [PubMed] Shaju, K.M.; Bruce, P.G. Macroporous Li(Ni1/3 Co1/3 Mn1/3 )O2 : A high power and high energy cathode for rechargeable lithium batteries. Adv. Mater. 2006, 18. [CrossRef] Canulescu, S.; Papadopoulou, E.L.; Anglos, D.; Lippert, T.; Schneider, W.; Wokaun, A. Mechanism of the laser plume expansion during the ablation of LiMn2 O4 . J. Appl. Phys. 2009, 105. [CrossRef] Kim, D.K.; Muralidharan, P.; Lee, H.-W.; Ruffo, R.; Yang, Y.; Chan, C.K.; Peng, H.; Huggins, R.A.; Cui, Y. Spinel LiMn2 O4 nanorods as lithium ion battery cathodes. Nano Lett. 2008, 8, 3948–3952. [CrossRef] [PubMed] Ohzuku, T.; Ueda, A.; Nagayama, M. Electrochemistry and structural chemistry of LiNiO2 (R3m) for 4 volt secondary lithium cells. J. Electrochem. Soc. 1993, 140, 1862–1870. [CrossRef] Swaminathan, R.; Willard, M.A.; McHenry, M.E. Experimental observations and nucleation and growth theory of polyhedral magnetic ferrite nanoparticles synthesized using an RF plasma torch. Acta Mater. 2006, 54, 807–816. [CrossRef] Girshick, S.L.; Chiu, C.-P.; McMurry, P.H. Time-dependent aerosol models and homogenous nucleation rates. Aerosol Sci. Technol. 1990, 13, 465–477. [CrossRef] © 2016 by the authors; licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons by Attribution (CC-BY) license (http://creativecommons.org/licenses/by/4.0/).
Synthesis of Lithium Metal Oxide Nanoparticles by Induction Thermal Plasmas Manabu Tanaka 1 , Takuya Kageyama 2 , Hirotaka Sone 2 , Shuhei Yoshida 3 , Daisuke Okamoto 2 and Takayuki Watanabe 1, * 1 2
3
*
Department of Chemical Engineering, Faculty of Engineering, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395, Japan; [email protected] Department of Chemical Systems and Engineering, Graduate School of Engineering, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395, Japan; [email protected] (T.K.); [email protected] (H.S.); [email protected] (D.O.) Chemical Engineering Course, School of Engineering, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395, Japan; [email protected] Correspondence: [email protected]; Tel./Fax: +81-92-802-2745
Academic Editors: Krasimir Vasilev and Melanie Ramiasa Received: 25 January 2016; Accepted: 29 March 2016; Published: 6 April 2016
Abstract: Lithium metal oxide nanoparticles were synthesized by induction thermal plasma. Four different systems—Li–Mn, Li–Cr, Li–Co, and Li–Ni—were compared to understand formation mechanism of Li–Me oxide nanoparticles in thermal plasma process. Analyses of X-ray diffractometry and electron microscopy showed that Li–Me oxide nanoparticles were successfully synthesized in Li–Mn, Li–Cr, and Li–Co systems. Spinel structured LiMn2 O4 with truncated octahedral shape was formed. Layer structured LiCrO2 or LiCoO2 nanoparticles with polyhedral shapes were also synthesized in Li–Cr or Li–Co systems. By contrast, Li–Ni oxide nanoparticles were not synthesized in the Li–Ni system. Nucleation temperatures of each metal in the considered system were evaluated. The relationship between the nucleation temperature and melting and boiling points suggests that the melting points of metal oxides have a strong influence on the formation of lithium metal oxide nanoparticles. A lower melting temperature leads to a longer reaction time, resulting in a higher fraction of the lithium metal oxide nanoparticles in the prepared nanoparticles. Keywords: thermal plasmas; lithium metal oxide; nanoparticle formation mechanism
1. Introduction Nanoparticles have become widely utilized due to their enhanced and unique properties relative to bulk materials. The preparation of nanoparticles can be classified into physical and chemical methods. The physical methods include mechanical milling [1,2], laser ablation [3–5], and other aerosol processes with energy sources to provide a high temperature. Among these methods, attractive material processing with thermal plasmas have been proposed for the nanoparticles production. This is because thermal plasmas offer unique advantages; high enthalpy to enhance reaction kinetics, high chemical reactivity, rapid quenching rate in the range of 103–6 K/s, and selectivity of atmosphere in accordance with the required chemical reactions. Thermal plasmas are capable of evaporating large amount of raw materials, even with high melting and boiling temperatures [6–9]. Furthermore, high-purity nanoparticles can be synthesized in an induction thermal plasma because thermal plasma can be generated in a plasma torch without internal electrodes [10,11]. These advantages of thermal plasmas have brought about advances in plasma chemistry and plasma processing [12–15]. Lithium metal oxides have attracted many researchers because of their unique properties as cathode for lithium-ion batteries [16–18], CO2 sorption material [19], and other magnetic, electrochemical materials. Layer structured LiCoO2 is widely employed as cathodes in commercial battery applications, Nanomaterials 2016, 6, 60; doi:10.3390/nano6040060
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Lithium metal oxides have attracted many researchers because of their unique properties as cathode for lithium-ion batteries [16–18], CO2 sorption material [19], and other magnetic, electrochemical Layer structured LiCoO2 is widely employed as cathodes in commercial Nanomaterials 2016, 6,materials. 60 2 of 9 battery applications, in spite of its toxicity and high cost. To solve the economic and environmental problems, alternatives of LiCoO2 have been intensively explored. One of the alternatives is spinelin spite of its toxicity and high cost. To solve the economic and environmental problems, alternatives structured LiMn2O4, which provides a promising high-voltage cathode material for lithium-ion of LiCoO2 have been intensively explored. One of the alternatives is spinel-structured LiMn2 O4 , which batteries owing to their high theoretical energy density, low cost, and eco-friendliness [18,20–22]. provides a promising high-voltage cathode material for lithium-ion batteries owing to their high LiNiO2 is also a candidate due to its excellent cycle life, with negligible capacity fading etc. [17,23]. theoretical energy density, low cost, and eco-friendliness [18,20–22]. LiNiO2 is also a candidate due to The liquid phase method is generally used in the synthesis of lithium metal oxide nanoparticles; its excellent cycle life, with negligible capacity fading etc. [17,23]. The liquid phase method is generally however, productivity of the nanoparticles in the liquid phase method is insufficient for industrial used in the synthesis of lithium metal oxide nanoparticles; however, productivity of the nanoparticles application. Therefore, the synthesis method of lithium oxide nanoparticles with a high productivity in the liquid phase method is insufficient for industrial application. Therefore, the synthesis method of is strongly demanded. lithium oxide nanoparticles with a high productivity is strongly demanded. Thermal plasmas are expected to be promising energy sources to fabricate nanoparticles at high Thermal plasmas are expected to be promising energy sources to fabricate nanoparticles at high productivity from micron-sized powder as raw materials. Here, one-step synthesis of lithium-metal productivity from micron-sized powder as raw materials. Here, one-step synthesis of lithium-metal oxide nanoparticles with induction thermal plasma is studied. The purpose of the present study is to oxide nanoparticles with induction thermal plasma is studied. The purpose of the present study synthesize the lithium metal oxide nanoparticles via the induction thermal plasma and to investigate is to synthesize the lithium metal oxide nanoparticles via the induction thermal plasma and to the formation mechanism of lithium-metal oxide nanoparticles. Different lithium metal systems—Li– investigate the formation mechanism of lithium-metal oxide nanoparticles. Different lithium metal Mn, Li–Cr, Li–Co, and Li–Ni—were compared to understand the formation mechanism. systems—Li–Mn, Li–Cr, Li–Co, and Li–Ni—were compared to understand the formation mechanism. 2. Results and Discussion 2. Results and Discussion 2.1. Experimental 2.1. Experimental Results Results Figure 11 shows shows X-ray X-ray diffraction diffraction spectra spectra of of the the prepared prepared nanoparticles nanoparticles by by the the induction induction thermal thermal Figure plasma in Li–Cr, and Li–Ni. In the of theofLi–Mn system, main plasma in different differentsystems—Li–Mn, systems—Li–Mn,Li–Co, Li–Co, Li–Cr, and Li–Ni. In case the case the Li–Mn system, diffraction peaks correspond to spinel-structured LiMn 2O4, while diffraction peaks of Mn3O4 are also main diffraction peaks correspond to spinel-structured LiMn2 O4 , while diffraction peaks of Mn3 O4 found. cases ofIn Li–Co LiCoO2 and LiCrO 2 were found as well as their are alsoInfound. casesand of Li–Cr, Li–Co layer-structured and Li–Cr, layer-structured LiCoO 2 and LiCrO2 were found oxides. In the Li–Ni case, Li 0.4Ni1.6O2 and unreacted Li2CO3 were confirmed. These results clearly as well as their oxides. In the Li–Ni case, Li0.4 Ni1.6 O2 and unreacted Li2 CO3 were confirmed. show the strong influence constituent metals onconstituent the formation of lithium oxide nanoparticles. These results clearly show of thethe strong influence of the metals on the formation of lithium Moreover, Figure 2 indicates composition of the prepared nanoparticles analyzed from X-ray oxide nanoparticles. Moreover, Figure 2 indicates composition of the prepared nanoparticles analyzed diffractometry (XRD) spectra. These compositions of the prepared nanoparticles were used to from X-ray diffractometry (XRD) spectra. These compositions of the prepared nanoparticles were used evaluate the ratio of metal that reacted with Li. Evaluated reaction ratio will be discussed in the to evaluate the ratio of metal that reacted with Li. Evaluated reaction ratio will be discussed in the following section. section. following LiMn2O4
Intensity [a.u.]
Li-Mn Li-Cr Li-Co
Mn3O4 LiCrO2 Cr2O3 LiCoO2 Li0.21Co0.79O Co3O4 Li0.4Ni1.6O2
Li-Ni
Li2CO3
10 20 30 40 50 60 70 80 90 2 [Degree] Figure (XRD) spectra of as-prepared nanoparticles by induction thermalthermal plasma Figure 1.1. X-ray X-raydiffractometry diffractometry (XRD) spectra of as-prepared nanoparticles by induction in different systems, Li–Mn, Li–Co, Li–Cr, and Li–Ni. plasma in different systems, Li–Mn, Li–Co, Li–Cr, and Li–Ni.
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Mole Fraction Fraction [%] [%] Mole
100 80 60
LiMn2O4 2 4
LiCrO2 2
LiCoO2 2
40 Li Co O Li0.21 Co0.79 O 0.21 0.79
Li Ni Li0.4 Ni1.6O O22 0.4 1.6
20 0
Mn Mn33O O44
Cr Cr22O O33
Co Co33O O44
Li Li22CO CO33
Mn
Cr
Co
Ni
Figure 2. Composition of prepared nanoparticles nanoparticles by induction induction thermal plasma plasma in different different systems, Figure Figure 2. 2. Composition Composition of of prepared prepared nanoparticles by by induction thermal thermal plasma in in different systems, systems, Li–Mn, Li–Co, Li–Cr, and Li–Ni. Li–Mn, Li–Mn, Li–Co, Li–Co, Li–Cr, Li–Cr, and and Li–Ni. Li–Ni.
Morphologies Morphologies and particle sizes of the the prepared prepared nanoparticles nanoparticles were were observed observed via via transmission transmission electron microscopy shows the representative TEM images and the (TEM). Figure 3 electron microscopy shows the representative TEM images and the particle particle size size distributions of the nanoparticles in different systems. Many spherical particles with 60 distributions of the nanoparticles in different systems. Many spherical particles with 60 nm nm in in mean mean diameter thethe Li–Ni system. In the of Li–Mn, Li–Co,Li–Co, and Li–Cr, of the particles diameter are areobserved observedinin Li–Ni system. In cases the cases of Li–Mn, and most Li–Cr, most of the with 50–80with nm in meannm diameters have polyhedral shapes including quadrangular, and particles 50–80 in mean diameters have polyhedral shapes includingpentagonal, quadrangular, hexagonal In particular, many particles many with aparticles hexagonal can be shape found can as shown in pentagonal,shapes. and hexagonal shapes. In particular, withshape a hexagonal be found Figure 3a.inHence, LiMn2 O4 isLiMn considered to have a to hexagonal shape because as shown Figurethe 3a. spinel-structured Hence, the spinel-structured 22O44 is considered have a hexagonal shape LiMn is a major product in the Li–Mn according to XRD results. because 22O44 is a major product in thesystem, Li–Mn system, according to XRD results. 2 O4LiMn
Figure 3.3. (a) Representative transmission electron microscopy (TEM) image and size 3.(a) (a)Representative Representative transmission electron microscopy (TEM)and image and particle size Figure transmission electron microscopy (TEM) image particle sizeparticle distribution distribution prepared induction thermal plasma in (b) in distribution of prepared nanoparticles nanoparticles bythermal induction thermal plasmasystem; in Li–Mn Li–Mn system; (b) that thatsystem; in Li– Li– of prepared of nanoparticles by inductionby plasma in Li–Mn (b)system; that in Li–Cr Cr system; (c) that in Li–Co system; (d) that in Li–Ni system. Cr system; (c) that in Li–Co system; (d) that in Li–Ni system. (c) that in Li–Co system; (d) that in Li–Ni system.
Scanning electron microscopy (SEM) observation was carried out to clarify morphology of Scanning electron microscopy (SEM) observation was carried out to clarify morphology of LiMn2O4 more specifically than TEM observation. Figure 4 shows the representative SEM image of LiMn22 O44 more specifically than TEM observation. Figure 4 shows the representative SEM image the prepared nanoparticles in the Li–Mn system. Many particles have truncated an octahedral shape
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as the shown in Figure 4. Previousinresearch on morphology of ferrite nanoparticles synthesized by the of prepared nanoparticles the Li–Mn system. Many particles have truncated an octahedral induction thermal plasma reported that the spinel-structured nanoparticles had a truncated shape as shown in Figure 4. Previous research on morphology of ferrite nanoparticles synthesized octahedral shapethermal [24]. The spinel-structured synthesized in thermalhad plasma have a by the induction plasma reported thatnanoparticles the spinel-structured nanoparticles a truncated truncated octahedral shape, although the stable structure of the spinel-structured particles are octahedral shape [24]. The spinel-structured nanoparticles synthesized in thermal plasma have a generally considered to be of an octahedral shape. The reason for this truncation is currently under truncated octahedral shape, although the stable structure of the spinel-structured particles are generally investigation. considered to be of an octahedral shape. The reason for this truncation is currently under investigation.
Figure 4. Representative Representativescanning scanningelectron electronmicroscopy microscopy (SEM) image of prepared nanoparticles in (SEM) image of prepared nanoparticles in Li– Li–Mn system. Mn system.
2.2. Nanoparticle Formation Mechanism
Homogeneous nucleation nucleationtemperatures temperatures of metals considered in the study present study were Homogeneous of metals considered in the present were estimated estimated based on theory nucleation theory non-dimensional considering non-dimensional surface tension [25]. The based on nucleation considering surface tension [25]. The homogeneous homogeneous rate J canasbe expressed as nucleation ratenucleation J can be expressed “ JJ
βijijnns22sSS 12 12
43 3 Θ 4Θ exp exp Θ ´ 2 2 27 plnSq 22π 27 ln S
c
˜
¸
(1) (1)
where where SS is is the the saturation saturation ratio ratio and and nnss is is the the equilibrium equilibrium saturation saturation monomer monomer concentration concentration at at temperature T. β is the collision frequency function. The dimensionless surface tension is given temperature T. β is the collision frequency function. The dimensionless surface tension is given by by following equation: thethe following equation: σs Θ“ 1 (2) kTs 1 (2) where σ is the surface tension and s1 is the monomer kT surface area. The surface tension and the saturation ratio have a dominant influence on determining the nucleation rate. Stable nuclei are where σ is the surface tension andnucleation s1 is the monomer surface surface and the ´3 ¨ s´The 1 . Hence, observed experimentally when the rate is over 1.0 cmarea. thetension corresponding saturation ratio have a dominant influence on determining the nucleation rate. Stable nuclei are value of the saturation ratio is defined as the critical saturation ratio. The detailed procedure to estimate −3·s−1. Hence, the corresponding value observed experimentally when the nucleation rate is over 1.0 cm the nucleation rate and corresponding nucleation temperature can be found in previous works [10,25]. of the saturation ratio is defined as the critical saturation ratio. The detailed procedure to estimate The relationship between the calculated nucleation temperature and the boiling and melting points the nucleation rate and corresponding nucleation temperature can be found in previous works is summarized in Figure 5. Because of the unknown properties of metal oxides, only melting[10,25]. point The relationship between the calculated nucleation temperature and the boiling and melting oxides are plotted for metal oxides. These temperatures indicate that the melting points of the oxides points is summarized in Figure 5. Because of ofpure the unknown properties of metalTherefore, oxides, only melting are higher than the nucleation temperatures metals in each Li–Me system. nucleation point oxides are plotted for metal oxides. These temperatures indicate that the melting points of the of metal oxides is considered to occur at first. Li oxide and metal vapors co-condense onto the nuclei oxides arethe higher than the nucleation temperatures of pure metals in each Li–Me system. Therefore, just after nucleation starts. nucleation of metal oxides is considered to occur at first. Li oxide and metal vapors co-condense onto the nuclei just after the nucleation starts.
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NiO Ni Co3O4
CrO2
Ni Co
Co3O4
Co
CrO2 Mn3O4
Mn2O3 MnO2
Li 0 0
Li
Melting point Nucleation temperature Boiling point Melting point
CoO Cr2O3 Cr MnO
Boiling point Cr2O3
Cr MnO
Mn3O4
Mn2O3 Mn
MnO2
Nucleation temperature
CoO NiO
Li2O
Mn
500
1000
500
1000
Li2O 1500
2000
Temperature [K] 1500 2000
2500
3000
3500
2500
3000
3500
Figure 5. Relationship between nucleation temperature and melting and boiling points of considered Temperature [K] metals 5. and metal oxides. Figure Relationship between nucleation temperature and melting and boiling points of considered Figure Relationship between nucleation temperature and melting and boiling points of considered metals 5. and metal oxides. The above mechanism metals and metal oxides. can be proposed as a common mechanism for all considered Li–Me
Ratio of Metal with Lithium Ratio of Reacted Metal Reacted with Lithium to Total to Metal Total [-] Metal [-]
systems the relationship between the temperature andconsidered the melting andsystems boiling The because above mechanism can be proposed as a nucleation common mechanism for all Li–Me The above mechanism can bethe proposed as a However, common mechanism forresults all considered Li–Me temperature of their oxides shows same trend. experimental show a different because the relationship between the nucleation temperature and the melting and boiling temperature systems because the relationship between the nucleation temperature andLi–Mn, the melting and boiling ratio of metal reactive with Li to total metal. In the cases of Li–Cr and high ratios the of their oxides shows the same trend. However, experimental results show a different ratio of of metal temperature of their oxides shows the same trend. However, experimental results show a different reactive metals obtained, low ratio was obtained in Li–Ni meltingmetals points reactive with Liwere to total metal. while In thea cases of Li–Cr and Li–Mn, high system. ratios ofThen, the reactive ratio of oxide metalin reactive with Li towere totalfocused metal. In the cases of Li–Crrate andofLi–Mn, high particles ratios of and the of each different system because the reaction metal oxide were obtained, while a low ratio was obtained in Li–Ni system. Then, melting points of each oxide in reactive metals were obtained, while a low ratio was obtained in Li–Ni system. Then, melting points the condensed wouldbecause drastically decreaserate after complete the growing different systemlithium were focused the reaction of metal oxidesolidification particles andofthe condensed of each oxide in different system were focused because the reaction rate of metal oxide particles and particles. lithium would drastically decrease after complete solidification of the growing particles. the condensed lithium would drastically after complete solidification the growing Figure 66 shows shows the relationship betweendecrease the lowest lowest melting temperature of metal metalofoxides oxides for each each Figure the relationship between the melting temperature of for particles. Li–Me system Li–Me system and and the the reaction reaction ratios. ratios. The Theresults resultssuggest suggestaalower lowermelting meltingpoint pointofofoxide oxideleads leadstotoa Figure 6 shows theThis relationship between the lowest melting temperature of metalthe oxides for each higher reaction ratio. can be explained by the different reaction time during nanoparticle a higher reaction ratio. This can be explained by the different reaction time during the nanoparticle Li–Me system and the reaction ratios. The results suggest a lower melting point of nanoparticles. oxide leads to A a formation process. ofof Li–Me oxide formation process. Figure Figure77summarizes summarizesthe theformation formationmechanism mechanism Li–Me oxide nanoparticles. higher reaction ratio. This can be explained by the different reaction time during the nanoparticle lower melting point of oxide leads to ato longer residence timetime of growing particles in a liquid-like state, A lower melting point of oxide leads a longer residence of growing particles in a liquid-like formation process. Figure 7 summarizes the formation mechanism of Li–Me oxide ananoparticles. A resulting in the longer reaction time with condensed lithium oxide. Consequently, higher reaction state, resulting in the longer reaction time with condensed lithium oxide. Consequently, a higher lower melting point of oxide leads to a longer residence time of growing particles in a liquid-like state, ratio canratio be obtained in the Li–Me system, in thatas of in Li–Mn and Li–Cr. OnLi–Cr. the other hand, a shorter reaction can be obtained in the Li–Meas system, that of Li–Mn and On the other hand, resulting in theof longer reactionparticles time with condensed lithium oxide. Consequently, a higher reaction residence time the growing in a liquid-like state leads to a shorter reaction time, resulting a shorter residence time of the growing particles in a liquid-like state leads to a shorter reaction time, ratio can be reaction obtained in theThese Li–Meresults system, as in that ofthe Li–Mn and Li–Cr. of On the other hand, aashorter in a lower suggest melting hasoxide strong resulting in a lower ratio. reaction ratio. These resultsthat suggest that thepoint melting metal point oxide of metal has residence time of the growing particles in a liquid-like state leads to a shorter reaction time, resulting influence on the reaction with lithium oxide. a strong influence on the reaction with lithium oxide. in a lower reaction ratio. These results suggest that the melting point of metal oxide has a strong influence on the reaction with lithium oxide. 0.6
0.5 0.6
Cr
0.4 0.5
Cr
0.3 0.4 0.2 0.3
Mn Co Mn Co
0.1 0.2 0.10500
Ni
1500 2000 Ni 2500 Temperature [K] 0 500 1000 1500 2000 2500 Figure Relationship between points [K]oxides Figure 6. 6. Relationship between lowest lowest melting meltingTemperature points of of metal metal oxides and and the the reaction reaction ratios ratios for for each each Li–Me system. Li–Me system. Figure 6. Relationship between lowest melting points of metal oxides and the reaction ratios for each Li–Me system. 1000
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Figure 7. 7. Conceptual Conceptual diagram diagram of of formation formation mechanism mechanism of of Li–Me Li–Me oxide oxide nanoparticles nanoparticles in in induction induction Figure thermal plasma. thermal plasma.
The above mechanism can explain the obtained results well, although this is still only a The above mechanism can explain the obtained results well, although this is still only a hypothesis. hypothesis. Further experimental and theoretical investigation will be required to understand the Further experimental and theoretical investigation will be required to understand the formation formation mechanism of complicated oxide nanoparticles in thermal plasmas. mechanism of complicated oxide nanoparticles in thermal plasmas. 3. Experimental 3. ExperimentalSection Section 3.1. Experimental Experimental Setup Setup and and Conditions Conditions 3.1. A schematic schematic illustration illustration of of the the experimental experimental setup setup for for Li–Me Li–Me oxide oxide nanoparticle nanoparticle fabrication fabrication is is A presented in in Figure Figure 8a. 8a. This This equipment equipment is is composed composed of of the the plasma the reaction chamber where where presented plasma torch, torch, the reaction chamber the nanoparticles 8b8b shows thethe enlarged illustration of the the nanoparticles are are synthesized, synthesized,and andthe thefilter filterunit. unit.Figure Figure shows enlarged illustration of plasma torch. HighHigh temperature plasma of more K was generated in the plasma by the plasma torch. temperature plasma of than more10,000 than 10,000 K was generated in thetorch plasma induction heating at 4 MHz. input power controlled at 20 kW. was Ar used forused the for carrier torch by induction heating at The 4 MHz. The inputwas power was controlled at Ar 20 kW. was the gas of the raw powder at 3 L/min and inner gas at 5 L/min. A mixture of argon and oxygen were used carrier gas of the raw powder at 3 L/min and inner gas at 5 L/min. A mixture of argon and oxygen for the plasma forming gasforming at 60 L/min. Mixture of LiMixture 2CO3 with diameter and metal or metal were used for the plasma gas at 60 L/min. of3.5 Li2μm COin 3 with 3.5 µm in diameter and oxide with 3–10 μm in mean diameter were injected from the powder by Arfeeder carrierbygas. metal or metal oxide with 3–10 µm in mean diameter were injected from feeder the powder Ar Different including Mn, Cr, Mn, Co, Cr, and compared to to investigate carrier gas.metals Different metals including Co,Ni andwere Ni were compared investigatethe the formation formation mechanism of of Li–Me Li–Me (Mn, (Mn, Cr, Cr, Co, Co, and andNi) Ni)nanoparticles. nanoparticles. The The composition composition ratio ratio of ofLi Li22CO CO33 to to metal metal mechanism was 0.5. The powder feed rate was fixed at 400 mg/min. These experimental conditions are listed in was 0.5. The powder feed rate was fixed at 400 mg/min. These experimental conditions are listed in Table 1. 1. Table Prepared nanoparticles were collected from the filter and the inner wall of the reaction chamber. Unevaporated raw materials were not confirmed according to SEM observation of the collected particles. This fact implies that the fed raw materials were completely evaporated in the high temperature region of the thermal plasma and converted into nanoparticles during the quenching process. Therefore, the mole fractions of the Li–Me oxides indicated in Figure 2 correspond to the yields of the Li–Me oxide in this nanoparticle fabrication process by the induction thermal plasma.
Figure 8. Schematic illustration of induction thermal plasma system for nanoparticles fabrication (a) and enlarged illustration of plasma torch (b).
for the plasma forming gas at 60 L/min. Mixture of Li2CO3 with 3.5 μm in diameter and metal or metal oxide with 3–10 μm in mean diameter were injected from the powder feeder by Ar carrier gas. Different metals including Mn, Cr, Co, and Ni were compared to investigate the formation mechanism of Li–Me (Mn, Cr, Co, and Ni) nanoparticles. The composition ratio of Li2CO3 to metal was 0.5. The powder feed rate was fixed at 400 mg/min. These experimental conditions are listed in Nanomaterials 2016, 6, 60 7 of 9 Table 1.
Figure 8. Schematic illustration of induction thermal plasma system for nanoparticles fabrication (a) and enlarged illustration illustration of of plasma plasma torch torch (b). (b). Table 1. Typical experimental conditions. Plasma Conditions Input power Frequency Pressure Sheath gas Inner gas Carrier gas Discharge time Feed rate
20 kW 4 MHz 101.3 kPa Ar: 57.5 L/min
O2 : 2.5 L/min Ar: 5 L/min Ar: 3 L/min 5 min 400 mg/min
Raw Materials System Raw powders Li/Me ratio
Li–Mn Li2 CO3 , MnO2
Li–Cr Li2 CO3 , Cr
Li–Co Li2 CO3 , Co
Li–Ni Li2 CO3 , Ni
0.5
3.2. Characterization of Prepared Nanoparticles The phase identification of the prepared nanoparticles was determined by X-ray diffractometry (XRD, Multiflex, Rigaku Co., Tokyo, Japan), operated with Cu Kα source (λ = 0.1541 nm). The diffraction data was collected using a continuous scan mode with a speed of 2 degree/min in the region of 10–90 degrees with a step size of 0.04 degrees. The accelerating voltage and applied current was 40 kV and 50 mA, respectively. The quantitative analysis of the composition of the prepared nanoparticles was conducted based on the whole-powder-pattern-decomposition (WPPD) method with the assumption that no amorphous particles were included in the prepared nanoparticles. The particle morphology and size distribution of the prepared nanoparticles were observed by TEM (JEM-2100HCKM, JEOL Ltd., Tokyo, Japan), operated at an accelerating voltage of 200 kV. The TEM specimens were prepared by dispersing the as-prepared nanoparticles in ethanol and placing a few drops of the dispersion on a carbon-grid. Furthermore, the 3D particle morphology was observed by field emission (FE)-SEM (SII TES+ Zeiss ULTRA55, Carl Zeiss, Oberkochen, Germany). 4. Conclusions Lithium metal oxide nanoparticles were synthesized in induction thermal plasma and formation mechanism was investigated. Obtained remarks are as follows:
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(a) Lithium metal oxide nanoparticles were synthesized in different Li–Me (Mn, Cr, Co, and Ni) systems. In the case of Li–Mn, Li–Cr, and Li–Co, lithium-metal oxide nanoparticles were successfully synthesized, while Li–Ni oxides were not synthesized in the Li–Ni system. (b) The spinel-structured LiMn2 O4 with a truncated octahedral shape was synthesized in Li–Mn system, although the stable shape of the spinel structure was an octahedral shape. (c) The relationship between nucleation temperature and boiling and melting points of the considered metals and their oxides suggests the following formation mechanism: Metal oxide starts to nucleate at first. Then, vapors of metal and lithium oxide co-condense on the metal nuclei with an oxidation reaction. (d) Melting point of metal oxides is an important factor in determining the final product of the Li–Me composite. A lower melting point of metal oxide leads to a longer reaction time, resulting in higher yields of the Li–Me composite. (e) Nanomaterial fabrication with induction thermal plasma enables the production of high-purity nanoparticles of Li–Me oxide at high productivity. Acknowledgments: The authors thank the Ultramicroscopy Research Center, Kyushu University for TEM and FE-SEM observation. The authors also thank the Center of Advanced Instrumental Analysis, Kyushu University for XRD analyses. Author Contributions: Manabu Tanaka, Hirotaka Sone and Takayuki Watanabe coordinated the study. Manabu Tanaka, Takuya Kageyama, Shuhei Yoshida and Daisuke Okamoto conducted the experiments. Takuya Kageyama, Hirotaka Sone and Shuhei Yoshida conducted analyses of the produced nanoparticles. Takuya Kageyama conducted the data analyses. Manabu Tanaka and Takayuki Watanabe prepared the manuscript. All authors read and approved the manuscript. Conflicts of Interest: The authors declare no conflict of interest.
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