• Journal of Electrochemical Science and Technology
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• v.2 no.3
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• pp.146-151
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• 2011

The formation of Li-Si-O phases, $Li_4SiO_4$ and $Li_2SiO_3$ from the starting materials SiO and $Li_2O$ are analyzed using Vienna Ab-initio Simulation (VASP) package and the total energies of Li-Si-O compounds are evaluated using Projector Augmented Wave (PAW) method and correlated the structural characteristics of the binary system SiO-$Li_2O$ with experimental data from electrochemical method. Despite $Li_2SiO_3$ becomes stable phase by virtue of lowest formation energy calculated through VASP, the experimental method shows presence of $Li_4SiO_4$ as the only product formed when SiO and $Li_2O$ reacts during slow heating to reach $550^{\circ}C$ and found no evidence for the formation of $Li_2SiO_3$. Also, higher density of $Li_4SiO_4$(2.42 g $ml^{-1}$) compared to the compositional mixture $1SiO_2-2Li_2O$ (2.226 g $ml^{-1}$) and better cycle capacity observed through experiment proves that $Li_4SiO_4$ as the most stable anode supported by better cycleabilityfor lithium ion battery remains as paradox from the point of view of VASP calculations.

• Nuclear Engineering and Technology
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• v.55 no.8
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• pp.2966-2976
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• 2023

A tritium breeder is a lithium-based material capable of producing tritium. Many researchers designing nuclear-fusion energy are studying tritium production using pebbles, which are solid-type breeders. The sphericity and size of the pebbles are critical in obtaining pebbles with good tritium-breeding efficiency. Furthermore, tritium-release efficiency can be increased by using pebbles with appropriate porosities. Promising raw materials for tritium-breeding materials include Li₄SiO₄ and Li₂TiO₃. Li₄SiO₄ has a higher lithium density than Li₂TiO₃ and exhibits excellent tritium-breeding efficiency. However, it has the disadvantage of being easily decomposed during the Li₄SiO₄-green-pebble sintering process because of its low structural stability at high temperatures and high lithium density. In this study, we attempted to determine the optimal conditions for manufacturing Li₄SiO₄ pebbles using the droplet-freeze-drying method. The optimal Li₄SiO₄ slurry conditions and sintering temperatures were determined. The optimal Li₄SiO₄ slurry-fabrication conditions were 3 wt% polyvinyl alcohol and 75 wt% Li₄SiO₄ based on the deionized-water weight content. The sintering temperature at which Li₄SiO₄ did not decompose and exhibited the optimum porosity of 10.8% was 900 ℃.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.25 no.5
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• pp.398-402
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• 2012

Synthesis of $Li_2MnSiO_4$ was attempted by the conventional solid-state reaction method, and the phase formation behavior according to the change of the calcination condition was investigated. When the mixture of the three source materials, $Li_2O$, MnO and $SiO_2$ powders, were used for calcination in air, it was difficult to develop the $Li_2MnSiO_4$ phase because the oxidation number of $Mn^{2+}$ could not be maintained. Therefore, two-step calcination was applied: $Li_2SiO_3$ was made from $Li_2O$ and $SiO_2$ at the first step, and $Li_2MnSiO_4$ was synthesized from $Li_2SiO_3$ and MnO at the second step. It was easy to make $Li_2MnSiO_3$ from $Li_2O$ and $SiO_2$. $Li_2MnSiO_4$ single phase was developed by the calcination at $900^{\circ}C$ for 24 hr in Ar atmosphere as the oxidation of $Mn^{2+}$ was prevented. However, the $Li_2MnSiO_4$ was ${\gamma}-Li_2MnSiO_4$, one of the polymorph of $Li_2MnSiO_4$, which could not be used as the cathode materials in Li-ion batteries. By applying the additional low temperature annealing at $400^{\circ}C$, the single phase ${\beta}-Li_2MnSiO_4$ powder was synthesized successfully through the phase transition from ${\gamma}$ to ${\beta}$ phase.

• Journal of the Korean Electrochemical Society
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• v.18 no.4
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• pp.143-149
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• 2015

Carbon-coated $Li_2MnSiO_4$ powders as the active materials for the cathode were synthesized by planetary ball milling and solid-state reaction, and their phase formation behavior and charge-discharge properties were investigated. Calcination temperature and atmosphere were controlled in order to obtain the ${\beta}-Li_2MnSiO_4$ phase, which was active electrochemically, and the carbon-coated $Li_2MnSiO_4$ active material powders with near single phase ${\beta}-Li_2MnSiO_4$ could be fabricated. The particles of the synthesized powders were secondary particles composed of primary ones of about 100 nm size. The carbon incorporation was essential to enable the Li ions to be inserted and extracted from $Li_2MnSiO_4$ active materials, and the initial capacity of 192 mAh/g could be obtained in the $Li_2MnSiO_4$ active materials with 4.8 wt% of carbon.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.30 no.7
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• pp.447-453
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• 2017

In this study, $Li_2MnSiO_4$ cathode material and LiPON solid electrolyte were manufactured into thin films, and the possibility of their use in thin-film batteries was researched. When the RTP treatment was performed after $Li_2MnSiO_4$ cathode thin-film deposition on the SUS substrate by a sputtering method, a ${\beta}-Li_2MnSiO_4$ cathode thin film was successfully manufactured. The LiPON solid electrolyte was prepared by a reactive sputtering method using a $Li_3PO_4$ target and $N_2$ gas, and a homogeneous and flat thin film was deposited on a $Li_2MnSiO_4$ cathode thin film. In order to evaluate the electrochemical properties of the $Li_2MnSiO_4$ cathode thin films, coin cells using only a liquid electrolyte were prepared and the charge/discharge test was conducted. As a result, the amorphous thin film of RTP treated at $600^{\circ}C$ showed the highest initial discharge capacity of about $60{\mu}Ah/cm^2$. In cases of coin cells using liquid/solid double electrolyte, the discharge capacities of the $Li_2MnSiO_4$ cathode thin films were comparable to those without solid LiPON electrolyte. It was revealed that $Li_2MnSiO_4$ cathode thin films with LiPON solid electrolyte were applicable in thin film batteries.

• Korean Chemical Engineering Research
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• v.40 no.6
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• pp.752-756
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• 2002

Green-emitting $Zn_2SiO_4:Mn$ phosphors for PDP(Plasma Display Panel) application were synthesized by colloidal seed-assisted spray pyrolysis process. The codoping with $Gd^{3+}/Li^+$, which replaces $Si^{4+}$ site in the willemite structure, was performed to improve the luminous properties of the $Zn_2SiO_4:Mn$ phosphors. The particles prepared by spray pyrolysis process using fumed silica colloidal solution had a spherical shape, small particle size, narrow size distribution, and non-aggregation characteristics. The $Gd^{3+}/Li^+$ codoping amount affected the luminous characteristics of $Zn_2SiO_4:Mn$ phosphors. The codoping with proper amounts of $Gd^{3+}/Li^+$ improved both the photoluminescence efficiency and decay time of $Zn_2SiO_4:Mn$ phosphor particles. In spray pyrolysis, the post-treatment temperature is another factor controlling the luminous performance of $Zn_2SiO_4:Mn$ phosphors. The $Zn_{1.9}SiO_4:Mn_{0.1}$ phosphor particles containing 0.1 mol% $Gd^{3+}/Li^+$ co-dopant had a 5% higher PL intensity than the commercial product and 5.7 ms decay time after post-treatment at $1,145^{\circ}C$.

• Proceedings of the Korean Vacuum Society Conference
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• 2010.08a
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• pp.324-324
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• 2010

핵융합의 고체형 증식(Helium Cooled Solid Breeder : HCSB) 블랑켓(Blanket Module)은 삼중수소 증식을 위해서 Li4SiO4, Li2TiO3, Li2O 및 Li2ZrO3 등의 페블이 고려되고 있다. 이러한 페블을 제조하기 위해서는 먼저 각각의 분말 제조가 선행되어야 한다. 한국의 Test Blanket Module(TBM)은 Li4SiO4 페블을 개발을 개발하여 사용할 예정이고 옵션으로 Li2TiO3 페블을 개발하는 것으로 되어 있다. Li4SiO4 페블을 개발하기 위해서 먼저 분말합성이 필수적이다. Li4SiO4 분말을 합성에 하기 위해서는 Lithium 금속염과 실리카 졸을 용매 및 폴리머 캐리어로서의 두 가지 기능을 하는 에틸렌글리콜에 첨가한 후 가열하여 완전히 용해시킨 후 혼합 용액을 건조시켜 겔형의 전구체를 제조한다. 이를 하소한 후 결정화시켜 Silicate 분말을 얻는데 이때의 건조, 하소 및 결정화 온도의 조건에 따른 분말의 크기 및 특성이 각각 다르다. 즉, 바인더 물질의 비율과 합성온도에 따라 특성이 약간씩 다른 분말을 얻을 수 있었다. 이렇게 얻어진 Silicate 분말은 지르코니아 볼을 이용하여 약 24 시간 동안 볼 밀링 과정을 통해 입도가 작은 미세한 Silicate 분말로 만들었다. 합성된 분말은 여러 가지 시험 및 분석을 통해서 검증되었으며, 불순물 등은 관찰되지 않았다.

• Bulletin of the Korean Chemical Society
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• v.32 no.12
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• pp.4205-4209
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• 2011

The $Li_2Mn_{0.5}Fe_{0.5}SiO_4$ silicate was prepared by blending of $Li_2MnSiO_4$ and $Li_2FeSiO_4$ precursors with same molar ratio. The one of the silicates of $Li_2FeSiO_4$ is known as high capacitive up to ~330 mAh/g due to 2 mole electron exchange, and the other of $Li_2FeSiO_4$ has identical structure with $Li_2MnSiO_4$ and shows stable cycle with less capacity of ~170 mAh/g. The major drawback of silicate family is low electronic conductivity (3 orders of magnitude lower than $LiFePO_4$). To overcome this disadvantage, carbon composite of the silicate compound was prepared by sucrose mixing with silicate precursors and heat-treated in reducing atmosphere. The crystal structure and physical morphology of $Li_2Mn_{0.5}Fe_{0.5}SiO_4$ was investigated by X-ray diffraction, scanning electron microscopy, and high resolution transmission electron microscopy. The $Li_2Mn_{0.5}Fe_{0.5}SiO_4$/C nanocomposite has a maximum discharge capacity of 200 mAh/g, and 63% of its discharge capacity is retained after the tenth cycles. We have realized that more than 1 mole of electrons are exchanged in $Li_2Mn_{0.5}Fe_{0.5}SiO_4$. We have observed that $Li_2Mn_{0.5}Fe_{0.5}SiO_4$ is unstable structure upon first delithiation with structural collapse. High temperature cell performance result shows high capacity of discharge capacity (244 mAh/g) but it had poor capacity retention (50%) due to the accelerated structural degradation and related reaction.

• Journal of Korean Ophthalmic Optics Society
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• v.7 no.2
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• pp.27-31
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• 2002

Quarternary $Li_2O-B_2O_3-Al_2O_3-SiO_2$ glasses were fabricated by the function of $R({\equiv}Li_2Omole%/B_2O_3mole%)$ and $K({\equiv}(Al_2O_3mole%+SiO_2mole%/B_2O_3mole%)$. The structures of these glasses were investigated through refractive index and Vicker's hardness. The refractive index increased as the increase of the polarizability in the glass network. In the region of low $Li_2O$ content, the refractive index increased due to the increase of the polarizability in the glass network but, in the region of high $Li_2O$ content, the rate of increase of the refractive index decreased due to the increase of the molar volume caused by the formation of $BO_3{^-}$ units with relatively high molar volume. And, the refractive index decreased as the increase of $Al_2O_3+SiO_2$ content with the molar volume in the glass network. The increase and decrease of vicker's hardness values for those glasses depended on the fraction of tetrahedral $BO_4$ units and it of triangle $BO_3{^-}$ units with non-bridging oxygen, respectively.

• New Physics: Sae Mulli
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• v.68 no.11
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• pp.1196-1202
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• 2018

$Li_2Sr_{1-x}Eu_xSiO_{4-{\alpha}}N_{\alpha}$ ($Li_2SrSiO_{4-{\alpha}}N_{\alpha}:Eu^{2+}$) phosphors were synthesized by using a solid state reaction (SSR) method with submicron $Si_3N_4$ and nano $Si_3N_4$ powders as the sources of Si and N, and the optical properties of those phosphors were studied. The studied phosphors showed efficient excitation characteristics over the broad range from 230 to 530 nm. Also, They showed broad emission spectra covering a range from 500 to 700 nm, with a peak at 568 nm, which was shifted longer wavelength by 18 nm as compared with that of commercial $YAG:Ce^{3+}$. Combined with a 450 nm blue LED chip, the results support the application of the $Li_2SrSiO_{4-{\alpha}}N_{\alpha}:Eu^{2+}$ phosphor as a luminescent material for a white-light source thaat is warmer than the commercial $YAG:Ce^{3+}$ white-light source. In addition, the $Li_2SrSiO_{4-{\alpha}}N_{\alpha}$ phosphors prepared from a submicron $Si_3N_4$ powder was found to emit a previously unreported self-activated luminescence in $Li_2SrSiO_{4-{\alpha}}N_{\alpha}$.