• Title/Summary/Keyword: $^6Li$ NMR

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Local Environments of Li in the Interlayer of Clay Minerals at Room and High Temperatures (상온 및 고온에서 점토광물 층간의 Li 환경)

  • Kim, Yeong-Kyoo;Lee, Ji-Eun
    • Journal of the Mineralogical Society of Korea
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    • v.20 no.3
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    • pp.193-201
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    • 2007
  • We used $^6Li$ and $^7Li$ MAS NMR to investigate the fate and local environments of Li in the interlayer of clay minerals such as hectorite, Woming-montmorillonite, beidellite, and lepidollite at room and high ($250^{\circ}C$) temperature. Although $^6Li$ NMR spectra show narrower peaks than those of $^7Li$ NMR, S/N ratio is low and there are no obvious differences in chemical shifts suggesting that it is difficult to apply $^6Li$ NMR to have information on the local environments of Li in the clay interlayers. $^7Li$ NMR spectra, however, show changes in the peak width and quadrupole patterns providing information on the local environments of Li in the interlayer even though changes in the chemical shift are not observed. In montmorillonite, two different local environments of Li are observed; one has a narrow peak with typical quadrupole patterns whereas another has a broad peak without those of the patterns. Changes in the peak width is also observed from broad to narrow in the $^7Li$ NMR spectra for beidellite but not for hectorite at high temperature. Our results suggest that the peak width change in the broad peak is attributed to the coordination changes in the water molecules around Li which is tightly bonded on the basal oxygen of Si tetrahedra as inner-sphere complexes. The narrow peak in montmorillnoite can be assigned to the Li bended as outer-sphere complexes.

Ex-situ 7Li MAS NMR Study of Olivine Structured Material for Cathode of Lithium Ion Battery

  • Lee, Youngil;An, JiEun;Park, Seul-A;Song, HyeYeong
    • Journal of the Korean Magnetic Resonance Society
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    • v.18 no.2
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    • pp.63-68
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    • 2014
  • $^7Li$ nuclear magnetic resonance (NMR) spectra have been observed for $LiMPO_4$ (M = Fe, Mn) samples, as a promising cathode material of lithium ion battery. Observed $^7Li$ shifts of $LiFe_{1-x}Mn_xPO_4$ (x = 0, 0.6, 0.8, and 1) synthesized with solid-state reaction are compared with calculated $^7Li$ shift ranges based on the supertranferred hyperfine interaction of Li-O-M. Ex situ $^7Li$ NMR study of $LiFe_{0.4}Mn_{0.6}PO_4$ in different cut-off voltage for the first charge process is also performed to understand the relationship between $^7Li$ chemical shift and oxidation state of metals affected by delithiation process. The increment of oxidation state for metals makes to downfield shift of $^7Li$ by influencing the supertranferred hyperfine interaction.

Preparation and cation mixing phenomena of LiCo$O_2$and $LiCo_{1-x}$$Ni_x$$O_2$ solid solutions (LiCo$O_2$$LiCo_{1-x}$$Ni_x$$O_2$고용체의 제조 및 양이온 혼합 현상)

  • 임창성;안홍주;강승민;하정수;고영신
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.9 no.6
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    • pp.601-605
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    • 1999
  • $LiCoO_2$and $LiCo_{1-x}$$Ni_x$$O_2$ solid solutions were fabricated by the solid state reaction process. The structural cation mixing phenomena were investigated using XRD, SEM, particle size analysis and $^7$Li NMR,The synthesized LiCoO$_2$ and $LiCo_{1-x}Ni_XO_2$ microcrystallines showed the hexagonal layered structures. Mean particle sizes were increased with the increase of the amount of nickel in the solid solutions. The cation mixing effects were increased as increasing the fraction of nickel(x), x = 0.3, 0.5, 0.7. the peak frequency of $^7$Li NMR was shifted to the higher frequency and the line width increased as increasing the amount of nickel in the solid solutions.

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Photo-induced Isomerization and Polymerization of (Z,Z)-Muconate Anion in the Gallery Space of [LiAl2(OH)6]+ Layers

  • Rhee, Seog-Woo;Jung, Duk-Young
    • Bulletin of the Korean Chemical Society
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    • v.23 no.1
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    • pp.35-40
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    • 2002
  • Photoreaction of guest organic anions in layered organic-inorganic hybrid materials was investigated. The layered hybrids were synthesized by an anion-exchange reaction of $[LiAl_2(OH)_6]Cl{\cdot}yH_2O$ layered double hydroxide with aqueous (Z,Z)- and (E,E)-muconates under inert atmospheric condition, to give new organicinorganic hybrids of $[LiAl_2(OH)_6]_2[(Z,Z)-C_6H_4O_4]{\cdot}zH_2O$ and $[LiAl_2(OH)_6]_2[(E,E)-C_6H_4O_4]{\cdot}H_2O$, respectively. The basal spacings calculated by XRPD of intercalates indicate that muconate anions have almost vertical arrangements against the host $[LiAl_2(OH)_6]^+$ lattices in the interlayer of organic-inorganic hybrid materials. When UV light was irradiated on the suspension of $[LiAl_2(OH)_6]_2[(Z,Z)-C_6H_4O_4]{\cdot}zH_2O$, the (Z,Z)-muconate anions of the gallery space of hybrids were polymerized in the aqueous media while it was isomerized into more stable (E,E)-muconate in the methanollic suspension in the presence of catalytic amount of molecular iodine. All the products were characterized using elemental analysis, TGA, XRPD, FT-IR, $^1H$ NMR and $^{13}C$ CP-MAS NMR.

Study of molecular motion by 1H NMR relaxation in ferroelectric LiH3(SeO3)2, Li2SO4·H2O, and LiN2H5SO4 single crystals

  • Park, Sung Soo
    • Journal of the Korean Magnetic Resonance Society
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    • v.20 no.1
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    • pp.1-6
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    • 2016
  • The proton NMR line widths and spin-lattice relaxation rates, $T_1^{-1}$, of ferroelectric $LiH_3(SeO_3)_2$, $Li_2SO_4{\cdot}H_2O$, and $LiN_2H_5SO_4$ single crystals were measured as a function of temperature. The line width measurements reveal rigid lattice behavior of all the crystals at low temperatures and line narrowing due to molecular motion at higher temperatures. The temperature dependences of the proton $T_1^{-1}$ for these crystals exhibit maxima, which are attributed to the effects of molecular motion by the Bloembergen - Purcell - Pound theory. The activation energies for the molecular motions of $^1H$ in these crystals were obtained. From these analysis, $^1H$ in $LiH_3(SeO_3)_2$ undergoes molecular motion more easily than $^1H$ in $LiN_2H_5SO_4$ and $Li_2SO_4{\cdot}H_2O$ crystals.

The Oxyanions of Calix[4]arene:The NMR Investigation of the Structure of the Oxyanions of Calix[4]arene

  • 남규천;김대순;김종민
    • Bulletin of the Korean Chemical Society
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    • v.18 no.6
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    • pp.636-640
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    • 1997
  • The structure and conformational behavior of the oxyanions of calix[4]arene have been studied by the NMR spectrum. The structure of the oxyanions of calix[4]arene was completely dependent upon the counter cation in present. All of the anions derived from in the presence of NaH and KH appear to exist as a cone conformation, whereas those produced with lithium cation such as n-butyllithium and LiOD show a more varied conformational behavior. The mono and tetraanions with lithium cation exist as a cone conformation, the trianions appear to exist as a partial cone conformation, and the dianions appear to disproportionate to the mono and trianions. The conformational stability decreases in the order of $Li^+$ oxyanion > $Na^+$ oxyanion > $K^+$ oxyanion.

Analysis of Gingerol Compounds of Raw Ginger (Zingiber officinale Roscoe) and Its Paste by High Performance Liquid Chromatograph-Mass Spectrometry (LC/MS) (LC/MS에 의한 원료생강 및 생강 페이스트 중의 Gingerol 화합물 분석)

  • 조길석
    • Journal of the Korean Society of Food Science and Nutrition
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    • v.29 no.5
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    • pp.747-751
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    • 2000
  • This study was carried out to improve the analysis method of gingerol compounds from ginger (Zingiber officinale Roscoe). Pungent components of ginger were extracted by acetone and lisolated by thin layer chromatography (TLC) and high performance liquid chromatography (HPLC) with LiChrosorb RP-18 column. Three homologues of gingerols were identified by HPLC-mass spectrometry (LC/MS) and nuclear magnetic resonance (NMR). The contents of [6]-, [8]- and [10]-gingerols in three homologues identified were 635.3 mg%, 206.6 mg% and 145.7 mg% in raw ginger, and were 418.2 mg%, 142.6 mg% and 103.3 mg% in ginger paste, respectively.

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Synthesis, Characterization and Complexation Behavior Investigations of Novel Bis- and Tris-crown Ethers

  • Huang, Zhi Bin;Kim, Sung-Hong;Chang, Seung-Hyun
    • Bulletin of the Korean Chemical Society
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    • v.27 no.6
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    • pp.893-898
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    • 2006
  • Novel bis- and tris-crown ethers were synthesized from 1-aza and diaza-crown ethers with 2-acryloyloxy-methyl crown ethers through Michael addition. The synthesized bis- and tris-crown ethers were characterized by their elemental analyses, $^1H$-NMR, $^{13}C$-NMR, mass spectra, IR spectra, respectively. The complexation behavior of the bis- and tris-crown ethers with $Li^+$, $Na^+$, $Na^+$, $Rb^+$, $Cs^+$ was examined by $^1H$-NMR, FAB mass, and UV spectrometry.

13C NMR-Study of 1,1-Dipotassio-2,3,4,5-Tetraphenyl-1-Silacyclopentadienide Dianion [SiC4Ph4] 2-·2[K+ ] and 1,1-Dipotassio-2,3,4,5-Tetraphenyl-1- Germacyclopentadienide Dianion [GeC4Ph4] 2-·2[K+ ]

  • Hong, Jang-Hwan
    • Journal of Integrative Natural Science
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    • v.10 no.3
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    • pp.131-136
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    • 2017
  • The chemical shifts in the $^{13}C$ NMR spectra of 2,3,4,5-tetraphenyl-1-silacyclopentdienide dianion $[SiC_4Ph_4]^{2-}{\cdot}2[K^+]$ (3) and 2,3,4,5-tetraphenyl-1-germacyclopentdienide dianion $[GeC_4Ph_4]^{2-}{\cdot}2[K^+]$ (4) were compared to those of $[SiC_4Ph_4]^{2-}{\cdot}2[Li^+]$ (5), $[SiC_4Ph_4]^{2-}{\cdot}2[Na^+]$ (6), and $[GeC_4Ph_4]^{2-}{\cdot}2[Li^+]$ (7). The average polarizations in two phenyl groups of two potassium salts are decreased over 15% to 20% comparing to those of the lithium salts and sodium salt {$[EC_4Ph_4]^{2-}{\cdot}2[M^+]$ (E=Si, Ge, M=Li, Na) due to the effect of the counter potassium cation.

The Electrochemical Properties on the Silver Doped Vanadium Oxide Xerogel (미량의 은이 첨가된 바나듐산화물 전극)

  • Park Heai-Ku;Kim, Gun-Tae;Lee, Man-Ho
    • Journal of the Korean Electrochemical Society
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    • v.5 no.1
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    • pp.1-6
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    • 2002
  • Silver doped vanadium pentoxides with a doping ratio Ag/V ranging from 0.03 to 0.11 were synthesized by sol-gel process, and $Li/Ag_xV_2O_5$ cell was investigated by the electrochemical methods. It appears to be amorphous layered material and entangled fibrous textures has been grown to form anisotropic corrugated fibrils. NMR measurements revealed that several different kinds of $Li^+$ ions exist in the lithium intercalated xerogel electrodes and the average cell potential was about 3.0V vs. $Li/Li^+$. The cell capacity of the silver doped $Ag_xV_2O_5$ xerogel cathodes was more than 359 mAh/g at discharge current 10mA/g and cycle efficiency $94\%$ was achieved.