• Journal of Electrochemical Science and Technology
• /
• 제14권2호
• /
• pp.152-161
• /
• 2023

Vanadium redox flow batteries (VRFBs) have been considered one of promising power sources for large scale energy storage systems (ESS) because of their excellent cycle performance and good safety. However, VRFBs still have a few challenging issues, such as poor Coulombic efficiency due to vanadium crossover between catholyte and anolyte, although recent efforts have shown promise in electrochemical performance. Herein, the vanadium complexes with various glyme ligands have been examined as active materials to suppress vanadium crossover between catholyte and anolyte, thus improving the Coulombic efficiency of VRFBs. The conventional Nafion membrane has a channel size of ca. 10 Å, whereas vanadium cation species are small compared to the Nafion membrane channel. For this reason, vanadium cations can permeate through the Nafion membrane, resulting in significant vanadium crossover during cycling, although the Nafion membrane is a kind of ion-selective membrane. In this regard, various glyme additives, such as 1,2-dimethoxyethane (monoglyme), diethylene glycol dimethyl ether (diglyme), and tetraethylene glycol dimethyl ether (tetraglyme) have been examined as complexing agents for vanadium cations to increase the size of vanadium-ligand complexes in electrolytes. Since the size of vanadium-glyme complexes is proportional to the chain length of glymes, the vanadium permeability of the Nafion membrane decreases with increasing the chain length of glymes. As a result, the vanadium complexes with tetraglyme shows the excellent electrochemical performance of VRFBs, such as stable capacity retention (90.4% after 100 cycles) and high Coulombic efficiency (98.2% over 100 cycles).

• Bulletin of the Korean Chemical Society
• /
• 제7권1호
• /
• pp.15-20
• /
• 1986

Modified technique in calculating the dipole moments for square pyramidal complexes has been developed and then the dipole moments for bisacetylacetonato(oxo)vanadium(Ⅳ) complexes are calculated, adopting this approach. The calculated dipole moments for bisacetylacetonato(oxo)vanadium(Ⅳ) in benzene and bisacetylacetonato(oxo)vanadium in dioxane solutions are in agreement with the observed values. The calculated dipole moments of bisacetylacetonato(oxo)vanadium(Ⅳ) in dioxane solution is slightly higher than that of bisacetylacetonato(oxo)vanadium(Ⅳ) in benzene. Such a result may suggest that bisacetylacetonato(oxo)vanadium(Ⅳ) interact with dioxane molecule to form bisacetylacetonato(oxo)vanadium(Ⅳ)-dioxane adduct. This calculated dipole moments are also in agreement with the experimental results.

• 대한화학회지
• /
• 제8권4호
• /
• pp.147-152
• /
• 1964

有機溶媒(benzene)에 의한 抽出法을 利用하고, 分光光度法에 의한 몰比法과 連續變化法을 써서, V(IV)-cupferrate와 V(V)-cupferrate의 化學沮成이 水溶液相에서 有機溶媒相으로 分配된 다음에도 雙하지 않을 것이라는 假定밑에서, 水溶液의 酸性度에 따르는 cupferrate 錯化合物의 化學組成을 決定하였다. V(IV)-cupferrate의 benzene 溶液에서의 最大吸光波長은 pH에 따라 445$m{\mu}$ 또는 450$m{\mu}$이고, V(V)-cupferrate의 그것은 pH 1.8以下에서는 pH에 無關하게 445$m{\mu}$이었다. V(V)-cupferrate의 化學組成은 沈澱이 形成되는 水溶液의 pH에 따라 다르며, pH 1.0 以下에서는 $VCupf_4$, pH 1.3∼1.7에서는 $HVOCupf_3$ 또는 $VCupf_4$와 $VOCupf_2$의 거의 같은 몰씩으로된 混合物이고, pH 1.8∼4.3에서는 $VOCupf_2$이었다. V(V)-cupferrate의 化學組成은 水溶液의 pH에 따라 變化가 없고, pH 1.8 以下에서는 $HVO_2Cupf_2$이었다.

• 한국자기공명학회논문지
• /
• 제1권1호
• /
• pp.1-6
• /
• 1997

Several dioxovanadate (V) complexes are synthesized and studied by solution and solid-state 51V NMR spectroscopy. In the results, large 51V chemical shift anisotropy ({{{{ DELTA delta }}a = -800 ∼720 ppm) and quadrupole coupling (e2q /h = 7.50 ∼ 9.16 MHz) were observed in the solid-state complexes. The isotropic chemical shifts of the solid samples are very close to the values obtained from solution measurements.

• Korean Chemical Engineering Research
• /
• 제43권1호
• /
• pp.33-38
• /
• 2005

피콜리네이트 착화제가 들어있는 제염 폐액에서 바나듐 및 철 이온종의 평행분배 거동을 pH 값과 조성이 다른 여러 조건에서 모사하였다. 피콜리네이트 대 바나듐의 몰비를 일정한 값으로 고정하고 금속 이온의 농도를 변화시킬 경우 평행분배 곡선의 형태는 바나듐에 대한 피콜리네이트의 농도가 6배인 고농도 및 3배인 저농도 LOMI 제염 조건의 용액에서 모두 크게 바뀌지 않았다. 그러나 저농도 피콜리네이트 조건의 용액에서는 철(II)-피콜리네이트의 평행분배 곡선의 형태가 많이 변화하였는데, 이와 같은 현상은 용액에 들어있는 철에 대한 피콜리네이트의 상대적인 양이 부족하기 때문에 일어나며 바나듐(III) 및 철(II) 이온종이 피콜리네이트 착화물을 형성하는 안정도 상수(stability constant)의 차이에서 비롯된다. 본 연구에서 구한 평형분배 곡선은 이온교환 조작과 같은 LOMI 제염 폐액의 처리 과정에서 용액의 조건 변화에 따른 반응 현상을 예측하거나 이해하는데 매우 유용하게 활용될 수 있다.

• Bulletin of the Korean Chemical Society
• /
• 제14권5호
• /
• pp.557-561
• /
• 1993

The interaction of vanadium(V) with various a-hydroxycarboxylate ligands in aqueous solution at pH 3.2 have been studied by $^{51}V$ and $^{13}C$ NMR spectroscopies. From the results it is supposed that vanadates mainly form the octahedral complexes with lactate, 2-hydroxybutyrate, glycerate, and malate. While, vanadates form the trigonal-bipyramidal complexes with glycolate, tartarate, and 2-hydroxy-3-methylbutyrate, and tetrahedral complexes with pyruvate(diol), 2-hydroxyisobutyrate, and 2-hydroxy-3-methylbutyrate. The bipyramidal products are formed as monomeric compounds. The octahedral products are formed as dimeric compounds with no evidence for a significant proportion of the monomeric derivatives. The complexes are mainly formed through the coordination at the carboxylate and the 2-hydroxyl groups of the ligands.

• Bulletin of the Korean Chemical Society
• /
• 제24권7호
• /
• pp.1014-1016
• /
• 2003

• 대한화학회지
• /
• 제45권3호
• /
• pp.213-218
• /
• 2001

Peroxo-vanadium(V) 화합물인 $VO(O_2)_2(pic)^{2-}$와 $VO(O_2)(nta)^{2-}$ 그리고 $VO(O_2)(dipic)^-$는 pH4.0의 수용액 안에서 thiolato-cobalt(III)화합물인 $(en)_2$Co$($SCH_2CH_2NH_2$)^{2+}$와 산소 원자 전이 반응을 일으킨다. 이들의 산소 원자 전이 반응에서 각각(35$\pm$1)와 $(4.8{\pm}0.4){\times}10^{-2}$ 그리고 $(8.6{\pm}0.5){\times}10^{-4}$의 속도상수($M^{-1}$$S^{-1}$)을 얻었다. $VO(O_2)_2(pic)^{2-}$에 배위되어 있는 peroxide는 산소 원자 전이 반응에서 활성화되어지나 $VO(O_2)(nta)^{2-}$ 와 $VO(O_2)(dipic)^-$에 배위되어 있는 peroxide는 불활성화된다. 우리는 이 논문에서 peroxo vanadium(V) 화합물의 산소 원자 전이의 반응 경로는 친전자성의 peroxide 리간드가 친핵성의 substrate와 직접적인 반응에 의하여 이루어진다고 제안하였다.

• Bulletin of the Korean Chemical Society
• /
• 제13권1호
• /
• pp.22-26
• /
• 1992

The solution structures of the vanadium(V) complexes of iminodiacetate analogues, such as iminodiacetate (IDA), methyliminodiacetate (MeIDA), ethyliminodiacetate (EtIDA), benzyliminodiacetate (BzIDA), pyridine-2,6-dicarboxylate (DPA), and 2-hydroxyethyliminodiacetate (HEIDA), have been studied by $^{13}C-$ and $^{51}V$-NMR spectroscopy. Assuming that the complexes have a $cis-VO_2$ core, IDA, MeIDA, EtIDA, and BzIDA act as facial tridentate ligands to form octahedral complexes, whereas DPA coordinates to $VO_2^+$ as a meridional tridentate. And one water molecule fulfills the remaining site to satisfy the coordination number of six. But HEIDA coordinates to $VO_2^+$ through one IDA moiety and one hydroxyl group, acting as a tetradenate.

• Journal of Photoscience
• /
• 제9권2호
• /
• pp.412-414
• /
• 2002

Several peroxovanadium(V) complexes with an organic chelate ligand decompose spontaneously, depending on the nature of the chelate ligand. The self-decomposition reactions of the dinuclear peroxovanadium(V) complex with 2-oxo-l,3-diaminopropane-N,N,N',N'-tetraacetate (dpot) and the peroxovanadium(V) complexes with N-carboxymethylhistidinate (cmhist) and histamine-N,N-diacetate (histada) accompany the reduction of vanadium(V) to vanadium(IV). This implies that the peroxide anion acts as a reducing agent and thus the peroxide is oxidized in the decomposition process of the peroxovanadium(V) complexes. The oxidized dioxygen species have been characterized spectrophotometrically. Superoxide anion has been detected in 2-3 % yields using the reduction of cytochrome c method and chemiluminescence method utilized MCLA as a fluorescer. Singlet oxygen has also been detected in higher yields on the basis of chemiluminescence of tryptophan.