ОСОБЛИВОСТІ БУДОВИ ТА ЕЛЕКТРОПРОВІДНОСТІ НЕВОДНИХ ЕЛЕКТРОЛІТІВ НА ОСНОВІ БІС(САЛІЦИЛО)БОРАТІВ ТА БІС(ОКСАЛАТО)БОРАТІВ ЛУЖНИХ МЕТАЛІВ
The structure and coordination environment of non-aqueous electrolytes based on bis(salicyl)borates of lithium, sodium, potassium, tetramethylammonium (MeBSB) and bis(oxalato)borates from lithium to cesium (MeBOB) using NMR spectroscopy have been investigated. Bis(salicyl)borates (BSB) and bis(oxala...
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| Дата: | 2019 |
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| Автори: | , , , , , , , , |
| Формат: | Стаття |
| Мова: | Англійська |
| Опубліковано: |
V.I.Vernadsky Institute of General and Inorganic Chemistry
2019
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| Назва журналу: | Ukrainian Chemistry Journal |
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Репозитарії
Ukrainian Chemistry Journal| _version_ | 1871465507681468416 |
|---|---|
| author | Diamant, Viktor Trachevskii, Volodymyr Pershina, Katherine Ogenko, Volodymyr Donchu, Chen Huawen, Hu Min, Chen Xiaowen, Wang Menglei, Chang |
| author_facet | Diamant, Viktor Trachevskii, Volodymyr Pershina, Katherine Ogenko, Volodymyr Donchu, Chen Huawen, Hu Min, Chen Xiaowen, Wang Menglei, Chang |
| author_institution_txt_mv | [
{
"author": "Viktor Diamant",
"institution": "Vernadsky Institute of General and Inorganic Chemistry N.A.S of Ukraine, Kiev, Palladin av., 32\/34,03142 Ukraine"
},
{
"author": "Volodymyr Trachevskii",
"institution": "G. V. Kurdyumov Institute for Metal Physics of the N.A.S. of Ukraine 36 Academician Vernadsky Boulevard, UA-03142 Kyiv, Ukraine"
},
{
"author": "Katherine Pershina",
"institution": "Vernadsky Institute of General and Inorganic Chemistry N.A.S of Ukraine, Kiev, Palladin av., 32\/34,03142 Ukraine"
},
{
"author": "Volodymyr Ogenko",
"institution": "Vernadsky Institute of General and Inorganic Chemistry N.A.S of Ukraine, Kiev, Palladin av., 32\/34,03142 Ukraine"
},
{
"author": "Chen Donchu",
"institution": "School of Materials Science and Energy Engineering, Foshan University, Jiangwan Ferst Road, Chancheng, Foshan 528000, Guangdong, China"
},
{
"author": "Hu Huawen",
"institution": "School of Materials Science and Energy Engineering, Foshan University, Jiangwan Ferst Road, Chancheng, Foshan 528000, Guangdong, China"
},
{
"author": "Chen Min",
"institution": "School of Materials Science and Energy Engineering, Foshan University, Jiangwan Ferst Road, Chancheng, Foshan 528000, Guangdong, China"
},
{
"author": "Wang Xiaowen",
"institution": "School of Materials Science and Energy Engineering, Foshan University, Jiangwan Ferst Road, Chancheng, Foshan 528000, Guangdong, China"
},
{
"author": "Chang Menglei",
"institution": "School of Materials Science and Energy Engineering, Foshan University, Jiangwan Ferst Road, Chancheng, Foshan 528000, Guangdong, China"
}
] |
| author_sort | Diamant, Viktor |
| baseUrl_str | https://ucj.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2026-07-22T08:23:40Z |
| description | The structure and coordination environment of non-aqueous electrolytes based on bis(salicyl)borates of lithium, sodium, potassium, tetramethylammonium (MeBSB) and bis(oxalato)borates from lithium to cesium (MeBOB) using NMR spectroscopy have been investigated. Bis(salicyl)borates (BSB) and bis(oxalate)borates (BOB) of alkali metals and organic cations are considered as promising electroconductive components of electrolytes of modern chemical sources of current (lithium, sodium ion batteries and super-capacitors). The salts were synthesized by the microwave radiation method. The 13C and 11B NMR spectra analysis determined the presence of symmetric structure in BOB anion and the presence of two optical conformations of the BSB anion with labile coordination environment of boron. The conformations of the BSB are the result of the ion contact pairs formation. In the case of tetramethylammonium cation the presence of conformations are depended on the reactive medium.
The conformational lability of the coordination sphere of NaBSB dissolved in DMAA is connected with increasing of the integral intensity of carboxyl group singles relatively signals of carbon atoms in fragments of another functional affiliation when the time delay between radio frequencies varies within 2-15 seconds. The difference in the structure of these anions leads to a change in the thermal dependence of the electrical conductivity of BSB and the transport of ions in non-aqueous solvents. Maximum electrical conductivity of salt solutions in DMFA is achieved at close concentrations of 0.75 m for KBSB and 0.77-1 m for NaBSB. The solubility of BSB is better than the BOB. Based on the measurements of the conductivity and the data of electrochemical impedance spectroscopy (the angle of inclination of spectra in the Nyquist coordinates in the low frequency range, the phase angle shift at a frequency) it was proposed the existence of two ways of ions and charge transfer in the electrolytes: diffusion and relay transport. The possibility of formation of a labile salt complex with a solvent due to hydrogen bonds is established.
  |
| doi_str_mv | 10.33609/0041-6045.85.3.2019.49-55 |
| first_indexed | 2025-09-24T17:43:28Z |
| format | Article |
| fulltext |
UDK 544.6 doi: 10.33609/0041-6045.85.3.2019.49-55
V.A.Diamant1, V.V.Trachevskii2, K.D.Pershina1*, V.M.Ogenko1, Chen Dongchu3,
Hu Huawen3, Chen Min3, Wang Xiaowen3, Chang Menglei3
SPECIALTIES OF THE STRUCTURE AND CONDUCTIVITY
OF THE NON-AQUEOUS ELECTROLYTES BASED ON ALKALI METAL
BIS (SALICYL) BORATES AND BIS (OXALATO) BORATES
1 V.I.Vernadsky Institute of General and Inorganic Chemistry of National Academy
of Sciences of Ukraine, 32/34 Academic Palladin Avenue, Kiev, 03142, Ukraine
2 G.V.Kurdyumov Institute for Metal Physics of National Academy of Sciences
of Ukraine, 36 Academic Vernadsky Boulevard, Kyiv, 03142, Ukraine
3 School of Materials Science and Energy Engineering, Foshan University,
Jiangwan First Road, Chancheng, Foshan, 528000, Guangdong, China
* e-mail: Pershina@ionc.kiev.ua
The structure and coordination environment of non-aqueous electrolytes based on bis (salicyl)
borates of lithium, sodium and potassium, and bis (oxalato) borates from lithium to cesium
using NMR spectroscopy have been investigated. The NMR spectra analysis of 13C and 11B
found the presence of R-, S-enantiomers in bis (salicyl) borate anion with a labile coordinati-
on sphere of boron in the presence of a solvent. This difference affects the final structure of
the electrolytes and leads to a change in the thermal dependence of the electrical conductivity
of bis (salicyl) borates and the ways of ions transport relatively bis (oxalate) borates in non-
aqueous solvents.
K e y w o r d s: non-aqueous electrolyte, alkali metal bis (salicyl) borates, conductivity, structure,
labile complex, ion transport.
INTRODUCTION. Electrolytes are the key
components of all the modern chemical power so-
urces (CPS). Their main function is to ensure the
conductivity between the electrodes, to form the
capacity and the ability to cycle. Bis (salicyl) bo-
rates and bis (oxalato) borates of alkali metals
and organic cations are promising electroconduc-
tive components of electrolytes of modern CPS
(lithium-, sodium-ion batteries and super-capaci-
tors) [1–4]. In this case it is very necessary to
have the representation about solvents influence
on the electrolytes structure and conducting pro-
perties of salt-solvent system. Some approaches
adjust these properties through combinations of
solvents with different dynamic viscosities and
dielectric permeability values. In particular, high
conductivity values are achieved by obtaining a
stable electrolyte layer on the anodes surface [5].
Another option of increasing the electrolyte ion
conductivity is the using of lithium salts solu-
tions with organic anions in dimethyl sulfoxide
(DMSO), propylene carbonate or other aprotic di-
polar solvents. However, the modern study have
clarified that the main role of the conductivity
formation had a specific cluster-based supra-mo-
lecular architecture of the electrolyte in case of
full salt dissociation [6–10]. Such clusters stabi-
lize due to the equilibrium between the processes
of interconversion, and their production rate (in-
cluding salvato splited or contact pairs) depends
on the salt-solvent ratio [6–10].
Thus, the aim of current work is the deter-
mination of the relationship between the structu-
res and conductivity of electrolytes based on alka-
li metals bis (salicyl) borates and bis (oxalato)
borates with the solvent nature.
© V.A.Diamant, V.V.Trachevskii, K.D.Pershina, V.M.Ogenko, Chen Dongchu, Hu Huawen,
Chen Min, Wang Xiaowen, Chang Menglei, 2019
Фізична хімія
ISSN 0041-6045. УКР. ХІМ. ЖУРН., 2019, т. 85, № 3 49
mailto:Pershina@ionc.kiev.ua
EXPERIMENTAL PART. The synthesis was
done by microwave method by keeping the mix-
ture of stoichiometric components during 10–15
min [11]. The final product was recrystallized
from dry isopropanol. The obtained mixture was
analyzed using ANANCE 400 spectrometer (Bru-
ker, Germany).
Samples for NMR studies 13C and 11В were
prepared by obtaining a saturated solution of bis-
(saltillo)borate sodium (NaBSB), bis(salicyl)bo-
rate potassium (KBSS) in dimethyl sulfoxide
(DMSO), dimethylformamid (DMFA) and dime-
thylacetamide (DMAA) in proportion of 0.3–0.4 g
per 1 g of the solvent. Boric acid solution in water
and tetramethylsilane in DMSO were used as stan-
dards for NMR spectra recording. The formation
of R-, S-enantiomers was recorded using the 13C
NMR spectral chemical shift of the carbon signals
in carboxyl group.
Temperature dependences of electrical con-
ductivity were measured on the Metrohm Auto-
lab-30 30 PGSTAT.301N electrochemical module
using a 2-electrode isolated 2 cm3 cell with the
platinum electrodes (constant cell value was 24.135
Ohms). The temperature regime was maintained
using a thermostat with a measurement error ± 1
oC. Before measurements, the samples have been
incubated at respective temperature for 30 min for
achieved equilibrium in the solution.
RESULTS AND DISCUSSION. The analysis of
11B NMR spectra have shown that similar to the
bis(oxalato)borate (BOB–) spectrum of bis(sali-
cyl)borate (BSB–) anion in dimethyl sulfoxide
(DMSO) is characterized by one boron atom sig-
nal and has a stronger shift by δ = –11.5 м.d. BSB–
in comparison with BOB– signal δ = –7.1 м.d. The
BSB– spectra of salts with all three cations have
the same δ signal positions and are identical to
the spectrum of bis(oxalato) and LiBSB. In con-
trast to the BOB– there were 6 carbon signals of
the benzene ring and one signal of the carboxyl
group identified for BSB– anion in the NMR
spectrum. The BSB– spectra for salts with all
three cations have the same δ signal positions and
are identical to the bis(oxalato) spectrum of lithi-
um borate (LiBSB). In contrast to the BOB–
there were 6 carbon signals of the benzene ring
and one signal of the carboxyl group identified
for BSB– anion in the NMR spectrum. In the
13C NMR spectra of bis(oxalato)borate there is
only an intense signal at δ = 157.36 ppm, which
is responsible for all four carboxyl groups. The
two carboxyl groups bis(salicyl)borate in the spe-
ctrum of the NaBSB solution in DMAA (1
mol/kg) have two separate signals 167 and 162
ppm respectively (Fig. 1, a,b).
The carbon atoms of carboxylic groups ex-
Fig. 1. Spectrum 13C-NMR: a – NaBSB in DMAA
1 m 20 °C; b – LiBOB in DMSO 1 m 20 °C.
а
b
V.A.Diamant, V.V.Trachevskii, K.D.Pershina, V.M.Ogenko, Chen Dongchu et al.
50 ISSN 0041-6045. УКР. ХІМ. ЖУРН., 2019, т. 85, № 3
press by two signals in the spectra of solutions
of LiBSB and NaBSB in dimethylacetamide,
which points to the presence of R-S-isomers of
complex ions (Fig. 2). Conformational lability of
the coordination sphere of the sodium bis(salicyl)
borate upon dissolution in DMAA leads to the
doubling of the integrated intensity of singlet car-
boxyl groups compared with the signals of the
carbon atoms in fragments of another functional
group at delays of the time between RF pulses in
range 2–15 seconds.
It is well know that the R-enantiomer of such
salts take part in the formation of the contact ion
pairs in DMSO, that means it could has tendency
to form supramolecular structures [6–10]. In the
dimethylformamide solution of tetramethylam-
monium salt, as well as for alkali metal salts, two
signals of carbon atoms of the carboxyl group are
observed, while the value of chemical shifts of
the carbon atoms 4, 5 and 3, 6 signals are signi-
ficantly separated, which can be explained by the
ability to form the salt-solvent hydrogen bonds
due to steric effect [6–10] (table 1).
The existence of an intermolecular hydrogen
bonds system is a condition for the implementa-
tion of the relay mechanism. Therefore, the proba-
bility of realization of the relay charge transfer
in electrolytes with the corresponding architectu-
re increases. Thus, the electrical conductivity mea-
sured at different temperatures has been depen-
dent on the salt concentration. There conductivi-
ties of the sodium and potassium bis(salicyl)bora-
tes solutions in DMFA were identified in a wide
T a b l e 1
The 13C NMR signals spectrum classification
(δBSB
– ppm)
LiBSВ NaBSВ Me4NBSВ Carbon
atomsDMAA DMFA DMAA
166.92 167 172.917 171.5 C1=O
162.35 162 171.73 — C1*=O
137.12 137 137 137 C7–O
132 132 133.44 133.2 C3–C6
131.98 131.9
121.17 120.67 133.35 133.2 C4–C5
120.68 121.17 133.32
118.53 119 — — C2–C
Fig. 2. Optical isomerism of bis(salicyl)borate
ion a (R), b (S).
a b
Fig. 3. Temperature dependence of electrical conduc-
tivity of KBSB solutions in DMFA: 1 – 0.5; 2 – 0.77;
3 – 0.985; 4 – 1.7; 5 – 3; 6 – 4 mol/kg
Fig. 4. The temperature dependence of electrical con-
ductivity of NaBSB solutions in DMFA: 1 – 0.5;
2 – 0.75; 3 – 1.0; 4 – 2.0 mol/kg.
Specialties of the structure and conductivity ...
ISSN 0041-6045. УКР. ХІМ. ЖУРН., 2019, т. 85, № 3 51
concentration and temperature range (Fig. 3, 4).
The maximum electrical conductivity of soluti-
ons in DMFA is reached at concentrations clo-
se to 0.75 mol/kg (for KBSB) and 0.77–1 mol/
kg (for NaBSB). This means, that in this case a
new system is able to ion transfer through relay
mechanism (Fig. 2, b). This concentration ran-
ge is wider for sodium ions than for potassium
ions with similar values of their solubility (tab-
le 2). Such dependence was not found for salts
with BOB-anions, since they (except for lithi-
um salts) have weak solubility, low electrical
conductivity and no isomers (table 3). Sodium
BOB dissolves well in DMFA and DMSO but
its solubility is much weaker in acetonitrile and
carbonate esters, which effects the solutions con-
ductivity of the following salts [12, 13].
Further analysis of impedance spectra of these
salts approved the existence of an area that has
maximum electrical conductivity and is characte-
rized by a 45o slope angle of spectral curves in
Nyquist coordinates in the low-frequency range.
According to literature data, such spectrum proves
the existence of diffusion phenomena in the elect-
rochemical system [14]. The angle slopes of the
curves decrease with the temperature rising (Fig.
5, a,b), which could be explained by a decreasing
of the part of ions diffusion transport. However,
the following increase of electrical conductivity re-
veals the existence of a second ion transport path-
T a b l e 2
The solubility of bis(salicyl)borates of sodium
and potassium (NaBSB and KBSB) in amide
solvents and DMSO
Solvent NaBSB KBSB
Carbamide 1 mol : 10 mol 1 mol : 10 mol
Acetamide 1 mol : 10 mol 1 mol : 10 mol
DMSO ~ 1.1 M ~ 1.1 M
DMFA ~ 4 M (1:2.92) ~ 3.94 М (1:3.3)
N-methyl acetamide ~ 2.3 М (1:5.62) 0.69 M
N-methyl acetamide ~ 4 M (1:2.92) Not identified
Propylene carbonate — 0.73 M
T a b l e 3
The electrical conductivity value of LiBОB
and LiBSB 0.6 mol/kg
LiBSB1 LiBSB2 LiBOB3
t, oC σ, mS/cm t, oC σ, mS/cm t, oC σ, mS/cm
20 0.62 26 1.25 17 3.58
25 0.74 43 1.83 24 4.16
39 1.14 61 2.62 25 4.20
57 1.52 31 4.74
1 LiBSB of propylene carbonate; 2 LiBSB of ethyle-
ne carbonate-dimethyl carbonate; 3 LiBOB of ethylene
carbonate-dimethyl carbonate.
Fig. 5. Impedance spectra of 0.75 mol/kg DMFA solu-
tions in Nyquist coordinates in the temperature range
25–70 °C: а – KBSB, b – NaBSB.
а
b
V.A.Diamant, V.V.Trachevskii, K.D.Pershina, V.M.Ogenko, Chen Dongchu et al.
52 ISSN 0041-6045. УКР. ХІМ. ЖУРН., 2019, т. 85, № 3
way, based on the relay mechanism. On the other
hand, a significant phase angle shift is typical for
all the studied systems. According to the AC the-
ory, this indicates the presence of two wave forms
of electric current in the system and the correspon-
ding difference between the cycles of these waves
[15] (table 4). In accordance with what was stated
above, there are two streams of charge carriers in
the system.
Only one maximum shift in phase angle at
a frequency of 102 Hz is possible for the systems
with a maximum conductivity value and it would
be equal to two salts with a similar concentration.
The presence of two BSB conformations and two
wave forms according to the 13C NMR spectra
suggests the formation of a labile borate complex
with a solvent that has the maximum electrical
conductivity and depends on the salt concentra-
tion. Knowing the recorded activity in the coor-
dination sphere of bis(salicyl)borate and that the
relay mechanism is implemented to transfer the
boron between neighboring coordination nodes du-
ring migration through the sulfocation membra-
ne, let us assume the existence of a pseudo-di-
mensional structure of electrolyte solutions based
on bis(salicyl)borate anion [16]. Then, it allows the
implementation of the relay charge transfer mecha-
nism [17, 18]. Also, the results prove the assumpti-
on [19] about the existence of a certain ratio bet-
ween the fragments of supramolecular formations,
that is, the effect of R- and S-enantiomers of bis-
(salicylo)borate-anion with a labile coordination en-
vironment of boron on the formation of conduc-
tive properties of the electrolyte and the formation
of an additional ion transport channel due to the
implementation of the relay mechanism.
CONCLUSIONS. The 13C and 11B NMR
spectra studies by varying the time delay between
the radiofrequency pulses of non-aqueous elec-
trolytes based on bis(salicyl)borates and bis(oxa-
lato)borate lithium have established that the car-
boxyl groups atoms are not equal in the bis(sali-
cyl)borat-anion due to the emergence of two
enantiomers in bis(salicyl)borat-anion with labile
coordination environment of boron. Based on the
electrical conductivity measurements and the
spectroscopy data of electrochemical impedance,
we suggest two charge transfer pathways in the
electrolytes based on bis(salicyl)borates: diffusion
and the relay, which is in concordance with the
results of NMR spectra studies. Based on the data
comparison of NMR, CEI and concentration de-
pendences of electrical conductivity in the obtai-
ned electrolyte system, the possibility of forming
a pseudopolymer labile complex due to the for-
mation of hydrogen bonds between the investi-
gated borates and the solvent was established.
ОСОБЛИВОСТІ БУДОВИ ТА ЕЛЕКТРОПРОВІД-
НОСТІ НЕВОДНИХ ЕЛЕКТРОЛІТІВ НА ОСНОВІ
БІС(САЛІЦИЛО)БОРАТІВ ТА БІС(ОКСАЛАТО)БО-
РАТІВ ЛУЖНИХ МЕТАЛІВ
В.А.Діамант1, В.В.Трачевський2, К.Д.Перши-
на1*, В.М.Огенко1, Д.Чен3, Х.Ху3, М.Чен3,
К.Ванг3, М.Чангі3
1 Інститут загальної та неорганічної хімії
ім. В.І.Вернадського НАН України, просп. Акаде-
міка Палладіна, 32/34, Київ, 03142, Україна
T a b l e 4
The values of frequency dependencies of EIS solu-
tions KBSB in DMFA and NaBSB in DMFA at the
room temperature
Csalts,
mol/kg Electrolyte ϕ, o f, Hz a(f), o
0.5 KBSB + DMFA 80 103 30
65 10–1
0.6 KBSB + DMFA 80 101.5 55
0.77 KBSB + DMFA 80 102 45
0.98 KBSB + DMFA 83 101.5 35
1.7 KBSB + DMFA 83 100.3 30
3.0 KBSB + DMFA 80 103 55
71 10–2
4.33 KBSB + DMFA 74 101.5 55
63 10–2
0.5 NaBSB + DMFA 80 103 45
0.75 NaBSB + DMFA 80 102 45
1.0 NaBSB + DMFA 80 102 45
2.0 NaBSB + DMFA 80 101.5 45
71 10–2
N o t e: ϕmax — maximum shift in the phase angle;
f — maximum frequency of the phase angle shift;
a(f) — the angle of the spectrum inclination.
Specialties of the structure and conductivity ...
ISSN 0041-6045. УКР. ХІМ. ЖУРН., 2019, т. 85, № 3 53
2 Інститут металофізики ім. Г.В.Курдюмова
НАН України, бульвар Академіка Вернадського,
36, Київ, 03142, Україна
3 Школа матеріалознавства та енергетичної
інженерії, Університет Фошань, Цзянвань Пер-
ший Шлях, Чанчен, Фошань, 528000, Гуандун, Китай
* e-mail: Pershina@ionc.kiev.ua
Досліджено структуру та координаційне се-
редовище неводних електролітів на основі біс-
(саліцило)боратів літію, натрію, калію, тетраме-
тиламонію (MeBSB) і біс(оксалато)боратів від лі-
тію до цезію (MeBOB) за допомогою ЯМР-спек-
троскопії. Біс(саліцило)борати (BSB) і біс(окса-
лато)борати (BOB) лужних металів і органічних
катіонів розглядаються як перспективні електро-
провідні компоненти електролітів сучасних хіміч-
них джерел струму (літій та натрій іонних первин-
них та вторинних батарей і суперконденсаторів).
Солі синтезували методом НВЧ-випромінюван-
ня. Дослідженням спектрів ЯМР 13C та 11B визна-
чили наявність симетричної структури в аніоні BOB
та двох оптичних конформацій аніона BSB з лабі-
льним координаційним середовищем бору. Опти-
чна активність BSB є результатом формування
іонних контактних пар. У разі катіона тетраметила-
монію наявність оптичної активності залежить від
реактивної складової середовища. Конформаційна
лабільність координаційної сфери NaBSB, розчи-
неного в DMAA, пов’язана з підвищенням інте-
гральної інтенсивності сигналів карбоксильних
груп щодо сигналів атомів вуглецю в фрагмен-
тах іншої функціональної приналежності, коли за-
тримка між радіочастотними імпульсами зміню-
ється протягом 2–15 секунд. Різниця в структу-
рі цих аніонів призводить до зміни температурної
залежності електропровідності BSB і транспорту
іонів у неводних розчинниках. Максимальна елек-
тропровідність розчинів солей у ДМФА досяга-
ється при близьких концентраціях 0.75 моль/кг
для KBSB і 0.77–1 моль/кг для NaBSB. Розчин-
ність для солей BSB в амідах та інших АДР краща,
ніж для солей BOB. Причому розчинність для BSB
практично незмінна від Li+ до K+, а для BOB різко
спадає від Li+ до K+ і далі незмінна до Cs+. На
основі вимірювань електропровідності та даних
спектроскопії електрохімічного імпедансу (кут
нахилу спектрів у координатах Найквіста в низь-
кочастотному діапазоні, кут нахилу фази при ча-
стоті) запропоновано існування двох способів тран-
спорту іонів і зарядів в електролітах: дифузійний і
естафетний транспорт. Встановлена можливість
утворення лабільного сольового комплексу з роз-
чинником за рахунок водневих зв’язків.
К л ю ч о в і с л о в а: неводний електроліт,
біс(саліцил)борати лужних металів, провідність,
структура, лабільний комплекс, транспорт іонів.
ОСОБЕННОСТИ СТРОЕНИЯ И ЭЛЕКТРОПРОВО-
ДНОСТИ НЕВОДНЫХ ЭЛЕКТРОЛИТОВ НА ОС-
НОВЕ БИС(САЛИЦИЛО)БОРАТОВ И БИС(ОКСА-
ЛАТО)БОРАТОВ ЩЕЛОЧНЫХ МЕТАЛЛОВ
В.А.Диамант1, В.В.Трачевский2, К.Д.Перши-
на1*, В.М.Огенко1, Д.Чен3, Х.Ху3, М.Чен3,
К.Ванг3, М.Чанг3
1 Институт общей и неорганической химии
им. В.И.Вернадского НАН Украины, просп. Ака-
демика Палладина, 32/34, Киев, 03142, Украина
2 Институт металлофизики им. Г.В.Курдюмо-
ва НАН Украины, бульвар Академика Вернад-
ского, 36, Киев, 03142, Украина
3 Школа материаловедения и энергетической
инженерии, Университет Фошань, Цзянвань
Первая Дорога, Чанчен, Фошань, 528000,
Гуандун, Китай
* e-mail: Pershina@ionc.kiev.ua
Исследована структура и координационное
окружение неводных электролитов, состоящих из
бис(салицило)боратов лития, натрия, калия и
бис(оксалато)боратов от лития до цезия с исполь-
зованием ЯМР-спектроскопии. Анализ спектров
ЯМР 13С и 11В установил присуствие двух кон-
формаций в бис(салицило)борат-анионе с лаби-
льным координационным окружением бора в
присутствии растворителя. Это различие в стру-
ктуре анионов влияет на конечное строение эле-
ктролитов и приводит к изменению термической
зависимости электропроводимости бис(салици-
ло)боратов и путей переноса ионов относительно
бис(оксалато)боратов в неводных растворителях.
К л ю ч е в ы е с л о в а: неводный электролит,
бис(салицил)бораты щелочных металлов, прово-
димость, структура, лабильный комплекс, транс-
порт ионов.
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Specialties of the structure and conductivity ...
ISSN 0041-6045. УКР. ХІМ. ЖУРН., 2019, т. 85, № 3 55
56 ISSN 0041-6045. УКР. ХІМ. ЖУРН., 2019, т. 85, № 3
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| id | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-37 |
| institution | Ukrainian Chemistry Journal |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2026-07-23T01:03:08Z |
| publishDate | 2019 |
| publisher | V.I.Vernadsky Institute of General and Inorganic Chemistry |
| record_format | ojs |
| resource_txt_mv | ucjorgua/e0/b6a59e4f74a017c5ec31dcbd1ee3e9e0.pdf |
| spelling | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-372026-07-22T08:23:40Z Specialties of the structure and conductivity of the non-aqueous electrolytes based on alkali metal bis (salicyl) borates and bis (oxalate) borates ОСОБЕННОСТИ СТРОЕНИЯ И ЭЛЕКТРОПРОВОДНОСТИ НЕВОДНЫХ ЭЛЕКТРОЛИТОВ НА ОСНОВЕ БИС(САЛИЦИЛО)БОРАТОВ И БИС(ОКСАЛАТО)БОРАТОВ ЩЕЛОЧНЫХ МЕТАЛЛОВ ОСОБЛИВОСТІ БУДОВИ ТА ЕЛЕКТРОПРОВІДНОСТІ НЕВОДНИХ ЕЛЕКТРОЛІТІВ НА ОСНОВІ БІС(САЛІЦИЛО)БОРАТІВ ТА БІС(ОКСАЛАТО)БОРАТІВ ЛУЖНИХ МЕТАЛІВ Diamant, Viktor Trachevskii, Volodymyr Pershina, Katherine Ogenko, Volodymyr Donchu, Chen Huawen, Hu Min, Chen Xiaowen, Wang Menglei, Chang non-aqueous electrolyte, alkali metal bis (salicyl) borates, conductivity, structure, labile complex, ion transport. The structure and coordination environment of non-aqueous electrolytes based on bis(salicyl)borates of lithium, sodium, potassium, tetramethylammonium (MeBSB) and bis(oxalato)borates from lithium to cesium (MeBOB) using NMR spectroscopy have been investigated. Bis(salicyl)borates (BSB) and bis(oxalate)borates (BOB) of alkali metals and organic cations are considered as promising electroconductive components of electrolytes of modern chemical sources of current (lithium, sodium ion batteries and super-capacitors). The salts were synthesized by the microwave radiation method. The 13C and 11B NMR spectra analysis determined the presence of symmetric structure in BOB anion and the presence of two optical conformations of the BSB anion with labile coordination environment of boron. The conformations of the BSB are the result of the ion contact pairs formation. In the case of tetramethylammonium cation the presence of conformations are depended on the reactive medium. The conformational lability of the coordination sphere of NaBSB dissolved in DMAA is connected with increasing of the integral intensity of carboxyl group singles relatively signals of carbon atoms in fragments of another functional affiliation when the time delay between radio frequencies varies within 2-15 seconds. The difference in the structure of these anions leads to a change in the thermal dependence of the electrical conductivity of BSB and the transport of ions in non-aqueous solvents. Maximum electrical conductivity of salt solutions in DMFA is achieved at close concentrations of 0.75 m for KBSB and 0.77-1 m for NaBSB. The solubility of BSB is better than the BOB. Based on the measurements of the conductivity and the data of electrochemical impedance spectroscopy (the angle of inclination of spectra in the Nyquist coordinates in the low frequency range, the phase angle shift at a frequency) it was proposed the existence of two ways of ions and charge transfer in the electrolytes: diffusion and relay transport. The possibility of formation of a labile salt complex with a solvent due to hydrogen bonds is established.   V.I.Vernadsky Institute of General and Inorganic Chemistry 2019-06-07 Article Article Physical chemistry Физическая xимия Фізична xімія application/pdf https://ucj.org.ua/index.php/journal/article/view/37 10.33609/0041-6045.85.3.2019.49-55 Ukrainian Chemistry Journal; Vol. 85 No. 3 (2019): Ukrainian Chemistry Journal; 49-55 Украинский химический журнал; ##issue.vol## 85 ##issue.no## 3 (2019): Украинский химический журнал; 49-55 Український хімічний журнал; Том 85 № 3 (2019): Український хімічний журнал; 49-55 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/37/19 Copyright (c) 2019 Viktor Diamant, Volodymyr Trachevskii, Katherine Pershina, Volodymyr Ogenko, Chen Donchu, Hu Huawen, Chen Min, Wang Xiaowen, Chang Menglei https://creativecommons.org/licenses/by-nc/4.0 |
| spellingShingle | Diamant, Viktor Trachevskii, Volodymyr Pershina, Katherine Ogenko, Volodymyr Donchu, Chen Huawen, Hu Min, Chen Xiaowen, Wang Menglei, Chang ОСОБЛИВОСТІ БУДОВИ ТА ЕЛЕКТРОПРОВІДНОСТІ НЕВОДНИХ ЕЛЕКТРОЛІТІВ НА ОСНОВІ БІС(САЛІЦИЛО)БОРАТІВ ТА БІС(ОКСАЛАТО)БОРАТІВ ЛУЖНИХ МЕТАЛІВ |
| title | ОСОБЛИВОСТІ БУДОВИ ТА ЕЛЕКТРОПРОВІДНОСТІ НЕВОДНИХ ЕЛЕКТРОЛІТІВ НА ОСНОВІ БІС(САЛІЦИЛО)БОРАТІВ ТА БІС(ОКСАЛАТО)БОРАТІВ ЛУЖНИХ МЕТАЛІВ |
| title_alt | Specialties of the structure and conductivity of the non-aqueous electrolytes based on alkali metal bis (salicyl) borates and bis (oxalate) borates ОСОБЕННОСТИ СТРОЕНИЯ И ЭЛЕКТРОПРОВОДНОСТИ НЕВОДНЫХ ЭЛЕКТРОЛИТОВ НА ОСНОВЕ БИС(САЛИЦИЛО)БОРАТОВ И БИС(ОКСАЛАТО)БОРАТОВ ЩЕЛОЧНЫХ МЕТАЛЛОВ |
| title_full | ОСОБЛИВОСТІ БУДОВИ ТА ЕЛЕКТРОПРОВІДНОСТІ НЕВОДНИХ ЕЛЕКТРОЛІТІВ НА ОСНОВІ БІС(САЛІЦИЛО)БОРАТІВ ТА БІС(ОКСАЛАТО)БОРАТІВ ЛУЖНИХ МЕТАЛІВ |
| title_fullStr | ОСОБЛИВОСТІ БУДОВИ ТА ЕЛЕКТРОПРОВІДНОСТІ НЕВОДНИХ ЕЛЕКТРОЛІТІВ НА ОСНОВІ БІС(САЛІЦИЛО)БОРАТІВ ТА БІС(ОКСАЛАТО)БОРАТІВ ЛУЖНИХ МЕТАЛІВ |
| title_full_unstemmed | ОСОБЛИВОСТІ БУДОВИ ТА ЕЛЕКТРОПРОВІДНОСТІ НЕВОДНИХ ЕЛЕКТРОЛІТІВ НА ОСНОВІ БІС(САЛІЦИЛО)БОРАТІВ ТА БІС(ОКСАЛАТО)БОРАТІВ ЛУЖНИХ МЕТАЛІВ |
| title_short | ОСОБЛИВОСТІ БУДОВИ ТА ЕЛЕКТРОПРОВІДНОСТІ НЕВОДНИХ ЕЛЕКТРОЛІТІВ НА ОСНОВІ БІС(САЛІЦИЛО)БОРАТІВ ТА БІС(ОКСАЛАТО)БОРАТІВ ЛУЖНИХ МЕТАЛІВ |
| title_sort | особливості будови та електропровідності неводних електролітів на основі біс(саліцило)боратів та біс(оксалато)боратів лужних металів |
| topic_facet | non-aqueous electrolyte alkali metal bis (salicyl) borates conductivity structure labile complex ion transport. |
| url | https://ucj.org.ua/index.php/journal/article/view/37 |
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