НОВІ НЕВОДНІ ЕЛЕКТРОЛІТИ НА ОСНОВІ КОРДИНАЦІЙНИХ СПОЛУК БОРУ
The review provides a classification of electrolytes for modern chemical power sources, supercapacitors, sodium and lithium-ion batteries depending on changes in the physicochemical properties of salts and the products of their interaction with the solvent. A comparative analysis of physicochemical...
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Ukrainian Chemistry Journal| _version_ | 1871465689796050944 |
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| author | Diamant, Viktor |
| author_facet | Diamant, Viktor |
| author_institution_txt_mv | [
{
"author": "Viktor Diamant",
"institution": "Vernadsky Institute of General & Inorganic Chemistry NAS Ukraine, 32\/34, Akad. Palladin Avenue, 03680 Kyiv, Ukraine"
}
] |
| author_sort | Diamant, Viktor |
| baseUrl_str | https://ucj.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2026-07-22T08:23:45Z |
| description | The review provides a classification of electrolytes for modern chemical power sources, supercapacitors, sodium and lithium-ion batteries depending on changes in the physicochemical properties of salts and the products of their interaction with the solvent. A comparative analysis of physicochemical properties of salts depending on the structure of the cation and anion, and the influence of these properties on the properties of final solutions of electrolytes on the example of different classes of ionic liquids and chelatoborates of alkali metals and ammonium was conducted. The dependence of the physicochemical properties of electrolytes (solubility, electrical conductivity of solutions and the range of potentials of electrochemical stability) on the nature of the chelate ligand, electron donor and electroacceptor substituents in the bis (chelate) borate anion is analyzed. The electrical conductivity of salt solutions and ranges of potentials of electrochemical stability of the corresponding electrolytes containing other anions and used for a long time in chemical current sources are carried out. The advantages and disadvantages of using liquid electrolytes compared to solid and polymer electrolytes in terms of similarity of their structures have been detected. It is shown that the nature of the chelate ligand, electro-donor and electro-acceptor substituents in the bis (chelato) borate anion is an important factor in regulating the interaction with aprotic dipolar solvents. Mixed salts with two different chelate ligands typically combine the best characteristics of the corresponding monochelate compounds, but the methods for their preparation and purification are technologically significantly more complex compared to monochelate compounds. The analysis of the mechanism of formation of a protective film on a surface of electrode materials, dependence of potential on its formation and on the chemical nature of ligands is made. It is noted that bis (chelato) borate salts are more environmentally friendly compared to fluorine-containing complex salts. Emphasis is placed on the physicochemical properties of solutions of the most promising chelatoborate salts for use in lithium and sodium ion batteries, supercapacitors and electrolytic capacitors, and it is shown that bis (oxalate) borates and bis (salicylate gold) borates occupy ) borates in terms of electrical conductivity, solubility and potential range of electrochemical stability. |
| doi_str_mv | 10.33609/2708-129X.87.03.2021.41-60 |
| first_indexed | 2025-09-24T17:43:38Z |
| format | Article |
| fulltext |
41
UDC 544.6.018+544.35 doi: 10.33609/2708-129X.87.03.2021.41-60
NOVEL NON-AQUEOUS ELECTROLYTES BASED ON COORDINATION
BORON COMPOUNDS
V. A. Diamant
Vernadsky Institute of General & Inorganic Chemistry NAS Ukraine, 32/34, Akad. Palladin Ave-
nue, 03680 Kyiv, Ukraine
Email: carbon.h.4@gmail.com
There view provides a classification of electrolytes for modern chemical power sources,
supercapacitors, sodium and lithium-ion batteries depending on changes in the physicochem-
ical properties of salts and the products of their interaction with the solvent. A comparative
analysis of physicochemical properties of salts depending on the structure of the cation and
anion, and the influence of these properties on the properties offinal solutions of electrolytes
on the example of different classes of ionic liquids and chelatoborates of alkalimetals and am-
monium was conducted. Emphasis is placed on the physicochemical properties of solutions
of the most promising chelatoborate salts for use in lithium and sodium-ion batteries, super
capacitors, and electrolytic capacitors, and it is shown that bis(oxalate)borates and bis(salicy-
lato)borates occupy borates in terms of electrical conductivity, solubility, and potential range
of electrochemical stability.
Key words: salt, cation, anion, solvent, ionic liquids, coordination compounds of boron,
electrolytes for electrochemical energy storages.
INTRODUCTION. The development of
modern chemical power sources, such as su-
percapacitors, sodium and lithiumion bat-
teries, requires electrolyte systems based
on non-aqueous solutions and ionic liquids
(molten salts at room temperature). The re-
search of electrolytes and the theory of their
structure has been the subject of the scientists’
attention during the last two centuries [1] due
to the transport of substances to the redox reac-
tion site and participation in the formation of
a double electrical layer at the electrode-elec-
trolyte boundary. An important class of salt
compounds whose solutions have been used
as electrolytes is bis(chelato)borates. Such salts
as bis(oxalato)borates and bis(salicylato)bo-
rates occupy the main place among all known
bis(chelato)borates in terms of electrical con-
ductivity, solubility, and the range of electro-
chemical stability potentials. Mixed salts with
two different chelate ligands typically combine
the best characteristics of the corresponding
monochelate compounds, and the methods for
their preparation and purification are much
more numerous compared to monochelate
compounds [2–5]. However, the transport
functions of these salts depend on the struc-
ture and composition of electrolytes, forming
NOVEL NON-AQUEOUS ELECTROLYTES BASED ON COORDINATION BORON COMPOUNDS
42 ISSN 2708-129X. Укр. хім. журн., 2021
PHYSICAL CHEMISTRY
their physical and chemical features [6]. To es-
tablish the factors that have the most impact
on the properties and prospects for the use of
such salts, it is necessary to consider and sum-
marize the impact of different organic cations,
boron content, anion interaction with protic
and aprotic solvents, and changes in the pro
perties of the electrolyte due to the ability for
the coordination of the salt to solvents.
THE EFFECT OF SOLVENTS ON THE
COMPOSITION AND STRUCTURE OF LI
QUID ELECTROLYTES
The modern classification concepts of
non-aqueous electrolytes based on the level
of their dissociation (strong and weak) be-
came obvious when a profound research of
ion processes in non-aqueous solvents be-
gan (P. Valden, Ch. Kraus, P. Fuoss, N A. Iz-
mailov) [1]. Indeed, it turns out that a lot of
electrolytes being able to dissociate fully in
water (hydrogen chloride, nitrogen and per-
chloric acid, and many other salts) are weak in
nonaqueous solvents, where they act according
to the low of mass action. It became clear that
the strength of the electrolyte (the ability to
dissociate into ions) is not its permanent prop-
erty, but is also determined by the solvent na-
ture. The more rational novel method divides
electrolytes into real electrolytes (ionophores)
and pseudo-electrolytes (ionogens). The iono-
phores are compounds existing already in the
ion form while being in a condensate state.
To put it in other words, they are inorganic
salts (NaCl, K2SO4) as well as organic salts
(N(C2H5)4Pic). On the opposite, the ionogens
form ions only while contacting with a sol-
vent. The ionogens include, for example, vine-
gar acid, benzoic acid, hydrogen chloride, and
others [1]. Thus, a solvent is an integral part
of an electrolyte, and its chemical and physical
properties influence greatly the further chang-
es in its electrolyte system properties. Nowa-
days, there are several solvent classifications.
First, the solvents are grouped according to
their composition [3]:
Molecular fluids (molecular combinations
which have covalent bonds only):
– ionic fluids (molten salts, ionic bonds
only);
– atomic fluids (fusible metals, they have
metallic bonds).
Second, based on their physical properties
[3]:
– low-temperature boiling (under 100 °С):
– high-temperature boiling (over 150 °С):
– medium-temperature boiling (over 100 °С,
but less than 150 °С).
Also, the solvents are classified as polar pro-
tic (aqueous) and non-polar aprotic (nonaque-
ous). Consequently, there are four different
types: protic polar and protic weak polar, apro-
tic polar, and aprotic non-polar solvents [7, 8].
Considerable attention has been devoted
during the last decades to the studies of ionic
fluids. They are divided into protic, aprotic
and zwitterionic fluids (where anion and cat-
ion are in the same molecule) [9]. The aprotic
ionic fluids are the most promising for the use
in chemical power sources thanks to low vapor
pressure over the solvent [10, 11, 12], broad flu-
id state region, a wide range of electrochemical
stability working potentials, low melting point,
moderate conductivity, (0.1–18 mS/cm2) [13],
hydrophobic nature and resistance to inflam-
mation [9, 14]. The flaws of ionic fluids include
high viscosity [13] and surface tension, which
lead to low cohesion with the electrodes. Thanks
to their remarkable features, the ionic fluids are
used more and more widely. For example, they
are used in nuclear power as liquid nuclear fuel
V. A. Diamant
43https://ucj.org.ua
UCJ № 3 / Vol. 87
carriers [11], as initiators in polymerization re-
actions [12], as compounds of electrolytes for
supercapacitors [9, 11–16], and lithium-ion bat-
teries [13]. According to this classification, the
bis(chelato)borates have many features of ionic
fluids. But till today, the impact of cations and
anions of such salts to change the properties of
electrolytes hasn’t good background.
ORGANIC CATION IMPACT
There exist two tendencies in the theoreti-
cal views of cation’s role in electrolyte: (1) the
main transport function as a current carrier
[1, 6], (2) agent of salt-solvent systems [15].
In the transport of current as charge carrier,
inorganic cations such as lithium, potassium,
and sodium cations usually take part [15].
Organic cations, as part of ionic liquids, have
more complex functions due to bigger sizes
and low mobility. Such properties change the
mechanism of charge transfer, which strongly
depends on the solvent nature [16, 17].
The most renowned agents of this class of
compounds are different salts of replaced imi-
dazolium and pyrrolidinecations and the salts
of tetraalkylammoniumcation [13]. The alter-
native studies are targeting the other cations:
Trialkylsulphonium, tetraalkylphosphonium,
alkylpyridinium, N-alkyltiosolinium, N, N-di-
alkyltriasolinium, N, N-dialkyloxasolinium
and N, N-dialkylpyrazolinium (Figure 1).
Figure 1 – The organic cations’ composition of trialkylsulphone, tetraalkylphosphone, tetraalkylamo-
nium, N-alkylimidazolinium, alkylpyrydinium, N-alkyltiozolinium, N, N-dialkyltriazolinium, N, N-di-
alkyloxazolinium and N, N-dialkylpirazolinium, N, N-dialkylpiperidinium, N, N-dialkylpirrolidinium.
NOVEL NON-AQUEOUS ELECTROLYTES BASED ON COORDINATION BORON COMPOUNDS
44 ISSN 2708-129X. Укр. хім. журн., 2021
PHYSICAL CHEMISTRY
It was found that for such solvents as
DMSO, propylene carbonate, and other apro-
tic dipolar solvents in the case of lithium salts
and organic cations, the electrolyte has a spe-
cific structure, which does not depend on dis-
sociation level. [18–22]. Ions in solution form
supramolecular structures – ion pairs separa
ted by a solvent and contact ion pairs, which
exist in a certain equilibrium depending on
the concentration [18–22]. If the transport
properties of alkali metal cations depend on
their solvation energy with solvents, then in
the case of an organic cation, since it is prac-
tically not solvated, it affects the properties of
the solution more due to size, symmetry, and
charge distribution.
ORGANIC ANION IMPACT
In the salts of novel electrolytes, the most
well-known anions are ClO4
-, PF6
- and BF4
- or
organic ions: trifluoroalkyl sulfates, triflu
oromethanesulfonimide and trifluorome
thanesulfonamethanides, and more recently
bis(chelato)borate and tris (chelated complex)
phosphates [23–30]. Decreasing the symme-
try of the anion, increasing its size, introduc-
ing functional groups, and changing the ratio
of the anion radius to the cation radius direct-
ly affect the melting temperature and solu
bility of the salt as in the case of the cation.
Therefore, the structure of the salt anion, as
well as the interaction with the solvent, affect
the structure of the solution and its transport
properties no less than the structure of the
cation [31–33].
However, charge transport can occur due
to a cation and an anion. This can be deter-
mined experimentally by measuring the trans-
fer numbers and comparing them. According
to the classical theories of electrolytic dissoci-
ation, it is believed that inorganic anions are
hardly solvated, while large organic anions do
not obey classical laws and can form togeth-
er with solvents structures similar to polymers
and solvate complexes. For ionic liquids in the
formation of polymer structures or in the for-
mation of zwitterion, the characteristic Grot-
thuss (relay) mechanism of charge transport
with the formation of free volume is realized
[34–35]. The presence of apseudopolymer
structure in the salt-solvent system changes
the transport function of electrolytes due to a
change in dielectric properties and conductiv-
ity [36–40].
Therefore, to account for the impact of the
anion on the properties of the electrolyte, it
is necessary to take into account the size and
steric properties of the anion, the nature of the
solvent, and the peculiarities of its interaction
with the anion. In this case, the most interest-
ing are the complex compounds of boron with
bidentate ligands.
COORDINATION COMPOUNDS OF
BORON
The literature confirms that despite the
possibility of the boron coordination number
of 3 or 4, bidentate ligands add to the coor-
dination diversity and even to the formation
of coordination polymers (table 1). Thus, the
boron compounds have predisposition to po-
lymerization while the coordination num-
ber of 4 is available. This must influence the
electrochemical and physical properties of
the electrolyte systems based on them. There-
fore, the synthesis method has an important
role to play. The solvents or neutral molecules
also can coordinate in the outer sphere, e.g.
H[B(OC5H11)4]*4C5H5N [41].
V. A. Diamant
45https://ucj.org.ua
UCJ № 3 / Vol. 87
Table 1
The composition and properties of the complex boron compounds
Type of a complex
The ability to polymerize
INFLUENCE OF THE ELECTROLYTE
SALT COMPOSITION ON THE MELTING
TEMPERATURE
One of the most important properties of an
aprotic ionic liquid is its melting point. The ana
lysis of the effect of steric and other factors on
the melting temperature of tetraalkylamonium
salts has identified the main traits influencing
the melting temperature: cation (RC) and ani-
on (RA) radius, cation symmetry and the ratio
of salt anion radius to cation radius [9, 31, 32].
1. The decrease in cation symmetry signifi
cantly influences the energy lattice and
lowers even more the melting point (ta-
ble 2). While the cation size grows at a
stable charge, the melting temperature of
tetraalkylamonium salt drops because of
a decrease in cation polarization power
and Coulomb power. The lattice energy
decreases respectively.
NOVEL NON-AQUEOUS ELECTROLYTES BASED ON COORDINATION BORON COMPOUNDS
46 ISSN 2708-129X. Укр. хім. журн., 2021
PHYSICAL CHEMISTRY
Table 2
Influence of cation symmetry on
the melting temperature [33]
of tetraalkylammonium salt Tmelt., К
403
378
295.15
383.15
2. Decrease in the melting temperature of
the tetraalkylammonium salt while the
RA/RK ratio increases (Figure 2).
3. The introduction of functional groups
into thetetraalkylammoniumcation also
helps to significantly decrease the melt-
ing point of tetraalkylammoniumsalts
(Table 3).When both the cation and an-
ion are of a big size, but RA/RK = 1, the
melting point will increase. Thus, the
conditions needed for tetraalkylammo-
nium salts to decrease their melting tem-
perature can be noted as:
RA/RC < 1 < RA/RC
N
N
S S
O
O
F3C
O
O CF3
N
N
S S
O
O
F3C
O
O CF3
N
N
S S
O
O
F3C
O
O CF3
N
N
S S
O
O
F3C
O
O CF3
Figure 2 – The effect of tetraalkylammonium salt’s melting temperature with increase of RA/RK ratio.
N
N
S S
O
O
F3C
O
O CF3
O
N
N
S S
O
O
F3C
O
O CF3
N
N
S S
O
O
F3C
O
O CF3
O
N
N
S S
O
O
F3C
O
O CF3
Table 3
The change of the melting point with
the introduction of functional groups into
tetraalkylammonium cation [33]
tetraalkylammonium salt Tmelt., К
277.65
295.15
With increase in molecular weight, the radi-
us ratio, radical branching or cation composi-
tion asymmetry lose their effect.
4. The reduction in anion symmetry has
less impact on melting properties, its ef-
fect is significant on thetetraalkylammo-
nium salt melting point.
Table 4 illustrates a melting point decrease
with increasing size of the anion and with re-
duction in its symmetry. With increase in mo-
lecular weight, the radius ratio, radical branch-
ing or cation composition asymmetry lose their
effect. For example, the melting temperature of
tetraalkylammonium salt with the same anion
V. A. Diamant
47https://ucj.org.ua
UCJ № 3 / Vol. 87
decreases when the radical in thetetraalkylam-
monium cation changes from methyl to octyl,
but it starts to increase with the formation of
nonyl [11].
The reduction in anion symmetry has less
impact on the melting point, but its effect is
significant in the case of tetraalkylammonium
salts (Table 4).
Table 4
Dependence of the melting temperature on
the size of the anion [33]
tetraalkylammonium salt Tmelt., К
383.15
356.15
342.15
260.15
278.15
264.15
Thus, the study of the effect of the structure
and symmetry of tetramethylammoniumbis
(chelato) borate ions on the change of melting
temperature is a task that facilitates the predic-
tion of the electrochemical properties of elec-
trolyte systems based on them.
COMPOSITION, STRUCTURE AND PRO
PERTIES OF POLYMERIC ELECTROLYTES
Solid electrolytes are divided according to
the structure into crystalline, amorphous (glass)
and polymeric ones. In crystalline and amor-
phous electrolytes, transport occurs due to the-
cation or anion sublattice. For them, there is a
transition temperature in the superionic state
(a dramatic change in the ionic conductivity
of the cation/anion is recorded) when half the
ionic lattice «melts» [1]. The polymeric electro-
lytes for lithium-ion batteries comprise most
often a solution of typical lithium salts: LiPF6,
LiBF4, LiAsF6, LiN(SO2CF3)2, and LiSO3CF3 in
simple and polyester polymers, for example in
polysiloxanes. The use of polymeric electrolytes
expands their capabilities in batteries. Table 5
presents the main characteristics of liquid elec-
trolytes (ionic liquids, solutions of salts in non-
aqueous solvents) and polymeric electrolytes.
Crystalline and vitreous solid electrolytes
have the same advantages for lithium energy
sources as polymeric electrolytes, the only prob-
lem is posed by their fragility. So far, the con-
ductivity of crystalline and vitreous solid mate-
rials is inferior to that of liquid electrolytes and
is approximately 10-4 – 10-5 Оhm–1·сm–1 at room
temperature [45]. Most studies are devoted to
lithium orthophosphate Li3PO4, lithium-substi-
tuted lanthanum titanate La2/3–xLi3xМе1/3–2xTiO3
(where Me is a cation vacancy). A non-stoichio
metric phase Li4GeO4–Li3VO4 in Li4GeO4 –
Li3PO4 is obtained [45].
N
N
S S
O
O
F3C
O
O CF3
N
S S
O
O
F2C
O
O CF2
CF3F3C
N
N
S S
O
O
F2C
O
O CF3
F3C
N
S
O
O
O O
(CF2)3 CF2H
N
S
O
O
O O
CF3
N
N
S
O
O
O O
CF2 CF2H
NOVEL NON-AQUEOUS ELECTROLYTES BASED ON COORDINATION BORON COMPOUNDS
48 ISSN 2708-129X. Укр. хім. журн., 2021
PHYSICAL CHEMISTRY
Table 5
Comparison of liquid and polymeric electrolytes properties when used
in chemical energy sources.
Properties Fluid electrolytes Polymer electrolytes
Electro conductivity High ion conductivity
(Et4NBF4 in acetonitril 60 mSm/sм [42],
typical electrolyte for lithium-ion battery 10
mSm/sм [43])
Low ionic conductivity
(10-4-10-7 mS / cm) [44]
Energetic power Low and medium power medium and high power
security Flows due to liquid state or gas is formed Does not flow
Design / packaging Solid protective case Slim, flexible, spatially
efficient, can be modeled for
blister packaging
No type of electrolyte, liquid, solid or poly
meric, has gained a decisive advantage over
others. The liquid electrolytes based on con-
centrated solutions can dry up and form a
salt film, which is inconvenient when sealing
the elements. Moreover, they require special
working conditions such as an extremely low
humidity level. In addition, liquid electrolytes
based on nonaqueous solutions have an expi-
ration date. Liquid electrolytes are quite expen-
sive and require a heavy case to assure a solid
construction of hermetic package. The damage
of the case leads to the failure of elements since
contact with moisture makes the electrolyte in-
compatible with its functions. Polymer electro
lyte compares favorably with liquid one. It does
not require massive housing and is more me-
chanically stable, but at the same time, it has
the same disadvantages as liquid electrolyte
when exposed to the humid air. While the solid
electrolytes compare favorably with the liquid
and some polymeric electrolytes, they are not
without their own drawbacks, e.g. low ionic
conductivity. Taking this into account, further
studies of solvents and temperature factors
influence the formation of conductivity type,
and the creation of conditions to increase the
ionic conductivity in bis(chelato)borate based
electrolyte systems is needed.
THE USE OF MONOVALENT CHELA-
TOBORATE CATIONS IN BATTERIES AND
SUPERCAPACITORS
Chelatoborates are highly heat-resistant
compared to chelatophosphates LiPF6 and
LiBF4.
An important feature of lithium bis(oxala-
to)borate and other lithium bis(chelato)borate
mixtures is the ability to induce a decomposi-
tion reaction in the case of cathode overload;
this slows down the voltage growth in the cell.
Thanks to this property, the dangerous side re-
actions of the cathode material with electrolyte
components can be prevented or reduced [46].
Borate electrolytes cause the formation of
a very thin stable lithium ion conductive layer
on the carbon anode of a lithium battery. It
is stable at high temperatures and prevents
therefore any hazardous reaction between the
charged anode and electrode. This layer pro-
motes the use of mangan spinel as a cathode
material [46]. The improvement of the pro-
tective layer due to the borate salt has opened
V. A. Diamant
49https://ucj.org.ua
UCJ № 3 / Vol. 87
new possibilities of electrolyte formation. For
example, this allowed us to avoid inconvenient
-to- use ethylene carbonate and to use propy
lene carbonate instead. In addition, it allows to
renounce the use of 1,3-dioxolane-2-on-com-
pounds and to use gamma lactones such as
gamma-butyrolactone [46] instead.
The review of the recently investigated chela-
toborate salts [2–5, 47–56] permits us to make
conclusions. Table 6 sums up the main charac-
teristics of chelatoborates and chelatophosphate
complexes of lithium salts, such as thermal sta-
bility, maximum solubility, electrical conduc-
tivity and electrochemical stability. The lithium
chelatoborates formed by phenolic ligands have
insufficient electrochemical stability and medi-
um electrical conductivity [3, 4, 5, 52, 54], and
this problem remains even after phenolic li-
gands have been flourinated[3, 5, 48, 53]. The
electrochemical stability of chelatophosphates
is, despite their good conductivity, below 4 V
[49, 50]. Moreover, their synthesis is compli-
cated and requires special conditions. The best
results can be obtained on chelates with ligands
containing a carboxyl group [47, 2, 5, 55, 56].
Lactate, malonate and croconatoborates have
insufficient solubility in aprotic dipolar solvents
and electrical conductivity despite their elec-
trochemical stability of about 5 V. Therefore,
bis(oxalato)borate and lithium bis(salicylato)
borate remain the most promising. The electri-
cal conductivity and electrochemical stability in
dipolar aprotic solvents in both of them is com-
parable to lithium hexaflurophosphate [47, 5].
Table 6
Physicochemical properties of chelato borates and lithium chelato phosphathes
Notation
keys
t, °C S, mol dm−3 σ, mScm−1 Electrochemical stability,
V
Lit.
Source
LBCB 250 0,14(EC+DME) 2,40(EC+DME) 5,5(PC) [47]
LCSB 328 0.16(EC+DME) 2.89(EC +DME) 5.0(PC) [47]
LіBSB 350 1.41(EC+DME) 5.08 (EC +DME) 4.3(PC) [47]
LiLOB 0.93 mol/kg (DME) 6.52(DME) 5.0(GBL) [2]
LiBLB 0.02 mol/kg(GBL) 0.01(GBL) >5.0(GBL) [2]
LBBB 250 0.290(PC+DME) 5.99(PC +DME) 3.6(PC) [3], [4]
LBDOB 256 0.302(PC +DME) 6.21(PC +DME) 3.7(PC) [3]
LіBOB 302 0.349(PC +DME) 7.79 (PC +DME) 4.5(PC) [5]
F3LBBB 256 0.283 (PC +DME) 6.43(PC +DME) 3.7(PC) [5] [48]
F3LBDOB 262 0.284(PC +DME) 6.55(PC +DME) 4.0(PC) [3], [48]
LiP(C2O4)3 150 20%(PC +1,2-DME) 9,7(PC +1,2-DME) 4.0(PC) [49]
LiTBP 150 0.5(EC +DME) 2.5(EC +DME) 3.7(PC) [50]; [51]
LBPB – – – 3.95(EC/DMK/PK=4/4/1) [52]
LiFSB – 0.42m (EC+DME) – 4.6(EC/DMK) [53]
F4LBDOB 270 0,4 m PC 4.0-4.1(*12)(PC) [5]
LNBDB 280 3.7(PC) [5]
LBBDB 270 4.1(PC) [54]
LiMOB 273 0.5(GBL)
0.08(PC)
5(GBL) 4.2(PC),
5(GBL)
[55]
[56]
NOVEL NON-AQUEOUS ELECTROLYTES BASED ON COORDINATION BORON COMPOUNDS
50 ISSN 2708-129X. Укр. хім. журн., 2021
PHYSICAL CHEMISTRY
Bis(oxalato)borate has a severe disadvan-
tage: it is able to interact with many different
kinds of cathodes, but only when being paired
with high- voltage anode materials or lithium
anode, which is explained by its (borate) high
reduction voltage in the first cycle.
However, the high price of lithium raw ma-
terials and limited lithium reserves in the Earth
crust hold increasing demand for high current
sources. Since lithium is a trace element, and
its considerable reserves can be found only
in South America, the ever-growing demand
can cause speculation and influence the geo-
political situation in the world. A promising
alternative to lithium-ion batteries is active-
ly searched sodium-ion batteries. Sodium is
an extremely common element and ten times
cheaper [57–61]. Table7 compares sodium and
lithium based systems [57]. It is also worth to
mention that metallic lithium melts at 180.5 °C
and sodium metal at 97.7 °C. And this fact be-
comes extremely important when using them
as anode materials. The low melting point of
sodium limits the usage of sodium anode. The
cathode and anode materials used in lithi-
um-ion batteries are similar to those in sodi-
um-ion batteries. However, some differences
between them were identified. For example:
Table 7
Comparison of sodium and lithium based systems
category lithium Sodium
Cation radius (Å) 0.76 1.06
Atomic density 6.9 g/mol 23 g/mol
Potential limit relative to Li/Li+ -3.04 V -2.71 V
the cost of the carbonate 3850 Euro/t 115 Euro/t
Metal capacity mA/h 3829 1165
Coordination grid Octahedron and tetrahedron Octahedron and prism
solid carbon and glassy carbon can be used as
anodes, graphite properties in contrast were
shown to be inadequate [57]. FePO4 is used as
cathode material [58–60, 62–65], NaFeO2 as
well as NaCrO2 [66–70] were resistant in con-
trast to the lithium analogs [71–73]. NaPF6 and
NaClO4 solutions in carbonate or Glim solvents
[57, 58, 61] can also be used as electrolytes when
with an aqueous electrolyte (sodium sulfate
solution), NaTi2(PO4)3 and Na2FePO4F [74] are
used as cathode and anode respectively.
Another important point is the presence of
a protective solid ion-conductive film on the
anode, which is formed as a result of destructive
interaction with the electrolyte and prevents it
from further destruction [61]. This film was
observed on the sodium anode when working
with a NaPF6 electrolyte in diglyme and tetra-
lin. This electrolyte was proved to stay stable
after being in operation with a sodium anode
[61] for 300 cycles. The combination of NaPF6
with other solvents or other salts with diglyme
and tetralin demonstrated significantly worse
results. Like lithium systems, bis(chelato)bo-
rate sodium salt was tested in non-aqueous
solvents [75]. Similar to lithium ion batteries,
V. A. Diamant
51https://ucj.org.ua
UCJ № 3 / Vol. 87
they create a protective film on the surface of
cathode and anode materials.
However, this class of compounds is very
little investigated in terms of solubility and
conductivity in non-aqueous solvents. The
only fact known is that bis(oxalato)borate and
bis(salicylato)sodium borate are well soluble in
DMFA and DMSO and very weakly soluble in
acetonitrile and carbonate esters, in addition to
the electrical conductivity data of these solu-
tions [75], [76]. To determine the potential im-
plication of bis(chelato)sodium borates, more
detailed studies on the solubility in ADR and
the electrochemical properties of these electro-
lytes are needed.
Recently, bis(chelato)borates of quaternary
ammonium cations have been widely studied
[1113, 77, 78, 31, 32, 79, 80]. They have a rath-
er high thermal stability (e.g. Et4NB(С2О4)2
~ 220°С) [78], but are inferior to Et4NBF4 in
electrochemical stability. According to the ana-
lyzed literature data, the electrochemical sta-
bility of thebis(chelato)borates of quaternary
ammonium cations does not correlate well with
the cation nature: for example, bis(oxalate)bo-
rate, bis(2,2’-bisphenol)borates Et4N
+, Ме4N
+
and tetraethylammoniumbis(1,2-ethoxy)bo-
rate, 2.5 V [77, 78]; 1-ethyl-3-methyl(oxalato)
borate, 2.4 V [79, p. 91]. Moreover, in contrast
to Et4NBF4bis(oxalato)borate, tetraalkylammo
niumcations are recommended, according to
the patent [81], as a protective additive to elec-
trolytes for lithium-ion batteries to protect the
aluminum current collectors and other metallic
parts of the battery structure from corrosion.
In addition, salicyloborates have been suc-
cessfully tested as electrolytes for aluminum
electrolytic capacitors [82], and oxalate-based
ionic liquids proved to be radiation resistant
and can be used in nuclear engineering [11].
We should mention electrolytes based on
lithium trifluoroacetate. CF3COOLi salt is
highly soluble only in water and is practically
insoluble in aprotic dipolar solvents (ADS); it
is traditionally used to prepare electrolytes in
industrial and laboratory lithium power sour
ces [28]. To eliminate these restrictions, this
salt was added to polymer electrolytes [83].
Researchers [34, 35] have solved this prob-
lem in an original way – by using complexing
agents for anions. The complexation of anions
is a much more promising factor, as it increases
both ion dissociation and lithium mobility. The
boron-containing anionic complexing agents
made it possible to obtain concentrated up to
1.2 M solutions of CF3COOLi, C2F5CO2Li and
even LiF (Fig. 3) [34, 35].
Figure 3 – Boron containing anionic complex-
ing agent [34].
It should be pointed out that the complexing
agent is introduced in an amount of 1 M per 1 M
of salt. These works are still of considerable
scientific interest, given the high chemical and
thermal resistance of CF3COOLi (170°C) [35]
and LiF (over 1000°C). The electrochemical
stability of multicomponent electrolytes with
CF3COОLi and LiF is also quite high and is
about 5 V in EC/DMC. But the process is sig-
nificantly complicated and becomes unprofita-
ble when the complexing agent is added.
NOVEL NON-AQUEOUS ELECTROLYTES BASED ON COORDINATION BORON COMPOUNDS
52 ISSN 2708-129X. Укр. хім. журн., 2021
PHYSICAL CHEMISTRY
The salt components
of the electrolyte
Recovery
potential at the
first cycle relative
to Li/Li+, V
0.97
0.89
The salt components
of the electrolyte
Recovery
potential at the
first cycle relative
to Li/Li+, V
1.71
1.02
1.60
Table 8
Reduction on the first cycle of the lithium bis(oxalate)borate, bis(salicylo, oxalate)borate,
bis(salicylo)borate and bis(malonato, salicylo)borate [84].
O
O
O
B
O
O
O
Li
O
O
O
O
B
O
O
O
OLi
O
O
O
O
B
O
O
O
OLi
O
O
O
B
Li
O
O
O
O
O
O
O
B
O
O
O
Li
O
O
O
O
B
O
O
O
OLi
O
O
O
O
B
O
O
O
OLi
O
O
O
B
Li
O
O
O
O
Figure 4 – Diagram of the reduction reaction and the formation of a solid electrolyte film on the elec-
trode surface.
V. A. Diamant
53https://ucj.org.ua
UCJ № 3 / Vol. 87
Based on the nature of the ligand in the first
cycle, various lithium chelate salts give rise to
a reduction peak, which disappears in subse-
quent cycles (table 8). The peak correlates with
salt decomposition, followed by the forma-
tion of a protective film with solid electrolyte
properties [84], [85], [86]. One of the possible
mechanisms of this process is illustrated by the
example of well-known lithium bis(oxalato)
borate (Fig. 4) [86].
The experiment with the salicylborate ani-
on has shown that the сoordination covalent
bond in the aromatic nucleus has caused a shift
of the reduction peak to higher potentials (ta-
ble 8). Voltammetry is a sensitive method to
detect impurities resulting from the hydroly-
sis of lithium chelate with water residues. The
process has been studied in detail on lithium
bis(oxalato)borate by gradually adding addi-
tional water to the electrolyte and identifying
the hydrolysis products (Fig. 5) additionally,
using IR spectroscopy and H1-NMR [86].
Figure 5 – Scheme of lithium bis(oxalato)borate hydrolysis [86].
Li
O
O
O
O
B
O
O
O
O
+ 2H2O
O
O
O
O
B
OH
OH
HO
HO
O
O
+
O
O
O
O
B
Li
OH + LiOH
Li
Conclusions
The literature analysis has shown that che-
late borates with boron-centered complex sali
cylborate anion are a modern and promising
basis for chemical power sources, which in-
clude features of ionic fluids and due to chang-
ing the nature of cation and anion symmetry,
could influence their electrochemical proper-
ties. Therefore, the use of other chelate borate
ligands in the synthesis of salts with their fur-
ther use in mixtures with different kinds of sol-
vents is relevant and promising.
The work was done within research
projects «Development of electro-
chemical systems with low overvoltage
of cathode and anode processes and high-
ly economical electrolyzers for obtaining
high purity hydrogen», № State Registration
0110U001650 (2012–2014) and «Synthesis
and physicochemical properties of inorganic
electrocatalyst systems based on modified
tungsten carbide metals Ib (Cu, Ag), IVb (Ti,
Zr, Hf) and Vb (V, Nb, Ta) subgroups, for al-
ternative electrochemical energy «, № State
Registration 0110U001650 (2015–2017).
NOVEL NON-AQUEOUS ELECTROLYTES BASED ON COORDINATION BORON COMPOUNDS
54 ISSN 2708-129X. Укр. хім. журн., 2021
PHYSICAL CHEMISTRY
НОВІ НЕВОДНІ ЕЛЕКТРОЛІТИ НА ОСНОВІ
КОРДИНАЦІЙНИХ СПОЛУК БОРУ
Діамант В. А.
Інститут загальної та неорганічної хімії
імені В. І. Вернадського НАН України, просп.
Акад. Палладіна, 32/34, Київ 03680, Україна
email: carbon.h.4@gmail.com
В огляді наведено класифікацію електро-
літів для сучасних хімічних джерел струму,
суперконденсаторів, натрій- та літій-іон-
них акумуляторів залежно від зміни фізи-
ко-хімічних властивостей солей та продук-
тів їхньої взаємодії з розчинником. Прове-
дено порівняльний аналіз фізико-хімічних
властивостей солей залежно від будови
катіону та аніону та вплив цих властивос-
тей на властивості кінцевих розчинів елек-
тролітів на прикладі різних класів йонних
рідин та хелатоборатів лужних металів та
амонію. Проаналізовано залежність фі-
зико-хімічних властивостей електролітів
(розчинність, електропровідність розчи-
нів та діапазон потенціалів електрохімічної
стійкості) від природи хелатного ліганду,
електродонорних та електроакцепторних
замісників у складі біс(хелато)боратного
аніона. Проведено співставлення електро-
провідністі розчинів солей та діапазонів
потенціалів електрохімічної стійкості від-
повідних електролітів, що містять інші
аніони і які довгий час використовували в
хімічних джерелах струму. Зазначено пе-
реваги та недоліки використання рідких
електролітів порівняно з твердими та по-
лімерними електролітами з точки зору по-
дібності їхніх структур. Показано, що при-
рода хелатного ліганду, електродонорних
та електроакцепторних замісників у складі
біс(хелато)боратного аніона є важливим
фактором регулювання взаємодії з апро-
тонними диполярними розчинниками.
Змішані солі із двома різними хелатними
лігандами, як правило, об’єднують найкра-
щі характеристики відповідних монохелат-
них сполук, але методи їхнього отримання і
очищення технологічно є значно ускладне-
ними порівняно з монохелатними сполука-
ми. Зроблено аналіз механізму утворення
захисної плівки на поверхні електродних
матеріалів, залежності потенціалу її утво-
рення від хімічної природи і будови лі-
гандів. Відзначено, що біс(хелато)боратні
солі є більш екологічно прийнятними по-
рівняно із фторовмісними комплексними
солями. Закцентовано увагу на фізико-хі-
мічних властивостях розчинів найбільш
перспективних хелатоборатних солей з ме-
тою застосування в літій- та натрій-іонних
акумуляторах, суперконденсаторах та елек-
тролітичних конденсаторах, та показано,
що біс(оксалато)борати та біс(саліцило)бо-
рати займають золотий перетин між усіма
відомими біс(хелато)боратами за електро-
провідністю, розчинністю та діапазоном
потенціалів електрохімічної стійкості.
Ключові слова: електроліти для літій-
іонних акумуляторів, біс(хелато)борати,
іонні рідини, координаційні сполуки бору,
суперконденсатори.
V. A. Diamant
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UCJ № 3 / Vol. 87
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Стаття надійшла 29.10.2020.
|
| id | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-288 |
| institution | Ukrainian Chemistry Journal |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2026-07-23T01:06:02Z |
| publishDate | 2021 |
| publisher | V.I.Vernadsky Institute of General and Inorganic Chemistry |
| record_format | ojs |
| resource_txt_mv | ucjorgua/a4/89f1ff55fdfa6685f67f77d5081f5da4.pdf |
| spelling | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-2882026-07-22T08:23:45Z NOVEL NON-AQUEOUS ELECTROLYTES BASED ON COORDINATION BORON COMPOUNDS НОВІ НЕВОДНІ ЕЛЕКТРОЛІТИ НА ОСНОВІ КОРДИНАЦІЙНИХ СПОЛУК БОРУ Diamant, Viktor salt, cation, anion, solvent, ionic liquids, coordination compounds of boron, electrolytes for electrochemical energy storages. The review provides a classification of electrolytes for modern chemical power sources, supercapacitors, sodium and lithium-ion batteries depending on changes in the physicochemical properties of salts and the products of their interaction with the solvent. A comparative analysis of physicochemical properties of salts depending on the structure of the cation and anion, and the influence of these properties on the properties of final solutions of electrolytes on the example of different classes of ionic liquids and chelatoborates of alkali metals and ammonium was conducted. The dependence of the physicochemical properties of electrolytes (solubility, electrical conductivity of solutions and the range of potentials of electrochemical stability) on the nature of the chelate ligand, electron donor and electroacceptor substituents in the bis (chelate) borate anion is analyzed. The electrical conductivity of salt solutions and ranges of potentials of electrochemical stability of the corresponding electrolytes containing other anions and used for a long time in chemical current sources are carried out. The advantages and disadvantages of using liquid electrolytes compared to solid and polymer electrolytes in terms of similarity of their structures have been detected. It is shown that the nature of the chelate ligand, electro-donor and electro-acceptor substituents in the bis (chelato) borate anion is an important factor in regulating the interaction with aprotic dipolar solvents. Mixed salts with two different chelate ligands typically combine the best characteristics of the corresponding monochelate compounds, but the methods for their preparation and purification are technologically significantly more complex compared to monochelate compounds. The analysis of the mechanism of formation of a protective film on a surface of electrode materials, dependence of potential on its formation and on the chemical nature of ligands is made. It is noted that bis (chelato) borate salts are more environmentally friendly compared to fluorine-containing complex salts. Emphasis is placed on the physicochemical properties of solutions of the most promising chelatoborate salts for use in lithium and sodium ion batteries, supercapacitors and electrolytic capacitors, and it is shown that bis (oxalate) borates and bis (salicylate gold) borates occupy ) borates in terms of electrical conductivity, solubility and potential range of electrochemical stability. V.I.Vernadsky Institute of General and Inorganic Chemistry 2021-04-23 Article Article Physical chemistry Физическая xимия Фізична xімія application/pdf https://ucj.org.ua/index.php/journal/article/view/288 10.33609/2708-129X.87.03.2021.41-60 Ukrainian Chemistry Journal; Vol. 87 No. 3 (2021): Ukrainian Chemistry Journal; 41-60 Украинский химический журнал; ##issue.vol## 87 ##issue.no## 3 (2021): Ukrainian Chemistry Journal; 41-60 Український хімічний журнал; Том 87 № 3 (2021): Український хімічний журнал; 41-60 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/288/160 Copyright (c) 2021 Viktor Diamant https://creativecommons.org/licenses/by-nc/4.0 |
| spellingShingle | Diamant, Viktor НОВІ НЕВОДНІ ЕЛЕКТРОЛІТИ НА ОСНОВІ КОРДИНАЦІЙНИХ СПОЛУК БОРУ |
| title | НОВІ НЕВОДНІ ЕЛЕКТРОЛІТИ НА ОСНОВІ КОРДИНАЦІЙНИХ СПОЛУК БОРУ |
| title_alt | NOVEL NON-AQUEOUS ELECTROLYTES BASED ON COORDINATION BORON COMPOUNDS |
| title_full | НОВІ НЕВОДНІ ЕЛЕКТРОЛІТИ НА ОСНОВІ КОРДИНАЦІЙНИХ СПОЛУК БОРУ |
| title_fullStr | НОВІ НЕВОДНІ ЕЛЕКТРОЛІТИ НА ОСНОВІ КОРДИНАЦІЙНИХ СПОЛУК БОРУ |
| title_full_unstemmed | НОВІ НЕВОДНІ ЕЛЕКТРОЛІТИ НА ОСНОВІ КОРДИНАЦІЙНИХ СПОЛУК БОРУ |
| title_short | НОВІ НЕВОДНІ ЕЛЕКТРОЛІТИ НА ОСНОВІ КОРДИНАЦІЙНИХ СПОЛУК БОРУ |
| title_sort | нові неводні електроліти на основі кординаційних сполук бору |
| topic_facet | salt cation anion solvent ionic liquids coordination compounds of boron electrolytes for electrochemical energy storages. |
| url | https://ucj.org.ua/index.php/journal/article/view/288 |
| work_keys_str_mv | AT diamantviktor novelnonaqueouselectrolytesbasedoncoordinationboroncompounds AT diamantviktor novínevodníelektrolítinaosnovíkordinacíjnihspolukboru |