JP2014082487A - Bn electrolytic material with accumulative, conductive and antibacterial properties - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a BN electrolytic material which has excellent conductive, accumulative, antibacterial, bacteria-removing and bactericidal properties and has high viscosity and high workability, a non-aqueous electrolyte for an electrical storage device, an electrical storage device, an antibacterial material and an antistatic agent using the BN electrolytic material.SOLUTION: The BN electrolytic material is formed from a charge-transfer conjugate which is a neutralization salt of one or two or more kinds of organic boron compounds with semipolar bonds and one or more kinds of amine compounds selected from the group of tertiary amine with totally 5 to 82 carbon atoms having at least one hydroxy radical and a polyamino compound having two or more basic nitrogen in a molecule, and which is a reaction product in a ratio of one basic nitrogen atom to one boron atom of the organic boron compound.

Description

  The present invention relates to a BN electrolyte material, a non-aqueous electrolyte for an electricity storage device, an electricity storage device, an antibacterial material, and an antistatic agent having electricity storage property, conductivity, antibacterial property, sterilization property, and bactericidal property.

  Conventionally, various ionic liquids are known as electrolytes in electrochemical devices such as electrolytes such as batteries and capacitors and plating baths (for example, Patent Document 1). However, the conventional ionic liquids are insufficient in both power storage and electrical conductivity, and have low viscosity, so that workability is poor and there is a problem that a sealing technique is necessary.

  On the other hand, charge transfer type conjugates (BN compounds) comprising reaction products of semipolar organic boron compounds and amine compounds have been known as antistatic agents (for example, Patent Documents 2 and 3).

Japanese Patent Laid-Open No. 2006-23689 Japanese Patent No. 2588576 Japanese Patent No. 2872817

  The present invention relates to a BN electrolyte material having excellent conductivity, power storage property, antibacterial property, sterilization property, and bactericidal property, and having high viscosity and excellent workability, and non-water for a power storage device using the BN electrolyte material An object is to provide an electrolytic solution, an electricity storage device, an antibacterial material, and an antistatic agent.

  As a result of earnest research on a charge transfer type conjugate (BN compound) comprising a reaction product of a semipolar organoboron compound and an amine compound, the present inventors have surprisingly found that the BN compound has an excellent electricity storage property, It has been found that it has antibacterial properties, bactericidal properties and bactericidal properties.

  That is, the BN electrolyte material having electrical storage properties and conductivity according to the present invention is one or more organic boron compounds having a semipolar bond, and a tertiary class having a total carbon number of 5 to 82 having at least one hydroxy group. A neutralized salt with an amine and one or more amine compounds selected from the group consisting of an amine and a polyamino compound having two or more basic nitrogen atoms in the molecule, with respect to one boron atom of the organoboron compound It consists of the charge transfer type | mold coupling body which is a reaction product in the ratio of one basic nitrogen atom.

  As the organoboron compound having a semipolar bond, known organoboron compounds having a semipolar bond can be widely used, and are not particularly limited. For example, the semipolar organoboron polymer compound described in Patent Document 2 And semi-polar organic boron compounds described in Patent Document 3, organoboron polymer compounds described in JP-B-3-53331, and the like.

  As the tertiary amine having 5 to 82 carbon atoms and having at least one hydroxy group, for example, a tertiary amine described in Patent Document 2 is preferably used. Examples of the polyamino compound having two or more basic nitrogen atoms in the molecule include a polyamino compound described in Patent Document 3 and a copolymer of dimethylaminoethyl (meth) acrylate and another monomer. It is done. In the present specification, methacrylic acid and acrylic acid are collectively referred to as (meth) acrylic acid. Examples of the other monomers include (meth) acrylic acid alkyl ester monomers, (meth) acrylic acid hydroxy (alkoxy) -containing ester monomers, (meth) acrylic acid alicyclic rings, aromatic rings, and heterocyclic rings. And one or more selected from the group consisting of vinyl group-containing ester monomers are preferred, and the other monomers are more preferably two or more.

  The BN electrolyte material of the present invention has excellent electrical conductivity with Rct (charge transfer resistance) of 3 kΩ or more and less than 10 kΩ, τ (relaxation time) of 200 msec or less, and Cs (dielectric constant equivalent) of less than 8 μF. Can have.

  The BN electrolyte material of the present invention can have excellent electric storage properties such that C × 100 is 100 or more, τ (relaxation time) is 300 msec or more, and Cs (dielectric constant equivalent) is 7 μF or more. is there.

  The BN electrolyte material of the present invention can have an ion dissociation property in which τ (relaxation time) is 200 msec or less and Cs (dielectric constant) is 8 μF or more, and is suitable as a reaction solvent for lithium ion batteries, for example.

  The nonaqueous electrolytic solution for an electricity storage device of the present invention is characterized by comprising only the BN electrolyte material of the present invention or containing the BN electrolyte material of the present invention. The non-aqueous electrolyte may contain a known organic solvent or an ion conductive salt as necessary.

  The electricity storage device of the present invention comprises the nonaqueous electrolyte for an electricity storage device of the present invention. The electricity storage device refers to a device or an element that can store electricity chemically, physically, or physicochemically, for example, a secondary battery such as a lithium ion battery, an electric double layer capacitor, an electrolytic capacitor, or the like. Examples include devices that can be discharged.

  The antibacterial material of the present invention includes the BN electrolyte material of the present invention. The BN electrolyte material of the present invention has excellent antibacterial properties, sterilization properties, and bactericidal properties, and can be applied to various uses that require antibacterial activity. For example, it is suitably used for antibacterial agents containing the BN electrolyte material of the present invention as an antibacterial component, antibacterial processed products such as antibacterial sprays, antibacterial paints, antibacterial resins, and antibacterial sheets.

  The antistatic agent of the present invention comprises the BN electrolyte material of the present invention. The BN electrolyte material of the present invention can be prevented from being charged with static electricity and can increase conductivity, and is preferably used as an antistatic agent.

  The BN electrolyte material of the present invention is excellent in power storage and electrical conductivity, has high viscosity (for example, 100,000 centipoise at 30 ° C.), has good workability, and does not require a sealing technique. Furthermore, the BN electrolyte material of the present invention has excellent antibacterial properties, sterilization properties, and bactericidal properties.

It is a schematic explanatory drawing which shows the meaning of the electrochemical characteristic which appears on a complex plane, and its equivalent circuit. It is a graph which shows the Nyquist diagram of BN-3. It is a graph which shows the relationship between Rct and C * 100 in the electrode interface of a BN compound. It is a graph which shows the relationship between the dielectric constant of a BN compound, and relaxation time. It is a graph which shows the electroconductivity of a BN compound. It is a graph which shows the electrical storage performance of a BN compound. It is a graph which shows the result of the comparative test of the potential window of a BN compound and an ionic liquid. It is a graph which shows the result of the charge-discharge comparison test of a BN compound and an ionic liquid. It is a photograph which shows the result of the control (at the time of start) using colon_bacillus | E._coli in an antibacterial activity test. It is a photograph which shows the result of BN-2 (after 24 hours) using colon_bacillus | E._coli in an antibacterial activity test. It is a photograph which shows the result of BN-5 (after 24 hours) using colon_bacillus | E._coli in an antibacterial activity test. It is a photograph which shows the result of BN-1-3 (after 24 hours) using colon_bacillus | E._coli in an antibacterial activity test. It is a photograph which shows the result of the control (after 24 hours) using colon_bacillus | E._coli in an antibacterial activity test. It is a photograph which shows the result of the control (at the start) using Staphylococcus aureus in the antibacterial activity test. It is a photograph which shows the result of BN-2 (after 24 hours) using Staphylococcus aureus in the antibacterial activity test. It is a photograph which shows the result of BN-5 (after 24 hours) using Staphylococcus aureus in the antibacterial activity test. It is a photograph which shows the result of BN-1-3 (after 24 hours) using Staphylococcus aureus in the antibacterial activity test. It is a photograph which shows the result of the control (after 24 hours) using Staphylococcus aureus in the antibacterial activity test.

  Embodiments of the present invention will be described below, but these are exemplarily shown, and it goes without saying that various modifications are possible without departing from the technical idea of the present invention.

  The present invention will be described more specifically with reference to the following examples. However, it is needless to say that these examples are shown by way of illustration and should not be construed in a limited manner.

  Table 1 below shows the names of the BN compounds used in the experiments of the present specification, the charge transfer resistance (Rct) and the surface resistivity (Ω / Sq) at the electrode interface.

In Table 1, the details of each BN compound are as follows.
<BN-1>
A low molecular weight BN compound obtained by equimolar reaction of diglyceryl borate (glycerin borate), C14 unsaturated, side chain dicarboxylic acid ester and polyoxyethylene stearylamine (7 mol addition).
<BN-1-1>
Low molecular weight BN compound obtained by equimolar reaction of diglycerin borate, C16 saturated, linear carboxylic acid ester and polyoxyethylene stearylamine.
<BN-1-2>
A low-molecular-weight BN compound obtained by equimolar reaction of di-glycerin borate, C16 saturated, linear carboxylic acid ester and polyoxyethylene stearylamine (7 mol addition).
<BN-1-3>
A low-molecular-weight BN compound obtained by an equimolar reaction between di-glycerin borate and polyoxyethylene stearylamine (7 mol addition).
<BN-1-4>
A low-molecular-weight BN compound obtained by reacting equimolar amounts of C15 saturated, linear carboxylic acid ester of polyoxyethyleneglycidyl glycerin borate (24 mol addition) and polyoxyethylene stearylamine (7 mol addition).
<BN-1-5>
A low molecular weight BN compound obtained by reacting polyoxyethylene diglycerin borate (24 mol addition) with C17 saturated, linear carboxylic acid ester and polyoxyethylene stearylamine (7 mol addition) in an equimolar amount.
<BN-1-6>
A low-molecular-weight BN compound obtained by an equimolar reaction between di-glycerin borate and polyoxyethylene stearylamine (15 mol addition).
<BN-1-7>
A low molecular weight BN compound obtained by reacting an equimolar amount of a C17 unsaturated, linear carboxylic acid ester of di-glycerin borate with polyoxyethylene stearylamine (15 mol addition).
<BN-1-8>
A low molecular weight BN compound obtained by reacting polyoxyethylene diglycerin borate (24 mol addition) and polyoxyethylene stearylamine (15 mol addition) in an equimolar amount.
<BN-1-9>
A low-molecular-weight BN compound obtained by reacting 1: 2 mol of diglycerin borate, C6 unsaturated, cyclic dicarboxylic acid diester and polyoxyethylene stearylamine (15 mol addition).
<BN-1-10>
A low-molecular-weight BN compound obtained by reacting 2: 1 mol of diglycerin borate with triethyldiamine.

<BN-5-4>
A low-molecular-weight BN compound obtained by reacting equimolar amounts of a C17 saturated, linear carboxylic acid ester of polyoxyethylene diglycerin borate (24 mol addition) and stearic acid dimethylaminopropylamide.
<BN-5-3>
A low molecular weight BN compound obtained by reacting equimolar amounts of C15 saturated, linear carboxylic acid ester of polyoxyethylene diglycerin borate (24 mol addition) and dimethylaminopropylamide stearate.
<BN-5-2>
Low molecular weight BN compound obtained by equimolar reaction of monostearyl diglycerin borate and dimethylaminopropylamide stearate.

<BN-2>
Polymeric BN compound obtained by equimolar reaction of diglycerin borate, C34 unsaturated, side chain dicarboxylic acid ester polymer boron compound and polyoxyethylene stearylamine (7 mol addition).
<BN-2 *>
Polymeric BN compound obtained by equimolar reaction of diglycerin borate, C34 unsaturated, side chain dicarboxylic ester polymeric boron compound and polyoxyethylene stearylamine (7 mol addition). Another lot of BN-2.
<BN2-5>
Polymeric BN compound obtained by reacting equimolar amounts of di-diglycerin borate (diglycerin borate polymer compound) and polyoxyethylene stearylamine (7 mol addition).
<BN2-6>
A low-molecular-weight BN compound obtained by reacting equimolar amounts of C2 dicarboxylic acid ester of diglycerin borate and polyoxyethylene stearylamine (7 mol addition).
<BN2-7>
A polymeric BN compound obtained by equimolar reaction of a higher molecular weight boron compound of di-glycerin borate, C34 unsaturated, side chain dicarboxylic acid ester and polyoxyethylene stearylamine (7 mole addition).

<BN-3>
Polymeric BN compound obtained by equimolar reaction between di-glycerin borate, C10 saturated, linear dicarboxylic acid polymeric boron compound and polyoxyethylene stearylamine (7 mol addition).

<BN-5>
Azo-based polymerization of dimethylaminoethyl methacrylate, 2-hydroxymethacrylate, and cyclohexyl methacrylate monomers in alcohol solvent at ratios of 0.3 mol%, 0.4 mol%, and 0.3 mol%, respectively. In the presence of an initiator, a polymeric BN compound obtained by equimolar reaction of a tertiary amine and diglyceryl borate in a copolymerization solution obtained by copolymerization.

A liquid sample (each BN compound) was filled in an ITO-deposited counter electrode glass cell (thickness 100 μm, effective area 1 cm ² ) having the structure shown in FIG. 1, and a maximum amplitude of 1.0 V between 0.1 Hz and 1 MHz between the electrodes. The impedance characteristics drawn on the complex plane by applying AC voltage were investigated. The result of BN-3 is shown in FIG. For each BN compound, a figure composed of a circular arc in a high frequency region and a straight line in a low frequency region as depicted in the Nyquist diagram (colle-coll plot) in FIG. 2 was drawn.

  Charge transport in the bulk because it has a corresponding charge transfer resistance while forming an electric double layer at the interface with the ITO electrode having a resistance value of around 200Ω, and also has a resistance caused by the diffusion of the material, which is a Warburg resistance. It is suggested that the mechanism is ion conductive. In particular, the BN compound is characterized by the presence of a rapid conduction: charge transfer process indicated by Rct at the electrode interface.

  Table 1 summarizes the correspondence relationship of the charge transfer resistance (the numerical value Rct on the real axis that can be read from the complex plan view) at the electrode interface of each BN compound.

Further, the value of the capacitance C calculated from the frequency f at the point where the capacitive impedance represented on the imaginary axis is maximized is obtained (C = 1 / 2πf · R), and the relationship is plotted in FIG. did. The vertical axis is 100 times the C value C × 100, which is an indicator of the charge capacity accumulated in the electric double layer at the electrode interface.
From FIG. 3, the relationship between the charge transfer resistance Rct at the electrode interface of various BN compounds and the charge capacity C accumulated in the electric double layer was approximated to the power of Rct. This suggests that the resistance in the equivalent circuit increases according to the molecular weight, while the capacitance settles at a substantially constant value.

  In order to investigate what physical factors this situation reflects, the frequency fc at which the loss (dielectric loss) ε ″ due to the external electric field of each compound is maximized in the frequency band described above is obtained from the graph, and the interface impedance 4 is plotted as a function of the measured value Cs obtained when the equivalent circuit is regarded as a series connection of C and R, and is summarized in Fig. 4. Calculated values of Cs, Rs, fc, and relaxation time τ (τ = 1 / 2πfc) ) Is shown in Table 2.

  Here, Cs is obtained from the real part of the dielectric constant, which means stored energy from the outside, that is, the actual dielectric constant, and the observed fc is a low frequency of about 0.3 to 6 Hz. The relaxation time τ is considered to be derived from the orientation polarization based on the dipole rotation moment of the molecule in the polarization that contributes to the dielectric constant (there are electronic polarization, atomic polarization, orientation polarization, etc. in order of increasing frequency).

  Here, when FIG. 4 is looked down on, the substituent R1 = H of the organoboron (B) skeleton is commonly used, and R2 is a linear monocarboxylic acid ester BN-1-1. Despite having the same molecular weight, it is easily presumed that since it has a carboxylic acid at the end, a hydrogen bond intervenes between the molecules and rotation orientation in the electric field tends to be hindered. Furthermore, BN-2 having a repeating structure with 5 to 6 constitutional units having the same dicarboxylic acid is considered to have a very large rotational obstacle due to its bulk as a molecule together with a branched chain. In addition, since BN-1-4 or 1-5 has the same linear monoester structure as 1-1, it can be seen that these five compounds are almost on the same line. BN-1-4 has an unsaturated bond in the ester moiety as compared to -1-5. Therefore, the electric field orientation is more linked to the dipole rotation moment reduction due to the introduction of a polar group (polyoxyethylene group) into the B skeleton. It is estimated that it is easy to do.

  Next, based on BN-1-4, which is considered to be most easily electric field oriented, the B skeleton does not contain bulky electron-withdrawing atoms (groups) and forms a structural pair as a salt. BN-1-3 having an electron withdrawing group on the other side and 1-6 having an increased number of electron withdrawing groups to the counter electrode N are considered to significantly increase the dielectric constant while maintaining the molecular orientation. For the same reason, it is expected that the dielectric constants of BN-1-5 and 1-8 containing bulky electron-withdrawing atoms (groups) in the B skeleton are low.

  In summary, the BN compound, which has an ohmic conduction mechanism at the electrode interface, has not only conductivity but also power storage performance by controlling the type and amount of substituents introduced into the B and N skeletons. It was found that it can be granted. This is because the molecular design with the BN structure as the core gives a high-speed charge transport function that does not depend on the diffusion of the substance in addition to the conventional ionization or antistatic application by ionic conduction. It became clear that it would also be possible to express electricity storage, which was a unique place.

Therefore, the following experiment was conducted in order to grasp the practical electrochemical performance of the BN compound.
(Conductivity test)
The conductive performance was evaluated by measuring the current flowing through the cell when a pulse voltage of 10 mV / 200 msec was applied to the cell containing the target substance. Actually, a cyclic voltammogram (CV) that is stepped up (stepped down) while being pulse-driven under the same conditions as described above was performed in the range of ± 2 V, and the current width at 0 V was measured from the CV image. The results are summarized in FIG.

  As a result, as shown in FIG. 5, it is understood that a compound having a small Rct and a large dielectric constant (for example, BN-1-3, 1-6, -3, etc.) applies to the group having excellent conductivity. It was. In particular, BN-3 has a high dielectric constant because it employs linear dicarboxylic acid and has high crystallinity despite the maximum degree of polymerization and high molecular weight. Therefore, it is necessary to consider the contribution of polarization current. However, from the CV diagram, since a substantially constant current value was shown in the range of ± 1.5 V, no contribution of the polarization current was observed. Similarly, BN-2, which is one digit larger in Rct, was able to pass a current about half the maximum current value because the voltage was as small as 10 mV and the application time was 200 msec, which is less than the relaxation time. It can be said to be a large value. It is worthy to note that a current value approximately three times the calculated value is obtained.

(Electricity test)
The above cell was charged at a constant voltage of 1.3 V for 3 minutes, held for 3 seconds, and then discharged at a constant current of 2 μA to measure the chargeability, and the previous capacity index C * The correspondence with 100 is summarized in FIG. This result suggests that the capacity index and the discharge time are in a substantially linear relationship as shown in FIG.

(Measurement of potential window and charge / discharge test)
Comparison and charge / discharge comparison of potential window (electrically stable potential region without undergoing redox) of BN-2 and conventional ionic liquid (1-n-butyl-3-methylimidazolium tetrafluoroborate, BMIMB4) Went. The comparison test of the potential window was performed under the conditions of CV (cyclic voltammogram), scanning speed 10 mV / sec (± 2 V), sample: 2 cm square 100 μm filling / ITO glass (surface resistance 20 Ω / cm). The charge / discharge comparison test was a comparison of the behaviors of 3 times, and was performed under the conditions of 1.3 V 30 sec charge rest 7 sec 5 μA discharge, sample: 2 cm square 100 μm filling / ITO glass (surface resistance 20 Ω / cm). The result of the potential window comparison test is shown in FIG. 7, and the result of the charge / discharge comparison test is shown in FIG.

  As shown in FIG. 7 and FIG. 8, when the BN compound (BN resin) is compared with the ionic liquid, the BN resin has a higher discharge start voltage of about 0.1 V and the discharge time is longer. It is considered that the power storage performance is superior to that of ionic liquids that are put to practical use.

(Surface resistivity measurement test)
In order to investigate the antistatic property of the ionic liquid, the surface resistivity of each BN compound was measured. Dissolve the BN compound in ethanol to make a 5% concentration solution, apply it to the surface of the PET film (untreated surface) with a wire bar (# 5) (dry coating thickness: 0.5 μm), and dry at 80 ° C. for 5 minutes. The surface resistivity was measured after storing in a humidifier (50-60% RH) for 1 day. The results are shown in Table 1.

(Antimicrobial test)
1) Preparation of test bacterium solution After culturing the test bacterium (E. coli or Staphylococcus aureus) on a normal agar medium (manufactured by Eiken Chemical Co., Ltd.) at 35 ° C. ± 1 ° C. for 18-24 hours, the solution (E. coli is purified water, Staphylococcus aureus was suspended in physiological saline and prepared so that the number of bacteria would be 10 ⁷ to 10 ⁸ / mL, and used as a test bacterial solution.

2) Test method 0.1 mL of the test bacterial solution was inoculated into 10 g of BN compounds (BN-2, BN-5, BN-1-3) to prepare a sample. The sample was stored at 35 ° C. ± 1 ° C., and after 24 hours, the sample was immediately 10 times on the SCDLP agar medium (manufactured by Nippon Pharmaceutical Co., Ltd.) (Staphylococcus aureus specimen (BN-2) was 100 times, S. aureus specimen (BN) 1-3) was diluted 1000 times), and the number of viable bacteria in the sample was measured using a SCDLP agar medium (manufactured by Nippon Pharmaceutical Co., Ltd.). The culture conditions were 2 days at 35 ° C. ± 1 ° C. by the pour plate culture method. By diluting the sample 10 times with the SCDLP medium (100 times for the Staphylococcus aureus specimen (BN-2) and 1000 times for the Staphylococcus aureus specimen (BN-1-3)), the influence of the specimen was reduced. It was confirmed by a preliminary test that the number of viable bacteria could be measured without receiving.
As a control, Escherichia coli was purified using purified water and Staphylococcus aureus using physiological saline, and the number of viable cells was also measured at the start (immediately after inoculation of the bacterial solution).
The results are shown in Table 3. Moreover, the photograph of the viable count plate after culture | cultivation was shown in FIGS.

  As shown in Table 3 and FIGS. 9 to 18, the BN compound had a great antibacterial property, sterilization property and bactericidal property.

Claims (10)

  From one or more organic boron compounds having a semipolar bond, a tertiary amine having a total of 5 to 82 carbon atoms having at least one hydroxy group, and a polyamino compound having two or more basic nitrogen atoms in the molecule Charge transfer that is a neutralized salt with one or more amine compounds selected from the group consisting of a reaction product at a ratio of one basic nitrogen atom to one boron atom of the organoboron compound A BN electrolyte material having electrical storage properties and electrical conductivity, characterized by comprising a mold combination.   2. Rct (charge transfer resistance) is 3 kΩ or more and less than 10 kΩ, and τ (relaxation time) is 200 msec or less and Cs (dielectric constant) is less than 8 μF. BN electrolyte material.   2. The BN electrolyte material according to claim 1, wherein C × 100 is 100 or more, τ (relaxation time) is 300 msec or more, and Cs (dielectric constant) is 7 μF or more.   2. The BN electrolyte material according to claim 1, which has an ion dissociation property in which τ (relaxation time) is 200 msec or less and Cs (dielectric constant) is 8 μF or more.   The amine compound is a copolymer of dimethylaminoethyl (meth) acrylate and another monomer, and the other monomer is a (meth) acrylic acid alkyl ester monomer or (meth) acrylic. It is one or more selected from the group consisting of acid hydroxy (alkoxy) -containing ester monomers, (meth) acrylic acid alicyclic / aromatic / heterocyclic and vinyl group-containing ester monomers The BN electrolyte material according to any one of claims 1 to 4.   A non-aqueous electrolyte for an electricity storage device, comprising only the BN electrolyte material according to any one of claims 1 to 5 or containing the BN electrolyte material.   An electricity storage device comprising the nonaqueous electrolyte for an electricity storage device according to claim 6.   The electric storage device according to claim 7, wherein the electric storage device is an electric double layer capacitor or a lithium ion battery.   An antibacterial material comprising the BN electrolyte material according to any one of claims 1 to 5.   An antistatic agent comprising the BN electrolyte material according to any one of claims 1 to 5.