阅读说明：本技术 电化学元件用电解质及其制造方法 (Electrolyte for electrochemical element and method for producing same ) 是由 林弘澈 于 2018-05-24 设计创作，主要内容包括：本发明涉及电化学元件用电解质及其制造方法,更详细而言,涉及应用于包含第一电极、与上述第一电极隔离的第二电极、及填充于上述第一电极和第二电极之间的电解质的电化学元件,且包含平均直径为2至12纳米(nm)范围、表面电位为-20mV以下的碳量子点阴离子与金属阳离子的盐形态的碳量子点离子化合物的电化学元件用电解质及其制造方法。本发明的电化学元件用电解质的阴离子和阳离子的解离能(dissociation energy)非常小而提高离子电导率,阴离子的迁移速度与金属阳离子相比,相对非常慢,因而能够实现仅利用金属阳离子迁移的电化学元件,且离子极化性大,阴离子的热化学/电化学稳定性高,因此不发生元件驱动中的副反应而能够大大提高电化学元件的稳定性和可靠性。(The present invention relates to an electrolyte for an electrochemical device and a method for producing the same, and more particularly, to an electrolyte for an electrochemical device, which is applied to an electrochemical device comprising a first electrode, a second electrode spaced apart from the first electrode, and an electrolyte filled between the first electrode and the second electrode, and which comprises a carbon quantum dot ion compound in the form of a salt of a carbon quantum dot anion and a metal cation having an average diameter in the range of 2 to 12 nanometers (nm) and a surface potential of-20 mV or less, and a method for producing the same. The electrolyte for electrochemical devices of the present invention has a very low dissociation energy (dissociation energy) between anions and cations to improve the ionic conductivity, and the migration rate of anions is relatively very slow compared to metal cations, so that an electrochemical device using only metal cation migration can be realized, and the electrochemical device has high ionic polarizability and high thermochemical/electrochemical stability of anions, and thus, side reactions during device driving do not occur, and the stability and reliability of the electrochemical device can be greatly improved.)

1. An electrolyte for an electrochemical element, which is applied to an electrochemical element comprising a first electrode, a second electrode separated from the first electrode, and an electrolyte filled between the first electrode and the second electrode, and which comprises a carbon quantum dot ionic compound in the form of a salt of a carbon quantum dot anion and a metal cation having an average diameter in the range of 2 to 12 nanometers (nm) and a surface potential of-20 mV or less.

2. The electrolyte for electrochemical elements according to claim 1, wherein the metal is an alkali metal, an alkaline earth metal, or a transition metal.

3. The electrolyte for electrochemical elements according to claim 2, wherein the metal is one or more selected from the group consisting of Li, Na, K, Mg, and Zn.

4. The electrolyte for electrochemical elements according to claim 1, wherein a reversible electrochemical redox reaction occurs at least one of the first electrode and the second electrode.

5. The electrolyte for electrochemical elements according to any one of claims 1 to 4, wherein the electrochemical element is one selected from the group consisting of a secondary battery, a solar cell, an electrochromic element, and an electroluminescent element.

6. The electrolyte for electrochemical elements according to claim 5, wherein the secondary battery is a lithium ion battery or a lithium polymer battery.

7. A method for manufacturing an electrolyte for electrochemical elements, comprising:

i) a step of mixing a carbon precursor and an acid, and performing hydrothermal synthesis at 80 to 120 ℃ to produce a carbon quantum dot having an average diameter in the range of 2 to 12 nanometers (nm) and a surface potential of-20 mV or less;

ii) a step of reacting the carbon quantum dots with metal ions to produce a carbon quantum dot anion-metal cation salt;

iii) a step of removing reaction impurities; and

iv) a step of classifying the carbon quantum dot ionic compounds according to size.

8. The method for manufacturing an electrolyte for electrochemical elements according to claim 4, wherein the metal is an alkali metal, an alkaline earth metal, or a transition metal.

9. The method for producing an electrolyte for electrochemical elements according to claim 5, wherein the metal is one or more selected from the group consisting of Li, Na, K, Mg and Zn.

Technical Field

The present invention relates to an electrolyte for an electrochemical device, a method for producing the same, and an electrochemical device comprising the electrolyte, and more particularly, to an electrolyte for an electrochemical device comprising a carbon quantum dot ion compound in the form of a salt of a carbon quantum dot anion and a metal cation having an average diameter in the range of 2 to 12 nanometers (nm) and a surface potential of-20 mV or less, which is applied to an electrochemical device comprising a first electrode, a second electrode spaced apart from the first electrode, and an electrolyte filled between the first electrode and the second electrode, and a method for producing the same.

Background

In general, the electrolyte means a substance that imparts conductivity to a solution and assists charge transfer during an electrochemical reaction. The electrolyte forms a resistive contact between the electrode and the solution by the movement of ions and ion exchange, and is therefore an essential component for the operation of the electrochemical device. The electrolyte does not directly participate in the oxidation/reduction reaction, but supports the electrochemical reaction. The electrolyte generally has a salt form, and is usually used in a liquid or gel form by dissolving it in a solvent, and in some cases, it is used by dispersing it in a solid.

However, in the conventional electrochemical device, the electrode material constituting the internal electrode comes into contact with the electrolyte to generate ions (H)⁺、Li⁺Etc.) and reversibility of insertion and extraction, there is a problem in stability. In many cases, an organic solvent is used for a liquid electrolyte mainly used at present, and the organic solvent has stability problems such as ignition, evaporation, and leakage. On the other hand, thoughThe solid electrolyte has been superior in stability compared with the liquid electrolyte so far, but has a low ionic conductivity, and there are problems such as an increase in interface contact resistance and the occurrence of element cracking phenomenon caused thereby.

A complex phenomenon occurs in an electrolyte containing a conductive salt. For example, as the concentration of salt increases, the ionic conductivity may become lower as the diffusion coefficient of the ions decreases due to the increase in viscosity. In addition, there is a difficulty in ensuring stability of the element due to side reactions with the electrode or other substances. In particular, the reliability of the electrochemical device is deteriorated due to the low diffusion coefficient and the low transport number of the metal cation, and for example, in the case of a lithium secondary battery, there is a problem that lithium ions compete with an ionic liquid. In the case where the diffusion coefficient of lithium ions is lower than that of the cations constituting the ionic liquid, the lithium ions are difficult to approach the electrode surface and may not be inserted into the electrode. Therefore, no electrochemical reaction occurs. In addition, LiPF is mainly used in lithium ion batteries currently used commercially₆As an electrolyte, this is because LiPF₆Has excellent overall physical properties such as ion mobility, ion pair dissociation degree, solubility, SEI formation, and the like. However, LiPF₆There are problems such as poor thermal stability and occurrence of side reactions even with a slight amount of water, and particularly, there is a side effect that continuous decomposition of an electrolyte is accelerated by the following side reactions at the time of temperature rise, gas is generated to expand a battery, and explosion is caused.

LiPF₆(s)+H₂O(g)→LiF(s)+OPF₃(g)+2HF(g) (2)

On the other hand, an electrochromic device (ECD) is a device in which the color of an electrochromic material changes due to an electro-oxidation-reduction reaction when an electric field is applied, thereby changing the light transmission characteristics, and the most successful products among the products using the electrochromic device include a vehicle mirror that automatically adjusts glare from the rear at night, and a vehicle mirror that can adjust glare according to lightThe strength of the window is automatically adjusted, namely a smart window (smart window). The smart window has a characteristic that the color becomes dark to reduce the amount of light when the sun is much and becomes light in the cloudy day, and the energy saving efficiency is excellent. Further, development of the display device to be applied to a display such as a photoelectric panel or an electronic book (e-book) is continuously progressing. The electrochromic element is similar to the constituent element of a battery, and means an electrochromic layer (anode)/electrolyte (Li)⁺、H⁺) A counter electrode layer (cathode) is formed into a thin film. Briefly explaining the principle of electrochromism: if Li is injected into an electrochromic layer (WxOy, MoxOy, etc.) as a reducing coloring substance⁺Or H⁺Such cations and electrons form a color, and become transparent when discharged. On the other hand, if Li is released into the counter electrode layer (VxOy, NixOy, etc.) as an oxidation coloring material⁺Or H⁺Such cations and electrons form a coloration and become transparent if injected.

The electrochromic layer constituting the electrochromic element is classified into a reduction coloring substance and an oxidation coloring substance, the reduction coloring substance is a substance that forms coloring when electrons are obtained, and typically, tungsten oxide is studied in a large amount. On the other hand, the oxidation coloring matter is a matter that forms coloring when electrons are lost, and typical examples thereof include nickel oxide, cobalt oxide, and the like. Further, as a representative electrochromic substance, there is V₂O₅、Ir(OH)x、NiOxHy、TiO₂、MoO₃Inorganic metal oxides such as PEDOT (poly-3,4-ethylenedioxythiophene), polypyrrole, polyaniline, polyazulene, polythiophene, polypyridine, polyindole, polycarbazole, polyazine, and polyquinone, and organic color-changing substances such as viologen, anthraquinone, and phenothiazine. In order to improve the safety and the color-changing efficiency of the electrochromic element, a method of directly attaching a color-changing substance to a working electrode (working electrode) has been developed. In such a case, the electric circuit of the electrochromic element is completed only when the ion storage medium is formed on the counter electrode and the electrolyte is contained between the electrodes. Therefore, in order to realize an electrochromic element having high efficiency and high stability, it is necessary to increase the content of the electrolyte, the color-changing substance, and the ion storage medium substanceElectrochemical properties, and improved structure within the electrochromic element. In the case of an electrochromic element and an electroluminescent element, the reliability of the electrochemical element is lowered due to a chelate (chelate complex) between an anion forming an electrolyte and a color-changing substance or a light-emitting substance. In order to improve such disadvantages, a large complex anion (large complex anion) structure, an organic ligand anion (organic ligand anion) structure, and the like have been attracting attention. In addition, tungsten oxide, which has been widely studied as an electrochromic substance, undergoes a non-reversible chemical reaction with lithium ions inserted into the electrochromic element to trap the lithium ions in the respective layers of the electrochromic element, whereby the respective layers of the electrochromic element are decomposed and separated into thin layers, and the characteristics of the electrochromic element are degraded, and electrochromic or deformation into a substance that may cause leakage of electricity of the element is no longer possible in a short time, and thus the function as an electrochromic element is lost (n.j.dudney, j.power Sources,89(2000) 17; g.leftionitis, s.papaethioniou, p.yianoulis, Solar Materials and Solar Cells (Solar Materials and Solar Cells),83(2004) 115).

In order to solve these problems, some attempts have been proposed. In recent years, solvent-free mixed electrolytes based on nanoscale organic/silica mixed substances (NOHM) have been combined with lithium salts [ Nugent, j.l. et al, adv.mater, 2010,22, 3677; lu, y, et al, j.mater.chem.,2012,22,4066]. The electrolyte has a uniformly dispersed nanoparticle core with polyethylene glycol (PEG) chains covalently bonded to the particles. The electrolyte provides a homogeneous liquid due to self-suspension, where the PEG oligomer functions both as a suspension medium for the nanoparticle core and as an ion-conducting network for lithium ion transport. WO2010/083041 discloses NOHM based mixed electrolytes comprising a polymeric corona doped with a lithium salt, i.e. a polymeric corona attached to a core of inorganic nanoparticles. Furthermore, chaefer, j.l. et al (j.mater.chem.,2011,21,10094) disclose Si0 covalently bound to a dense brush (dense brush) of oligomer-PEG chains doped with lithium salts, especially lithium bis (trifluoromethanesulfonimide)₂The nanoparticles are mixed electrolytes. The electrolyteManufactured from dimethyl ether of polyethylene glycol (PEGDME), provides excellent ionic conductivity. However, since anions of the lithium salt freely move through the electrolyte and 2/3, which is a current, is polarized at a high concentration due to the migration of the anions, internal resistance and voltage loss occur. Also, korean laid-open patent publication No. 10-2015-0004124 discloses a nanoparticulate organic hybrid characterized by comprising inorganic nanoparticles covalently grafted (covalently grafted) with one or more anions selected from organic sodium salts and organic lithium salts via a linker, wherein the nanoparticulate hybrid has the following chemical formula.

In the above formula, Np represents inorganic nanoparticles; l is a linking group selected from C1-C6 alkylene and phenyl-C1-C4-alkylene;

an anion which is an organic sodium salt or an organic lithium salt; x + is a sodium or lithium cation. Further, korean laid-open patent publication No. 10-2011-0003505 discloses an electrolyte for an electrochromic element, which is characterized in that a polymer is solvated in a mixture containing a substance having an amide group, a solvent having the following structure, and an ionizable substance capable of forming a solution together with the solvent.

(wherein X is a carbon atom, a nitrogen atom, an oxygen atom or an aryl group optionally having a substituent on the aromatic ring, wherein R2 is absent when X is a nitrogen atom, R1 and R2 are absent when X is an oxygen atom, and R1, R2 and R5 are absent when X is an aryl group; R1 is a hydrogen atom or a carbon-based group; R2 is a hydrogen atom or a carbon-based group; R3 is a hydrogen atom or a carbon-based group; R4 and R5 are each selected from a hydrogen atom and a carbon-based group; or R4 and R5 together form a carbon-based group to provide a ring structure to the above-mentioned solvent.)

However, conventional electrolytes for electrochromic elements, including those described in the above documents, have poor durability, and therefore, anions and cations constituting an ionic salt are deformed or react with a substance (electrode or substance participating in oxidation/reduction reaction) constituting an electrochemical element, thereby decreasing the durability of the electrochemical element.

On the other hand, the ionic conductivity of the electrolyte can be represented by charge amount × mobility, and in this case, in the case where the charge amount is low, the ionic conductivity may be reduced. This means that the resistance of the electrochemical element increases, and if the applied voltage is increased or the ionic salt concentration is increased in order to overcome such resistance, a problem occurs in that the durability of the element is reduced. For example, LiPF, which is one of lithium salts frequently used₆It is found from the molecular structure that the fluorine component of the hexafluorophosphate (hexafluorophosphate) anion reacts with moisture to cause a precipitation side reaction of Hydrogen Fluoride (HF), LiF, or the like, and the above-mentioned problems have not been solved. This is one of the important factors that reduce the reliability and stability of the lithium secondary battery. In addition, in the case of adding an ionic salt, cations and anions are accumulated at the cathode and the anode, respectively, due to an electric field formed by the element. This causes a serious polarization phenomenon in the device, a serious voltage drop (potential drop), and a reduction in device efficiency. That is, it is difficult to increase the ionic conductivity by increasing the lithium salt concentration. Therefore, there is a need for a novel salt (electrolyte) structure substance that is excellent in heat generation, electrochemical stability, and ionic conductivity.

In addition, in the case of a commercial lithium ion battery, it is difficult to use it as a large-scale electricity storage device due to the scarcity of lithium resources and the resulting increase in cost. In addition, dendritic formation of lithium metal within the battery presents safety issues that can lead to internal overheating and combustion. In order to solve such problems, the use of sodium (Na) has been attempted⁺) Potassium (K)⁺) Magnesium (Mg)²⁺) Such as the study of metal cations. However, it is difficult to find an electrode material suitable for such metal cations,Low ion conductivity, low energy density, etc., and yet still not commercially viable today. Therefore, there is a need to develop a novel electrolyte that is not only free from explosion and fire risks, but also applicable to high-performance electrochemical devices. Further, the physical properties required for the electrolyte are required to be flame retardant, nonvolatile, nontoxic, and the like for safety at the time of use and after disposal. For such substances, some kinds of electrolytes have been studied as substitutes for general liquid electrolytes having inorganic or organic characteristics. Typical materials used in the manufacture of polymers, polymer compositions, mixtures, gels, ionic liquids, ceramics or solid electrolytes may be simple lithium halides or SiS with improved grain boundary defects induced by inorganic matrices such as nano-particle oxides like beta-alumina, sodium super-ionic conductor (Nasicon) and silica₂+Li₂Vulcanized glass in the S + Lil system. However, due to the low ionic conductivity of the gel, solid electrolyte (10)^-4S/cm) and low energy density, which is not practical for commercial use. For example, in the case of a magnesium (Mg) secondary battery, since dendritic growth is not formed on the surface of an electrode during charge/discharge, it is attracting attention as a next-generation ion battery with high energy density and high output, but conventional inorganic ionic salts cannot be interchanged with Mg anodes. In addition, these are brittle substances, and cause stress, and sometimes crack (crack), in the electrolyte due to inevitable volume change during operation.

In order to obtain an electrolyte that accommodates volume changes, it is preferred to use an organic polymer matrix. Typical examples thereof include polyethylene oxide, polypropylene oxide, polyethylene imine, and copolymers thereof. These materials are combined with lithium bis (trifluoromethanesulfonylimide [ Li (CF) hereinafter referred to as LiTFSI₃SO₂)₂N]And lithium tetrafluoroborate (LiBF)₄) And the like are used in combination. The main disadvantage of all these polymer electrolytes is the bipolar (ambipolar) conductivity. When current is applied, both anions and cations have mobility, and in the current through the electrolyte, about 1/3 is transported by the cations, 2The/3 is transported by anions. This aspect is defined by t + ═ σ cation/σ cation + σ anion ═ D cation/D cation + D anion, quantified by σ and D transport number (transport number) t +, which are the conductivity and diffusivity, respectively, of the charge chemical species. In most battery electrode systems, only cations react at the electrode, with the result that electroneutrality (electroneutrality) causes salt to accumulate around the anode, depleting the salt near the cathode. Both the over-concentrated electrolyte and the depleted electrolyte have very low conductivity, and thus the polarization phenomenon (polarization) of the battery is greatly increased while the capacity is decreased. In order to solve these problems, some attempts have been proposed. For example, US 5,569,560 discloses a device comprising a strongly attached electron-removing unit CF₃SO₂To slow anion movement, whereby the lithium cations migrate larger scale currents in the electrochemical cell. However, the effect on the migration number t + is slight. In recent years, solvent-free mixed electrolytes based on nanoscale organic/silica mixed substances (NOHM) have been combined with lithium salts [ Nugent, j.l. et al, adv.mater, 2010,22, 3677; lu, y, et al, j.mater.chem.,2012,22,4066]. The electrolyte has a uniformly dispersed nanoparticle core with polyethylene glycol (PEG) chains covalently bonded to the particles. The electrolyte provides a homogeneous liquid due to self-suspension, where the PEG oligomer functions both as a suspension medium for the nanoparticle core and as an ion-conducting network for lithium ion transport. WO2010/083041 discloses NOHM based mixed electrolytes comprising a polymeric corona doped with a lithium salt, i.e. a polymeric corona attached to a core of inorganic nanoparticles. Furthermore, chaefer, j.l. et al (j.mater.chem.,2011,21,10094) disclose SiO covalently bonded to a dense brush (dense brush) of oligomer-PEG chains doped with lithium salts, especially lithium bis (trifluoromethanesulfonimide)₂The nanoparticles are mixed electrolytes. The electrolyte is made from polyethylene glycol dimethyl ether (PEGDME), providing excellent ionic conductivity. However, the anions of the lithium salt move freely through the electrolyte, and 2/3, which is a current, undergoes a high-concentration polarization phenomenon due to the migration of the anions, thereby generatingInternal resistance and voltage loss.

Therefore, attempts have been made to solve the above-described problems. Korean laid-open patent No. 10-2015-0052008 discloses a nano-fine particle organic mixture comprising inorganic nanoparticles covalently grafted (covalently grafted) with one or more anions of organic sodium or lithium salts through a linking group. In recent years, it has been reported that graphene quantum dots and the surface-oxidized graphene quantum dots are used as solid electrolytes for supercapacitors. In recent years, a paper for reporting supercapacitor characteristics by using Graphene quantum dots as an electrolyte ("Graphene quantum dots as an electrolyte for solid supercapacitors") (sci. rep.,2015,6,19292)) has also been published. However, in the aforementioned paper, there is no report that the electrochemical characteristics of the supercapacitor are improved when the graphene quantum dots are used as an electrolyte, and there is no example of applying the graphene quantum dots to an electrochemical element using an electrode in which an electrochemical reaction occurs at all at present.

Disclosure of Invention

Technical subject

Accordingly, an object of the present invention is to provide an electrolyte for an electrochemical device, which can induce decomposition (decomposition) of a substance or prevent deformation of an ionic salt by causing a reaction with an electrode material constituting an anode or a cathode of an electrochemical device in which a redox reaction occurs at an electrode, thereby preventing degradation of stability and performance of the electrochemical device and improving electrochemical durability, efficiency and performance of the electrochemical device, a method for manufacturing the same, and an electrochemical device including the same.

Means for solving the problems

In order to achieve the above technical object, the present invention provides an electrolyte for an electrochemical device, which is applied to an electrochemical device comprising a first electrode, a second electrode spaced apart from the first electrode, and an electrolyte filled between the first electrode and the second electrode, and which comprises a carbon quantum dot ion compound in the form of a salt of a carbon quantum dot anion and a metal cation having an average diameter in the range of 2 to 12 nanometers (nm) and a surface potential of-20 mV or less.

The present invention also provides an electrolyte for an electrochemical device, wherein the metal is an alkali metal, an alkaline earth metal, or a transition metal.

The present invention also provides an electrolyte for electrochemical devices, wherein the metal is at least one selected from the group consisting of Li, Na, K, Mg and Zn.

The present invention also provides an electrolyte for an electrochemical device, wherein a reversible electrochemical redox reaction occurs in at least one of the first electrode and the second electrode.

The present invention also provides an electrolyte for an electrochemical device, wherein the electrochemical device is one selected from the group consisting of a secondary battery, a solar battery, an electrochromic device, and an electroluminescent device.

The present invention also provides an electrolyte for an electrochemical device, wherein the secondary battery is a lithium ion battery or a lithium polymer battery.

Further, the present invention provides a method for producing an electrolyte for an electrochemical device, comprising: i) a step of mixing a carbon precursor and an acid, and performing hydrothermal synthesis at 80 to 120 ℃ to produce a carbon quantum dot having an average diameter in the range of 2 to 12 nanometers (nm) and a surface potential of-20 mV or less; ii) a step of reacting the carbon quantum dots with metal ions to produce a carbon quantum dot anion-metal cation salt; iii) a step of removing reaction impurities; and iv) a step of classifying the carbon quantum dot ionic compounds according to size.

The present invention also provides a method for producing an electrolyte for an electrochemical device, wherein the metal is an alkali metal, an alkaline earth metal, or a transition metal.

The present invention also provides a method for producing an electrolyte for an electrochemical device, wherein the metal is at least one selected from the group consisting of Li, Na, K, Mg and Zn.

Effects of the invention

The electrolyte for electrochemical devices of the present invention has a very low dissociation energy (dissociation energy) between anions and cations to improve the ionic conductivity, and a relatively slow migration rate of anions compared to metal cations, so that an electrochemical device that moves only with metal cations can be realized, and the electrochemical device has a high ionic polarizability and a high thermochemical/electrochemical stability of anions, and thus, a side reaction in driving the device does not occur, and the stability and reliability of the electrochemical device can be greatly improved.

Drawings

Fig. 1 (a) is an electron micrograph of a carbon quantum dot ionic compound applied to an electrochemical device of the present invention and a schematic view for understanding the structure, and fig. 1 (b) is a diagram of an absorption and emission region of the carbon quantum dot ionic compound;

fig. 2 is an understanding view for explaining a manufacturing process of carbon quantum dots for manufacturing the electrolyte for electrochemical elements of the present invention;

FIG. 3 is a result of measuring the surface charge intensity of the obtained carbon quantum dots based on the reaction temperature adjustment in example 1 as a production example of the electrolyte for electrochemical elements of the present invention;

fig. 4 (a) is a raman spectrum of carbon fiber and carbon quantum dots as raw materials of a carbon quantum dot ionic compound electrolyte manufactured according to the present invention, and fig. 4 (b) is an FT-IR spectrum of a Li-carbon quantum dot ionic compound;

fig. 5 is a result of X-ray photoelectron spectroscopy (XPS) of a lithium ion compound among carbon quantum dot ion compounds manufactured in example 1 of the present invention;

fig. 6 is a thermal analysis result of the carbon quantum dot ionic compound manufactured in example 1 of the present invention;

fig. 7 (a) is a structural view of a 3-electrode electrochemical cell composed of a first electrode (working electrode) containing a color-changing substance, a platinum (Pt) second electrode (counter electrode), and a reference electrode (Ag/AgCl) in an aqueous solution containing a carbon quantum dot ionic compound in example 1 of the present invention, and fig. 7 (b) is a result of cyclic voltammetry measurement based on a concentration of Ferricyanide (Ferricyanide);

FIG. 8 shows the results of Cyclic Voltammetry (CV) performed at a scanning rate of 0.02V/s under the above-described 3-electrode system of the present invention;

FIG. 9 shows the measurement results of oxidation/reduction current values of color-changing substances based on the scanning speed under the 3-electrode system condition as an example of the present invention;

fig. 10 is an electrochemical impedance spectrum (electrochemical impedance spectroscopy) measured by changing metal cations in carbon quantum dot ionic compounds under 3-electrode system conditions for the electrochemical devices of example 2 and comparative example 1;

FIG. 11 (a) is a result of measuring the lifetime of an electrochromic element by changing the kind of electrolyte used under the condition of 3-electrode system for the electrochromic element using light of 700nm for transmittance measurement in one embodiment of the present invention, and FIG. 11 (b) is a result of only (C-dot) out of the above results^-K⁺((C quantum dot)^-K⁺) Results expressed by separation of the results of the electrolyte permeability measurement;

FIG. 12 shows the measurement results of the luminescence intensity based on the concentration of the ionic compound of carbon quantum dots under the 2-electrode system condition for the electroluminescent device according to an embodiment of the present invention;

fig. 13 is a result of a charge/discharge experiment of a lithium secondary battery using a carbon quantum dot ionic compound according to an embodiment of the present invention;

fig. 14 (a) to (c) are cyclic voltammetry measurement results based on the concentrations of carbon quantum dot anion-lithium cation ion compound electrolytes manufactured according to the present invention (0.125, 0.25, and 0.5M, respectively), and fig. 14 (d) is a cyclic voltammetry measurement result measured for comparing the use of 1.1M LiPF6 electrolyte, respectively;

FIG. 15 (a) is a result of a cycle test at a current density of 160mA/g in the example of the present invention, and FIG. 15 (b) is a result of measuring a change in current density according to a difference in concentration;

FIG. 16 (a) is a result of measuring voltage-capacitance measured at electrodes of a lithium ion battery to which a carbon quantum dot ionic compound electrolyte of the present invention and a LiPF6 electrolyte are applied respectively in example 5 of the present invention,

fig. 16 (b) shows the result of differentiating the voltage;

fig. 17 measurement results of I0 and Iss (upper) and measurement results of R0 and Rss (lower) for calculating a charge transfer index of lithium ions as cations in a lithium ion battery using the electrolyte of the present invention.

Detailed Description

The present invention will be described in detail below with reference to the accompanying drawings.

In the present specification, the term "electrochemical device" means a device that performs an electrochemical reaction including a first electrode, a second electrode separated from the first electrode and forming an opposite electrode, and an electrolyte filled between the first electrode and the second electrode, wherein at least one of the first electrode and the second electrode generates a reversible electrochemical redox reaction; the term "carbon quantum dot" means a graphite oxide-form quantum dot having an average diameter in the range of 2 to 12nm, having at least one oxygen functional group capable of being an anion on the surface and/or edge thereof and having a surface potential of not more than (minus) 20mV, or a carbon quantum dot derivative formed by a polymerization reaction with an inducing group capable of polymerizing with the graphite oxide-form quantum dot; the "carbon quantum dot anion" means a carbon quantum dot in which the oxygen functional group is anionized. In the present invention, the first electrode may be a working electrode (working electrode) or an anode, and the second electrode forming the opposite electrode may be a counter electrode (counter electrode) or a cathode. At least one of such first and second electrodes is accompanied by a reversible electrochemical redox reaction. The electrochemical element of the present invention comprises a first electrode (working electrode); a second electrode (counter electrode) separated from the first electrode; and an electrolyte filled between the first electrode and the second electrode. Any electrochemical element, such as an electrochromic element, an electrochemical light-emitting element, a secondary battery, or a solar cell, is included in the electrochemical element of the present invention as long as it involves a reversible electrochemical redox reaction at a working electrode (substance) or an anode (cathode).

Fig. 1 (a) is an electron micrograph of a carbon quantum dot ionic compound applied to the electrochemical device of the present invention and a schematic view for understanding the structure, and fig. 1 (b) is a diagram of an absorption and emission region of the carbon quantum dot ionic compound. Fig. 2 is an understanding view for explaining a process of manufacturing a carbon quantum dot for manufacturing the electrolyte for electrochemical elements according to the present invention. As illustrated in fig. 1, the carbon quantum dot ionic compound electrolyte according to the present invention is a metal salt compound of a carbon quantum dot polyvalent anion and a metal cation, in which the carbon quantum dot anion and the metal cation are paired. In the present invention, the carbon quantum dot anion has a polyanion (A)^n-) The form (2) has an aromatic structure inside and has oxygen functional groups on the surface and the edge. Such carbon quantum dot anions are combined with metal cations to produce ionic compounds in the form of salts (salt). The electrolyte for electrochemical devices containing the carbon quantum dot ionic compound of the present invention can be expected to have the following characteristics. 1) Capable of forming ionic bonds with a wide variety of metal cations, such as alkali metals, alkaline earth metals, transition metals, and the like, due to surface negative charges; 2) due to large size and polyanion surface charge, the polarity (polarity) is large and the lattice energy (lattice energy) is low; 3) delocalization (delocalization) of the electron cloud is large due to resonance of the internal structure. Further, 4) since it is a macromolecular anion, there is almost no mass transport (mass transport) of the substance in the solution; 5) since the electrochemical/thermal stability prevents side reactions at the electrode interface, there is an advantage that the driving reliability of the element can be improved. The carbon quantum dot ionic compound of the present invention is very easy to disperse in an aqueous solution and a non-aqueous solution solvent, has low viscosity and volatility, and is relatively freely mixed with an organic solvent having a high dielectric constant (permittivity). Thereby, an electrolyte having high ionic conductivity can be realized.

In the present invention, the metal cation in the carbon quantum dot ionic compound may be an alkali metal, an alkaline earth metal, or a transition metal, and may be, for example, Li, Na, K, Mg, or Zn. The carbon quantum dot ionic compound may be used in the form of liquid, gel, or solid, and the content thereof may be adjusted as appropriate according to the form.

The carbon quantum dot ionic compound may be an organic-inorganic complex formed by adding a derivative compound. The derivative compound is not particularly limited, and may be any compound capable of inducing polymerization (polymerization). For example, a silane (silane) compound may be added to the produced ionic compound, and a gel electrolyte may be produced by a thermal crosslinking method.

The carbon quantum dots used for producing the electrolyte for electrochemical elements of the present invention have an average diameter in the range of 2 to 12nm, more preferably in the range of 5 to 8nm, and preferably have at least one oxygen functional group capable of becoming an anion on the surface and/or edges so that the surface potential is-20 mV or less. If the average diameter of the carbon quantum dots is less than 2nm, the carbon quantum dot anions move to the anode due to the potential formed by the electrodes of the electrochemical device, which causes t₊(ion transport number) is decreased, and the efficiency of the electrochromic element is decreased, and the lattice energy of the carbon quantum dots is decreased, resulting in a decrease in ion conductivity. On the other hand, when the average diameter of the carbon quantum dots is larger than 12nm, pi-pi interaction between the carbon quantum dots increases, which may cause aggregation phenomenon between the carbon quantum dots in the electrochromic device to progress crystallization and decrease reliability of the device. In addition, the carbon quantum dot ionic compound of the present invention is preferably adjusted so that the pH of the solution is in the range of 3 to 14 when dissolved in a solvent. The pH adjustment is adjusted according to the characteristics of the electrochemical element. For example, in the case of an electrochromic device using a prussian blue (prussian blue) substance, if the electrolyte solution has a pH of 5 or more, the electrochromic device is deformed by the induction of the color change substance, and the characteristics of the electrochromic device are lost. On the other hand, in the case of a lithium secondary battery in particular, the oxidative decomposition reaction of the electrolytic solution is accelerated in an acidic atmosphere. Therefore, the electrolyte for electrochemical devices should have both acid resistance and alkali resistance. The electrolyte for electrochemical devices of the present invention has strong resistance to both acids and bases, and therefore has very little restriction on the use environment. In addition, since thisThe chemical resistance of the sample, and thus can be used as an electrolyte suitable for biological experiments.

Fig. 2 is an understanding view for explaining a process of manufacturing a carbon quantum dot for manufacturing the electrolyte for electrochemical elements according to the present invention. As shown in fig. 2, the electrolyte for electrochemical elements of the present invention is manufactured by a method comprising the steps of: i) a step of dispersing a carbon precursor in an acid, and performing hydrothermal synthesis at 80 to 120 ℃ to produce a carbon quantum dot; ii) a step of reacting the carbon quantum dots with metal ions to produce a carbon quantum dot anion-metal cation salt; iii) a step of removing reaction impurities; and iv) a step of classifying the carbon quantum dot ionic compounds according to size.

The method for producing an electrolyte for electrochemical elements comprises i) a step of mixing a carbon precursor with an acid, and carrying out hydrothermal synthesis at 80 to 120 ℃ to produce carbon quantum dots. Since the step i) can be performed by a known method for producing a carbon quantum dot, the detailed description thereof will not be repeated. In the above steps, the characteristics (size, surface charge value) of the carbon quantum dots can be adjusted by changing the reaction temperature. For example, in the example of the present invention, when hydrothermal synthesis is performed at 80 degrees, 100 degrees and 120 degrees, the surface charges of the carbon quantum dots are-17, -23 and-28 mV, respectively, and the sizes are 10 nm, 8nm and 5.5nm, respectively.

The method for producing an electrolyte for electrochemical elements of the present invention comprises ii) a step of reacting the above-described carbon quantum dots with a metal ion to produce a carbon quantum dot anion-metal cation salt. The source of the metal ion is not particularly limited, and a metal salt exhibiting solubility in an aqueous solution, for example, a metal hydroxide or a metal carbonate, can be used. Specifically, examples of the source of the metal ion include potassium hydroxide, sodium hydroxide, lithium hydroxide, cesium hydroxide, potassium carbonate, and the like. At this time, the metal cation present in the carbon quantum dot anion may be selected according to the kind and amount of the metal cation precursor added, and the pH and concentration of the solution may be adjusted. For example (C-dot)_1-nx-K_nx ⁺In the case of ionic compounds, to produce K⁺0.5M solution at pH3, produced with carbon dissolved150ml of 5M KOH was added to the solution in the sub-dots.

The method for manufacturing an electrolyte for electrochemical elements of the present invention includes iii) a step of removing reaction impurities. After the reaction in the above ii), impurities such as unreacted carbon precursor need to be removed. The removal of impurities is not particularly limited, and in the examples of the present invention, the difference in solubility is utilized. In order to remove impurities (carbon quantum dot anions, salts), if a water-soluble organic solvent (ethanol, methanol) is mixed with the previously prepared solution at 1:1 v/v%, a white solid cake is precipitated in the process, and in order to extract only the supernatant (super) of the mixed solution, it is treated with an ultracentrifuge at 13,000RPM for 30 minutes. The process is repeated for 2-3 times, and only the supernatant without generating precipitates is extracted, so that impurities can be removed.

In the method for manufacturing an electrochemical device of the present invention, the carbon quantum dot anion-metal cation ion compounds obtained in this way are classified according to size. The above-described method of classifying the carbon quantum dot ionic compound based on the size is not particularly limited, and in the embodiment of the present invention, the carbon quantum dot ionic compound having a specific molecular weight or size is obtained by a dialysis method (dialysis). Thereby, a carbon quantum dot ionic compound dispersed in the aqueous solution and the organic solvent is produced. The size and metal cation concentration of the finally obtained carbon quantum dot anion-metal cation ion compound were confirmed by a transmission electron microscope and Inductively Coupled Plasma (ICP), respectively.

The electrolyte of the present invention can be used in a liquid state by dissolving it in a water-soluble solvent (methanol, ethanol), a water-insoluble solvent (acetonitrile, dimethyl carbonate, ethylene carbonate), an aqueous solution (aqueous solution), or the like, and in some cases, can be used in a gel state by dispersing it in a suitable dispersion medium/matrix.

The present invention is illustrated in more detail by the following examples. However, the following examples are illustrative for facilitating understanding of the present invention, and the scope of the present invention is not limited thereto.