WO2018217043A1 - Electrolyte for electrochemical device and preparation method therefor - Google Patents
Electrolyte for electrochemical device and preparation method therefor Download PDFInfo
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- WO2018217043A1 WO2018217043A1 PCT/KR2018/005922 KR2018005922W WO2018217043A1 WO 2018217043 A1 WO2018217043 A1 WO 2018217043A1 KR 2018005922 W KR2018005922 W KR 2018005922W WO 2018217043 A1 WO2018217043 A1 WO 2018217043A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to an electrolyte for an electrochemical device, a method for manufacturing the same, and more particularly to an electrochemical device including the electrolyte; A second electrode spaced apart from the first electrode; A salt form 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 charge of -20 mV or less, applied to an electrochemical device in which an electrolyte is filled between the first electrode and the second electrode.
- the present invention relates to an electrolyte for an electrochemical device including a phosphorus carbon quantum dot ionic compound, and a manufacturing method thereof.
- an electrolyte refers to a substance that imparts electrical conductivity to a solution and assists transfer of charge during an electrochemical reaction.
- the electrolyte allows for the formation of a resistive contact between the electrode and the solution through the flow of ions and ion exchange, which is 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 is generally in the form of a salt, which is usually used in a liquid or gel form by dissolving it in a solvent, but in some cases, it is also dispersed in a solid.
- the conventional electrochemical device has a problem in terms of stability because the electrode material constituting the internal electrode is in contact with the electrolyte and the reversibility of insertion and desorption of ions (H +, Li +, etc.) is broken.
- organic solvents are used in many cases.
- Organic solvents have stability problems such as ignition, evaporation, and leakage.
- solid electrolytes are still more stable than liquid electrolytes, but exhibit low ionic conductivity and have problems such as increased interfacial contact resistance and deterioration of devices.
- LiPF 6 is mainly applied to lithium ion batteries that are currently used commercially, because LiPF 6 has excellent overall physical properties such as ion mobility, ion pair dissociation, solubility, and SEI formation.
- LiPF6 has a problem of poor thermal stability and side reactions even in a small amount of water.In particular, when the temperature rises, the following side reactions accelerate the continuous decomposition of the electrolyte and induce the gas to inflate the battery and lead to explosion. There are side effects.
- electrochromic device refers to a device that changes the light transmission characteristics by changing the color of the electrochromic material by the electro-redox reaction in response to the application of an electric field, the application using the electrochromic device
- the most successful of the products include a rear view mirror for the car that automatically adjusts the glare of the light at the rear at night, and a smart window, a window that can be automatically adjusted according to the light intensity.
- the smart window is changed to a darker color tone to reduce the amount of light when there is a large amount of insolation, and the energy saving efficiency is excellent by changing to a lighter color tone on a cloudy day.
- the development to be applied to the display such as an electronic board (e-book), etc. is continuously made.
- An electrochromic device is similar to a battery component, and refers to a device in which an electrochromic layer (anode) / electrolyte (Li +, H +) / relative electrode layer (cathode) is thinned.
- an electrochromic layer anode
- electrolyte Li +, H +
- cathode relative electrode layer
- it is colored when the cation and electrons such as Li + or H + are injected into the electrochromic layer (WxOy, MoxOy, etc.) as a reducing coloring material, and becomes transparent when released.
- the positive electrode layer VxOy, NixOy, etc.
- the positive electrode layer which is an oxide coloring material, is colored when the cations and electrons such as Li + and H + are released, and becomes transparent when injected.
- the electrochromic layer constituting the electrochromic device is divided into a reducing coloring material and an oxidizing coloring material.
- the reducing coloring material is a material that is colored when obtaining electrons.
- the oxidative coloring material is a material that is colored when the electrons are lost, and examples thereof include nickel oxide and cobalt oxide.
- representative electrochromic materials include inorganic metal oxides such as V2O5, Ir (OH) x, NiOxHy, TiO2, and MoO3, PEDOT (poly-3,4-ethylenedioxythiophene), polypyrrole, polyaniline, polyazulene, polythiophene, poly There are conductive polymers such as pyridine, polyindole, polycarbazole, polyazine and polyquinone, and organic discoloring materials such as viologen, anthraquinone and phenocyazine.
- a method of directly attaching a color change material to a working electrode has been developed.
- an ion storage medium must be formed on the counter electrode and an electrolyte must be included between the two electrodes to complete the electric circuit of the electrochromic device. Therefore, in order to realize a high efficiency, high stability electrochromic device, it is necessary to improve the electrochemical properties of the electrolyte, the color change material, and the ion storage medium, and to improve the structure of the color change device.
- a chelate complex between the anion of the electrolyte and the color change material or the light emitting material is formed to reduce the reliability of the electrochemical device.
- a large complex anion structure, an organic ligand based anion structure, and the like have attracted attention.
- tungsten oxide which has been widely studied as an electrochromic material, causes irreversible chemical reaction with lithium ions embedded in an electrochromic device, and lithium ions are trapped in each layer of the electrochromic device, thereby causing each layer of the electrochromic device to be trapped. It decomposes, splits into thin layers, and deteriorates the characteristics of the electrochromic device, and it can be deformed into a material that can no longer electrochromate or cause the device to leak. (NJ Dudney, J. Power Sources, 89 (2000) 17; G. Leftheriotis, S. Papaefthimiou, P. Yianoulis, Solar Energy Materials and Solar Cells, 83 (2004) 115).
- WO2010 / 083041 also discloses a NOHM based hybrid electrolyte comprising a polymer corona doped with a lithium salt, a polymer corona attached to an inorganic nanoparticle core.
- chaefer, JL et al. J. Mater. Chem., 2011, 21, 10094
- the disclosed Si02 nanoparticle hybrid electrolyte is disclosed. This electrolyte is made from polyethylene glycol dimethyl ether (PEGDME) and provides good ion conductivity.
- PEGDME polyethylene glycol dimethyl ether
- Korean Patent Publication No. 10-2015-0004124 discloses a nanoparticulate organic hybrid material comprising inorganic nanoparticles covalently grafted with one or more anions of an organic sodium salt or an organic lithium salt through a linker group, Particulate hybrid material
- Nanoparticulate organic hybrid materials which are characterized by having: Wherein Np represents an inorganic nanoparticle; L is a linker group selected from a C1-C6 alkylene group and a phenyl-C1-C4-alkylene group;
- Korean Patent Publication No. 10-2011-0003505 includes a material having an amide group, and a solvent having the following structure:
- X is an aryl group optionally having a substituent on a carbon atom, a nitrogen atom, an oxygen atom or an aryl ring, provided that R2 does not exist when X is a nitrogen atom and R1 and R2 when X is an oxygen atom
- None is present, and when X is an aryl group, none of R1, R2 and R5 are present, 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 individually selected from hydrogen atoms or carbon-based groups, or R4 and R5 together form a carbon-based group to give a ring structure to the solvent; And a mixture of ionizable materials forming a solution with the solvent, an electrolyte characterized by solvating a polymer in the mixture.
- the electrolyte for the conventional electrochromic device including the above-mentioned document is deteriorated due to the weak durability and the anion and cation constituting the ionic salt, or the material (electrode, material participating in the oxidation / reduction reaction) and the electrochemical device Reaction reduces the durability of the electrochemical device.
- the ionic conductivity of the electrolyte can be expressed as the charge amount x mobility, where the ionic conductivity is lowered when the charge amount is low.
- LiPF 6 one of the lithium salts commonly used as an example, shows that the fluorine component of the hexafluorophosphate anion reacts with water to generate precipitation side reactions such as hydrogen fluoride (HF) or LiF, as described in the molecular structure. This is one of the important factors that hinder the reliability and stability of the lithium secondary battery.
- the commercialized lithium ion battery is difficult to be used as a large-scale power storage device due to the scarcity of lithium resources and the resulting cost increase.
- dendrites formation of lithium metal in batteries has a problem of stability causing internal overheating and combustion.
- metal cations such as sodium (Na + ), potassium (K + ), and magnesium (Mg 2 + ).
- metal cations such as sodium (Na + ), potassium (K + ), and magnesium (Mg 2 + ).
- metal cations such as sodium (Na + ), potassium (K + ), and magnesium (Mg 2 + ).
- the physical properties required for the electrolyte is required to be flame retardant, nonvolatile, non-toxic, etc. for safety during use and after disposal.
- electrolytes For these materials, several classes of electrolytes have been studied as replacements for conventional liquid electrolytes with inorganic or organic properties.
- Typical materials used in the manufacture of polymers, polymer composites, hybrids, gels, ionic liquids, ceramics or solid electrolytes are derived from inorganic matrices such as ⁇ -alumina and nanoparticle oxides such as Nasicon and silicon dioxide. It may be a simple lithium halide with improved grain boundaries defects or sulfide glass in a SiS 2 + Li 2 S + Lil system.
- an organic polymer mattress In order to obtain an electrolyte that is compliant with the change in volume, it is preferable to use an organic polymer mattress.
- Typical examples include polyethylene oxide, polypropylene oxide or polyethyleneimine and copolymers thereof. These materials are used in combination with suitable lithium salts such as lithium bis (trifluoromethane sulfonyl imide [Li (CF3S02) 2N] and lithium tetrafluoroborate (LiBF4), referred to below as LiTFSI.
- LiTFSI lithium bis (trifluoromethane sulfonyl imide
- LiBF4 lithium tetrafluoroborate
- the main disadvantage of the electrolyte is its ambipolar conductivity: When current is applied, both the anion and the cation are mobile such that about one third of the current through the electrolyte is carried by the cation and two thirds by the anion.
- ⁇ and D are the transport number t +, where conductivity and diffusion of each charge species is
- US 5,569,560 discloses the use of an anionic complexing agent comprising a polyamine with a strong electron-removing unit CF3S02 attached to slow the anion, whereby lithium cations are used on a larger scale in electrochemical cells.
- CF3S02 nanoscale organic / silica hybrid materials
- This electrolyte is self-suspended to provide a homogeneous fluid, wherein the PEG oligomers simultaneously act as a suspension medium for the nanoparticle core and as an ion-conducting network for lithium ion transport.
- WO2010 / 083041 also discloses a NOHM based hybrid electrolyte comprising a polymer corona doped with a lithium salt, a polymer corona attached to an inorganic nanoparticle core. Chaefer, J. L. et al. (J. Mater. Chem., 2011, 21, 10094) also covalently binds to dense brushes of oligo-PEG chains doped with lithium salts, in particular lithium bis (trifluoromethanesulfonimide).
- the disclosed Si02 nanoparticle hybrid electrolyte is disclosed.
- This electrolyte is made from polyethylene glycol dimethyl ether (PEGDME) and provides good ion conductivity.
- PEGDME polyethylene glycol dimethyl ether
- the negative ions of lithium salts move freely through the electrolyte, and two-thirds of the current is carried by the negative ions, resulting in high concentrations of polarization, thus causing internal resistance and voltage losses.
- Korean Patent Laid-Open Publication No. 10-2015-0052008 discloses nanoparticulate organic hybrid materials comprising inorganic nanoparticles covalently grafted with one or more anions of an organic sodium salt or an organic lithium salt via a linker group.
- a material oxidized the graphene quantum dots and the surface of the graphene quantum dots was used as a solid electrolyte of a supercapacitor.
- Graphene quantum dots as the electrolyte for solid state supercapacitors (Sci. Rep., 2015, 6, 19292)).
- there has been no report on the electrochemical characteristics of supercapacitors when using graphene quantum dots as an electrolyte and there are no examples of applying graphene quantum dots to electrochemical devices using electrodes in which electrochemical reactions occur.
- the technical problem to be achieved by the present invention is to react with the electrode material constituting the positive electrode or negative electrode constituting the electrochemical device that the redox reaction occurs in the electrode to cause decomposition (decomposition) of the material or deformation of the ionic salt
- the present invention and the first electrode; A second electrode spaced apart from the first electrode; Applied to an electrochemical device in which an electrolyte is filled between the first electrode and the second electrode, a salt form 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 An electrolyte for an electrochemical device including a phosphorus carbon quantum dot ionic compound is provided.
- the present invention also provides an electrochemical device electrolyte, characterized in that the metal is an alkali metal, alkaline earth metal or transition metal.
- the present invention also provides an electrolyte for an electrochemical device, characterized in that 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, characterized in that a reversible electrochemical redox reaction occurs in at least one electrode of the first electrode and the second electrode.
- the present invention provides an electrochemical device electrolyte, characterized in that the electrochemical device is one selected from the group consisting of a secondary battery, a solar cell, an electrochromic device and an electroluminescent device.
- the present invention provides an electrolyte for an electrochemical device, characterized in that the secondary battery is a lithium ion battery or a lithium polymer battery.
- the present invention i) mixing the carbon precursor and the acid and hydrothermally synthesized in the range of 80 to 120 °C to produce a carbon quantum dot having an average diameter range of 2 to 12 nanometers (nm) and the surface potential of -20mV or less, ; ii) reacting the carbon quantum dot with a metal ion to prepare a carbon quantum dot anion-metal cation salt; iii) removing the reaction impurities; iv) It provides a method for producing an electrolyte for an electrochemical device comprising the 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, characterized in that the metal is an alkali metal, alkaline earth metal or transition metal.
- the present invention provides a method for producing an electrolyte for an electrochemical device, characterized in that the metal is at least one selected from the group consisting of Li, Na, K, Mg and Zn.
- the electrolyte for an electrochemical device according to the present invention has a very small dissociation energy of anions and cations, and thus improves ionic conductivity. Since it is possible to build an electrochemical device, large ion polarization, and high anionic thermochemical / electrochemical stability, no side reactions occur during device driving, thereby greatly improving the stability and reliability of the electrochemical device.
- Figure 1 (a) is a schematic diagram for understanding the electron micrograph and structure of the carbon quantum dot ionic compound applied to the electrochemical device of the present invention, (b) is a graph showing the absorption and emission region of the carbon quantum dot ionic compound
- Figure 2 is an understanding for explaining the manufacturing process of the carbon quantum dots for producing an electrolyte for an electrochemical device of the present invention
- Figure 3 is the result of measuring the surface charge intensity of the carbon quantum dot obtained by adjusting the reaction temperature in Example 1 which is a preparation example of the electrolyte for an electrochemical device of the present invention
- Figure 4 (a) is the Raman spectrum of the carbon fiber and carbon quantum dots as the raw material of the carbon quantum dot ionic compound electrolyte prepared according to the present invention, (b) is the FT-IR spectrum of the Li-carbon quantum dot ionic compound
- FIG. 5 is an X-ray photoelectron spectroscopy (XPS) result of a lithium ion compound among carbon quantum dot ionic compounds prepared in Example 1 of the present invention.
- XPS X-ray photoelectron spectroscopy
- Example 6 is a thermal analysis of the carbon quantum dot ionic compound prepared in Example 1 of the present invention
- FIG. 7 (a) shows a first electrode (working electrode), a platinum (Pt) second electrode (relative electrode) and a reference electrode containing a discoloring material in an aqueous solution containing a carbon quantum dot ionic compound in Example 1 of the present invention.
- the structure of the three-electrode electrochemical cell composed of Ag / AgCl) and 7 (b) shows the results of cyclic voltammetry measurements according to the concentration of Ferricyanide.
- FIG. 10 is an electrochemical impedance spectroscopy of the electrochemical devices of Example 2 and Comparative Example 1 measured by varying metal cations in carbon quantum dot ionic compounds under three-electrode system conditions.
- Figure 11 (a) is a three-electrode for the electrochromic device in one embodiment according to the present invention Under the conditions of the system, 700 nm of light can be Measuring the transmittance using the result of measuring the life of the electrochromic device and (b) above Among the results, only the result of measuring permeability of (C-dot) -K + electrolyte was separated and displayed.
- Figure 14 (a) to (c) is each carbon quantum point anion-lithium prepared according to the present invention According to the concentration of the cationic ion electrolyte (0.125, 0.25 and 0.5M, respectively)
- the cyclic voltammetry measurement results and (d) show 1.1M LiPF6 electrolyte for comparison. Cyclic voltammetry measurement results measured using
- Figure 15 (a) is a result of cycling test under the condition of the current density of 160mA / g in the embodiment of the present invention and (b) is the result of measuring the current density change for each concentration
- FIG. 16 (a) shows the result of measurement of voltage-capacitance measured in an electrode of a lithium ion battery to which a carbon quantum dot ionic compound electrolyte and a LiPF6 electrolyte of the present invention are applied in Example 5 of the present invention, respectively, (b) with respect to voltage Differential results
- FIG. 17 shows I0 and Iss measurement results (top) and R0 and Rss measurement results (bottom) to calculate the charge transfer index of lithium ions as cations in a lithium ion battery to which an electrolyte of the present invention is applied.
- the term 'electrochemical device' refers to a first electrode, a second electrode spaced apart from the first electrode, and to form an electrically opposite electrode, and an electrolyte is filled between the first electrode and the second electrode, and an electrochemical reaction is performed.
- This device is performed, which means a device in which a reversible electrochemical redox reaction occurs in at least one of the first electrode and the second electrode, the term 'carbon quantum point' has an average diameter in the range of 2 to 12 nm
- At least one oxygen functional group capable of becoming an anion on the surface and / or the edge thereof is formed through a polymerization reaction with a quantum dot in the form of graphite oxide having a surface potential of-(minus) of 20 mV or less, or a polymerizable inductor with the quantum dot in the form of graphite oxide
- 'carbon quantum dot anion' refers to the carbon quantum dot of the oxygen functional group is anionized Mihanda.
- the first electrode may be a working electorde or an anode
- the second electrode forming an electrically opposite electrode may be a counter electorde or a cathode.
- At least one electrode of the first electrode or the second electrode is accompanied by a reversible electrochemical redox reaction.
- the electrochemical device of the present invention comprises a first electrode (working electrode); A second electrode (relative electrode) spaced apart from the first electrode; It includes an electrolyte filled between the first electrode and the second electrode.
- the electrochemical device of the present invention may be any electrochemical device that reversibly undergoes an electrochemical redox reaction at a working electrode (material) or a cathode (cathode) such as an electrochromic device, an electrochemical light emitting device, a secondary battery or a solar cell. do.
- Figure 1 (a) is a schematic diagram for understanding the electron micrograph and structure of the carbon quantum dot ionic compound applied to the electrochemical device of the present invention
- (b) is a graph showing the absorption and emission region of the carbon quantum dot ionic compound.
- Figure 2 is an understanding for explaining the manufacturing process of the carbon quantum dot for producing an electrolyte for an electrochemical device of the present invention.
- the carbon quantum dot ionic compound electrolyte of 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.
- Carbon quantum anion in the present invention has the form of a polyanionic (A n- ), the inside is an aromatic structure, and has oxygen functional groups on the surface and edge.
- the carbon quantum dot anion is combined with a metal cation to produce a salt type ionic compound.
- the electrolyte for an electrochemical device including the carbon quantum dot ionic compound of the present invention can be expected as follows. 1) Due to the surface negative charges, ionic bonds with various metal cations such as alkali metals, alkaline earth metals, and transition metals are possible. 3) Delocalization of the electron cloud is large due to resonance of the internal structure.
- the carbon quantum dot ionic compound of the present invention is not only easy to disperse in aqueous solutions and non-aqueous solvents, but also relatively free of mixing with organic solvents having low viscosity, low volatility, and high permittivity. Through this, an electrolyte having high ionic conductivity can be realized.
- the metal cation in the carbon quantum dot ionic compound may be an alkali metal, an alkaline earth metal or a transition metal, for example, Li, Na, K, Mg or Zn.
- the carbon quantum dot ionic compound can be used in liquid, gel, solid form, it is possible to adjust the appropriate content according to the form.
- the carbon quantum dot ionic compound may form an organic-inorganic complex by adding a derivative compound.
- the derivative compound is not particularly limited and may be any compound capable of inducing polymerization.
- a silane compound may be added to the prepared ionic compound, and a gel electrolyte may be prepared using a thermal crosslinking method.
- Carbon quantum dots applied to the preparation of the electrolyte for the electrochemical device of the present invention is at least one oxygen functional group having an average diameter in the range of 2 to 12 nm, more preferably in the range of 5 to 8 nm and may be anions on the surface and / or edges. It is preferable that it is provided and surface potential is -20mV or less. If the average diameter of the carbon quantum point is less than 2nm, the carbon quantum point anion is moved to the anode by the potential formed on the electrode of the electrochemical device, which decreases t + (ion transport number), resulting in a decrease in efficiency of the electrochromic device. In addition, the lattice energy of carbon quantum dots is reduced, resulting in a decrease in ion conductivity.
- 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. pH control is adjusted according to the characteristics of the electrochemical device. For example, in the case of an electrochromic device to which a prussian blue material is applied, when the electrolyte solution has a pH of 5 or more, the electrochromic device may disappear due to deformation of the color change material.
- the electrolyte for the electrochemical device should have both acid resistance and base resistance. Since the electrolyte for an electrochemical device of the present invention has a strong resistance not only to acids but also to base, there are very few restrictions on the use environment. In addition, this chemical resistance can be used as a suitable electrolyte for bio experiments.
- FIG. 2 is an understanding for explaining the manufacturing process of the carbon quantum dot for producing an electrolyte for an electrochemical device of the present invention.
- the electrolyte for the electrochemical device of the present invention comprises the steps of i) dispersing the carbon precursor in an acid and hydrothermally synthesized in the range of 80 to 120 °C to produce a carbon quantum dot; ii) reacting the carbon quantum dot with a metal ion to prepare a carbon quantum dot anion-metal cation salt; iii) removing the reaction impurities and iv) classifying the carbon quantum dot ionic compounds according to size.
- Electrolytic device electrolyte production method of the present invention comprises the steps of i) mixing the carbon precursor and the acid and hydrothermally synthesized in the range of 80 to 120 °C to produce a carbon quantum dot.
- Step i) may refer to a known carbon quantum dot manufacturing method will not be described further herein.
- the carbon quantum dot properties can be adjusted by varying the reaction temperature. For example, in hydrothermal synthesis at 80 degrees, 100 degrees, and 120 degrees in the embodiment of the present invention, the carbon quantum dot surface charges are -17, -23, and -28 mV, respectively, and the sizes are 10, 8, and 5.5 nm, respectively. It was.
- Electrolytic device manufacturing method for an electrochemical device of the present invention comprises the step of ii) reacting the carbon quantum point and the metal ion to prepare a carbon quantum point anion-metal cation salt.
- the source of the metal ions is not particularly limited, and metal salts showing solubility in aqueous solution, for example, metal hydroxides and metal carbonates, may be used.
- sources of the metal ions include potassium hydroxide, sodium hydroxide, lithium hydroxide, cesium hydroxide, potassium carbonate and the like.
- the metal cation present in the carbon quantum dot anion can be selected according to the type and amount of the metal cation precursor to be added, and the pH and concentration of the solution can be adjusted.
- Electrolytic device manufacturing method for an electrochemical device of the present invention comprises the step of removing iii) the reaction impurities. After step ii), it is necessary to remove impurities such as unreacted carbon precursors.
- the removal of impurities is not particularly limited and the solubility difference is used in the embodiment of the present invention.
- impurities carbon quantum anion, salt
- water-soluble organic solvent ethanol, methanol
- white solid masses are precipitated in this process.
- the carbon quantum dot anion-metal cation ion compound thus obtained is classified according to size.
- the classification technique of the carbon quantum dot ionic compound by size is not particularly limited, and in the exemplary embodiment of the present invention, a carbon quantum dot ionic compound having a specific molecular weight or size is obtained by using dialysis. Through this, a carbon quantum dot ionic compound dispersed in an organic solvent as well as an aqueous solution was prepared. The size and metal cation concentration of the finally obtained carbon quantum anion-metal cation ion compound were confirmed using a transmission electron microscope and an inductively coupled plasma (ICP), respectively.
- ICP inductively coupled plasma
- Electrolyte of the present invention can be dissolved in water-soluble solvents (methanol, ethanol), non-aqueous solvents (acetonitrile, dimethyl carbonate, ethylene carbonate), and an aqueous solution (aqueous) and used in the liquid phase, optionally in a suitable dispersion medium / matrix dispersed in a gel Available in form.
- water-soluble solvents methanol, ethanol
- non-aqueous solvents acetonitrile, dimethyl carbonate, ethylene carbonate
- aqueous solution aqueous
- the carbon quantum dot surface charges prepared at each temperature were ⁇ 17, ⁇ 23, and ⁇ 28 mV, respectively, and their sizes were 10, 8, and 5.5 nm.
- Compounds such as potassium hydroxide, sodium hydroxide, lithium hydroxide, cesium hydroxide, potassium carbonate, and the like were added to the carbon quantum dots to form carbon quantum dot anion-metal cation ionic compounds, respectively.
- the metal cation present in the carbon quantum dot anion can be selected according to the type and amount of the metal cation precursor to be added, and the pH and concentration of the solution can be adjusted.
- the carbon quantum dot anion-metal cation ion compound thus obtained was obtained by dialysis to obtain a carbon quantum dot ionic compound having a specific molecular weight or size. More specific method of permeation is as follows. (1) Soak the membrane in tertiary distilled water for 15 minutes. The membrane pore size used was 1 K ⁇ 12 K. Pretreatment was performed by dipping 80 ° 30 minutes in (2) 10 mM NaHCO 3 solution, (3) 30 minutes in 10 mM Na 2 EDTA, and finally (4) dipping water in tertiary distilled water for 80 degrees 15 minutes. (5) Inject the carbon quantum dot ionic compound into the pretreated membrane membrane and immerse it in the solvent to be used.
- Figure 4 (a) is the Raman spectrum of carbon fibers and carbon quantum dots as the raw material of the carbon quantum dot ionic compound electrolyte prepared according to the present invention
- (b) is the FT-IR spectrum of the Li-carbon quantum dot ionic compound.
- the disordered graphitic lattice D1 (approximately 1350 cm-1) band which was strong in carbon fibers, was reduced in the carbon quantum dot ionic compound and instead the intensity of the amorphous carbon band D3 (approximately 1500 cm-1) was increased.
- the disordered graphitic lattice D1 approximately 1350 cm-1 band
- Example 5 is an X-ray photoelectron spectroscopy (XPS) result of a lithium ion compound among carbon quantum dot ionic compounds prepared in Example 1 of the present invention.
- XPS X-ray photoelectron spectroscopy
- FIG. 6 is a thermal analysis result of the carbon quantum dot ionic compound powder obtained in the embodiment of the present invention.
- the carbon quantum dot ionic compound electrolyte according to the invention it can be seen that decomposition starts at a temperature of about 600 °C or more it can be seen that the thermal stability is very excellent.
- a carbon quantum dot ionic compound prepared with a carbon quantum dot having a size of 5.5 nm among the carbon quantum dots prepared in Example 1 was used.
- the carbon quantum point anion-potassium cation electrolyte was applied to the electrochromic device, the carbon quantum point anion-sodium cation was applied to the electrochemical light emitting device, and the carbon quantum point anion-lithium cation was applied to the lithium secondary battery system.
- FIG. 7 (a) shows a first electrode (working electrode), a platinum (Pt) second electrode (relative electrode) and a reference electrode containing a discoloring material in an aqueous solution containing a carbon quantum dot ionic compound in Example 1 of the present invention.
- the structure of the three-electrode electrochemical cell composed of Ag / AgCl) and 7 (b) are cyclic voltammetry measurements according to Ferricyanide concentration
- FIG. 8 shows a 0.02 V / s scan rate under the three-electrode system conditions of the present invention. This is the result of performing cyclic voltammetry (CV) at. Specific experimental conditions of the above experiment are as follows.
- a color change material is formed using a conductive transparent substrate in an aqueous solution containing 0.05 M HCl, 0.05 MK 3 Fe (CN) 6 , and 0.05 M FeCl 3 6H 2 O.
- the thickness of the discolored material is controlled by controlling the current and time by using a time-potential potentiation method (chronopotentiometry).
- the color change material was formed on the first electrode (working electrode) for 40 uA and 140 s.
- the conductive transparent substrate was immersed in 5 mM ZnCl 2 , 0.1 M KCl, and oxygen-saturated aqueous solution, and then ZnO buffer layer was formed for 1000 s while applying ⁇ 1 V at room temperature.
- the transparent electrode in which the ZnO buffer layer was continuously formed was immersed in 0.5 mM ZnCl 2 , 0.1 M KCl, and saturated oxygen solution, and then ZnO NWs layer (nanowire layer) was applied at 80 ° C. and 1000 s while applying -1 V. Formed. This was used as a second electrode (relative electrode).
- the first electrode (working electrode) and the second electrode (relative electrode) were attached in the form of a sandwich using a thermal tape. At this time, the distance between the two electrodes is 60um. Subsequently, a carbon quantum dot ionic compound having a concentration of 0.5 M was charged with Li, Na, and K, respectively, through the fine holes formed in the second electrode. At this time, the pH of the aqueous electrolyte solution was adjusted to 4.
- Comparative example 1 Manufacture of electrochromic device containing potassium chloride electrolyte
- An electrochromic device was manufactured in the same manner as in Example 1, except that 0.5 M potassium chloride (KCl) was used as the electrolyte.
- KCl potassium chloride
- FIG. 8 illustrates a 0.02 under a three-electrode system including a first electrode, a platinum (Pt) second electrode, and a reference electrode (Ag / AgCl) including a discoloring material in an aqueous solution containing a carbon quantum dot ionic compound according to an embodiment of the present invention.
- Cyclic voltammetry (CV) results at V / s scan rate.
- the characteristics of the electrochromic device were analyzed by applying voltage at -0.14 / 0.4 V and 10 s / 10 s (50% duty cycle) by using a chronoamperometry method.
- oxidation current is a color reaction (PB)
- reduction current is a colorless reaction (colorless)
- Table 1 below shows the diffusion rate values according to the metal cations of the carbon quantum dot ionic compound under the three-electrode system conditions.
- Figure 11 (a) is a three-electrode system for the electrochromic device in one embodiment according to the present invention Under the conditions, it changes the type of electrolyte applied and uses 700nm light
- the results of measuring the lifetime of the electrochromic device by measuring the transmittance and (b) are among the above results This is the result of separating and displaying only the measurement result of permeability of (C-dot) -K + electrolyte.
- the discoloration efficiency values of 0.5 M KCl and (C-dot) + -K - electrolyte were measured as 81.6 cm 2 C -1 and 103.0 cm 2 C -1 , respectively. Therefore, electrochromic devices containing carbon quantum dot ionic compounds It is relatively good in electrochromic stability and discoloration efficiency. Table below 3 summarizes the change in absorbance of the stomach.
- the carbon quantum anion-metal cation ion compound electrolyte of the present invention has excellent performance as an electrolyte, and particularly, durability is much superior to the conventional electrolyte.
- a thin film of TiO 2 particles is formed on the surface of the cathode.
- the negative electrode and the positive electrode are attached using a thermal tape.
- FIG. 12 is a light emission intensity measurement result according to the carbon quantum dot ion compound concentration under the two-electrode system conditions for the electroluminescent device in one embodiment according to the present invention.
- the carbon quantum point anion-metal cation ion compound concentration is increased, the ionic conductivity is improved, so that the resistance in the device is reduced and eventually the light emission intensity is increased.
- FIG. 13 shows the results of measuring the specific capacitance measured after charging and discharging the carbon quantum anion-lithium metal cation ion compound electrolyte of the present invention instead of the LiPF 6 electrolyte of the conventional secondary battery.
- the negative electrode of the battery was constructed using Li 4 Ti 5 O 12 (active material), 10 wt% PVDF (binder), NMP (Solvent), and the positive electrode was graphite.
- the concentration of the carbon quantum point anion-lithium metal cation ion compound electrolyte was 0.5M. As can be seen in Figure 13, it was found that a stable charge / discharge cycle is observed in the secondary battery as an example of the electrochemical device of the present invention.
- the 0.25M sample showed unstable anodic region from 2.5 V or higher, while the 0.5M sample showed a slight anodic / cathodic peak, although slightly shifted from 1.6 V, which is the theoretical Li ion intercalation / deintercalation region of LTO. I could see that.
- Table 4 below shows the results of measuring polarization according to each concentration.
- FIG. 15 (a) is the result of the 0.5M concentration electrolyte, (b) is the result of measuring the cycle for each concentration.
- Figure 15 it can be seen that the rate characteristic of the relatively high concentration of 0.5M sample is the best, and when the average capacity of each current density is calculated, the capacity of 0.5 sample is the best at all current density Dose was shown. Table 5 summarizes the results.
- FIG. 16 (a) shows the result of measurement of voltage-capacitance measured in an electrode of a lithium ion battery to which a carbon quantum dot ionic compound electrolyte and a LiPF6 electrolyte of the present invention are applied in Example 5 of the present invention, respectively, (b) with respect to voltage Differential result. As shown in FIG.
- Formula 1 is a formula for obtaining the ion mobility index of the cation.
- the formula has a number from 0 to 1, and the closer to 1, the higher the contribution of charge transfer by cation.
- Equation 1 can be expressed as shown in Equation 2 below to measure the ion mobility index of Li ions.
- t Li Lithium transference number
- V Applied potential
- R O Initial resistance of the passivation layer
- R SS Resistance of the passivation layer
- I O Initial current
- I SS Steady state current.
- the carbon quantum point anion-lithium cation ionic compound electrolyte of the present invention was found to be 1.5 to 2 times higher charge transfer index by the cation than LiPF6.
- t Li when t Li is small, the overall resistance of the cell due to concentration polarization of anions in the electrolyte is increased.
- the cation yield is influenced by the temperature, the concentration of salt in the electrolyte and the radius of the ions, and the high t Li seen in the electrolyte of the present invention in the above experiments is due to the large anion radius of the carbon dot.
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Abstract
Description
도 11(a)는 본 발명에 따른 일 실시예에서 전기변색소자에 대하여 3 전극
시스템 조건하에서 적용되는 전해질 종류를 변화시키며 700 nm의 빛을
이용하여 투과도를 측정하여 전기변색소자의 수명을 측정한 결과 및 (b)는 위
결과 중 (C-dot)-K+ 전해질의 투과도 측정결과만을 분리하여 표시한 결과[Correction under Article 91 of the Rule 17.07.2018]
Figure 11 (a) is a three-electrode for the electrochromic device in one embodiment according to the present invention
Under the conditions of the system, 700 nm of light can be
Measuring the transmittance using the result of measuring the life of the electrochromic device and (b) above
Among the results, only the result of measuring permeability of (C-dot) -K + electrolyte was separated and displayed.
도 14(a) 내지 (c)는 각각 본 발명에 따라 제조한 탄소양자점 음이온-리튬
양이온 이온화합물 전해질의 농도(각 0.125, 0.25 및 0.5M)에 따른
순환전압전류법 측정결과 및 (d)는 비교를 위하여 1.1M LiPF6 전해질을
사용하여 측정한 순환전압전류법 측정결과[Correction under Article 91 of the Rule 17.07.2018]
Figure 14 (a) to (c) is each carbon quantum point anion-lithium prepared according to the present invention
According to the concentration of the cationic ion electrolyte (0.125, 0.25 and 0.5M, respectively)
The cyclic voltammetry measurement results and (d) show 1.1M LiPF6 electrolyte for comparison.
Cyclic voltammetry measurement results measured using
또한, 실시예 2 및 비교예 1에서 제조한 전기변색소자의 내구성을 시험하였다.
도 11(a)는 본 발명에 따른 일 실시예에서 전기변색소자에 대하여 3 전극 시스템
조건하에서 적용되는 전해질 종류를 변화시키며 700nm의 빛을 이용하여
투과도를 측정하여 전기변색소자의 수명을 측정한 결과 및 (b)는 위 결과 중
(C-dot)-K+ 전해질의 투과도 측정결과만을 분리하여 표시한 결과이다. 도 11에서
볼 수 있는 바와 같이, 종래 KCl 전해질을 사용한 전기변색 소자의 경우,
변색효율이 50 cycles 이내에서 초기 절반 이하 수준으로 감소하는데 비해 본
발명의 실시예인 (C-dot)-K+ 을 사용한 전기변색 소자의 경우, 1000 cycles 후에도
변색효율이 일정하게 유지됨을 알 수 있다. 이는 (C-dot)-K+ 전해질을 사용한
전기변색 소자 내구성이 우수하다는 것을 의미한다. 구체적으로는 (1)
(C-dot)-K+ 이온 화합물이 전해질 역할을 수행함을 의미하며, (2) (C-dot)-K+
전해질의 전기화학적 내구성이 우수하며, (3) 소자 내에서 일어나는 전기화학
부반응이 적다는 것을 의미한다. 변색 효율 (coloration efficiency. CE)은 발색
상태 또는 소색 상태에 필요한 전하량으로부터 흡광도의 변화 (ΔOD(λ) = log Tb/Tc, Tb 및 Tc는 700 nm에서 투과값을 의미함)에 의해 결정된다.
0.5 M KCl 및 (C-dot)+-K- 전해질의 변색 효율값은 각각 81.6 cm2C-1와 103.0 cm2C-1 로 측정되었다.
따라서 KCl 전해질에 비해 탄소양자점 이온화합물이 포함된 전기변색소자가
상대적으로 전기변색 안정성 및 변색 효율이 우수하다는 것을 나타낸다. 하기 표
3에 위 흡광도 변화 등을 정리하였다.[Correction under Article 91 of the Rule 17.07.2018]
In addition, the durability of the electrochromic devices prepared in Example 2 and Comparative Example 1 was tested.
Figure 11 (a) is a three-electrode system for the electrochromic device in one embodiment according to the present invention
Under the conditions, it changes the type of electrolyte applied and uses 700nm light
The results of measuring the lifetime of the electrochromic device by measuring the transmittance and (b) are among the above results
This is the result of separating and displaying only the measurement result of permeability of (C-dot) -K + electrolyte. In Figure 11
As can be seen, in the case of the electrochromic device using a conventional KCl electrolyte,
Discoloration efficiency decreases to less than half of the initial level within 50 cycles.
In the case of the electrochromic device using the embodiment (C-dot) -K +, even after 1000 cycles
It can be seen that the discoloration efficiency is kept constant. This is done using (C-dot) -K + electrolyte
It means that the electrochromic device durability is excellent. Specifically (1)
(C-dot) -K + means that the ionic compound acts as an electrolyte, and (2) (C-dot) -K +
Excellent electrochemical durability of electrolyte, (3) electrochemical
It means less side reactions. Coloration efficiency (CE)
It is determined by the change in absorbance from the amount of charge required for the state or discoloration state (ΔOD (λ) = log T b / T c , T b and T c mean the transmission values at 700 nm).
The discoloration efficiency values of 0.5 M KCl and (C-dot) + -K - electrolyte were measured as 81.6 cm 2 C -1 and 103.0 cm 2 C -1 , respectively.
Therefore, electrochromic devices containing carbon quantum dot ionic compounds
It is relatively good in electrochromic stability and discoloration efficiency. Table below
3 summarizes the change in absorbance of the stomach.
0.1250.125 | 0.250.25 | 0.50.5 | |
80 mA/g80 mA / g | 193.47193.47 | 194.28194.28 | 194.33194.33 |
160 mA/g160 mA / g | 166.45166.45 | 161.96161.96 | 171.67171.67 |
240mA/g240mA / g | 148.38148.38 | 151.61151.61 | 162162 |
320 mA/g320 mA / g | 121.36121.36 | 134.46134.46 | 149.33149.33 |
400 mA/g400 mA / g | 78.9178.91 | 104.28104.28 | 134.33134.33 |
Claims (9)
- 제1전극과,; 상기 제1전극과 이격된 제2전극 및; 상기 제1전극과 제2전극 사이에 전해질이 충진되는 전기화학소자에 적용되며, A first electrode; A second electrode spaced apart from the first electrode; It is applied to an electrochemical device in which an electrolyte is filled between the first electrode and the second electrode,평균직경이 2 내지 12 나노미터(nm) 범위이고 그 표면전위가 ―20mV 이하인 탄소 양자점 음이온과 금속 양이온의 염 형태인 탄소양자점 이온화합물을 포함한 전기화학소자용 전해질.An electrolyte for an electrochemical device comprising 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.
- 제1항에 있어서,The method of claim 1,상기 금속은 알칼리금속, 알칼리토금속 또는 전이금속인 것을 특징으로 하는 전기화학소자용 전해질.The metal is an electrochemical device electrolyte, characterized in that the alkali metal, alkaline earth metal or transition metal.
- 제2항에 있어서,The method of claim 2,상기 금속은 Li, Na, K, Mg 및 Zn으로 이루어진 군으로부터 선택된 1종 이상인 것을 특징으로 하는 전기화학소자용 전해질. The metal is an electrochemical device electrolyte, characterized in that at least one selected from the group consisting of Li, Na, K, Mg and Zn.
- 제1항에 있어서,The method of claim 1,상기 제1전극 및 제2전극의 적어도 하나의 전극에서 가역적 전기화학적 산화환원반응이 일어나는 것을 특징으로 하는 전기화학소자용 전해질.Reversible electrochemical redox reaction occurs in at least one electrode of the first electrode and the second electrode.
- 제1항 내지 제4항 중 어느 한 항에 있어서.The method according to any one of claims 1 to 4.전기화학소자는 이차전지, 태양전지, 전기변색소자 및 전기발광소자로 구성된 군으로부터 선택된 1종인 것을 특징으로 하는 전기화학소자용 전해질.Electrochemical device is an electrolyte for an electrochemical device, characterized in that one selected from the group consisting of a secondary battery, a solar cell, an electrochromic device and an electroluminescent device.
- 제5항에 있어서,The method of claim 5,상기 이차전지는 리튬이온전지 또는 리튬폴리머전지인 것을 특징으로 하는 전기화학소자용 전해질.The secondary battery is an electrolyte for an electrochemical device, characterized in that a lithium ion battery or a lithium polymer battery.
- i)탄소전구체와 산을 혼합하고 80 내지 120℃ 범위에서 수열합성하여 평균직경이 2 내지 12 나노미터(nm) 범위이고 그 표면전위가 ―20mV 이하인 탄소양자점을 제조하는 단계,; i) mixing the carbon precursor and the acid and hydrothermally synthesized at 80 to 120 ° C. 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)상기 탄소양자점과 금속 이온을 반응시켜 탄소양자점 음이온-금속 양이온 염을 제조하는 단계,; ii) reacting the carbon quantum dot with a metal ion to prepare a carbon quantum dot anion-metal cation salt;iii)반응 불순물을 제거하는 단계 및; iii) removing the reaction impurities;iv)탄소양자점 이온화합물을 크기에 따라 분류하는 단계를 포함한 전기화학소자용 전해질 제조방법.iv) A method for preparing an electrolyte for an electrochemical device, comprising classifying carbon quantum dot ionic compounds according to size.
- 제4항에 있어서,The method of claim 4, wherein상기 금속은 알칼리금속, 알칼리토금속 또는 전이금속인 것을 특징으로 하는 전기화학소자용 전해질 제조방법.The metal is an electrochemical device electrolyte manufacturing method, characterized in that the alkali metal, alkaline earth metal or transition metal.
- 제5항에 있어서,The method of claim 5,상기 금속은 Li, Na, K, Mg 및 Zn으로 이루어진 군으로부터 선택된 1종 이상인 것을 특징으로 하는 전기화학소자용 전해질 제조방법.The metal is an electrolyte manufacturing method for an electrochemical device, characterized in that at least one selected from the group consisting of Li, Na, K, Mg and Zn.
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