KR20200000575A - UV curable polyurethane-solid electrolyte and the method for manufacturing thereof - Google Patents

Abstract

The present invention relates to a UV-curable urethane polymer-solid electrolyte and a manufacturing method thereof. According to an embodiment of the present invention, the manufacturing method of the UV-curable urethane polymer-solid electrolyte comprises the following steps: preparing a UV-curable urethane polymer solution; adding a lithium-based solid electrolyte to the polymer solution to prepare a mixed solution; and UV curing the mixed solution.

Description

UV curable polyurethane polymer-solid electrolyte and its manufacturing method

The present invention relates to a UV curable urethane polymer-solid electrolyte and a method for preparing the same. Embodiments of the present invention include a method of preparing a UV-curable urethane polymer-solid electrolyte by mixing a UV-curable urethane polymer and a lithium-based solid electrolyte.

The electrolyte of a lithium secondary battery is classified into a liquid electrolyte and a solid electrolyte according to the phase of the electrolyte. The liquid electrolyte shows high ion conductivity (10 ^-3 S / cm) at room temperature, but the nonaqueous electrolyte is easily volatilized and flammable, which may cause leakage. This reduces the efficiency of the cell and has a problem of limiting the size of the battery. On the other hand, solid electrolytes have improved defects in liquid electrolytes, and even if a battery breaks due to an accident, electrolytes do not leak out, so there is little risk of ignition or explosion, and stability is secured, and miniaturization and light weight are possible.

In the present invention, the lithium-based solid electrolyte has good mechanical properties but low lithium ion conductivity, and the polymer electrolyte has low mechanical properties but better lithium ion conductivity than lithium-based solid electrolyte. To prepare a polymer-solid electrolyte mixed with this, to enhance the advantages of each.

Korean Patent Publication No. 10-0344910 Korean Patent Publication No. 10-0683939

An object of the present invention is to provide a method for producing an electrolyte having thermal and chemical stability by mixing and using a UV-curable urethane polymer and a lithium-based solid electrolyte in an optimal manufacturing method.

UV curable urethane polymer-solid electrolyte production method according to an embodiment of the present invention comprises the steps of preparing a UV curable urethane polymer solution; Preparing a mixed solution by adding a lithium-based solid electrolyte to the UV curable urethane polymer solution; And UV curing the mixed solution.

The preparing of the UV curable urethane polymer solution may include adding an isocyanate, an alkylene oxide-based polyol or a silicone-based polyol, and adding an acrylate.

Before the step of preparing a mixed solution by adding a lithium-based solid electrolyte to the polymer solution, a solution containing a cellulose-based polymer may be added to the polymer solution.

Lithium Lanthanum Titanium oxide (LLT), Lithium Lanthanum Zirconium Phosphate (LLZO), Lithium Aluminum Germanium Phosphate (LAGP), Lithium Aluminum Titanium Phosphate (LATP), Li ₄ SnS ₄ series, LSPS (Li ₁₀ SnP ₂₎ At least one selected from the group consisting of S ₁₂ ) system and Thio-LISICON system may be added.

The preparing of the mixed solution by adding a lithium-based solid electrolyte to the polymer solution may include adding a lithium salt.

UV curing the mixed solution may be added a photopolymerization initiator, a thermal polymerization initiator or a thermosetting initiator.

The isocyanate may be added in an amount of 0.5 to 50% based on 100 parts by weight of the sum of the alkylene oxide-based polyol and the silicone-based polyol.

The isocyanate is 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene 1,6-diisocyanate, isophorone diisocyanate, paratoluenesulfonyl isocyanate, dicyclomethane 4,4 '-diisocyanate, Diphenylmethane 4,4-diisocyanate, 2,4'-diisocyanate, 2,2, -diisocyanate, dodecane 1,12-diisocyanate, 2-ethyltetramethylene 1,4-diisocyanate and 2-methyl At least one selected from the group consisting of pentamethylene 1,5-diisocyanate.

The alkylene oxide-based polyol may be any one or more selected from the group consisting of polyethylene polyol, polypropylene polyol and polybutylene polyol.

The molecular weight of the alkylene oxide-based polyol may be 400 to 200,000.

The silicon-based polyol may be represented by the following Chemical Formula 1.

[Formula 1]

(Where R1, R2, R3, and R4 are H, an alkyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, or a benzyl group having 1 to 12 carbon atoms)

The molecular weight of the silicone-based polyol may be 400 to 200,000.

The acrylate may be any one or more of monofunctional to 8 functional group acrylates.

The acrylate may be added in an amount of 0.5 to 20% based on 100 parts by weight of the sum of the alkylene oxide-based polyol and the silicon-based polyol.

LiPF ₆ , LiCl 0 ₄ , LiCF ₃ S0 ₃ , LiBFS ₄ , LiAsF ₆ , Li (CF ₃ S0 ₂ ) ₂ N, LiCo0 ₂ , LiNi0 ₂ , LiMn0 ₂ , LiMn ₂ 0 ₄ , Li (Ni _a Co _{b Mn c), LiNi 1 -} y Co y 0 2, LiCo 1 - y Mn y 0 2, LiNi 1 -y Mn y O 2, Li (Ni a Co b Mn c) 0 4. _{LiMn 2 - x Ni x 0 4} , LiMn 2 - z Co z 0 4, LiCoP0 4, and LiFeP0 may be at least one selected from the group consisting of _4.

The lithium salt may be added in an amount of 5 to 50% based on 100 parts by weight of the UV curable urethane polymer solution.

UV curable urethane polymer-solid electrolyte according to an embodiment of the present invention is excellent in lithium ion dissociation ability, high conductivity, excellent thermal, chemical, physical and mechanical strength and stable to improve the performance of the lithium secondary battery.

1 is a process flow diagram illustrating a method for preparing a UV curable urethane polymer-solid electrolyte according to an embodiment of the present invention.
2 is a graph showing the ion conductivity according to the embodiment and the comparative example of the present invention.
3 is a graph showing charge and discharge characteristics according to an embodiment of the present invention.
4 is a graph showing an impedance measurement result according to an embodiment of the present invention.
5 is a graph showing the tensile strength according to the embodiment and the comparative example of the present invention.

Hereinafter, the present invention will be described in more detail with reference to Examples. Since these examples are only for illustrating the present invention, the scope of the present invention is not to be construed as being limited by these examples.

UV curable urethane polymer-solid electrolyte according to an embodiment of the present invention to prepare a UV curable urethane polymer solution (ST10), adding a lithium-based solid electrolyte to the UV curable urethane polymer solution to prepare a mixed solution (ST20) And UV curing the mixed solution (ST30).

Preparing a UV curable urethane polymer solution according to an embodiment of the present invention (Fig. 1 ~ ST10) may include adding an isocyanate, an alkylene oxide-based polyol or a silicone-based polyol, and adding an acrylate. .

The isocyanate and polyol are crosslinked by the urethane reaction of Scheme 1 to form a polymer electrolyte capable of impregnating a nonvolatile solvent.

Scheme 1

In one embodiment according to an embodiment of the present invention, the present invention may proceed as in Scheme 2 or Scheme 3.

Scheme 2

Scheme 3

The polymer electrolyte composition is a non-volatile solvent containing a redox pair and isocyanate and polyol in a container and stirred with a stirrer to prepare a polymer solution in a solution state.

The isocyanate 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene 1,6-diisocyanate, isophorone diisocyanate, paratoluenesulfonyl isocyanate, dicyclomethane 4,4-diisocyanate, diphenyl Methane 4,4-diisocyanate, 2,4-diisocyanate, 2,2, -diisocyanate, dodecane 1,12-diisocyanate, 2-ethyltetramethylene 1,4-diisocyanate and 2-methylpentamethylene 1 At least one selected from the group consisting of, 5-diisocyanate.

The isocyanate compound is preferably added in an amount of 0.5 to 50%, more preferably 10 to 40%, and more preferably 20 to 30% with respect to 100 parts by weight of the alkylene oxide-based polyol and the silicon-based polyol combined. Can be.

The alkylene oxide-based polyols have excellent lithium dissociation ability due to electron donor characteristics, but because of their high crystallinity, their ionic conductivity is low to 10 ^-8 S / cm, and thus requires modification. On the other hand, silicon-based polyols have a low glass transition (Tg) temperature, which facilitates the movement of ions due to improved molecular chain motion, and thus has a high ion conductivity of 10 ^-4 S / cm. Do. In the embodiment of the present invention, both of the alkylene oxide-based polyol and the silicone-based polyol may be used in order to take advantage of each of the advantages.

The alkylene oxide-based polyol has a polyvalent hydroxyl group, for example, polymer polyols such as polyethylene glycol, polypropylene glycol, ethylene glycol-propylene glycol copolymers, ethylene glycol, 1,2-propylene glycol, 1,3- Butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedi Methanol, 1,4-bis- (β-hydroxy) benzene, ρ-xylenediol, phenyldiethanol amine, methyldietinolamine, 3,9-bis (20hydroxy-1,1-dimethyl) 2,4 , 8,10-tetraoxaspiro [5,5] untegan and the like can be used.

Among the alkylene oxide-based polyols, as the multifunctional polyol, trifunctional polyethylene glycol, trifunctional polypropylene glycol, trifunctional (ethylene glycol-propylene glycol) copolymer, bifunctional polyethylene glycol, bifunctional polypropylene glycol And bifunctional (ethylene glycol-propylene glycol) copolymers. In addition, a tetrafunctional or more than polyfunctional polyol can also be used. Preferably, at least one selected from the group consisting of polyethylene polyol, polypropylene polyol and polybutylene polyol.

Since the alkylene oxide-based polyol has a higher molecular weight, the curing reactivity is lower, so that polyethylene glycol is more reactive than polypropylene glycol.

In the case of the polymer, an alkylene oxide-based polyol having a molecular weight of 400 to 200,000 can be used. If the molecular weight of the polymer polyol is too small, the bendability of the cross-linked polyurethane resin is lowered, whereas if the weight average molecular weight is too large, the curing reactivity is inferior.

The silicon-based polyol may be represented by Formula 1 below.

[Formula 1]

 (Where R1, R2, R3, and R4 are H, an alkyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, or a benzyl group having 1 to 12 carbon atoms)

 The molecular weight of the silicone-based polyol may be 400 to 200,000.

The acrylate may be any one or more of monofunctional to 8 functional group acrylates. Specific examples of the bifunctional monomer mainly used include 1,6-hexanedioldi (meth) acrylate, ethylene glycoldi (meth) acrylate, neopentylglycoldi (meth) acrylate, triethyleneglycoldi (meth) acrylic And bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like. Specific examples of the trifunctional or higher polyfunctional photopolymerizable compound include pentaerythritol tetra (meth) acrylate, trimethylol propane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, and propoxysilane. Tited trimethylol propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, methylol propane tri (meth) acrylate, thipentaerythritol penta (meth) acrylate, ethoxylated dipenta erythritol Hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, dipentaerythritol web (meth) acrylate, and the like.

The acrylate is added to the oligomer formed by the reaction of the polyol and the isocyanate, as an example according to an embodiment of the present invention may be a reaction as shown in Scheme 3 below.

Scheme 3

The acrylate may be added in an amount of 0.5 to 20%, more preferably 3 to 15%, and more preferably 5 to 10% based on 100 parts by weight of the alkylene oxide-based polyol and the silicon-based polyol combined. In this case, the reaction may proceed at a temperature of 60 to 120 ℃.

An embodiment of the present invention after preparing a UV-curable urethane polymer solution (Fig. 1 ~ ST10), before adding a lithium-based solid electrolyte to the polymer solution to prepare a mixed solution (Fig. 1. ~ ST20) before the cellulose-based Polymers can be added.

Cellulose-based polymers act as a passage for lithium ions, by introducing such a cross-linked structure can improve the excellent battery properties and physical properties.

The cellulose-based polymer may be represented by the following formula (2).

[Formula 2]

The cellulose is 2 to 50%, more preferably 10 to 35%, most preferably 20 to 30% by weight of the polymer solution prepared in the step (~ ST10) of preparing the UV curable urethane polymer solution of FIG. As much as can be added.

Lithium-based solid electrolyte in the step of preparing a mixed solution by adding a lithium-based solid electrolyte to the UV-curable urethane polymer solution according to an embodiment of the present invention (Fig. 1. ~ ST20) is LLT (Lithium Lanthanum Titanium oxide), LLZO (Lithium Lanthanum It may be any one selected from the group consisting of Zirconium Phosphate (LGP), Lithium Aluminum Germanium Phosphate (LAGP), Lithium Aluminum Titanium Phosphate (LATP), Li ₄ SnS ₄ system, Li ₁₀ SnP ₂ S ₁₂ system, and Thio-LISICON system. .

Acrylate added in the step of preparing the UV-curable urethane polymer solution (Fig. 1 ~ ST10) has a double bond to prevent the progress to the polymer because it has a problem that the viscosity is gradually increased to the polymer during storage Stabilizers are needed. However, urethane acrylate is UV cured to produce the desired electrolyte, so adding a large amount of stabilizer can delay the UV curing rate and cause problems in the process.

The lithium-based solid electrolyte is added to the acrylate structure can be easily introduced, and it is possible to express more excellent secondary battery characteristics.

According to an embodiment of the present invention, the step of preparing a mixed solution by adding a lithium-based solid electrolyte to a UV-curable urethane polymer solution may include adding a lithium salt.

Containing such lithium salt improves the ionic conductivity of the polymer electrolyte.

The lithium salt is in the form of oxides, sulfides, selenides, halides, and the like as LiPF ₆ , LiCl 0 ₄ , LiCF ₃ S0 ₃ , LiBFS ₄ , LiAsF ₆ , Li (CF ₃ S0 ₂ ) ₂ N, LiCo0 ₂ , LiNi0 ₂ , LiMn0 ₂ , LiMn ₂ 0 ₄ , Li (Ni _a Co _b Mn _c ), LiNi _{1 - y} Co _y 0 ₂ , LiCo _{1 - y} Mn _y 0 ₂ , LiNi _{1 - y} Mn _y O ₂ , Li (Ni _a Co _b Mn _c ) 0 ₄ . _{LiMn 2 - x Ni x 0 4} , LiMn 2 - z Co z 0 4, LiCoP0 4, and LiFeP0 may be at least one selected from the group consisting of _4.

The lithium salt may be added in an amount of preferably 5 to 50%, more preferably 15 to 35% based on 100 parts by weight of the UV curable urethane polymer solution. As the lithium salt content increases in the electrolyte, the ion conductivity increases, but when the lithium salt is present in the electrolyte composition at a predetermined ratio or more, the association of ions occurs, thereby decreasing the mobility of the ions and reducing the charge carrier.

UV curing step (Fig. 1 ~ ST30) of the mixed solution according to an embodiment of the present invention to produce a polymer-solid electrolyte having thermal, chemical, physically stable and mechanical strength by irradiating UV to the mixed solution to form a crosslinked state need.

As a polymerization initiator, a photoinitiator, a thermal polymerization initiator, or a thermosetting initiator is used. Oxime compound ethanone-1- [9-ethyl-6- (2-methyl benzoyl) -9H-carbazol-3-yl] -1- (0-acetyl oxime) (trade name Irgacure® Oxe02, BASF), o -Ethoxycarbonyl-a-oxyimino-1-phenylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholino propane-1-one, ethylbenzoin ether, Isopropylbenzoin ether, a-methylbenzoinethyl ether, benzoin phenylether, a-acyl oxime ester, 2-ethyl anthraquinone, 2-chloroanthraquinone, thioxanthone, isopropyl thioxanthone can be used As the thermosetting initiator, azoisotyyronitrile-based, peroxide-based, etc. may be used.

These polymerization initiators may be used alone or in combination of two or more thereof, and the content thereof may be included in an amount of 0.1 to 1 parts by weight based on 100 parts by weight of the mixed solution prepared in step ST20 of FIG. It may be included in 0.1 to 0.5 parts by weight. When the content of the polymerization initiator is in the above range, the desired polymer-solid electrolyte can be obtained in high yield without decreasing the reactivity of the polymerization reaction.

< Example  A> UV Curable Urethane Polymer - Solid electrolyte  Produce

Example  One

19.6 lg of HDI (hexamethylene diisocyanate), 50 g of Si-Polyol (Mw 5,000, LGA-876, TEGO) and 120 g of polyethylene glycol (Mw 1,000, Kumho Chemical) were added, and then 60 to 70 ° C under N ₂ atmosphere, Stir for 3 hours. As the reaction proceeded, it became a viscous transparent liquid.

67.7 g of pentaerythritol triacrylate was added to a mixture of HDI-polysiloxane oligomer and HDI-polyethylene glycol oligomer, and stirred for 3 hours at 60 to 70 ° C. under N ₂ atmosphere. After completion of the reaction, it was analyzed by an infrared analyzer to confirm that the NCO characteristic peak of 2250cm ^-1 disappeared.

4 g of the above-mentioned HDI-polyethylene acrylate and HDI-polysiloxane acrylate mixture, 6 g of NMP, and 6 g of acetone were mixed with a solution of 1.2 g of hydroxy-propyl cellulose, followed by stirring at 250 rpm for 3 minutes. Additionally solid electrolyte Li _{0 . 33} La _{0 . 55} Ti0 ₃ After 2 g wetting, it was stirred at 250 rpm for 3 minutes. When the stirring was completed, the liquid electrolyte lM LiPF ₆ EC: DMCl6g, lrgacure® Oxe02 was added and soaked in a glove box, followed by stirring for 3 minutes. After curing with a UV curing device at a wavelength of 385nm to prepare a UV-curable urethane polymer-solid electrolyte.

Example  2

34.85 g of TDI (toluene diisocyanate), 40 g of Si-Polyol (Mw 5,000, LGA-876, TEGO) and 80 g of polyethylene glycol (Mw 1,000, Kumho Chemical) were added, and then 60 to 70 ° C for 3 hours under N ₂ atmosphere. Was stirred. As the reaction proceeded, it became a viscous transparent liquid.

67.7 g of pentaerythritol triacrylate was added to a TDI-polysiloxane oligomer and a TDI-polyethylene glycol oligomer mixture, and the mixture was stirred at 60 ° C. to 70 ° C. for 3 hours under an N ₂ atmosphere. After completion of the reaction, it was analyzed by an infrared analyzer to confirm that the NCO characteristic peak of 2250cm ^-1 disappeared.

A solution of 1.2 g of hydroxy-propyl cellulose dissolved in 3.5 g of TDI-polysiloxane acrylate and TDI-polyethylene glycol acrylate mixture, 6 g of NMP, and 6 g of acetone was mixed, followed by stirring at 250 rpm for 3 minutes. Further, the solid electrolyte Li _0.33 La _0.55 Ti0 ₃ 2g was soaked and stirred at 250 rpm for 3 minutes. When the stirring was completed, the liquid electrolyte lM LiPF ₆ EC: DMCl6g, lrgacure® Oxe02 was added and soaked in a glove box, followed by stirring for 3 minutes. After curing with a UV curing device at a wavelength of 385nm to prepare a UV-curable urethane polymer-solid electrolyte.

Comparative example

34.85 g of TDI (toluene diisocyanate), 40 g of Si-Polyol (Mw 5,000, LGA-876, TEGO) and 80 g of polyethylene glycol (Mw 1,000, Kumho Chemical) were added, and then 60 to 70 ° C for 3 hours under N ₂ atmosphere. Was stirred. As the reaction proceeded, it became a viscous transparent liquid.

4 g of TDI-polysiloxane oligomer and a mixture of TDI-polyethylene glycol, NMP 6 g, and acetone 6 g were mixed with a solution of 1.2 g of hydroxy-propyl cellulose, followed by stirring at 250 rpm for 3 minutes. Additionally solid electrolyte Li _{0 . 33} La _{0 . 55} Ti0 ₃ 2 g were soaked and stirred at 250 rpm for 3 minutes. When the stirring was completed, the liquid electrolyte lM LiPF ₆ EC: DMCl6g, lrgacure® Oxe02 was added and soaked in a glove box, followed by stirring for 3 minutes. After curing with a UV curing device at a wavelength of 385nm to prepare a UV-curable urethane polymer-solid electrolyte.

Example  3

50 g of MDI (methylene diisocyanate), 45 g of Si-Polyol (Mw 5,000, LGA-876, TEGO) and 90 g of polyethylene glycol (Mw 1,000, Kumho Chemical) were added, and then 60 to 70 ° C. for 3 hours under N ₂ atmosphere. Stirred. As the reaction proceeded, it became a viscous transparent liquid.

67.7 g of pentaerythritol triacrylate was added to a mixture of MDI-polysiloxane oligomer and MDI-polyethylene glycol oligomer, and stirred for 3 hours at 60 ° C. to 70 ° C. under N ₂ atmosphere. After completion of the reaction, it was analyzed by an infrared analyzer to confirm that the NCO characteristic peak of 2250cm ^-1 disappeared.

The solution of 1.2 g of hydroxy-propyl cellulose dissolved in 3.5 g of MDI-polysiloxane acrylate and MDI-polyethylene glycol acrylate mixture, NMP 6 g, and acetone 6 g was mixed, followed by stirring at 250 rpm for 3 minutes. Further, the solid electrolyte Li _0.33 La _0.55 Ti0 ₃ 1.8g was soaked and stirred at 250 rpm for 3 minutes. When the stirring was completed, the liquid electrolyte lM LiPF ₆ PC: DMCl6g, lrgacure® Oxe02 was added and soaked in a glove box, followed by stirring for 3 minutes. After curing with a UV curing device at a wavelength of 385nm to prepare a UV-curable urethane polymer-solid electrolyte.

Example  4

52 g of IPDI (isophorone diisocyanate), 50 g of Si-Polyol (Mw 5,000, LGA-876, TEGO) and 90 g of polyethylene glycol (Mw 1,000, Kumho Chemical) were added, and then 60 to 70 ° C for 3 hours under N ₂ atmosphere. Was stirred. As the reaction proceeded, it became a viscous transparent liquid.

67.7 g of pentaerythritol triacrylate was added to the mixture of IPDI-polysiloxane oligomer and IPDI-polyethylene glycol oligomer, and stirred for 3 hours at 60 ° C. to 70 ° C. under N ₂ atmosphere. After completion of the reaction, it was analyzed by an infrared analyzer to confirm that the NCO characteristic peak of 2250cm ^-1 disappeared.

A solution of 1.2 g of hydroxy-propyl cellulose dissolved in 3.5 g of the IPDI-polysiloxane acrylate and IPDI-polyethylene glycol acrylate mixture, 6 g of NMP, and 6 g of acetone was mixed, followed by stirring at 250 rpm for 3 minutes. Further, the solid electrolyte Li _0.33 La _0.55 Ti0 ₃ 2g was soaked and stirred at 250 rpm for 3 minutes. When the stirring is completed, the liquid electrolyte lM LiPF ₆ PC: DMCl6g, lrgacure® Oxe02 is added, soaked in a glove box and stirred for 3 minutes. After curing with a UV curing device at a wavelength of 385nm to prepare a UV-curable urethane polymer-solid electrolyte.

< Example  B> Preparation of Cell

Before assembling the coin cell, a polymer-solid electrolyte was applied on an anode in a glove box in an argon atmosphere and dried for 20 hours, and then assembled in the above order. As a positive electrode, Li (Ni _0.6 Mn _0.2 Co _0.2 ) O ₂ , Li metal was used as the cathode, and interposed between SUS electrodes having a 16Φ area.

< Experimental Example  1> ion conductivity, Charge and discharge Impedance characteristics evaluation

2, 3 and 4 are graphs illustrating the ion conductivity, the charge / discharge characteristics, and the impedance of the cell prepared in Example B of the present invention.

Ion conductivity (σ) was calculated using the following equation.

σ = t / (A × R)

(t: thickness of electrolyte, A: area of sample, R: resistance of sample measured through impedance)

Impedance was measured in the range of 10 mHz ~ 1 MHz using VSP (BioLogic Co., France).

Charging and discharging characteristics were progressed to 0.1 C using PNE (SC, P & E Solution, Korea). The current was 0.340 mA and the voltage range was 3.0-4.3 V.

In the case of Examples 1 to 4, which performed all the steps according to an example of the present invention, a UV curable urethane polymer-solid electrolyte could be prepared, but in the comparative example, a film-type solid polymer-solid electrolyte could not be prepared, Electrolyte was prepared and did not have mechanical properties.

In the case of Examples 1 to 4 which performed all the manufacturing steps according to an embodiment of the present invention, a polymer-solid electrolyte in the form of a flexible film was prepared, unlike in the case of the comparative example, and the evaluation results of the charge and discharge characteristics of the battery were obtained. Excellent results were obtained (FIGS. 2 and 3).

Examples 1 and 2 and Examples 3 and 4 have different kinds of isocyanates and liquid electrolytes, but there are no significant differences in ionic conductivity and charge / discharge test results, and the physical properties of the resulting film were observed even after UV curing (Fig. 2. And Figure 3.).

However, in the case of Example 2, the form of the film produced by using the aromatic isocyanate is yellow, but Examples 1, 4, and 5 was made of a non-colored film. However, there was no significant difference between the ion conductivity and the charge / discharge test results (FIGS. 2 and 3).

When the UV-curable urethane polymer-solid electrolyte according to Examples 1 to 4, which performed all the manufacturing steps according to one embodiment of the present invention, was used, it was found that the degree of resistance increase after 10 times and 20 times of charge and discharge was not large. Could be (FIG. 4).

< Experimental Example  2> Measurement of tensile strength

5 is a graph measuring film tensile strength of the cell prepared in Example B of the present invention. The film was measured using a tensile strength analyzer by making a sample of 25mm x 25mm x 1mm (width x length x thickness).

It was confirmed that the tensile strength of the UV curable urethane polymer-solid electrolyte according to Examples 1 to 4, which performed all the manufacturing steps according to one embodiment of the present invention, showed a higher value than that of the comparative example (Fig. 5. ).

Examples 1 and 2 and Examples 3 and 4 have different kinds of isocyanate and liquid electrolyte, but there is no significant difference in the tensile strength measurement results, and the physical properties of the resulting film are similarly observed even after UV curing (FIG. 5).

Claims (16)

Preparing a UV curable urethane polymer solution;
Preparing a mixed solution by adding a lithium-based solid electrolyte to the UV curable urethane polymer solution; And
UV curing the mixed solution; comprising
UV Curable Urethane Polymer-Solid Electrolyte Production Method.
The method of claim 1,
Preparing the UV curable urethane polymer solution,
Adding an isocyanate, alkylene oxide based polyol or silicone based polyol and
Adding acrylate
UV Curable Urethane Polymer-Solid Electrolyte Production Method.
The method of claim 1,
Before preparing a mixed solution by adding a lithium-based solid electrolyte to the polymer solution
Adding a solution containing a cellulose polymer to the polymer solution
UV Curable Urethane Polymer-Solid Electrolyte Production Method.
The method of claim 1,
Lithium Lanthanum Titanium oxide (LLT), Lithium Lanthanum Zirconium Phosphate (LLZO), Lithium Aluminum Germanium Phosphate (LAGP), Lithium Aluminum Titanium Phosphate (LATP), Li ₄ SnS ₄ series, LSPS (Li ₁₀ SnP ₂₎ S ₁₂ ) system and Thio-LISICON system comprising the addition of any one or more selected from the group consisting of
UV Curable Urethane Polymer-Solid Electrolyte Production Method.
The method of claim 1,
The preparing of the mixed solution by adding a lithium-based solid electrolyte to the polymer solution may further include adding a lithium salt.
UV Curable Urethane Polymer-Solid Electrolyte Production Method.
The method of claim 1,
UV curing the mixed solution is to add a photopolymerization initiator, a thermal polymerization initiator or a thermosetting initiator
UV Curable Urethane Polymer-Solid Electrolyte Production Method.
The method of claim 2,
The isocyanate is added in an amount of 0.5 to 50% based on 100 parts by weight of the sum of the alkylene oxide-based polyol and the silicone-based polyol.
UV Curable Urethane Polymer-Solid Electrolyte Production Method.
The method of claim 2,
The isocyanate is 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene 1,6-diisocyanate, isophorone diisocyanate,
Paratoluenesulfonyl isocyanate, dicyclomethane 4,4-diisocyanate, diphenylmethane 4,4-diisocyanate, 2,4-diisocyanate, 2,2-diisocyanate, dodecane 1,12-diisocyanate, 2 At least one selected from the group consisting of ethyltetramethylene 1,4-diisocyanate and 2-methylpentamethylene 1,5-diisocyanate
UV Curable Urethane Polymer-Solid Electrolyte Production Method.
The method of claim 2,
The alkylene oxide-based polyol is at least one selected from the group consisting of polyethylene polyol, polypropylene polyol and polybutylene polyol
UV Curable Urethane Polymer-Solid Electrolyte Production Method.
The method of claim 2,
The molecular weight of the alkylene oxide-based polyol is 400 to 200,000
UV Curable Urethane Polymer-Solid Electrolyte Production Method.
The method of claim 2,
The silicon-based polyol is represented by the formula
UV Curable Urethane Polymer-Solid Electrolyte Production Method.
[Formula 1]

(Where R1, R2, R3, and R4 are H, an alkyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, or a benzyl group having 1 to 12 carbon atoms)
The method of claim 2,
The molecular weight of the silicone-based polyol is 400 to 200,000
UV Curable Urethane Polymer-Solid Electrolyte Production Method.
The method of claim 2,
The acrylate is any one or more of mono- to 8-functional acrylate
UV Curable Urethane Polymer-Solid Electrolyte Production Method.
The method of claim 2,
The acrylate is added in an amount of 0.5 to 20% based on 100 parts by weight of the alkylene oxide-based polyol and the silicon-based polyol combined
UV Curable Urethane Polymer-Solid Electrolyte Production Method.
The method of claim 5,
LiPF ₆ , LiCl 0 ₄ , LiCF ₃ S0 ₃ , LiBFS ₄ , LiAsF ₆ , Li (CF ₃ S0 ₂ ) ₂ N, LiCo0 ₂ , LiNi0 ₂ , LiMn0 ₂ , LiMn ₂ 0 ₄ , Li (Ni _a Co _{b Mn c), LiNi 1 -} y Co y 0 2, LiCo 1 - y Mn y 0 2, LiNi 1 -y Mn y O 2, Li (Ni a Co b Mn c) 0 4. _{LiMn 2 - x Ni x 0 4} , LiMn 2 - z Co z 0 4, which comprises adding at least one selected from LiCoP0 _4, and the group consisting of ₄ LiFeP0
UV Curable Urethane Polymer-Solid Electrolyte Production Method.
The method of claim 5,
The lithium salt is added in 5 to 50% content based on 100 parts by weight of the UV curable urethane polymer solution
UV Curable Urethane Polymer-Solid Electrolyte Production Method.

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