Carbon dioxide remover, lithium secondary battery comprising same, and method for manufacturing same

Abstract

The present invention relates to a carbon dioxide remover comprising: a composition comprising a carbon dioxide removal component; and a sealed container comprising an accommodation space for accommodating the composition therein, wherein the sealed container forms a continuous phase.

Description

Carbon dioxide removal agent, lithium secondary battery containing the same, and method for manufacturing the same

[0001] Cross-citation with related applications

[0002] This application claims the benefit of priority based on Korean Patent Application No. 10-2024-0144637 filed on October 22, 2024, and all contents disclosed in the document of said Korean Patent Application are incorporated herein as part of this specification.

[0003]

[0004] Technology field

[0005] The present invention relates to a carbon dioxide removal agent, a lithium secondary battery containing the same, and a method for manufacturing the same.

[0006]

[0007] Recently, as the application areas of lithium-ion batteries have rapidly expanded to include not only power supply for electronic devices such as electrical, electronic, telecommunications, and computers, but also power storage for large-area devices such as automobiles and power storage systems, there is a growing demand for lithium-ion batteries that are high-capacity, high-output, and highly stable.

[0008] A lithium secondary battery is generally manufactured by applying a material mixed with a positive electrode active material capable of inserting and extracting lithium ions or a negative electrode active material capable of absorbing and releasing lithium ions, and optionally a binder and a conductive material, to a positive electrode current collector and a negative electrode current collector, respectively, to produce a negative electrode and a positive electrode, stacking them on both sides of a separator to form an electrode assembly of a predetermined shape, and then inserting this electrode assembly and a non-aqueous electrolyte into a battery case.

[0009] Lithium secondary batteries can be classified into cylindrical, prismatic, and pouch-type secondary batteries depending on their structure. Among these, pouch-type secondary batteries are manufactured by housing the electrode assembly within a pouch-type sheet and then sealing the sheet; compared to other types of secondary batteries, they have a simple structure and a high capacity per unit volume, making them widely used in automotive batteries or energy storage devices.

[0010] The case of such a pouch-type secondary battery is a pouch-type sheet designed to protect the electrodes and electrolyte from the outside, and is composed of a metal membrane and a polymer material for sealing. In this case, the polymer material for sealing is primarily a thermoplastic and heat-fusible material composed of olefin-based materials such as polypropylene and polyethylene.

[0011] Meanwhile, during the charging and discharging process of lithium secondary batteries, gases including nonpolar molecules such as carbon dioxide, methane, hydrocarbons, and hydrogen, as well as carbon monoxide and hydrogen fluoride, are generated, with carbon dioxide accounting for the largest proportion. Due to these generated gases, the pressure inside the sealed battery increases, and if the pressure continues to increase, the seal of the electrical case may be destroyed.

[0012] Gas generated inside a pouch-type secondary battery cannot pass through the metal membrane and can be partially released through the polymer material. However, the polymer material has low permeability to the gas and has a narrow surface area through which the gas can be released, so there is a problem in that it is difficult to suppress the increase in internal pressure.

[0013] As a solution to these problems, Korean Patent Publication No. 10-2014-0147200 (Patent Document 1) discloses a carbon dioxide adsorption material utilizing the cross-linking reaction of an amine. However, according to the above Patent Document 1, the carbon dioxide adsorption material inevitably contains an excess amount of amine due to the adsorption mechanism in which the amine reacts with carbon dioxide. However, if the carbon dioxide adsorption material contains an excess amount of amine, the amine reacts with the electrolyte inside the battery, causing degradation of the electrolyte components and consequently leading to a problem of reduced battery performance. Furthermore, even if the remover of the above Patent Document 1 is used inside a lithium secondary battery, it does not have a protective layer to separate it from the electrolyte, so it is mixed with the electrolyte, resulting in poor stability and problems such as degradation due to side reactions and gas generation. Therefore, the carbon dioxide adsorption material of the above Patent Document 1 is not suitable for use in adsorbing carbon dioxide generated inside the battery.

[0014] In addition, Japanese Patent Publication No. 2003-077549 (Patent Document 2) discloses the use of carbon materials such as activated carbon and carbon black as gas absorbents, and the use of a micro-material to suppress the wetting of the gas absorbent by a non-aqueous solvent. However, according to Patent Document 2, since the micro-material corresponds to a powder in the form of a powder rather than a continuous film, it is not possible to completely prevent the wetting of the gas absorbent by allowing a non-aqueous solvent to flow in through the spaces between the powder particles. Furthermore, when forming a film with such powder, the solvent used is extremely limited, and there is a problem in that it is difficult to form a dense structure due to residual solvent during the film formation process, making it difficult to achieve complete blockage of contact with the non-aqueous solvent.

[0015] In addition, Japanese Publication No. 2015-092493 (Patent Document 3) discloses a gas absorbent and a heat-meltable capsule containing the same. However, when the temperature of the heat-meltable capsule exceeds a certain level, it melts and comes into contact with a non-aqueous solvent, and when the gas absorbent comes into contact with the non-aqueous solvent, the gas absorbent begins to degenerate and the absorption efficiency is significantly reduced. However, since the purpose of Patent Document 3 is for the gas absorbent to diffuse into the battery case by the heat-meltable capsule, it does not recognize the need to block contact between the gas absorbent and the non-aqueous solvent.

[0016] (Patent Document 1) KR 10-2014-0147200 A

[0017] (Patent Document 2) JP 2003-077549 A

[0018] (Patent Document 3) JP 2015-092493 A

[0019]

[0020] The problem to be solved by the present invention is to provide a carbon dioxide removal agent capable of improving stability by removing gas generated during the charging and discharging of a secondary battery, thereby preventing the breakdown of the seal of a lithium secondary battery case due to an increase in internal pressure of the secondary battery.

[0021] In addition, the problem to be solved by the present invention is to minimize side reactions with the electrolyte in the lithium secondary battery to prevent degradation of the removal agent and to improve stability, thereby improving the performance of the lithium secondary battery.

[0022]

[0023] The present invention provides a carbon dioxide removal agent, a lithium secondary battery containing the same, and a method for manufacturing the same.

[0024] (1) The present invention provides a carbon dioxide removal agent comprising a composition including a carbon dioxide removal component and a sealed container having a receiving space for accommodating the composition inside, wherein the sealed container forms a continuous phase.

[0025] (2) The present invention provides a carbon dioxide removal agent according to (1), wherein the carbon dioxide removal component comprises a first compound having one or more epoxy groups; and a second compound, wherein the second compound comprises one or more selected from the group consisting of amine compounds, quaternary ammonium salts, imidazolium salts, pyridinium salts, phosphonium salts, zeolites, metal-organic frameworks, metal halogen salts, metal oxides, and alkanolamine compounds.

[0026] (3) The present invention provides a carbon dioxide removal agent according to (2), wherein the carbon dioxide removal component comprises 30% by weight or more and 99.995% by weight or less of the first compound; and 0.005% by weight or more and less than 70% by weight of the second compound.

[0027] (4) The present invention provides a carbon dioxide removal agent in which, in any one of (1) to (3), the carbon dioxide removal component is in a liquid state.

[0028] (5) The present invention provides a carbon dioxide removal agent in which, in any one of (1) to (4), the sealing container is of the sealing type or the tube type.

[0029] (6) The present invention provides a carbon dioxide removal agent in any one of (1) to (5), wherein the sealed container is impermeable to liquid or powder and permeable to carbon dioxide gas.

[0030] (7) The present invention provides a carbon dioxide removal agent in which, in any one of (1) to (6), the sealing container comprises one or more selected from the group consisting of fluorine-based, epoxy-based, olefin-based, imide-based, and ester-based compounds.

[0031] (8) The present invention provides a carbon dioxide removal agent in which, in any one of (1) to (7), the receiving space includes an empty space in addition to the composition.

[0032] (9) The present invention provides a carbon dioxide removal agent in which, in any one of (1) to (8), the receiving space comprises an empty space of 5 volume% or more and 50 volume% or less relative to the volume of the receiving space.

[0033] (10) The present invention provides a carbon dioxide removal agent in any one of (1) to (9), wherein the sealing container has an elongation of 10% or more as measured based on the specimen specifications of ASTM D638.

[0034] (11) The present invention provides a carbon dioxide removal agent in which, in any one of (1) to (10), an external protective layer formed on the outer surface of the sealing container is further included, and the external protective layer comprises an epoxy resin.

[0035] (12) The present invention provides a lithium secondary battery comprising a carbon dioxide removal agent according to any one of (1) to (11) above.

[0036] (13) The present invention provides a method for manufacturing a carbon dioxide removal agent comprising the steps of: manufacturing a composition containing a carbon dioxide removal component (S1); receiving the composition manufactured in step (S1) in a sealed container with a portion open (S2); and sealing the portion open of the sealed container (S3).

[0037] (14) The present invention provides a method for manufacturing a carbon dioxide removal agent, wherein the step (S1) of manufacturing a composition containing the carbon dioxide removal component in (13) comprises: a step (S1-1) of mixing 30 parts by weight or more and 99.995 parts by weight or less of an epoxy compound containing two or more epoxy groups and 0.005 parts by weight or more and less than 70 parts by weight of an amine compound, and a step (S1-2) of reacting the mixture mixed in the step (S1-1) at a temperature of 50°C or more and 150°C or less.

[0038] (15) The present invention provides a method for manufacturing a carbon dioxide removal agent, wherein the step (S1) of manufacturing a composition containing the carbon dioxide removal component in (13) comprises: 30 parts by weight or more and 99.995 parts by weight or less of an epoxy compound containing one or more epoxy groups; and 0.005 parts by weight or more and less than 70 parts by weight of one or more compounds selected from the group consisting of quaternary ammonium salts, phosphonium salts, zeolites, metal-organic frameworks, metal halogen salts and metal oxides (S1-1').

[0039]

[0040] The carbon dioxide removal agent of the present invention can improve stability by adsorbing gases generated during the charging and discharging of a lithium secondary battery, thereby preventing the breakdown of the seal of the lithium secondary battery case caused by an increase in the internal pressure of the lithium secondary battery.

[0041] In addition, the carbon dioxide remover of the present invention includes a sealed container, thereby preventing contact with the electrolyte when included in a lithium secondary battery, preventing denaturation and gas generation of the carbon dioxide remover, maintaining the performance of the carbon dioxide remover, and maintaining the high performance of the lithium secondary battery.

[0042] In addition, the carbon dioxide removal agent of the present invention includes a continuous-phase sealed container, thereby completely preventing the introduction of a non-aqueous solvent to wet the composition containing the carbon dioxide removal component contained therein, and can maintain a high level of carbon dioxide removal efficiency for a long time without alteration of the composition.

[0043] In addition, the carbon dioxide remover of the present invention includes a specific proportion of empty space within the sealed container, thereby preventing cracking or destruction of the sealed container caused by the increasing expansion pressure as the reaction for adsorbing gas generated during the charging and discharging of the lithium secondary battery proceeds, and enabling the high performance of the carbon dioxide remover to be maintained for a long period.

[0044]

[0045] Figure 1 is a photograph showing the results of a discoloration test on the carbon dioxide removers of Example 11 and Comparative Example 5.

[0046] Figure 2 shows the degree of discoloration of the electrolyte and adsorbent over time in Comparative Example 1.

[0047] Figure 3 shows the removal performance of the carbon dioxide removal agent of Comparative Example 1.

[0048] Figure 4 shows the amount of carbon dioxide removed according to the content of quaternary ammonium salt.

[0049] Figure 5 shows the amount of carbon dioxide removed over time according to the content of quaternary ammonium salt.

[0050]

[0051] Hereinafter, the present invention will be described in more detail to aid in understanding the invention. In this case, terms and words used in this specification and claims should not be interpreted as being limited to their ordinary or dictionary meanings, but should be interpreted in a meaning and concept consistent with the technical spirit of the invention, based on the principle that the inventor can appropriately define the concept of the terms to best describe his invention.

[0052] The terms used in this specification are used merely to describe exemplary embodiments and are not intended to limit the invention. The singular expression includes the plural expression unless the context clearly indicates otherwise.

[0053] In this specification, terms such as “comprising,” “comprising,” or “having” are intended to specify the existence of the implemented features, numbers, steps, components, or combinations thereof, and should not be understood as precluding the existence or addition of one or more other features, numbers, steps, components, or combinations thereof.

[0054]

[0055] carbon dioxide remover

[0056] The present invention provides a carbon dioxide removal agent comprising a composition including a carbon dioxide removal component and a sealed container having a receiving space for accommodating the composition including the carbon dioxide removal component, wherein the sealed container has no distinct boundaries and forms a continuous phase.

[0057] The carbon dioxide removal agent of the present invention can be used to remove carbon dioxide generated during the charging and discharging of lithium secondary batteries. It can also be used in plants that emit large amounts of carbon dioxide, a greenhouse gas, such as thermal power plants, or in indoor spaces, underground areas, and vehicle interiors where carbon dioxide concentrations must be maintained below a certain level. Additionally, it can be used to purify biogas generated in sewage treatment plants, landfills, etc. Specifically, the carbon dioxide removal agent of the present invention can improve the stability of lithium secondary batteries by removing gases generated during the charging and discharging of lithium secondary batteries, thereby preventing the breakdown of the seal of the lithium secondary battery case caused by an increase in internal pressure.

[0058] Meanwhile, conventional carbon dioxide removal agents used in lithium secondary batteries were used without a separate coating layer or sealed container, resulting in contact with the electrolyte. This contact caused degradation of both the electrolyte and the carbon dioxide removal agent. Furthermore, in addition to this degradation, a problem of rapid deterioration in carbon dioxide removal performance occurred.

[0059] Figure 2 shows the degree of discoloration of the electrolyte and adsorbent over time in Comparative Example 1, and Figure 3 shows the removal performance of the carbon dioxide remover in Comparative Example 1. Referring to Figures 2 and 3, it was confirmed that when only the remover was introduced without the electrolyte, more than 15 cc of carbon dioxide was removed, whereas when 1 mL of the electrolyte was introduced together, carbon dioxide adsorption did not occur, and instead, the volume of the pouch continuously increased. Therefore, it can be confirmed that when the electrolyte is present, even if carbon dioxide is present, the side reaction with the electrolyte occurs more strongly than the carbon dioxide removal reaction, and as a result, gaseous side reaction substances are generated.

[0060] Furthermore, even if a coating layer and a sealed container are provided, if a separate fastening part or adhesive layer is formed, or a separate passage is formed, cracks and gaps occur through this, making it difficult to completely block the electrolyte. Additionally, even if a coating layer and a sealed container are provided, a problem arises in which the coating layer and the sealed container break as the volume of the remover expands as carbon dioxide gas adsorption proceeds.

[0061] In addition, when carbon dioxide adsorbents or removers and small liquid materials are mixed together, since they are mixed in a powder or granular form, it is difficult to completely block them from the electrolyte, and there is a problem that the effect of preventing wetting by non-aqueous solvents is structurally limited.

[0062] Accordingly, the inventor of the present invention has invented a carbon dioxide remover that prevents gas generation and degradation caused by contact between the carbon dioxide remover and the electrolyte, and maintains high carbon dioxide adsorption performance for a long time without the sealed container breaking even after a long period of time. The carbon dioxide remover of the present invention comprises a composition containing a carbon dioxide removal component and a sealed container containing a receiving space, and by receiving the composition containing the carbon dioxide removal component within the sealed container, contact between the composition containing the carbon dioxide removal component and the electrolyte in a lithium secondary battery can be prevented.

[0063] In addition, the sealing container is formed in a continuous phase. The continuous phase refers to a state in which the sealing container is formed integrally without a structurally distinct boundary and molecular chains are intertwined without discontinuity. Here, the distinguished boundary refers to a physical or structural boundary formed by physically connecting two or more components, and the two or more components refer, for example, to a structural boundary or joint between a main body or base part and a connecting part, a lid or cover, etc.

[0064] In addition, the sealing container may form a continuous phase as a single material or form a continuous phase as two or more materials. For example, a continuous phase as a single material can be formed by heat-sealing both ends or edges of a tubing or film made of one material, and a continuous phase as two materials can be formed by heat-sealing both ends of a tubing made of one material with another material.

[0065] In this way, the sealed container of the present invention can achieve hermetic isolation from the electrolyte as a continuous phase without forming any boundaries by heat-sealing the boundary lines of a film, sheet, tubing, etc., through a heat sealer, or by forming a coating layer on the outer surface of a tube. Since hermetic isolation from the electrolyte is achieved, the composition containing the carbon dioxide removal component contained in the sealed container can maintain a high level of carbon dioxide removal efficiency for a long time without denaturation.

[0066] In addition, the carbon dioxide remover of the present invention includes a specific proportion of empty space in addition to the carbon dioxide remover within the sealed container, and even if the composition containing the carbon dioxide removal component expands as the carbon dioxide absorption reaction proceeds, the expansion pressure is not immediately transmitted to the sealed container due to the empty space within the sealed container, thereby preventing the sealing container from breaking due to the expansion of the composition containing the carbon dioxide removal component.

[0067]

[0068] According to one embodiment of the present invention, the carbon dioxide removal component comprises a first compound and a second compound containing one or more epoxy groups, and the second compound may comprise one or more selected from the group consisting of amine compounds, quaternary ammonium salts, imidazolium salts, pyridinium salts, phosphonium salts, zeolites, metal-organic frameworks, metal halogen salts, metal oxides, and alkanolamine compounds. Here, the first compound may be an epoxy compound containing an epoxy group, and the second compound may be a catalyst compound that induces the reaction between the epoxy compound and carbon dioxide to form a cyclic carbonate group.

[0069] The composition containing the carbon dioxide removal component may, for example, include a polyfunctional epoxy compound containing one or more epoxy groups; an amine-based compound or a quaternary ammonium salt; and a reaction product thereof. The carbon dioxide removal component means a material unit that adsorbs and removes carbon dioxide, comprising a compound or a part derived therefrom.

[0070] The composition containing the carbon dioxide removal component described above may, specifically, be a composition containing a polyfunctional epoxy compound having two or more epoxy groups and an amine-based compound, and the composition may be cured and in a solid state.

[0071] In addition, the composition containing the carbon dioxide removal component may be a composition containing a monofunctional or polyfunctional epoxy compound containing one or more epoxy groups and a quaternary ammonium salt, and may be in an uncured solid or liquid state.

[0072] Most conventional carbon dioxide adsorbents adsorb gases via physical adsorption, which corresponds to adsorption utilizing pores in materials such as activated carbon and zeolites. However, since this physical adsorption method relies on adsorption through pores rather than through chemical reactions, it cannot adsorb only the intended gas; consequently, the adsorption selectivity is significantly inferior, leading to a problem of reduced adsorption efficiency for the desired gas. Furthermore, physical adsorption carries the risk of re-releasing the adsorbed carbon dioxide relatively easily due to bonding through weak interactions. In contrast, the composition containing the carbon dioxide removal component of the present invention includes a polyfunctional epoxy compound containing epoxy groups, which corresponds to chemical adsorption. Since this adsorbs only carbon dioxide, it exhibits excellent adsorption selectivity. Additionally, chemical adsorption is highly unlikely to re-release the adsorbed carbon dioxide due to strong chemical bonding, thereby enabling the maintenance of a stable gas pressure state within the battery.

[0073] According to one embodiment of the present invention, a composition comprising the carbon dioxide removal component may include the first compound in an amount of 30% by weight or more and 99.995% by weight or less, and the second compound in an amount of 0.005% by weight or more and less than 70% by weight. For example, a composition comprising the carbon dioxide removal component may include the first compound in an amount of 30 wt% or more, 35 wt% or more, 40 wt% or more, 45 wt% or more, 50 wt% or more, 60 wt% or more, 65 wt% or more, 70 wt% or more, 75 wt% or more, 80 wt% or more, 85 wt% or more, 87 wt% or more, 99.995 wt% or less, 98 wt% or less, 97 wt% or less, 96 wt% or less, 95 wt% or less, 94 wt% or less, 93 wt% or less, 92 wt% or less, 91 wt% or less, and 90 wt% or less, and the second compound in an amount of 0.005 wt% or more, 0.01 wt% or more, 0.1 wt% or more, 0.5 wt% or more, 1 wt% or more, 2 wt% or more, 3 wt% or more, 4 wt% or more, and 5 wt% It may contain 6 wt% or more, 7 wt% or more, 8 wt% or more, 9 wt% or more, 10 wt% or more, less than 70 wt%, 65 wt% or less, 60 wt% or less, 55 wt% or less, 50 wt% or less, 45 wt% or less, 35 wt% or less, 30 wt% or less, 25 wt% or less, 23 wt% or less, 21 wt% or less, 20 wt% or less, 19 wt% or less, 18 wt% or less, 17 wt% or less, 16 wt% or less, 15 wt% or less, 14 wt% or less, 13 wt% or less, 12 wt% or less, and 11 wt% or less. When a composition containing the carbon dioxide removal component contains the first compound and the second compound in the above amounts, the carbon dioxide removal performance can be improved by retaining a high amount of epoxy groups that activate the carbon dioxide removal reaction within the composition containing the carbon dioxide removal component.

[0074] Hereinafter, a carbon dioxide removal component in which the first compound is an epoxy compound containing two or more epoxy groups and the second compound is an amine-based compound, and a carbon dioxide removal component in which the first compound is an epoxy compound containing one or more epoxy groups and the second compound is a quaternary ammonium salt are described by way of example.

[0075] According to one embodiment of the present invention, the composition comprising the carbon dioxide removal component may include an activating group represented by the following chemical formula 1, formed by the reaction of the epoxy group of the epoxy compound and the amine compound.

[0076] Specifically, the composition containing the carbon dioxide removal component may include an epoxy compound-derived portion formed from an epoxy compound and an amine compound-derived portion formed from an amine compound. Here, the derived portion may refer to the repeating unit itself, which includes both a bonding portion formed by each compound participating in a reaction and a functional group portion that does not participate in a reaction and retains the functional group as is.

[0077] [Chemical Formula 1]

[0078]

[0079] In the above chemical formula 1, R 1 may be the remainder of a polyfunctional epoxy compound containing two or more epoxy groups, and R 2 to R 4 It may be the remainder of an amine compound.

[0080] The polyfunctional epoxy compound-derived portion and the amine compound-derived portion may simultaneously include an activating group represented by Chemical Formula 1 and may exhibit a form combined with the activating group represented by Chemical Formula 1.

[0081] According to one embodiment of the present invention, the epoxy compound included in the composition together with the amine compound may be a polyfunctional epoxy compound containing two or more epoxy groups. If the epoxy compound included in the composition together with the amine compound is a monofunctional epoxy compound having only one epoxy group, the carbon dioxide adsorption capacity may be reduced because the epoxy group acts only to form a solid state by curing and does not maintain the activating group at a sufficient level.

[0082] As a specific example, the polyfunctional epoxy compound may comprise three or more epoxy groups, and more specifically examples include 1,4-butanediyl diglycidyl ether, 3-[bis(glycidyloxymedyl)methoxy]-1,2-propanediol, diglycidyl 1,2-cyclohectanedicarboxylate, 1,7-octadiene diepoxide, dipentene-diepoxide, 1,2-epoxy-4-epoxyethylcyclohexene, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexene carboxylate, bisphenol A diglycidyl ether, tris(4-hydroxyphenyl)methane triglycidyl ether, trimethylolpropane triglycidyl ether, o-cresol novolac, poly(ethylene-co-glycidyl methacrylate), and poly(ethylene-co-methyl It may be one or more selected from the group consisting of acrylate-co-glycidyl methacrylate, etc.

[0083] According to one embodiment of the present invention, the amine compound may be an amine of the NH3 type, but may be one or more selected from the group consisting of primary amines, secondary amines, and tertiary amines in order to improve reactivity for forming an activating group represented by Formula 1 through a reaction between the epoxy group of the polyfunctional epoxy compound and the amine compound. As a specific example, the primary amine, secondary amine, and tertiary amine may each include an electron-donating group.

[0084] According to one embodiment of the present invention, the amine compound may be one or more selected from the group consisting of polyethyleneimine, tetraethylenepentaamine, triethylenetetraamine, pentaethylenehexaamine, diethylenetriamine, 2,4,6-tris(dimethylaminomethyl)phenol, etc.

[0085]

[0086] According to one embodiment of the present invention, the activator may react with carbon dioxide to form a cyclic carbonate group. That is, the composition containing the carbon dioxide removal component according to the present invention may adsorb carbon dioxide by the reaction of the activator and carbon dioxide to form a cyclic carbonate group, rather than by adsorption of carbon dioxide through a reaction between an amine or ammonium and carbon dioxide. As a specific example, the reaction in which the activator and carbon dioxide react to form a cyclic carbonate group may be represented by the following reaction scheme 1.

[0087] [Reaction Equation 1]

[0088]

[0089] As shown in Reaction Scheme 1 above, when the activator reacts with carbon dioxide, a cyclic carbonate group is formed, and accordingly, the amino group existing in a state bound to the activator is reduced to the form of an amine compound or quaternary ammonium before reacting with the epoxy group, which can form the activator group represented by Chemical Formula 1 again through a reaction with other epoxy groups remaining in the composition containing the carbon dioxide removal component. Therefore, the composition containing the carbon dioxide removal component according to the present invention can maintain carbon dioxide adsorption capacity depending on the content of epoxy groups remaining in the composition containing the carbon dioxide removal component.

[0090]

[0091] According to one embodiment of the present invention, a composition comprising the carbon dioxide removal component may include the epoxy compound and the quaternary ammonium salt. The epoxy compound included in the composition together with the quaternary ammonium salt may be a monofunctional or polyfunctional epoxy compound containing one or more epoxy groups. Since the quaternary ammonium salt does not participate in the curing reaction of the epoxy group but participates entirely as a catalyst only in the absorption reaction between the epoxy group and carbon dioxide, the epoxy compound may be included in the composition as a monofunctional epoxy compound containing one epoxy group.

[0092] The above monofunctional or polyfunctional epoxy compound may have a low molecular weight or epoxy value and a boiling point of 80°C or higher. In this case, a high amount of carbon dioxide removal per unit g can be obtained, and the problem of pressure rise due to vaporization can be prevented when an abnormal temperature rise occurs during operation in the battery.

[0093] The monofunctional epoxy compound may include one or more selected from the group consisting of 1,2-epoxycyclopentane, glycidol, 1,2-epoxycyclohexane, 1,2-epoxyhexane, ethyl glycityl ether, allyl glycityl ether, glycidyl isopropyl ether, benzyl glycidyl ether, glycidyl phenyl ether, 1,2-epoxydecane, tert-butyldimethylsilyl(S)-glycidyl ether, cyclopentene oxide, and 3,4-epoxytetrahydrofuran.

[0094] According to one embodiment of the present invention, the quaternary ammonium salt is NR4 +It may be in the form of an anion of a halogen. Here, R may be an alkyl group or an aryl group substituted or unsubstituted with one or more atoms selected from the group consisting of O, N, Si, S, and P, etc. The quaternary ammonium salt may be a tetraalkylammonium halide, and specifically, may be one or more selected from the group consisting of triethylbenzylammonium chloride, triethylbenzylammonium bromide, triethylbenzylammonium iodide, tetra-n-butylammonium bromide, tetrahexylammonium chloride, trimethylbenzylammonium chloride, tetramethylammonium iodide, cetyltrimethylammonium bromide, tetraethylammonium bromide, and phenyltrimethylammonium tribromide, etc.

[0095] According to one embodiment of the present invention, the quaternary ammonium salt can act as a catalyst to promote a reaction that adsorbs carbon dioxide by the epoxy group reacting with carbon dioxide to form a cyclic carbonate group. Specifically, the epoxy group can be activated by the interaction between the Lewis acid contained in the quaternary ammonium salt and the oxygen atom of the epoxy group. The ring forming the epoxy group is opened by a nucleophilic substitution reaction of a halogen anion on the carbon atom with the lowest degree of substitution of the activated epoxy group, and an intermediate of the epoxy group can be formed. Subsequently, carbon dioxide is introduced into the negatively charged intermediate of the epoxy group, and a 5-carbon cyclic carbonate is formed through the substitution of the halogen anion and the formation of a carbonate intermediate, while the quaternary ammonium salt can be regenerated as a catalyst.

[0096] [Reaction Equation 2]

[0097]

[0098] In the above reaction scheme 2,

[0099] The above R 5 may be the remainder of a polyfunctional epoxy compound containing one or more epoxy groups, and

[0100] Above A + is NR4+ It could be,

[0101] The above R may be a substituted or unsubstituted alkyl group or an aryl group, and

[0102] The above X - It can be an anion of a halogen element.

[0103]

[0104] Meanwhile, the composition containing the carbon dioxide removal component may include a compound that simultaneously contains an epoxy group and an ammonium group within a single molecule. When the composition includes a compound that simultaneously contains an epoxy group and an ammonium group within a single molecule, a relatively larger amount of epoxy groups is contained, which may improve the carbon dioxide removal capacity. For example, the compound may include glycidyl trimethylammonium.

[0105]

[0106] According to another embodiment of the present invention, the second compound may comprise one or more selected from the group consisting of phosphonium salts, imidazolium salts, pyridinium salts, zeolites, metal-organic frameworks, metal halogen salts, metal oxides, and alkanolamine compounds; the zeolite may comprise ZIF-90; the metal-organic framework may comprise Cr-MIL-101, Fe-MIL-101, or Ni(salphen)-MOF; the metal halogen salt may comprise LiBr KBr or KI; the metal oxide may comprise MgO, CaO, ZnO, ZrO2, La2O3, or CeO2; and the alkanolamine compound may comprise N,N-dimethylethanolamine, N,N-dimethylpropanolamine, or N,N-diethylethanolamine. The second compound may induce the formation of a cyclic carbonate structure by reacting the epoxy group of an epoxy compound with carbon dioxide.

[0107]

[0108] According to another embodiment of the present invention, the activator may react with carbon dioxide to form a polycarbonate polymer. As a specific example, the reaction in which the activator reacts with carbon dioxide to form a polycarbonate polymer may be represented by the following reaction scheme 3.

[0109] [Reaction Equation 3]

[0110]

[0111] As shown in Reaction Scheme 3 above, when the activator reacts with carbon dioxide, the activator is a catalyst (X - An intermediate stabilized by ) is formed, and then carbonate groups are formed by the insertion of carbon dioxide, and a polycarbonate polymer is formed in which carbonate groups are repeated through the alternating insertion of new activators and carbon dioxide. The polycarbonate can be formed by a salen metal complex catalyst and an onium (ammonium or phosphonium) co-catalyst. In addition, the polycarbonate has a high molecular weight, which may be advantageous for safety as there is less concern about leakage or volatilization outside the sealed container.

[0112] Meanwhile, the above-mentioned cyclic carbonate can also be converted into polycarbonate by a ring-opening reaction, and as a result, the product produced by the activator may be a mixture of cyclic carbonate and polycarbonate.

[0113]

[0114] According to one embodiment of the present invention, a composition containing the carbon dioxide removal component may be in a liquid or solid state, and the solid state may be a powder or a solidified powder. In the case of a composition containing the carbon dioxide removal component in the solid state, a polyfunctional epoxy compound and an amine compound may be mixed. In this case, the amine compound may participate in a curing reaction in which epoxy groups are connected to each other as a curing agent, and may also participate in an absorption reaction in which epoxy groups are combined with carbon dioxide as a catalyst. Therefore, as the composition containing the carbon dioxide removal component in the solid state is stored for a long time, the curing reaction proceeds, and the capacity to remove carbon dioxide may decrease as the curing reaction proceeds. However, the composition in the solid state may have the advantage of being easily applied to various forms of carbon dioxide removal agents, such as sheet form or powder form, through processing.

[0115] In addition, according to one embodiment of the present invention, a composition containing the carbon dioxide removal component of the present invention may be in the liquid state, and this may be prepared by mixing a polyfunctional epoxy compound and a quaternary ammonium salt. In the case of a composition containing a carbon dioxide removal component in the liquid state using a quaternary ammonium salt, it does not participate in the curing reaction of the epoxy group, but rather participates entirely as a catalyst only in the absorption reaction between the epoxy group and carbon dioxide, thus having the advantage of not reducing the capacity to remove carbon dioxide.

[0116]

[0117] According to another embodiment of the present invention, the carbon dioxide removal component of the present invention may comprise only an amine-based compound. In this case, the amine-based compound may be one or more selected from the group consisting of primary amines and secondary amines. For example, each of the primary amine and the secondary amine may comprise an electron-donating group.

[0118] As a more specific example, the above amine compound may be one or more selected from the group consisting of monoethanolamine, diethanolamine, exylamine, octylamine, 2-ethyl-1-hexylamine, decylamine, dibutylamine, N-heptylmethylamine, pyridine, ethylenediamine, tris(2-aminoethyl)amine, etc.

[0119] [Reaction Equation 4]

[0120]

[0121] As shown in Chemical Formula 4 above, when the amine compound reacts alone with carbon dioxide, a salt of carbamic acid and ammonium is formed, which can remove gaseous carbon dioxide.

[0122]

[0123] According to one embodiment of the present invention, the sealing container may be of the sealing type or the tube type. The sealing container may be manufactured by accommodating a composition containing the carbon dioxide removal component while a portion is open, and sealing the open portion of the sealing container.

[0124] In the case of the above sealing type, two sheets of tape, film, or sheet of a specific material are overlapped, and the rest, excluding the open portion, i.e., the edges, are sealed in a “U” shape using a heat fusion method, then a composition containing a carbon dioxide removal component is injected, and the open portion, i.e., the last side, is sealed again.

[0125] Here, the sealing of the sealing type described above can be performed by a thermal fusion method in which polymer chains included in the parts of the sealed container that do not bond to each other but form gaps or openings are intertwined and bonded. Unlike simple physical fastening methods such as bolt / nut assembly, zipper bag fastening, or screw caps, this causes the polymer resin constituting the sealed container to form a continuous phase. This thermal fusion method can be performed when the polymer material constituting the sealed container is pressurized at a temperature above its melting point, which can be achieved through direct heating using a heated heat source. Additionally, the thermal fusion method may be performed using heating with vibration. Specifically, thermal fusion can be achieved by causing direct friction on the bonding surface through vibration and then heating the polymer material to a temperature above its melting point through this friction, or by a temperature rise caused by the vibration of the polymer chains themselves. When performed using the vibration of the polymer chains themselves, the heating effect can be enhanced if the polymer chains contain polar functional groups. Furthermore, the thermal fusion method may be performed using laser heating. Specifically, when the material of the bonding surface is heated by the laser and reaches a temperature above the melting point of the polymer material, a continuous phase of the resin can be formed through the entanglement of polymer chains. Additionally, the continuous phase of the polymer resin in the sealing container can be formed by heating the polymer itself of the sealing container with the laser, or by dispersing a dye capable of absorbing the laser within the sealing container and heating it with the dye.

[0126] The above-described tubular type may be a form in which a tube made of a specific material with a portion open is prepared, a composition containing a carbon dioxide removal component is injected into the tube through the open portion, and then the open portion is sealed by closing it using a stopper or the like. Since the method of closing using the stopper or the like is a physical seal, a continuous phase cannot be formed by closing the stopper or the like alone, and the outer surface of the tube may be coated to form a continuous phase. The method of coating the outer surface of the tube may be carried out by immersing the tube in a liquid polymer solution and then curing it into a solid phase. Alternatively, it may be carried out by melting a polymer material that has a solid phase at room temperature at a high temperature, immersing the tube in the polymer material, and cooling it at room temperature to solidify it.

[0127] In addition, the above tubular shape can be implemented using a heat fusion method on a tube or tubing-shaped material, and can also correspond to the tubular shape of the present invention even when a composition containing the carbon dioxide removal component is received in a partially open state without limitation to a specific shape, and then the open part is sealed.

[0128] Meanwhile, in the case of the previously used micromaterial, since it is mixed in powder form with the adsorbent to inhibit the wetting of the adsorbent, it is difficult to completely block contact with the electrolyte. When a coating layer is formed, contact can be blocked on all sides of the adsorbent, but there was a problem in that cracks occurred in the coating layer due to the expansion of the adsorbent when used for a long period of time, making it difficult to maintain continuous performance.

[0129] In the case of the sealed container of the present invention, unlike the formation of a liquid material or a coating layer, since it is of the sealing or tubular type, it is possible to prevent all sides of the composition containing the carbon dioxide removal component from coming into contact with the electrolyte, and by including an empty space, the occurrence of cracks due to expansion can be prevented. In addition, since a separate mixing process between the adsorbent and the liquid material or coating composition is not required, manufacturing processability can be increased.

[0130]

[0131] According to one embodiment of the present invention, the sealed container may be impermeable to liquid or powder and permeable to carbon dioxide. Specifically, the liquid may be an electrolyte of a lithium secondary battery or a composition containing a carbon dioxide removal component, the powder may be a composition containing a carbon dioxide removal component, and the carbon dioxide may be in a gaseous state. Here, impermeability means not only that the liquid or powder is blocked from passing through but also that a significantly small amount of liquid or powder passes through.

[0132] It is desirable that the above-described sealed container has excellent permeability to carbon dioxide gas so that carbon dioxide gas can be smoothly removed by a composition containing a carbon dioxide removal component contained therein, and at the same time, it is desirable that it has poor permeability to liquid or powder to prevent contact between the composition containing the carbon dioxide removal component and the electrolyte outside the sealed container. Accordingly, the sealed container of the present invention comprises a material that is permeable to carbon dioxide gas and impermeable to liquid or powder, thereby enabling excellent permeability of carbon dioxide gas without separate gas passages or fastening parts, and can possess impermeability properties by significantly slowing down the permeation rate of liquid or powder.

[0133]

[0134] In addition, according to one embodiment of the present invention, the sealed container may have a ratio of the permeability of oxygen dioxide (O2) to the permeability of water (H2O) of 2500 or more and 5000 or less. For example, the ratio of the permeability of carbon dioxide to the permeability of water may be 2500 or more, 2700 or more, 2900 or more, 3000 or more, 3100 or more, 3300 or more, 3500 or more, 3700 or more, 3900 or more, 4000 or more, 5000 or less, 4900 or less, 4700 or less, 4500 or less, 4300 or less, and specifically, 3000 or more and 4700 or less. The water mentioned above corresponds to a polar substance, and carbon dioxide corresponds to a non-polar substance; the sealed container may have high permeability to these non-polar substances and impermeability to polar substances. When corresponding to the above ratio range, the sealed container can block contact between the electrolyte and the composition containing the carbon dioxide removal component, and can efficiently remove carbon dioxide gas.

[0135] In addition, the sealed container may include pores, and the average particle size of the pores may be 0.2 nm or more and 0.5 nm or less. For example, the average particle size of the pores of the sealed container may be 0.2 nm or more, 0.22 nm or more, 0.25 nm or more, 0.27 nm or more, 0.29 nm or more, 0.3 nm or more, 0.5 nm or less, 0.45 nm or less, 0.42 nm or less, 0.4 nm or less, 0.37 nm or less, 0.35 nm or less, and 0.33 nm or less. When the average particle size of the pores satisfies the above range, carbon dioxide gas is easily permeable, while electrolytes in liquid or powder form are not permeable, thereby preventing the deterioration of the composition containing the carbon dioxide removal component.

[0136] The average particle size of the above pores can be measured by magnifying the sample surface 2,500 times using a transmission electron microscope and an aberration-corrected transmission electron microscope, and then determining the pore size by measuring the major axis length among the surface pores identified within a randomly sampled range (width 10 μm or more, height 15 μm or more) in the measured image. The number of measurements is set to at least 10, and the average and maximum values ​​of the pore sizes obtained after measurement can be calculated.

[0137]

[0138] According to one embodiment of the present invention, the sealing container may comprise one or more selected from the group consisting of fluorine-based, epoxy-based, olefin-based, imide-based, and ester-based compounds. For example, the fluorine-based compound may comprise one or more selected from the group consisting of polytrifluoroethylene, polytetrafluoroethylene, polychlorotrifluoroethylene, polyhexafluoropropylene, polyvinylidene fluoride, polyvinyl fluoride, polyfluorinated ethylenepropylene, and perfluoroalkoxyalkanes. Specifically, the fluorine-based compound may comprise polytetrafluoroethylene, perfluoroalkoxyalkanes, or polyfluorinated ethylenepropylene.

[0139] In addition, the epoxy compound may be one or more selected from the group consisting of bisphenol type, such as bisphenol A type, bisphenol F type, bisphenol S type and their hydrodegeners; novolak type, such as phenol novolak type or cresol novolak type; nitrogen-containing cyclic type, such as triglycidyl isocyanurate type or hydantoin type; alicyclic type; aliphatic type; aromatic type, such as naphthalene type or biphenyl type; glycidyl type, such as glycidyl ether type, glycidylamine type, or glycidyl ester type; dicyclo type, such as dicyclopentadiene type; ester type; and ether ester type. Specifically, the epoxy compound may include pentaerythritol glycidyl ether containing four or more epoxy groups.

[0140] The above olefin compound may be one or more selected from the group consisting of polyethylene, polypropylene, and polybutene. Specifically, the polyolefin compound may include a thermoplastic compound such as a homopolymer or copolymer formed by polymerizing monomers such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, and 1-hexene. The homopolymer may be, for example, polyethylene, polypropylene, or polybutene, and specifically may include polypropylene.

[0141] The above olefin-based compound is chemically stable and impermeable to liquids and powders, while permeable to gases. However, since the physical stability and durability of a sealed container containing the olefin-based compound are not at a high level, a coating layer containing an epoxy-based compound may be formed on the surface of the sealed container containing the olefin-based compound to improve this. Additionally, it may be hydrophilically treated to improve contact with the external protective layer described later.

[0142] In addition, the imide-based polymer may comprise one or more selected from the group consisting of polyamic acid and polyamic acid ester. Specifically, the imide-based compound may include an imide-based compound formed using polyamic acid as a precursor, or a compound formed by imidizing at high temperature using poly(pyromellitic dianhydride-co-4,4'-oxydianiline) and an amic acid solution as precursors.

[0143] In addition, the ester compound may be one or more selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, and polyethylene naphthalate, and specifically, the ester compound may be polyethylene terephthalate.

[0144] The above-described sealed container may be impermeable to liquids or powders and permeable to carbon dioxide by including one or more selected from the group consisting of fluorine-based, epoxy-based, olefin-based, imide-based, and ester-based compounds.

[0145]

[0146] According to one embodiment of the present invention, the sealing container includes a receiving space, and the receiving space may further include an empty space in addition to the composition containing the carbon dioxide removal component. By including a specific proportion of empty space in addition to the carbon dioxide removal agent within the sealing container, the carbon dioxide removal agent of the present invention prevents the expansion pressure from being directly transmitted to the sealing container due to the empty space within the sealing container, even if the composition containing the carbon dioxide removal component expands as the carbon dioxide absorption reaction proceeds. This prevents the sealing container from breaking due to the expansion of the composition containing the carbon dioxide removal component.

[0147] According to one embodiment of the present invention, the carbon dioxide removal agent may satisfy the following Equation 1. More specifically, the empty space is calculated as the difference between the volume value (B) of the receiving space and the initial volume value (C) of the composition, and the volume value of the receiving space and the initial volume value of the composition may satisfy the following Equation 1.

[0148] [Equation 1]

[0149]

[0150] In the above Equation 1,

[0151] The above A is a carbon dioxide removal capacity value of a composition containing a carbon dioxide removal component expressed in weight% units, and

[0152] The above B is cm 3 It is a volume value of the accommodation space expressed in units,

[0153] The above C is cm 3 It is an initial volume value of a composition containing a carbon dioxide removal component expressed in units, and

[0154] The above D is g / cm² 3 It is the initial density value before the carbon dioxide removal reaction of a composition containing a carbon dioxide removal component expressed in units, and

[0155] The above D' is g / cm² 3 It is the density value after the carbon dioxide removal reaction of a composition containing a carbon dioxide removal component expressed in units.

[0156] In addition, in the above formula 1, D' / D may be 0.6 or more and 2.0 or less, and exemplarily, the D' / D value may be 0.60 or more, 0.65 or more, 0.70 or more, 0.75 or more, 0.80 or more, 0.85 or more, 0.90 or more, 0.95 or more, 1.00 or more, 2.00 or less, 1.95 or less, 1.90 or less, 1.85 or less, 1.80 or less, 1.75 or less, 1.70 or less, 1.65 or less, 1.60 or less, 1.55 or less, 1.50 or less, 1.45 or less, 1.40 or less, 1.35 or less, 1.30 or less, 1.25 or less, 1.20 or less, 1.15 or less, 1.10 or less, and 1.05 or less. Here, the density values ​​of D and D' in Equation 1 above may be densities measured at room temperature.

[0157] The initial volume (C) of the composition containing the carbon dioxide removal component must be equal to or lower than the receiving space (B), and this may vary depending on the carbon dioxide removal capacity (A) of the composition containing the carbon dioxide removal component, and Equation 1 represents the relationship between C and B. A to D and D' may each be unitless numbers of defined physical property values. Additionally, the carbon dioxide removal capacity value of the composition may be the weight gain rate of the composition, and for example, if the weight of the composition becomes 1.2 g after carbon dioxide removal based on 1 g of the composition, 0.2 g of carbon dioxide has been removed, and the removal capacity value or weight gain rate may correspond to 20 wt%.

[0158] The above-mentioned receiving space may include an empty space of 5% or more and 50% or less of the total volume of the above-mentioned receiving space. The empty space may vary depending on the removal capacity of the composition. For example, the above-mentioned receiving space may include an empty space of 5 volume% or more, 7 volume% or more, 9 volume% or more, 10 volume% or more, 12 volume% or more, 15 volume% or more, 17 volume% or more, 19 volume% or more, 20 volume% or more, 21 volume% or more, 23 volume% or more, 25 volume% or more, 27 volume% or more, 29 volume% or more, 30 volume% or more, 31 volume% or more, 33 volume% or more, 35 volume% or more, 50 volume% or less, 49 volume% or less, 47 volume% or less, 45 volume% or less, 44 volume% or less, 42 volume% or less, 40 volume% or less, 38 volume% or less, and 37 volume% or less, specifically, an empty space of 25 volume% or more and 42 volume% or less. As the composition containing the carbon dioxide removal component contained within the sealed container adsorbs and removes carbon dioxide, the composition containing the carbon dioxide removal component may gradually expand. In this case, if the receiving space includes the empty space within the specified numerical range, even if the composition containing the carbon dioxide removal component expands, the expansion pressure is not immediately transmitted to the sealed container due to the empty space within the sealed container, thereby preventing the sealing container from breaking due to the expansion of the composition containing the carbon dioxide removal component.

[0159] Considering the volume of the above empty space, the initial volume of the composition that can be contained in a sealed container may be 50 volume% or more, 52 volume% or more, 54 volume% or more, 56 volume% or more, 58 volume% or more, 60 volume% or more, 90 volume% or less, 89 volume% or less, 87 volume% or less, 85 volume% or less, 83 volume% or less, 81 volume% or less, 80 volume% or less, 78 volume% or less, 76 volume% or less, 74 volume% or less, 72 volume% or less, 70 volume% or less, 68 volume% or less, and 65 volume% or less. When a composition having the above initial volume is introduced into a sealed container, the sealed container is not broken by the expansion of the composition and can maintain excellent performance for a long time.

[0160] According to one embodiment of the present invention, the sealing container may have an elongation of 10% or more as measured based on the specimen specifications of ASTM D638, and may satisfy the relationship between the elongation and the removal capacity according to the following Equation 2.

[0161] [Equation 2]

[0162]

[0163] In the above Equation 2,

[0164] The above A is a carbon dioxide removal capacity value of a composition containing a carbon dioxide removal component expressed in weight% units, and

[0165] The above E is the elongation value of the sealed container expressed in % units, and

[0166] The above D is g / cm² 3 It is the initial density value before the carbon dioxide removal reaction of a composition containing a carbon dioxide removal component expressed in units, and

[0167] The above D' is g / cm² 3 It is the density value after the carbon dioxide removal reaction of a composition containing a carbon dioxide removal component expressed in units.

[0168] The above A, D, D', and E may each be a unitless number of defined physical property values.

[0169] The above elongation represents a characteristic that allows the sealed container to be maintained without cracking or breaking when the interior of the sealed container expands as the carbon dioxide removal reaction occurs within the sealed container; for example, in Equation 2 above, the value of A is 30 wt%, and the initial density D before the removal reaction is 1.00 g / cm³ 3 , density D' after the elimination reaction is 0.9 g / cm³ 3 In this case, the above elongation rate E can be calculated as 13%.

[0170] In addition, the elongation rate of the sealing container may, for example, be 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 100% or more, and specifically, 100% or more. When the elongation rate of the sealing container satisfies the above range, it can maintain excellent performance for a long time without breaking due to the expansion of the composition contained inside.

[0171] In addition, the sealed container of the present invention can simultaneously satisfy the numerical ranges of the empty space and the elongation rate. Even if the elongation rate is satisfied, if the numerical range of the empty space is not satisfied, the expansion inside the sealed container continues during the operation of the lithium secondary battery for a long time, causing the thickness of the sealed container to increase. This results in deviation from the cell specifications, which may lead to a decrease in battery efficiency.

[0172]

[0173] According to one embodiment of the present invention, the sealing container may further include an external protective layer on the outer surface of the sealing container, and the external protective layer may include an epoxy resin or a fluoropolymer. The external protective layer is disposed on the outside of the sealing container and, specifically, may be disposed in close contact with the outer surface of the sealing container. As described in the tubular type, the external protective layer may form a coating layer on the outer surface of the sealing container. Since the external protective layer forms a continuous phase as described above and is disposed in close contact with the outer surface of the sealing container as a continuous phase, it can prevent the sealing container from breaking or being destroyed by the expansion pressure of the composition containing the carbon dioxide removal component and can serve to prevent the penetration of the electrolyte. The sealing container may be manufactured by including the carbon dioxide removal component through a physical fastening method and then forming the external protective layer.

[0174] In addition, the following method can be used to manufacture a sealed container including the above-mentioned external protective layer.

[0175] First, a sealed container can be manufactured by first sealing three sides in a “C” shape using a film of one or more materials selected from the group consisting of the above-mentioned fluorine-based, epoxy-based, olefin-based, imide-based, and ester-based compounds, then injecting a composition containing the above-mentioned carbon dioxide removal component, and then sealing the last side through heat fusion. Subsequently, a sealed container with a protective layer formed on the outside can be manufactured by forming a coating layer containing an epoxy-based resin on the outer surface of the sealed container.

[0176] Alternatively, a sealed container may be manufactured by injecting a composition containing the carbon dioxide removal component into the interior of a tube having one side open, the tube containing one or more materials selected from the group consisting of the above-mentioned fluorine-based, epoxy-based, olefin-based, imide-based, and ester-based compounds, and sealing the open side using a stopper or the like. Subsequently, a coating layer containing an epoxy-based compound may be formed on the outer surface of the sealed container to finally manufacture a sealed container with a protective layer formed on the outside. The epoxy-based compound may be the same as or a different type from the epoxy-based compound that may be included in the sealed container described above.

[0177]

[0178] Method for manufacturing carbon dioxide remover

[0179] The present invention provides a method for manufacturing the carbon dioxide removal agent.

[0180] According to one embodiment of the present invention, the method for manufacturing a carbon dioxide removal agent may include the step of manufacturing a composition containing a carbon dioxide removal component (S1), the step of receiving the composition manufactured in step (S1) in a sealed container with a portion open (S2), and the step of sealing the portion open of the sealed container (S3).

[0181]

[0182] According to one embodiment of the present invention, the step (S1) of preparing a composition containing the carbon dioxide removal component may include a step (S1-1) of mixing 30 parts by weight or more and 99.995 parts by weight or less of an epoxy compound containing two or more epoxy groups and 0.005 parts by weight or more and less than 70 parts by weight of an amine compound, and a step (S1-2) of reacting the mixture mixed in the step (S1-1) at a temperature of 50°C or more and 150°C or less.

[0183] In addition, according to one embodiment of the present invention, the step (S1) of preparing a composition containing the carbon dioxide removal component may include: 30 parts by weight or more and 99.995 parts by weight or less of an epoxy compound containing one or more epoxy groups; and the step (S1-1') of mixing 0.005 parts by weight or more and less than 70 parts by weight of one or more compounds selected from the group consisting of quaternary ammonium salts, phosphonium salts, zeolites, metal-organic frameworks, metal halogen salts and metal oxides.

[0184] The above step (S1-1) is a step of mixing reactants to form a carbon dioxide removal agent, and is characterized by mixing a polyfunctional epoxy compound in an amount equal to or greater than that of an amine compound or a quaternary ammonium salt in order to increase the content of residual epoxy groups in the carbon dioxide removal agent and maintain the activating groups at a sufficient level in accordance with the purpose of the present invention. As previously explained, the amine compound may be mixed in an amount within the above numerical range to proceed with sufficient solidification. In addition, the quaternary ammonium salt may be mixed in an amount within the above numerical range to increase the capacity to adsorb carbon dioxide.

[0185]

[0186] According to one embodiment of the present invention, the step (S1-2) may be a step for proceeding with the formation of an activating group by reacting a polyfunctional epoxy compound with an amine compound or a quaternary ammonium salt, and the reaction may be carried out at a temperature of 50°C or higher, 60°C or higher, 70°C or higher, 80°C or higher, or 90°C or higher, and may also be carried out at a temperature of 150°C or lower, 140°C or lower, 130°C or lower, 120°C or lower, 110°C or lower, or 100°C or lower.

[0187] According to one embodiment of the present invention, the step (S1-2) may be performed for 2 hours or more, 3 hours or more, 4 hours or more, or 5 hours or more, and may also be performed for 10 hours or less, 9 hours or less, 8 hours or less, 7 hours or less, or 6 hours or less.

[0188] According to one embodiment of the present invention, the carbon dioxide remover manufactured through the steps of receiving the composition in a sealed container with a portion open (S2) and sealing the portion open of the sealed container (S3) may be manufactured differently depending on whether the sealed container is of the sealing type or the tube type. The sealing type may be manufactured by overlapping two sheets of a tape, film, or sheet of a specific material, sealing the remainder excluding the open portion—that is, the edge portion—in a “U” shape using a heat sealer, injecting a composition containing a carbon dioxide removal component, and then sealing the open portion again. Additionally, the sealing type may be manufactured by placing the composition containing the carbon dioxide removal component between the two films or sheets, and then sealing the edge portion of the film or sheet using an adhesive or curing it using an epoxy compound. Furthermore, the sealing type may be manufactured by placing the composition containing the carbon dioxide removal component between two tapes laminated with the material of the sealed container described above and an acrylic adhesive, and then sealing it by the acrylic adhesive placed on the inner surface of the tape.

[0189] In addition, the above-mentioned tubular shape can be manufactured by preparing a part of a specific material, namely a screw tube with one side open, injecting a composition containing a carbon dioxide removal component into the tube, and then sealing the open side using a stopper or the like. In addition, the above-mentioned tubular shape can be manufactured by injecting a composition containing a carbon dioxide removal component into a tubing with both ends open, and then heat-sealing both ends using a heat sealer.

[0190]

[0191] lithium secondary battery

[0192] The present invention provides a lithium secondary battery comprising the carbon dioxide removal agent.

[0193] According to one embodiment of the present invention, the lithium secondary battery comprises an electrode assembly, an electrolyte, and a secondary battery case containing the electrode assembly and the electrolyte, and the carbon dioxide removal agent may be included inside the secondary battery case. Specifically, the carbon dioxide removal agent may be included on the inner surface of the secondary battery case.

[0194] More specifically, when the secondary battery case is cylindrical, the carbon dioxide removal agent may be included in the internal space of the core where the electrode assembly is wound, in the form of a cylinder with a diameter smaller than the core diameter, or included in the upper or lower part of the case in the form of a cylinder having a diameter similar to the diameter of the electrode assembly, or included by being wound in the form of a sheet on the outer surface of the electrode assembly.

[0195] In addition, if the case of the secondary battery is a pouch type, the carbon dioxide removal agent may be included in a sheet form adjacent to the laminated surface of the electrode assembly, or included on the side of the electrode assembly in the form of a circular cylinder or a rectangular bar. Furthermore, the carbon dioxide removal agent may not be limited to the aforementioned forms and may be included in other forms at other locations. The electrode assembly may include a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode.

[0196]

[0197] According to one embodiment of the present invention, the positive electrode may comprise a positive electrode current collector and a positive electrode active material layer located on the positive electrode current collector.

[0198] According to one embodiment of the present invention, the positive current collector may include a highly conductive metal, and is not particularly limited as long as it facilitates the adhesion of the positive active material layer and is non-reactive within the voltage range of the battery. The positive current collector may be, for example, stainless steel, aluminum, nickel, titanium, calcined carbon, or aluminum or stainless steel surface treated with carbon, nickel, titanium, silver, etc. Additionally, the positive current collector may typically have a thickness of 3 μm to 500 μm, and may form fine irregularities on the surface of the current collector to increase the adhesion of the positive active material. It may be used in various forms, such as a film, sheet, foil, net, porous body, foam, nonwoven fabric, etc.

[0199] According to one embodiment of the present invention, the positive active material layer may include, together with the positive active material, a conductive material and a binder optionally as needed. In this case, the positive active material may be included in an amount of 80% to 99% by weight, more specifically 85% to 98.5% by weight, based on the total weight of the positive active material layer, and may exhibit excellent capacity characteristics within this range.

[0200] According to one embodiment of the present invention, the positive active material is LiCoO2, LiCoPO4, LiNiO2, Li x Ni a Co b M 1 c M 2 d O2(M 1 and M 2Each is independently selected from the group consisting of Al, Mn, Cu, Fe, V, Cr, Mo, Ga, B, W, Mo, Nb, Mg, Hf, Ta, La, Ti, Sr, Ba, Ce, F, P, S, and Y, and 0.9≤x≤1.1, 0 <a<1.0, 0<b<1.0, 0≤c<0.5, 0≤d<0.5, a+b+c+d=1이다.), LiMnO2, LiMnO3, LiMn2O3, LiMn2O4, LiMn 2-e M 3 e O2(M 3 ...is one or more selected from the group consisting of Co, Ni, Fe, Cr, Zn, and Ta, and 0.01≤e≤0.1), Li2Mn3M 4 O8(M 4 is one or more selected from the group consisting of Ci, Ni, Fe, Cu and Zn), and may be one selected from the group consisting of LiFePO4, Li2CuO2, LiV3O8, V2O5, Cu2V2O7 and lithium metal.

[0201] According to one embodiment of the present invention, the binder of the positive active material layer serves to improve adhesion between positive active material particles and adhesion between the positive active material and the current collector. Specific examples include polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinyl alcohol, polyacrylonitrile, polymethyl methacrylate, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, polytetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), sulfonated-EPDM, styrene butadiene rubber (SBR), fluororubber, polyacrylic acid, and polymers in which hydrogens thereof are substituted with Li, Na, or Ca, or various copolymers thereof, and one of these alone or a mixture of two or more may be used. The above binder may be included in an amount of 0.1% to 15% by weight relative to the total weight of the positive active material layer.

[0202] According to one embodiment of the present invention, the conductive material of the positive electrode active material layer is used to impart conductivity to the electrode, and in the battery being constructed, any material having electronic conductivity without causing chemical changes can be used without special limitations. Specific examples include graphite such as natural graphite or artificial graphite; carbon-based materials such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, thermal black, and carbon fibers; metal powder or metal fibers such as copper, nickel, aluminum, and silver; conductive tubes such as carbon nanotubes; conductive whiskers such as zinc oxide or potassium titanate; conductive metal oxides such as titanium oxide; or conductive polymers such as polyphenylene derivatives, and one of these alone or a mixture of two or more may be used. The conductive material may be included in an amount of 0.1% to 15% by weight based on the total weight of the positive electrode active material layer.

[0203] According to one embodiment of the present invention, the anode may be manufactured according to a conventional anode manufacturing method. Specifically, the anode may be manufactured by applying a composition for forming an anode active material layer, prepared by dissolving or dispersing the anode active material and, optionally, a binder, a conductive material, and a dispersant in a solvent, onto an anode current collector, followed by drying and rolling, or by casting the composition for forming an anode active material layer onto a separate support and then laminating the film obtained by peeling from the support onto an anode current collector.

[0204] According to one embodiment of the present invention, the solvent may be a solvent generally used in the relevant technical field, such as dimethyl sulfoxide (DMSO), isopropyl alcohol, N-methylpyrrolidone (NMP), dimethylformamide (DMF), acetone, or water, and one of these alone or a mixture of two or more may be used. The amount of solvent used is sufficient to dissolve or disperse the cathode active material, conductive material, binder, and dispersant, taking into account the coating thickness of the slurry and the manufacturing yield, and to have a viscosity that can exhibit excellent thickness uniformity when coated for cathode manufacturing thereafter.

[0205] According to one embodiment of the present invention, the cathode may comprise a cathode current collector and a cathode active material layer located on the cathode current collector.

[0206] According to one embodiment of the present invention, the negative electrode current collector is not particularly limited as long as it has high conductivity without causing chemical changes in the battery, and for example, copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper or stainless steel surface-treated with carbon, nickel, titanium, silver, etc., and aluminum-cadmium alloy may be used. In addition, the negative electrode current collector may typically have a thickness of 3 μm to 500 μm, and, similar to the positive electrode current collector, fine irregularities may be formed on the surface of the current collector to strengthen the bonding strength of the negative electrode active material. For example, it may be used in various forms such as a film, sheet, foil, net, porous body, foam, nonwoven fabric, etc.

[0207] According to one embodiment of the present invention, the negative electrode active material layer may optionally include a binder and a conductive material together with the negative electrode active material.

[0208] According to one embodiment of the present invention, the negative electrode active material may be a compound capable of reversible intercalation and deintercalation of lithium. Specific examples include carbonaceous materials such as artificial graphite, natural graphite, graphitized carbon fiber, and amorphous carbon; metallic compounds capable of alloying with lithium, such as Si, Al, Sn, Pb, Zn, Bi, In, Mg, Ga, Cd, Si alloy, Sn alloy, or Al alloy; metal oxides capable of doping and dedoping lithium, such as SiOβ (0<β<2), SnO2, vanadium oxide, and lithium vanadium oxide; or composites comprising the metallic compound and the carbonaceous material, such as Si-C composites or Sn-C composites, and any one or more of these may be used. Additionally, a metallic lithium thin film may be used as the negative electrode active material. Furthermore, the carbon material may include low-crystallinity carbon and high-crystallinity carbon. Representative examples of low-crystallinity carbon include soft carbon and hard carbon, while representative examples of high-crystallinity carbon include amorphous, plate-like, flake-like, spherical, or fibrous natural or artificial graphite, Kish graphite, pyrolytic carbon, mesophase pitch-based carbon fiber, meso-carbon microbeads, mesophase pitches, and high-temperature calcined carbon such as petroleum or coal tar pitch-derived cokes. The above-mentioned cathode active material may be included in an amount of 80% to 99% by weight based on the total weight of the cathode active material layer.

[0209] According to one embodiment of the present invention, the binder of the negative electrode active material layer is a component that assists in the bonding between the conductive material, the active material, and the current collector, and is typically added in an amount of 0.1% to 10% by weight based on the total weight of the negative electrode active material layer. Examples of such binders include polyvinylidene fluoride (PVDF), polyvinyl alcohol, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, polytetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), sulfonated-EPDM, styrene-butadiene rubber, nitrile-butadiene rubber, fluororubber, and various copolymers thereof.

[0210] According to one embodiment of the present invention, the conductive material of the negative electrode active material layer may be added in an amount of 10% by weight or less, preferably 5% by weight or less, based on the total weight of the negative electrode active material layer, as a component for further improving the conductivity of the negative electrode active material. Such conductive material is not particularly limited as long as it has conductivity without causing chemical changes in the battery, and for example, graphite such as natural graphite or artificial graphite; carbon black such as acetylene black, ketjen black, channel black, furnace black, lamp black, thermal black; conductive fibers such as carbon fibers or metal fibers; fluorinated carbon; metal powder such as aluminum or nickel powder; conductive whiskers such as zinc oxide or potassium titanate; conductive metal oxides such as titanium oxide; conductive materials such as polyphenylene derivatives may be used.

[0211] According to one embodiment of the present invention, the cathode may be manufactured by applying and drying a composition for forming a cathode active material layer, prepared by dissolving or dispersing a cathode active material and optionally a binder and a conductive material in a solvent, onto a cathode current collector, or by casting the composition for forming a cathode active material layer onto a separate support and then laminating the film obtained by peeling from the support onto a cathode current collector.

[0212] According to one embodiment of the present invention, the separator separates the negative electrode and the positive electrode and provides a pathway for the movement of lithium ions. It can be used without special limitations as long as it is typically used as a separator in a lithium secondary battery, and it is particularly desirable that it has low resistance to the movement of electrolyte ions and excellent electrolyte moisture retention capacity. Specifically, a porous polymer film, such as a porous polymer film made of a polyolefin-based polymer like an ethylene homopolymer, a propylene homopolymer, an ethylene / butene copolymer, an ethylene / hexene copolymer, and an ethylene / methacrylate copolymer, or a laminated structure of two or more layers thereof may be used. In addition, a conventional porous nonwoven fabric, such as a nonwoven fabric made of high-melting-point glass fibers or polyethylene terephthalate fibers, may be used. Furthermore, a coated separator containing a ceramic component or a polymer material may be used to ensure heat resistance or mechanical strength, and it may optionally be used in a single-layer or multi-layer structure.

[0213] According to one embodiment of the present invention, the electrolyte may include an organic liquid electrolyte, an inorganic liquid electrolyte, a solid polymer electrolyte, a gel-type polymer electrolyte, a solid inorganic electrolyte, a molten inorganic electrolyte, etc., which are usable when manufacturing a lithium secondary battery, but are not limited thereto. As a specific example, the electrolyte may include an organic solvent and a lithium salt.

[0214] According to one embodiment of the present invention, the organic solvent may be used without special limitations as long as it can serve as a medium through which ions involved in the electrochemical reaction of the battery can move. Specifically, the organic solvent may be an ester-based solvent such as methyl acetate, ethyl acetate, γ-butyrolactone, or ε-caprolactone; an ether-based solvent such as dibutyl ether or tetrahydrofuran; a ketone-based solvent such as cyclohexanone; or an aromatic hydrocarbon-based solvent such as benzene or fluorobenzene. Carbonate-based solvents such as dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (MEC), ethyl methyl carbonate (EMC), ethylene carbonate (EC), and propylene carbonate (PC); alcohol-based solvents such as ethyl alcohol and isopropyl alcohol; nitriles such as R-CN (where R is a straight-chain, branched, or cyclic hydrocarbon group having 2 to 20 carbon atoms and may include a double bond, a directional ring, or an ether bond); amides such as dimethylformamide; dioxolanes such as 1,3-dioxolane; or sulfolanes may be used. Among these, a carbonate-based solvent is preferred, and a mixture of a cyclic carbonate (e.g., ethylene carbonate or propylene carbonate, etc.) having high ionic conductivity and high dielectric constant that can improve the charge / discharge performance of the battery, and a low-viscosity linear carbonate-based compound (e.g., ethylmethyl carbonate, dimethyl carbonate or diethyl carbonate, etc.) is more preferred.

[0215] According to one embodiment of the present invention, the lithium salt may be used without special limitations as long as it is a compound capable of providing lithium ions used in a lithium secondary battery. Specifically, as the anion of the lithium salt, F - , Cl - , Br - , I - , NO3 - , N(CN)2 - , BF4 - , CF3CF2SO3 - , (CF3SO2)2N - , (FSO2)2N - , CF3CF2(CF3)2CO - , (CF3SO2)2CH - , (SF5)3C - , (CF3SO2)3C - , CF3(CF2)7SO3 - , CF3CO2 - , CH3CO2 - , SCN - and (CF3CF2SO2)2N - The lithium salt may be at least one selected from the group consisting of LiPF6, LiClO4, LiAsF6, LiBF4, LiSbF6, LiAlO4, LiAlCl4, LiCF3SO3, LiC4F9SO3, LiN(C2F5SO3)2, LiN(C2F5SO2)2, LiN(CF3SO2)2, LiCl, LiI, or LiB(C2O4)2. It is preferable to use the lithium salt within the range of 0.1 M to 2.0 M. When the concentration of the lithium salt falls within the above range, the electrolyte has appropriate conductivity and viscosity, so it can exhibit excellent electrolyte performance and lithium ions can move effectively.

[0216] According to one embodiment of the present invention, in addition to the electrolyte components, the electrolyte may further include one or more additives for the purpose of improving the lifespan characteristics of the battery, suppressing the decrease in battery capacity, and improving the discharge capacity of the battery, such as, for example, a haloalkylene carbonate-based compound such as difluoroethylene carbonate, pyridine, triethylphosphite, triethanolamine, cyclic ether, ethylene diamine, n-glyme, triamide hexaphosphate, nitrobenzene derivative, sulfur, quinone imine dye, N-substituted oxazolidinone, N,N-substituted imidazolidine, ethylene glycol dialkyl ether, ammonium salt, pyrrole, 2-methoxyethanol, or aluminum trichloride. In this case, the additive may be included in an amount of 0.1% to 5% by weight based on the total weight of the electrolyte.

[0217]

[0218] A lithium secondary battery containing a carbon dioxide removal agent according to the present invention exhibits excellent stability by adsorbing gases generated during charging and discharging, thereby preventing the breakdown of the seal of the secondary battery case due to an increase in internal pressure of the secondary battery. Therefore, it is useful in fields such as portable devices like mobile phones, laptop computers, and digital cameras, and electric vehicles such as hybrid electric vehicles (HEVs) and electric vehicles (EVs).

[0219] The lithium secondary battery according to the present invention can be used not only as a battery cell used as a power source for a small device, but can also preferably be used as a unit cell in a medium-to-large battery module comprising a plurality of battery cells.

[0220] Accordingly, according to one embodiment of the present invention, a battery module including the lithium secondary battery as a unit cell and a battery pack including the same are provided.

[0221] According to one embodiment of the present invention, the battery module or battery pack may be used as a power source for one or more medium-to-large devices, including a power tool; an electric vehicle (EV), a hybrid electric vehicle, and a plug-in hybrid electric vehicle (PHEV); or a power storage system.

[0222]

[0223] Hereinafter, embodiments of the present invention are described in detail so that those skilled in the art can easily implement the invention. However, the present invention may be embodied in various different forms and is not limited to the embodiments described herein.

[0224]

[0225] <Preparation Example>

[0226] Preparation Example 1

[0227] Composition 1 containing a solid carbon dioxide removal component was prepared by thoroughly mixing 95 parts by weight of trimethylolpropane triglycidyl ether (Kukdo Chemical Co., YH-300) as a polyfunctional epoxy compound and 5 parts by weight of 2,4,6-tris(dimethylaminomethyl)phenol (Sigma Aldrich, DMP30) as an amine compound, and reacting the mixture in an oven at 90°C for 6 hours.

[0228]

[0229] Preparation Example 2

[0230] Composition 2 containing a liquid carbon dioxide removal component was prepared by carrying out the same procedure as in Preparation Example 1, except that 5 parts by weight of triethylbenzylammonium chloride (TCI Chemical) was mixed as a quaternary ammonium salt instead of the amine compound 2,4,6-tris(dimethylaminomethyl)phenol (Sigma Aldrich, DMP30) in Preparation Example 1, and the mixture was not reacted in an oven at 90°C for 6 hours. Even if some solid ammonium salt remained undissolved, it was used in a dispersed state after stirring without separate purification.

[0231]

[0232] Preparation Example 3

[0233] Composition 3 containing a liquid carbon dioxide removal component was prepared by carrying out the same procedure as in Preparation Example 2, except that 2-ethylhexyl glycidyl ether (TCI Chemical Co., Ltd.) was used as a monofunctional epoxy compound instead of trimethylolpropane triglycidyl ether as a polyfunctional epoxy compound in Preparation Example 2.

[0234]

[0235] Preparation Example 4

[0236] Composition 4 containing a liquid carbon dioxide removal component was prepared by carrying out the same procedure as in Preparation Example 2 above, except that tetrabutylphosphonium tetraphenylborate (TCI Chemical Co.) was used as the quaternary phosphonium salt instead of triethylbenzylammonium chloride as the quaternary ammonium salt in Preparation Example 2 above.

[0237]

[0238] <Examples and Comparative Examples>

[0239] Example 1

[0240] A fluorinated ethylene propylene (FEP) film with a thickness of 100 μm was cut to a size of 5 cm x 5 cm, and then three sides were heat-sealed in a “U” shape using a heat sealer (SK-510, Sambotech Co.) to produce a pouch-shaped sealed container with one side open. 0.1 g of Composition 2, which contains the carbon dioxide removal component prepared in Preparation Example 2, was injected into the sealed container, and the remaining side was sealed to produce a carbon dioxide removal agent in a sealed container in which a continuous phase of fluorinated ethylene propylene was formed.

[0241]

[0242] Example 2

[0243] A polypropylene (PP) film with a thickness of 100 μm was cut to a size of 5 cm x 5 cm, and then three sides were heat-sealed in a “U” shape using a heat sealer (SK-510, Sambotech Co., Ltd.). Then, 0.1 g of composition 2 containing the carbon dioxide removal component prepared in Preparation Example 2 was injected, and the remaining side was heat-sealed to deposit the composition containing the carbon dioxide removal component in a sealed container. Subsequently, corona discharge was applied to both sides of the heat-sealed film-shaped sealed container containing the carbon dioxide removal component at an output intensity of 500 W and a film transport speed of 12 m / min. Subsequently, a solution was prepared by mixing 95 parts by weight of pentaerythritol glycidyl ether (Showa Denko, Shofree) and 5 parts by weight of 2,4,6-tris(dimethylaminomethyl)phenol (Sigma Aldrich, DMP30), and then the outer surface of the sealed container was sufficiently soaked with the solution. After placing it on the top of the release treatment surface of a release film (MRF-38, Mitsubishi Polyester), it was cured in an oven at 100°C for 1 hour, then sufficiently soaked again with the solution, and then cured in an oven at 100°C for 16 hours to produce a carbon dioxide removal agent in which a continuous phase of the epoxy cured product was formed as an outer protective layer of the sealed container.

[0244]

[0245] Example 3

[0246] 0.2 g of composition 2 containing the carbon dioxide removal component prepared in Preparation Example 2 was injected into a 1.5 mL polypropylene screw tube (Sterile, 2231-S0), and the composition containing the carbon dioxide removal component was sealed with a cap. Subsequently, a solution was prepared by mixing 95 parts by weight of pentaerythritol glycidyl ether (Showa Denko, Shofree) and 5 parts by weight of 2,4,6-tris(dimethylaminomethyl)phenol (Sigma Aldrich, DMP30), and then the outer surface of the sealed tube was sufficiently soaked with the solution. Then, the sealed cap was placed upside down on the top of the release treatment surface of the release film (MRF-38, Mitsubishi Polyester) so that it was spaced apart from the bottom, and then cured in an oven at 100°C for 1 hour. After that, the tube was sufficiently soaked in the solution again and then cured in an oven at 100°C for 16 hours to produce a carbon dioxide removal agent in which a continuous phase of the epoxy cured product was formed as an outer protective layer of the sealed container.

[0247]

[0248] Example 4

[0249] A circular tubing made of fluorinated ethylene propylene (FEP) material with a thickness of 0.5 mm, an inner diameter of 2.0 mm, and an outer diameter of 3.0 mm was cut to 4.5 cm, and a rod made of FEP material with an outer diameter of 2.0 mm was cut to 0.5 cm and inserted into one end of the tubing so that the end of the rod aligned with the end of the tubing. The end of the tubing into which the rod was inserted was heated with a heat gun set to 400 ℃ to heat-fuse the rod and the tubing so that a continuous phase of the FEP polymer components was formed. Subsequently, Composition 2 containing the carbon dioxide removal component prepared in Preparation Example 2 was injected into the tubing at a rate of 0.06 g. Subsequently, a rod of the same material and specifications as the rod made of the above FEP material was cut to 1.3 cm, and the cut rod was inserted into the remaining unheat-fused end of the tubing containing the above composition 2 so that the ends of the rod and the tubing aligned, and the rod and the tubing were heat-fused by heating with a heat gun set to 400 ℃, thereby producing a carbon dioxide removal agent in which a composition containing a carbon dioxide removal component was supported in a sealed container in which a continuous phase of FEP was formed.

[0250] In addition, since the length of the tubing not filled by the rod (accommodation space) is measured as 2.7 cm and the length filled by composition 2 is 1.8 cm and the cross-sectional area of ​​the tubing is the same, the volume% filled by composition 2 within the accommodation space inside the sealed container is calculated to be about 67 volume% and the empty space is calculated to be about 33 volume%.

[0251]

[0252] Example 5

[0253] A carbon dioxide removal agent was prepared by carrying out the same procedure as in Example 4 above, except that tubing and rods made of perfluoroalkoxyalkan (PFA) material were used, in which a composition containing a carbon dioxide removal component was supported in a continuous-phase sealed container made of PFA material.

[0254]

[0255] Example 6

[0256] A carbon dioxide removal agent was prepared by carrying a composition containing a carbon dioxide removal component in a continuous phase sealed container in which PTFE and PFA were heat-fused, by carrying out the same procedure as in Example 4, except that tubing made of polytetrafluoroethylene (PTFE) and a rod made of perfluoroalkoxyalkane (PFA) were used.

[0257]

[0258] Example 7

[0259] A carbon dioxide removal agent containing a composition containing a carbon dioxide removal component was prepared by carrying out the same procedure as in Example 1, except that instead of composition 2, 0.1 g of molecular sieve 3A (Molecular sieve 3A 1 / 16 in. rod, Daejeong Hwakum) was dried at 200°C for 1 day and then cooled at room temperature for 10 minutes before injection.

[0260]

[0261] Example 8

[0262] A carbon dioxide removal agent containing a composition containing a carbon dioxide removal component was prepared by carrying out the same procedure as in Example 1, except that composition 1 (0.1 g) containing the carbon dioxide removal component prepared in Preparation Example 1 was injected instead of composition 2.

[0263]

[0264] Example 9

[0265] A carbon dioxide removal agent containing a composition containing a carbon dioxide removal component was prepared by carrying out the same procedure as in Example 1, except that composition 3 (0.1 g) containing the carbon dioxide removal component prepared in Preparation Example 3 was injected instead of composition 2.

[0266]

[0267] Example 10

[0268] A carbon dioxide removal agent containing a composition containing a carbon dioxide removal component was prepared by carrying out the same procedure as in Example 1, except that composition 4 (0.1 g) containing the carbon dioxide removal component prepared in Preparation Example 4 was injected instead of composition 2.

[0269]

[0270] Example 11

[0271] A carbon dioxide removal agent containing a composition containing a carbon dioxide removal component was prepared by carrying out the same procedure as in Example 3, except that powdered composition 1 (0.2 g) containing the carbon dioxide removal component prepared in Preparation Example 1 was injected instead of composition 2, and cured only once in an oven at 95°C for 16 hours.

[0272]

[0273] Comparative Example 1

[0274] 0.1g of only composition 1 containing the carbon dioxide removal component prepared in Preparation Example 1 above was used without a separate sealed container.

[0275]

[0276] Comparative Example 2

[0277] 0.1g of composition 2 containing the carbon dioxide removal component prepared in Preparation Example 2 above was used without a separate sealed container.

[0278]

[0279] Comparative Example 3

[0280] As a liquid material, polytetrafluoroethylene (PTFE) powder with an average particle size of 8 μm and the powder of Composition 1 containing the carbon dioxide removal component prepared in Preparation Example 1 were added in a weight ratio of 1:1, and then mixed at room temperature for 10 minutes to prepare a carbon dioxide removal agent, and 0.1 g was used.

[0281]

[0282] Comparative Example 4

[0283] A carbon dioxide removal agent containing a composition containing a carbon dioxide removal component in a sealed container was prepared by carrying out the same procedure as Comparative Example 3, except that Composition 2 containing the carbon dioxide removal component prepared in Preparation Example 2 was used instead of Composition 1, and 0.1g of the composition containing the carbon dioxide removal component was used.

[0284]

[0285] Comparative Example 5

[0286] A solution was prepared by mixing 95 parts by weight of pentaerythritol glycidyl ether (Showa Denko, Shofree) and 5 parts by weight of 2,4,6-tris(dimethylaminomethyl)phenol (Sigma Aldrich, DMP30). Then, about 0.15 g of Composition 1, which contains a carbon dioxide removal component and is shaped into a circular disc with a diameter of 1 cm and a height of 0.15 cm in the same manner as in Preparation Example 1, was sufficiently soaked in the prepared solution and cured in an oven at 100°C for 1 hour. Afterward, the solution was sufficiently soaked again and cured in an oven at 100°C for 16 hours to produce a carbon dioxide removal agent in which a continuous phase of the epoxy cured product is formed as an external protective layer of a sealed container and there is no separate empty space inside.

[0287]

[0288] Comparative Example 6

[0289] After preparing a screw tube made of polytetrafluoroethylene (PTFE) with a 2 mL specification (Korea Science, F1057-005), 0.2 g of composition 1 containing the carbon dioxide removal component prepared in Preparation Example 1 was injected into the screw tube, and the tube cap was closed and sealed to produce a carbon dioxide removal agent in which the PTFE is physically bound without forming a continuous phase.

[0290]

[0291] Comparative Example 7

[0292] A carbon dioxide removal agent containing a composition containing a carbon dioxide removal component was prepared by carrying out the same procedure as in Example 4 above, except that tubing made of polyethylene (PE) material with an outer diameter of 4 mm and an inner diameter of 2 mm and a rod with an outer diameter of 2 mm were used, 0.04 g of composition 2 containing the carbon dioxide removal component prepared in Preparation Example 2 was used, and a heat gun was set to 260 ℃.

[0293]

[0294] Experimental Example 1 - Measurement of Electrolyte Discoloration and Carbon Dioxide Removal Amount

[0295] Two aluminum pouches (manufactured by DNP, EL408PH, 500) were cut to a size of 13 cm x 10 cm, and three sides were heat-sealed in a “U” shape to form a pouch-shaped pouch with one side open. Subsequently, the carbon dioxide remover prepared in the above examples and comparative examples, 40 cc of carbon dioxide, and 3 cc of electrolyte (solvent: EC / DMC / DEC=25wt% / 50wt% / 25wt%, salt: LiPF6=1.0M, additive: VC=2wt%) were injected into the pouch, and the remaining side was heat-sealed to produce a completely sealed pouch. The amount of carbon dioxide removal component used was the specification described in the above examples and comparative examples, and 0.1 g was used unless otherwise noted. The initial volume (A) of the pouch prepared above was measured at room temperature, and subsequently, after storing the completely sealed pouch at 60°C for 45 days and cooling the stored pouch at room temperature for 120 minutes, the change in volume (AB) of the pouch at room temperature (B) was measured, and the change in volume per weight of the carbon dioxide removal component ((AB) / C), calculated by dividing the change in volume by the weight (C) of the carbon dioxide removal component introduced into the pouch, was calculated in cm 3 The values ​​are shown in Table 1 in units of / g. When measuring the volume change, sealed blank samples containing the same electrolyte and carbon dioxide were prepared, except that the carbon dioxide removal agent was not included. If a volume change occurred under the same storage conditions, it was corrected by reflecting it in the volume change amount. For example, if the volume change of the blank sample is (-)0.2cm 3 and the volume change of the sample in the experimental example is (-)10.2 cm 3 In this case, correcting for this, the change in sample volume is (-)10.0 cm 3It was calculated as such. In addition, the above pouch was opened to check the color change of the internal electrolyte, and the results of the check are shown in Table 1. The color change of the electrolyte was indicated by comparing it with the color of the electrolyte when the above blank sample was opened: ◎ if there was no discoloration, ○ if the discoloration was slight and transparent, and X if discoloration occurred and the electrolyte became opaque, turning brown to black.

[0296] Distinctive electrolyte discoloration * Carbon dioxide removal amount (cm²) 3 / g)**Example 1 ○148 Example 2 ◎75 Example 3 ◎45 Example 4 ◎150 Example 5 ○150 Example 6 ○147 Example 7 ○15 Example 8 ○95 Example 9 ○68 Example 10 ○15 Example 11 ◎35 Comparative Example 1 X(-)49 Comparative Example 2 X(-)50 Comparative Example 3 X(-)43 Comparative Example 4 X(-)45 Comparative Example 5 X8 Comparative Example 6 X60 Comparative Example 7 X135

[0297] * Degree of discoloration: No change-◎, Slight change-○, Brown discoloration-X** Indicated by a (-) value if the pouch volume has expanded compared to the initial size.

[0298]

[0299] Referring to Table 1 above, in the case of Examples 1 to 11 using a carbon dioxide removal agent containing a composition containing a carbon dioxide removal component in a continuous phase sealed container having a receiving space, it can be confirmed that contact with the electrolyte is effectively blocked to prevent discoloration, and the amount of carbon dioxide removed is also at an excellent level.

[0300] On the other hand, in Comparative Examples 1 and 2, which used only a composition containing a carbon dioxide removal component without including a sealing container, and Comparative Examples 3 and 4, which used a mixture of a composition containing a carbon dioxide removal component and a micromaterial, discoloration occurred because contact with the electrolyte was not blocked, and the carbon dioxide removal efficiency was reduced, resulting in a carbon dioxide removal amount inferior to that of the example. Furthermore, in Comparative Example 5, which did not provide a separate empty space even though a sealing container was included, and Comparative Example 6, where the sealing container was not a continuous phase, a small amount of carbon dioxide removal was performed, but discoloration due to contact with the electrolyte eventually occurred, resulting in a carbon dioxide removal amount inferior to that of the example. Additionally, in Comparative Example 7, which used PE tubing as a sealing container, the sealing container formed a continuous phase, and the carbon dioxide removal amount was equivalent to that of the example; however, because the electrolyte blocking characteristics were insufficient compared to fluoropolymer materials, discoloration of the electrolyte occurred, confirming that the carbon dioxide removal efficiency would decrease with long-term use.

[0301]

[0302] Experimental Example 2 - Evaluation of Battery Characteristics

[0303] We measured whether battery performance degradation occurred as a carbon dioxide removal agent was introduced into the battery.

[0304]

[0305] Cell manufacturing method

[0306] As a method for manufacturing a cell for evaluation, raw materials were prepared by punching out the anode and cathode to a uniform size and cutting the separator. (Anode: 30 x 42 mm, Cathode: 31 x 43 mm, Separator: 35 x 46 mm) The raw materials, punched out and cut to a uniform size, were arranged so that the separator was positioned between the anode and cathode, and with the cathode positioned at the top, they were fixed in place through a lamination process under conditions of a pressure of 410 kgf, a time of 8 sec, and a temperature of 84 ℃ to prevent movement.

[0307] Aluminum and nickel leads (width: 5.0 mm, length: 33.0 mm, thickness: 0.1 mm) were welded to the exposed portions of the positive and negative electrodes, respectively, to allow current and voltage to be applied to the manufactured cell. Subsequently, a pouch was cut to a width of 100 mm and a length of 120 mm to accommodate the laminated electrodes and form a cell. The laminated electrodes were placed inside the cut pouch, and one side was sealed by folding the top and bottom in half to a width of 100 mm and a length of 60 mm. Then, two sides were sealed by heat-fusion sealing the left and top tab sections at 180°C. Finally, a cell was manufactured with three sides sealed and one right side open.

[0308] To activate the cell, 250 µL of electrolyte was injected through the right side of the open pouch, and the cell was completely sealed using 180°C heat fusion sealing. Stabilization was performed for more than 10 hours under 25°C conditions to ensure that the injected electrolyte could properly wet the electrodes and separator inside the cell. Subsequently, the cell was charged to a State of Charge (SOC) of 30% using a PNE 5V / 0.5A charger / discharger under a current condition of 0.1C. Afterward, the cell was removed from the charger / discharger, the gas pocket portion of the pouch was cut off by approximately 1 cm, and the carbon dioxide removal agent of the above example or comparative example was injected into the space that does not come into direct contact with the electrode. The open side was then fused and the cell was sealed again. Through the above manufacturing process, the shape of the cell with the applied carbon dioxide removal agent was completed.

[0309]

[0310] Cell evaluation method

[0311] The evaluation method for the cell containing the carbon dioxide removal agent involved checking the cell's capacity and resistance as initial performance, and comparing the rate of change relative to the initial performance after 100 charge / discharge cycles at a temperature of 45 ℃ to check for performance degradation of the cell due to the application of the carbon dioxide removal agent.

[0312] The Hybrid Pulse Power Characterization (HPPC) method was utilized to evaluate the initial cell characteristics. Cells manufactured using a PNE 5V / 0.5A charger / discharger were subjected to three charge / discharge cycles under conditions of 0.33C current and 25°C temperature, with the third discharge capacity used as the initial capacity. Resistance was calculated by measuring the voltage change (ΔV) over a 0-10 second period under conditions of 50% SOC and 2.5C current (A). (R=ΔV / A)

[0313] The cells for which the initial evaluation was completed were charged and discharged at a temperature of 45°C with a current of 0.33C. After every 100 charge and discharge cycles, the discharge capacity was confirmed by HPPC re-measurement at room temperature of 25°C and is shown in Table 2. As a criterion for determining the degradation of cell performance caused by the carbon dioxide removal agent, the results of blank cells manufactured and evaluated using the same method as above, except that the carbon dioxide removal agent was not introduced, were compared with the examples and comparative examples in which the carbon dioxide removal agent was introduced.

[0314]

[0315] Classification HPPC Capacity (mAh) after 100 charge / discharge cycles Capacity degradation rate compared to blank cell Blank cell 45.6 - Example 445.5 (-)0.2% Example 545.3 (-)0.7% Comparative Example 241.1 (-)10%

[0316] Referring to Table 2 above, it can be confirmed that Examples 4 and 5, which used a carbon dioxide removal agent containing a composition including a carbon dioxide removal component in a continuous phase sealed container having a receiving space according to the present invention, had superior HPPC capacity compared to Comparative Example 2, which does not include a sealed container, and the capacity reduction rate was also lower compared to Comparative Example 2.

[0317]

[0318] Experimental Example 3 - Ratio of Epoxy Compound and Quaternary Ammonium Salt

[0319] The ratio of the epoxy compound and the quaternary ammonium salt was adjusted, and experiments on the carbon dioxide removal capacity according to the said ratio were conducted. Carbon dioxide gas was injected into a pouch (DNP) containing a composition containing a carbon dioxide removal component, which was a mixture of trimethylolpropane triglycidyl ether (Kukdo Chemical, YH-300) as a polyfunctional epoxy compound and triethylbenzylammonium chloride (BAC) (Sigma-Aldrich) as a quaternary ammonium salt. The pouch was then sealed, and the volume of carbon dioxide removal per gram of the composition containing the carbon dioxide removal component was measured by the change in volume under a temperature condition of 60°C. The measurement results are shown in Figures 4 and 5.

[0320] Figure 4 shows the amount of carbon dioxide removed according to the content of quaternary ammonium salt, measured at intervals of 1 day, 6 days, 12 days, and 40 days. Figure 5 shows the amount of carbon dioxide removed over time according to the content of quaternary ammonium salt. Referring to Figures 4 and 5, it can be confirmed that when the content of quaternary ammonium salt is 0.005 wt% or less, the maximum removal capacity of carbon dioxide does not reach 40 cc / g and the carbon dioxide removal rate is considerably slow, thus indicating a decrease in carbon dioxide removal efficiency. Additionally, when the content of quaternary ammonium salt is 70 wt% or more, the carbon dioxide removal rate is relatively good, but since the maximum removal capacity does not reach 20 cc / g, it can be confirmed that the carbon dioxide removal efficiency is also low.

[0321]

[0322] Experimental Example 4 - Internal packing rate of carbon dioxide removal component

[0323] The volume of the carbon dioxide removal component increases after the carbon dioxide removal reaction, and assuming that all of the carbon dioxide removal component reacted with carbon dioxide, the volume increase rate (R) is expressed by Equation 3 below.

[0324] [Equation 3]

[0325] R = V1 / V0= M1*D0 / (M0*D1) = (M0+M CO2 )*D0 / (M0*D1)

[0326]

[0327] In the above Equation 3, the definition of each symbol is as follows.

[0328] R: Volume increase rate of carbon dioxide removal component

[0329] V0: Initial volume of carbon dioxide removal component,

[0330] V1: Volume of product after carbon dioxide removal reaction of carbon dioxide removal component,

[0331] M0: Initial weight of carbon dioxide removal component,

[0332] M1: Weight of the product after the carbon dioxide removal reaction of the carbon dioxide removal component,

[0333] M CO2 : Weight of carbon dioxide reacted with carbon dioxide removal components,

[0334] D0: Density of carbon dioxide removal component,

[0335] D1: Density of the product after the carbon dioxide removal reaction of the carbon dioxide removal component.

[0336]

[0337] In addition, assuming that all carbon dioxide removal components react with carbon dioxide, the filling rate (F) of the carbon dioxide removal component that can fill the internal space can be expressed as the reciprocal of the volume increase rate (R) of the carbon dioxide removal component, as shown in Equation 4 below.

[0338] [Equation 4]

[0339] F = 1 / R

[0340]

[0341] Equation 1 for deriving the empty space ratio of the present specification can be derived by combining Equations 3 and 4. In Equation 1, C / B represents the volume value of the removed component relative to the volume of the receiving space, and signifies the filling rate (F). The right-hand side of Equation 1 ((100 / (100+A))×(D' / D)) can be expressed as the reciprocal of the volume increase rate (1 / R).

[0342] The volume increase rate (R) was measured using Composition 2, which contains the carbon dioxide removal component prepared in Preparation Example 2, as the carbon dioxide removal component, and the change in internal volume after the carbon dioxide removal reaction according to the initial filling rate was compared. Specifically, circular tubing with the same cross-sectional area was used so that the change in length of the filled carbon dioxide removal component could be converted into a change in volume. Except for the carbon dioxide removal agent prepared in the same manner as Example 5 and evaluated for 30 days at 60°C without using an electrolyte, the average volume increase rate (R) of the carbon dioxide removal component obtained by measuring three times in the same manner as Experimental Example 1 is shown in Table 3 below.

[0343]

[0344] Classification (Number of Times) Carbon Dioxide Removal Component Packing Length (mm) Length After Carbon Dioxide Removal Reaction (mm) Volume Increase Rate (R) #1 17.5 19.5 1.11 #2 17.2 19.5 1.13 #3 17.0 19.3 1.14 Average 17.2 19.4 1.13

[0345] Referring to Table 3 above, it can be seen that the average value of the volume increase rate (R) is 1.13. Therefore, assuming that all of the carbon dioxide removal components react with carbon dioxide, the filling rate F (=1 / R) that can fill the internal space is calculated to be 0.88 (88%). In addition, the empty space rate can be calculated as 12%.

[0346] In additional experiments, the situation occurring in the above experimental example was verified when the actual filling rate was 0.88 or higher. The experiment was conducted in the same manner as above, except that the loading length of the carbon dioxide removal component was different, and the change in internal space due to the difference in filling rate was verified and is shown in Table 4 below.

[0347]

[0348] Classification Carbon Dioxide Removal Component Filling Length (mm) Filling Rate Conversion Length After Carbon Dioxide Removal Reaction (mm) Length Increase Rate Tubing Outer Diameter Increase (mm) Example A 1 7.2 0.6 4 19.4 1.1 3 None Example B 2 2.0 0.8 1 24.9 1.1 3 None Comparative Example A 2 4.5 0.9 1 27.0 1.1 0 0.0 4

[0349] The filling rate conversion in Table 4 above was calculated by dividing the filling length of the carbon dioxide removal component of Examples A, B and Comparative Example A by the tubing length of 27.0 mm.

[0350] When a sealed container is manufactured with the carbon dioxide removal component completely filled without any empty space, the pressure inside the container increases due to the volume expansion of the component caused by the carbon dioxide removal reaction. This internal pressure is transmitted to the sealed container of the carbon dioxide remover and can cause the breakdown of the continuous phase sealing layer. If the sealing layer is destroyed, there is a risk of leakage of the internal carbon dioxide removal component or side reactions in the electrolyte caused by the inflow of electrolyte. Therefore, it is necessary to determine the filling ratio of the carbon dioxide removal component to ensure that an appropriate amount of empty space exists inside the sealed container.

[0351] Accordingly, if the filling rate (F) of the carbon dioxide removal component is 0.88 (88 volume%) or higher, or the void ratio is 0.12 (12 volume%) or lower, there is a risk of the sealing layer breaking due to an increase in internal pressure. In addition, if the filling rate of the carbon dioxide removal component becomes too low compared to F, the carbon dioxide removal efficiency per unit of carbon dioxide remover decreases further. It is desirable to set the filling rate at a level similar to or lower than F, taking into account a safety margin. However, exceptionally, if this can be overcome by durability such as the high breakage elongation of the sealing layer, a filling rate value greater than F may be set.

[0352] Referring to Table 4 above, among the three samples, Comparative Example A, which has a filling length of 24.5 mm, unlike Examples A and B, became filled with the carbon dioxide removal component without any empty space inside the sealed container tubing after the carbon dioxide removal reaction, and showed a length increase rate of 1.10, which is smaller than 1.13. In addition, the outer diameter of the tubing increased differently from the other samples, which is expected to be because expansion occurred in the direction of the tubing's cross-sectional area, as further expansion in the length direction of the tubing became impossible due to the absence of internal space.

[0353] Therefore, it can be confirmed that when a carbon dioxide removal component of a certain level (F) or higher is filled, an internal pressure is generated sufficient to cause deformation of the internal receiving space of the sealed container after the carbon dioxide removal reaction. Deformation of the internal receiving space can cause deformation of the external dimensions compared to the initial setting when a carbon dioxide removal agent is applied inside the battery. Therefore, it is preferable to set the filling rate so that the above deformation does not occur, and in the case of Composition 2 used in Experimental Example 4, the filling rate needs to be set to 88 volume% or less or the empty space rate to 12 volume% or more.

Claims

1. A composition comprising a carbon dioxide removal component; and It includes a sealed container comprising a receiving space for accommodating the above composition inside, and The above-mentioned sealed container is a carbon dioxide removal agent that forms a continuous phase.

2. In Claim 1, The above carbon dioxide removal component comprises a first compound containing one or more epoxy groups; and a second compound, and A carbon dioxide removal agent comprising one or more selected from the group consisting of the second compound, quaternary ammonium salt, imidazolium salt, pyridinium salt, phosphonium salt, zeolite, metal-organic framework, metal complex, metal halogen salt, metal oxide, and alkanolamine compound.

3. In Claim 2, A carbon dioxide removal agent comprising the above carbon dioxide removal component comprising 30% by weight or more and 99.995% by weight or less of the first compound; and 0.005% by weight or more and less than 70% by weight of the second compound.

4. In Claim 1, The above carbon dioxide removal component is a carbon dioxide removal agent in a liquid state.

5. In Claim 1, The above-mentioned sealed container is a carbon dioxide remover that is of the sealing type or tube type.

6. In Claim 1, The above-mentioned sealed container is a carbon dioxide removal agent that is impermeable to liquids or powders and permeable to carbon dioxide gas.

7. In Claim 1, The above-mentioned sealed container is a carbon dioxide removal agent comprising one or more selected from the group consisting of fluorine-based, epoxy-based, olefin-based, imide-based, and ester-based compounds.

8. In Claim 1, The above-mentioned receiving space is a carbon dioxide removal agent that includes an empty space.

9. In Claim 1, A carbon dioxide removal agent in which the above-mentioned receiving space includes an empty space of 5% or more and 50% or less relative to the volume of the above-mentioned receiving space.

10. In Claim 1, The above-mentioned sealed container is a carbon dioxide remover having an elongation of 10% or more as measured based on the specimen specifications of ASTM D638.

11. In Claim 1, It further includes an external protective layer formed on the outer surface of the above-mentioned sealed container, and The above-mentioned outer protective layer is a carbon dioxide removal agent comprising an epoxy resin.

12. A lithium secondary battery comprising a carbon dioxide removal agent according to any one of claims 1 to 11.

13. Step of preparing a composition containing a carbon dioxide removal component (S1); Step (S2) of receiving the composition prepared in step (S1) in a sealed container with a portion open; and A method for manufacturing a carbon dioxide remover comprising the step (S3) of sealing an open portion of the above-mentioned sealed container.

14. In Claim 13, The step (S1) of preparing a composition containing the above carbon dioxide removal component is, A step (S1-1) of mixing 30 parts by weight or more and 99.995 parts by weight or less of an epoxy compound containing two or more epoxy groups and 0.005 parts by weight or more and less than 70 parts by weight of an amine compound; and A method for manufacturing a carbon dioxide removal agent comprising the step (S1-2) of reacting the mixture mixed in the above step (S1-1) at a temperature of 50 ℃ or higher and 150 ℃ or lower.

15. In Claim 13, The step (S1) of preparing a composition containing the above carbon dioxide removal component is, A method for manufacturing a carbon dioxide removal agent comprising the step (S1-1') of mixing 30 parts by weight or more and 99.995 parts by weight or less of an epoxy compound containing one or more epoxy groups; and 0.005 parts by weight or more and less than 70 parts by weight of one or more compounds selected from the group consisting of quaternary ammonium salts, phosphonium salts, zeolites, metal-organic frameworks, metal halogen salts and metal oxides.

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