JPWO2019059368A1 - A carbon dioxide absorber, a non-aqueous electrolyte storage battery containing the carbon dioxide absorber, and a method for separating and recovering carbon dioxide gas. - Google Patents

Abstract

The present invention comprises a carbon dioxide gas absorber containing a mixture of an amine-based polymer having an amino group in a repeating unit and an alcohol compound and having a water content of less than 10% by mass, and non-water containing the carbon dioxide gas absorber. Regarding electrolyte storage batteries.

Description

The present invention relates to a carbon dioxide gas absorber, a non-aqueous electrolyte storage battery containing the carbon dioxide gas absorber, and a method for separating and recovering carbon dioxide gas.

In recent years, mobile terminals such as mobile phones, notebook personal computers, and pad-type information terminal devices have become very popular. Mobile terminals are required to be more comfortable to carry, and with the rapid progress of miniaturization, thinning, weight reduction and high performance, the batteries used in form terminals are also becoming smaller, thinner, lighter and lighter. High performance is required. Lithium-ion secondary batteries are often used as secondary batteries used as power sources for such mobile terminals. For non-aqueous electrolyte batteries such as lithium ion secondary batteries, positive and negative electrodes are installed via a separator, and LiPF ₆ , LiBF ₄ , LiTFSI (lithium (bistrifluoromethylsulfonylimide)), LiFSI (lithium (bisfluorosulfonylimide)). )) Has a structure in which a lithium salt such as) is stored in a container together with an electrolytic solution in which a lithium salt is dissolved in an organic liquid such as ethylene carbonate.

In recent years, electric double layer capacitors have been attracting attention as backup power supplies, auxiliary power supplies, etc., and development focusing on the performance of activated carbon as electrodes for electric double layer capacitors has been widely made. Electric double layer capacitors that use activated carbon as polar electrodes have excellent capacitance, so demand for electrical device electrode applications is growing rapidly with the development of the electronics field. Further, recently, in addition to miniaturization of conventional memory backup power supplies and the like, development of large-capacity products used for auxiliary power supplies such as motors has been carried out. The electric double layer capacitor has a structure in which two parts of a polar electrode sheet are installed via a separator and stored in a container together with an organic electrolytic solution such as propylene carbonate in which tetraethylammonium tetrafluoroborate is dissolved.

In non-aqueous electrolyte storage batteries such as non-aqueous electrolyte secondary batteries and electric double layer capacitors, deterioration and destruction due to outgas generated from the inside during operation becomes a problem. Heat treatment and aging methods are generally used to release outgas, but in these methods, the released gas is easily absorbed again by the electrolyte and the sealing can, and due to changes in the operating environment. There is a problem that the gas is re-emitted and the battery is deteriorated or destroyed. In particular, carbon dioxide (carbon dioxide gas) is easily reabsorbed, and an absorber capable of occluding outgas is desired in a non-aqueous electrolyte storage battery.

On the other hand, conventionally, carbon dioxide (carbon dioxide) contained in exhaust gas emitted from thermal power plants, steel mills, chemical factories, etc. has been separated by various methods. For example, exhaust gas from a large-scale facility. As a method suitable for the treatment, a method is typically known in which an exhaust gas is passed through an aqueous solution in which an amine compound is dissolved to react and separate the amine and carbon dioxide. For example, Patent Document 1 describes a carbon dioxide absorbing polymer having a repeating unit having a secondary or tertiary amino group, and a carbon dioxide absorbing material containing 10% by mass or more of water. Further, Patent Document 2 describes a gas absorber containing hydrogel particles of a polymer compound having an amino group. Such a method of chemically absorbing carbon dioxide in an aqueous solution of an amine-based material can also be used as an occlusion method of carbon dioxide. In particular, the intensity of action with carbon dioxide can be changed depending on the amine species, and re-emission can be performed. Since it can be reduced, it is suitable for storing carbon dioxide gas released inside the electronic element and protecting it from deterioration and destruction.

Japanese Unexamined Patent Publication No. 2012-30222 International Publication No. 2016/024633 Pamphlet

However, since the carbon dioxide absorbent disclosed in Patent Document 1 is based on a polymer composed of a secondary or higher amine, it has poor reactivity with carbon dioxide and is not always satisfactory in the amount of carbon dioxide absorbed. It didn't go. Further, the gas absorber disclosed in Patent Document 2 has a small amount of amino groups that can be contained in the hydrogel particles of the polymer compound, and the volume density tends to decrease due to the presence of particle gaps. The amount of absorption was not always satisfactory.

Further, since the conventional carbon dioxide gas absorbers as described in the above patent documents all absorb carbon dioxide gas by reacting amine and carbon dioxide gas in the presence of water, the usage form may be liquid. It becomes a gel containing a large amount of water, and its usage environment and usage are likely to be limited. In particular, these carbon dioxide gas absorbers that utilize the reaction in the presence of water are not suitable as carbon dioxide gas absorbers used in non-aqueous electrolyte storage batteries, and these are applied as carbon dioxide gas absorbers for non-aqueous electrolyte storage batteries. Even so, it is difficult for the carbon dioxide absorber disclosed in Patent Document 1 to obtain sufficient storage performance because the release temperature of the absorbed carbon dioxide is less than 100 ° C. Further, in a gas absorber in which a porous body is impregnated with polymer compound particles having an amino group or an amine-based material as disclosed in Patent Document 2, a compound having the shape of particles or pores and an amino group. The distribution of carbon dioxide is not constant, and the absorption or release of carbon dioxide gas tends to be biased in the gas absorber, which may cause local deterioration or destruction when used in a non-aqueous electrolyte storage battery.
Further, since it is necessary to heat water having a large specific heat, the method for separating and recovering carbon dioxide gas based on a gas-liquid reaction is a step of separating and recovering carbon dioxide gas from a carbon dioxide gas absorber after absorbing carbon dioxide gas from exhaust gas or the like. Efficiency and operability tend to be inferior to treatment by a solid reaction.

Therefore, an object of the present invention is to provide a carbon dioxide gas absorber suitable for a wide range of applications, which can realize a high absorption amount of carbon dioxide gas and can stably and efficiently separate and recover carbon dioxide gas at a high temperature. And. Another object of the present invention is to provide a non-aqueous electrolyte storage battery having stable charge / discharge performance without deterioration or destruction of the storage battery due to outgas generated from the inside of the storage battery.

The present inventors have arrived at the present invention as a result of diligent studies to solve the above problems. That is, the present invention includes the following preferred embodiments.
[1] A carbon dioxide gas absorber composed of a mixture containing an amine-based polymer having an amino group and an alcohol compound in a repeating unit and having a water content of less than 10% by mass.
[2] The carbon dioxide absorber according to the above [1], wherein the carbon dioxide outgassing temperature is 100 ° C. or higher and 300 ° C. or lower.
[3] The amine-based polymer is selected from the group consisting of polyethyleneimine, polyallylamine, polyacrylamide, polytetramethyleneimine, polyvinylamine, dicyandiamide-formalin condensate and dicyandiamide-alkylene (polyamine) condensate. ] Or the carbon dioxide gas absorber according to [2].
[4] The carbon dioxide gas according to any one of [1] to [3] above, wherein the alcohol compound is selected from the group consisting of monosaccharides, oligosaccharides, polysaccharides, polyvinyl alcohol and its derivatives, and polyphenols and their derivatives. Absorber.
[5] The carbon dioxide gas absorber according to any one of [1] to [4] above, which is in the form of a film, a film, a sheet, a fiber or a powder.
[6] The carbon dioxide absorber according to any one of [1] to [5] above, wherein the water content is 500 ppm or less.
[7] A non-aqueous electrolyte storage battery comprising the carbon dioxide gas absorber according to the above [6].
[8] The non-aqueous electrolyte storage battery according to the above [7], which is a non-aqueous electrolyte secondary battery.
[9] The non-aqueous electrolyte storage battery according to the above [7], which is an electric double layer capacitor.
[10] The carbon dioxide gas absorber according to any one of [1] to [6] is brought into contact with a gas containing carbon dioxide gas to allow the carbon dioxide gas absorber to absorb the carbon dioxide gas, and the carbon dioxide gas is absorbed. A method for separating and recovering carbon dioxide gas, which comprises separating and recovering carbon dioxide gas from the carbon dioxide gas absorber.

According to the present invention, it is possible to provide a carbon dioxide gas absorber suitable for a wide range of applications, which can realize a high absorption amount of carbon dioxide gas and can stably and efficiently separate and recover carbon dioxide gas at a high temperature. .. Further, according to the present invention, it is possible to provide a non-aqueous electrolyte storage battery having stable charge / discharge performance without deterioration or destruction of the storage battery due to outgas generated from the inside of the storage battery.

Hereinafter, embodiments of the present invention will be described in detail. The scope of the present invention is not limited to the embodiments described here, and various modifications can be made without impairing the gist of the present invention.

<Carbon dioxide absorber>
The carbon dioxide absorber of the present invention comprises a mixture containing an amine-based polymer having an amino group in a repeating unit and an alcohol compound.
In the present invention, the amine-based polymer is a polymer having at least one nitrogen atom serving as a primary amine, a secondary amine or a tertiary amine in the main chain and / or side chain of the polymer. Say. The amine-based polymer used to constitute the carbon dioxide absorber of the present invention may exist as a final carbon dioxide absorber composed of a mixture with an alcohol compound at a water content of less than 10% by mass (usually a solid). It is not particularly limited as long as it is in the form of), and any conventionally known amine-based polymer can be used.

In the present invention, for example, the amine-based polymer includes primary amine, secondary amine, and tertiary amine compounds such as ethyleneimine, allylamine, vinylformamide, vinylacetamide, acrylamide, amino acids, melamine, urea, and vinylpyrrolidone. In addition to the synthetic polymer compound synthesized by using it, it may be a naturally occurring polymer compound, for example, a secondary product of a microorganism.

In the present invention, the amine-based polymer is a polymer having at least one selected from a primary amino group, a secondary amino group and a tertiary amino group in a repeating unit. Such a polymer may be a polymer having at least one selected from a primary amino group, a secondary amino group and a tertiary amino group in one repeating unit, and one such polymer. The above repeating unit may be a random, grafted, or block copolymerized polymer.

Specific examples of the amine-based polymer that can be used for the carbon dioxide gas absorber of the present invention include alkyleneimine polymers such as polyethyleneimine, polypropyleneimine, polybutyleneimine, and polytetramethyleneimine, polyallylamine, and polyvinylamine. , Polyacrylamide, dicyandiamide-formalin condensate, dicyandiamide-alkylene (polyamine) condensate, polylysine, melamine resin, modified melamine resin, melamine-urea resin, amino group-containing polymer such as polyphosphate melamine; urea resin, ethyleneurea resin, etc. Can be mentioned. Among them, from the viewpoint of being easily water-soluble and mixable with alcohol compounds, it is composed of a group consisting of polyethyleneimine, polyallylamine, polyacrylamide, polytetramethyleneimine, polyvinylamine, dicyandiamide-formalin condensate and dicyandiamide-alkylene (polyamine) condensate. Amine-based polymers selected from polyethyleneimine, polyallylamine and polyacrylamide are more preferred because of the preferred amine-based polymers, which are readily available and low cost. These may be used alone or in combination of two or more.

In the present invention, the amine-based polymer preferably contains a primary amino group, and preferably contains a primary amino group and at least one of a secondary amino group and a tertiary amino group. More preferred. By including the primary amino group, the amount of absorption into carbon dioxide can be increased, and in particular, in an environment where water is scarce (for example, 5% by mass or less with respect to the carbon dioxide absorber) or water is substantially absent. In the environment, the absorption of carbon dioxide gas can be advantageously improved. Further, by containing at least one of a secondary amino group and a tertiary amino group in addition to the primary amino group, the absorbed carbon dioxide gas can be stably retained. When the amine-based polymer contains at least one of a secondary amino group and a tertiary amino group in addition to the primary amino group, the proportion of the primary amino group contained in the amine-based polymer is amine-based. It is preferably 25% or more, more preferably 30% or more, still more preferably 35% or more, based on the total amino groups of the polymer. When the ratio of the primary amino group is at least the above lower limit value, the reactivity with carbon dioxide gas is improved, and a carbon dioxide gas absorber having a high absorption amount for carbon dioxide gas can be obtained. Further, from the viewpoint of stably retaining the absorbed carbon dioxide gas, the ratio of the primary amino group is preferably 80% or less with respect to the total amino group of the amine polymer.

In a preferred embodiment of the present invention, the carbon dioxide gas absorber contains at least one of a secondary amino group and a tertiary amino group in one molecule as an amine-based polymer in addition to the primary amino group. It is also preferable to include a polymer containing a primary amino group, a secondary amino group and a tertiary amino group in one molecule. Also, in another preferred embodiment of the present invention, the amine-based polymer may be a polymer mixture, which also comprises a polymer containing a primary amine and a polymer of a secondary amine and a tertiary amine. A mixture with a polymer containing at least one of them is preferable. Even when two or more kinds of polymers are combined, it is preferable that the ratio of the primary amino group to the total amino group in the total amine polymer is in the same range as described above.

In the present invention, the amount of amino groups in the amine-based polymer is preferably 15% by mass or more, more preferably 25% by mass or more, based on the total amount of the amine-based polymer. When the amount of amino groups in the amine-based polymer is equal to or higher than the above lower limit, it becomes easy to secure a sufficient range of carbon dioxide absorbable amount required for various uses, and the carbon dioxide gas absorbency and stable retention are excellent. A carbon dioxide absorber can be obtained. Since the amount of carbon dioxide that can be absorbed tends to increase as the amount of amino groups in the amine polymer increases, the upper limit thereof is not particularly limited, but is usually 90% by mass or less and 80% by mass. It is preferably less than or equal to 60% by mass or less. If it is less than the above upper limit, the workability tends to be excellent.

In the present invention, the weight average molecular weight of the amine-based polymer is preferably 2000 or more, more preferably 5000 or more, further preferably 10000 or more, preferably 100,000 or less, and more preferably 80,000 or less. , More preferably 70,000 or less. When the weight average molecular weight of the amine-based polymer is at least the above lower limit value, the carbon dioxide absorber is likely to be solidified, and when it is at least the above upper limit value, it is difficult for the amine-based polymer to solidify by itself, so that it is easy to mix. The weight average molecular weight of the amine-based polymer can be determined by using, for example, gel permeation chromatography (GPC).

In the present invention, the alcohol compound is a compound having at least one hydroxyl group, and in order to obtain a solid carbon dioxide gas absorber, it is preferable to select a solid alcohol compound at room temperature in the present invention. Examples of such alcohol compounds include monosaccharides, oligosaccharides, polysaccharides, polyvinyl alcohols and derivatives thereof, polyphenols and derivatives thereof, and the like. These alcohol compounds may be used alone or in combination of two or more.

Specific examples of the monosaccharide include glucose, fructose, galactose and the like. Examples of the oligosaccharide include saccharose, sorbitol, xylitol and the like. In addition, examples of the polysaccharide include starch and its derivatives, cellulose and its derivatives, and the like.

Examples of the starch and its derivatives include corn starch (corn starch); wheat starch; potato starch; tapioca starch; rice starch; dextrin; amylose; amylopectin; purulan; high amylose corn starch; hydroxyalkyl starch such as hydroxypropyl starch; dihydroxy. Dihydroxyalkyl starches such as propyl starch; dihydroxyalkylpurulans such as dihydroxypropylpurran and the like can be mentioned.

Examples of the cellulose and its derivatives include regenerated cellulose; powdered cellulose; microcrystalline cellulose; hydroxyalkyl cellulose such as hydroxyethyl cellulose and hydroxypropyl cellulose; and dihydroxyalkyl cellulose such as dihydroxypropyl cellulose.

In the present invention, when a polysaccharide is used as the alcohol compound, its molecular weight varies depending on the number and types of repeating units of the polysaccharide, and is not limited, but may be 5000 to 1,000,000 in weight average molecular weight. It is preferably 1000 to 20000, and more preferably 1000 to 20000. The weight average molecular weight can be determined by using, for example, gel permeation chromatography (GPC).

Since the alcohol compound has high plasticity and good processability, the alcohol compound in the present invention is preferably polyvinyl alcohol and a derivative thereof. Alternatively, a polyvinyl alcohol modified so as to interact with the amine-based polymer may be used.

In the present invention, when polyvinyl alcohol is contained as the alcohol compound, the average degree of polymerization thereof is preferably 1000 to 100,000, more preferably 1000 to 80,000, and further preferably 1500 to 60000. When the average degree of polymerization of polyvinyl alcohol is within the above range, the molding processability and handleability are improved, and the mechanical properties such as the strength and elongation of the obtained carbon dioxide absorber can be improved. The degree of saponification of polyvinyl alcohol may be, for example, 90 mol% or more, preferably 95 mol% or more, and more preferably 98 mol% or more. When the degree of saponification of polyvinyl alcohol is within the above range, the hygroscopicity is low and the handleability is good.

The carbon dioxide absorber of the present invention comprises a mixture containing an amine-based polymer and an alcohol compound. The mixing ratio (mass ratio) of the amine polymer and the alcohol compound in the mixture constituting the carbon dioxide absorber is preferably 5: 1 to 1: 5, and more preferably 3: 1 to 1: 3. It is more preferably 2: 1 to 1: 1. When the mixing ratio of the amine polymer and the alcohol compound is within the above range in the mixture constituting the carbon dioxide absorber, the carbon dioxide absorption performance of the carbon dioxide absorber can be enhanced, and the strength, elongation, etc. are mechanical. The nature can be improved. In addition, the moldability and handleability are improved. When the amine polymer and / or the alcohol compound are mixed in the form of an aqueous solution or the like in the mixture constituting the carbon dioxide absorber, the above mixing ratios mean the ratios as solids, respectively.

The mixture constituting the carbon dioxide gas absorber of the present invention may contain components other than the amine-based polymer and the alcohol compound. Examples of such a component include a component that is blended as an additive in a conventional carbon dioxide gas absorber, and specifically, a dispersion stabilizer, a viscosity modifier, a polymer other than an amine-based polymer, and a defoamer. Examples thereof include foaming agents, plasticizers, heat stabilizers (melt stabilizers), deodorants, ultraviolet absorbers, antistatic agents, lubricants, colorants, desiccants, fillers, processing aids, flame retardants and the like.

When the mixture constituting the carbon dioxide gas absorber of the present invention contains components other than the amine-based polymer and the alcohol compound, the total amount of the amine-based polymer and the alcohol compound with respect to the total mass of the mixture is 90% by mass or more as a solid content. Is more preferable, 95% by mass or more is more preferable, and 98% by mass or more is further preferable. The solid content referred to here refers to a component obtained by removing the amount of a solvent such as water from the mixture constituting the carbon dioxide gas absorber.

The water content of the carbon dioxide absorber of the present invention is preferably less than 10% by mass, preferably 8% by mass or less, and preferably 5% by mass or less, based on the total mass of the carbon dioxide absorber. More preferably, it is 2% by mass or less, and particularly preferably. The lower limit of the water content is not particularly limited, and is usually 0.1% by mass or more, but may be 0% by mass. When the water content is 10% by mass or more, it becomes difficult for the carbon dioxide gas absorber to maintain the solid shape. The carbon dioxide gas absorber of the present invention has a lower water content than the conventional carbon dioxide gas absorber, and has a high absorbency of carbon dioxide gas in the absence of water. Therefore, it is suitably used in a wide range of applications such as non-aqueous electrolyte storage batteries, food, pharmaceutical and cosmetic packaging containers in an environment where it is necessary to reduce the amount of water or in an environment where it is preferable that there is no water. Can be done. In addition, since it can be used in a solid state without using water, it is easy to handle and it is possible to easily separate and recover the absorbed carbon dioxide gas from the absorber. Therefore, for example, a thermal power plant or an ironworks. It can be suitably used in a carbon dioxide gas separation and recovery system in a large-scale facility that discharges a large amount of carbon dioxide gas such as a chemical factory.

When the carbon dioxide absorber of the present invention is used in a non-aqueous electrolyte storage battery described later, its water content is preferably 500 ppm or less, more preferably 400 ppm or less, still more preferably 300 ppm or less, and particularly preferably 250 ppm or less. When the water content is 500 ppm or less, the occurrence of performance deterioration of the non-aqueous electrolyte storage battery can be suppressed. Therefore, the lower the water content of the carbon dioxide absorber, the more preferable it is, ideally 0 ppm, but from the viewpoint of production efficiency and the like, the lower limit is usually 100 ppm or more.

The water content of the carbon dioxide absorber of the present invention controls the amount of water in the mixture containing the amine polymer and the alcohol compound, and the heating conditions and drying conditions when the carbon dioxide absorber is prepared (molded, etc.) from the mixture. Etc. can be adjusted by controlling the above.

The carbon dioxide outgassing temperature of the carbon dioxide gas absorber of the present invention is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, further preferably 140 ° C. or higher, particularly preferably 150 ° C. or higher, and preferably 300 ° C. or lower. , More preferably 250 ° C. or lower, further preferably 230 ° C. or lower, and particularly preferably 220 ° C. or lower. When the carbon dioxide gas release temperature is at least the above lower limit value, carbon dioxide gas can be stably and efficiently absorbed, separated and recovered under high temperature, and when it is at least the above upper limit value, the alcohol compound and the amine polymer are decomposed. And thermal deterioration can be suppressed.

The carbon dioxide outgassing temperature of the carbon dioxide absorber can be controlled, for example, by selecting the type, combination, mixing ratio, water content, shape, etc. of the amine-based polymer or alcohol compound to be used. For example, in order to raise the carbon dioxide gas release temperature, it is possible to increase the ratio of the primary amine and increase the ratio of the alcohol compound. On the other hand, in order to lower the carbon dioxide gas release temperature, it is possible to increase the water content, increase the total ratio of the secondary and tertiary amino groups in the amine-based polymer, and the like.

The carbon dioxide absorber of the present invention is usually a solid, and its shape is not particularly limited, and a film-like, film-like, sheet-like, fibrous, powder-like, depending on a desired usage environment and application. It may be in various forms such as granular and gel. Since it is easy to handle and can be used for various purposes, it is preferably in the form of a film, a film, a sheet, a fiber, and a powder.

In the present invention, when the shape of the carbon dioxide absorber is film-like, film-like or sheet-like, the thickness thereof can be appropriately determined according to the environment and application of use, and may be, for example, 1 to 500 μm. , 5 to 200 μm is preferable.

The carbon dioxide absorber of the present invention can be produced, for example, by stirring and mixing an amine-based polymer, an alcohol compound, and other components as necessary, and molding the obtained mixture into a desired shape. it can. When preparing a mixture of an amine-based polymer and an alcohol compound, the mixture can be easily handled by appropriately dissolving the amine-based polymer and / or the alcohol compound in a solvent such as water and mixing as an aqueous solution. The solvent at this time may be appropriately selected depending on the type and amount of the amine-based polymer and alcohol compound used. Examples of the solvent include water, an alcohol solvent, dimethyl sulfoxide and the like.

The stirring and mixing conditions (temperature, time, stirring speed, etc.) when mixing the amine-based polymer and the alcohol compound may be appropriately determined according to the type and amount of the amine-based polymer and the alcohol compound to be used.

Then, the mixture is applied onto the base material, the solvent is removed by drying, and then the base material is peeled off to obtain a carbon dioxide gas absorber in the form of a film, a film, a sheet, or the like. The base material is not particularly limited, and for example, a plastic film such as polyester, a release paper, a metal plate, a glass plate, or the like can be used. Examples of the drying method include a natural drying method, a ventilation drying method, a heat drying method and a vacuum drying method, and the solvent contained in the mixture can be efficiently removed, so that the drying method is preferably heat drying. The heating temperature is not particularly limited, and may be, for example, 50 to 150 ° C., preferably 80 to 120 ° C. The drying time may be appropriately adjusted depending on the heating temperature and the like, and may be, for example, 1 to 60 minutes, preferably 3 to 30 minutes.

In the fibrous carbon dioxide absorber, a mixture of an amine polymer and an alcohol compound is heated to an aqueous solution at a concentration of 40 to 60% by mass, and a cross-linking agent such as ammonium sulfate is added to 0.5 by mass with respect to the weight of the polyvinyl alcohol polymer. It can be produced by adding 10% by mass to prepare a spinning stock solution having a temperature of 90 to 140 ° C., pressurizing the mixture, discharging the solution into air through a nozzle hole, and performing dry spinning. Further, a powdery carbon dioxide gas absorber can be produced by pulverizing a solid obtained by heating and drying a mixture of an amine-based polymer (an aqueous solution) and an alcohol compound (an aqueous solution).

<Non-water electrolyte storage battery>
Since the carbon dioxide gas absorber of the present invention has a low absorption water content and is usually in a solid state, it can efficiently occlude outgas generated from the inside during operation without affecting the performance of the non-aqueous electrolyte storage battery. Therefore, the present invention is intended for a non-aqueous electrolyte storage battery containing the carbon dioxide water absorber of the present invention. The non-aqueous electrolyte storage battery of the present invention may be in the form of a non-aqueous electrolyte secondary battery, an electric double layer capacitor, a lithium ion capacitor or the like.

A non-aqueous electrolyte secondary battery generally has a positive electrode and a negative electrode, and a separator and an electrolytic solution arranged between the positive electrode and the negative electrode. The non-aqueous electrolyte secondary battery of the present invention can be manufactured using known materials and techniques. For example, when the non-aqueous electrolyte secondary battery is a lithium secondary battery, the positive electrode materials include, for example, TiS ₂ , TiS ₃ , amorphous MoS ₃ , Cu ₂ V ₂ O ₃ , and amorphous V ₂ O-P _2. Transition metal oxides such as O ₅ , MoO ₃ , V ₂ O ₅ , and V ₆ O ₁₃ and lithium-containing composite metal oxides such as LiCoO ₂ , LiNiO ₂ , LiMnO ₂ , and LiMn ₂ O ₄ can be used.

A positive electrode material, a conductive auxiliary agent such as metal powder, a conductive polymer, acetylene black, and carbon black, and a binder such as SBR, NBR, acrylic rubber, hydroxyethyl cellulose, carboxymethyl cellulose, and polyvinylidene fluoride are mixed with water or an organic dispersion medium. To prepare a positive electrode slurry, for example, it can be applied to a positive electrode current collector such as aluminum and the solvent is dried to obtain a positive electrode.

Examples of the negative electrode material include conductivity of amorphous carbon, graphite, natural graphite, mesocarbon microbeads (MCMB), pitch carbon fiber, carbon black, activated carbon, carbon fiber, hard carbon, soft carbon, mesoporous carbon, polyacene and the like. Carbonous materials such as polymers, composite metal oxides represented by SiO _x , SnO _x , LiTIO _x , other metal oxides, lithium metals, lithium-based metals such as lithium alloys, and metals such as TiS ₂ and LiTiS _2. Compounds and composite materials of metal oxides and carbonaceous materials can be used.

The negative electrode material and the same conductive auxiliary agent and binder as the positive electrode are mixed with water or an organic dispersion medium to prepare a slurry for the negative electrode, which is applied to a negative electrode current collector such as copper to dry the solvent. Can be the negative electrode.

The electrolytic solution may be liquid or gel as long as it is used for a normal non-aqueous electrolyte secondary battery, and a battery that functions as a battery may be appropriately selected according to the type of negative electrode material and positive electrode material. Good. As the electrolyte, any known lithium salt can be used, for _{example, LiClO 4, LiBF 6, LiPF} 6, LiCF 3 SO 3, LiCF 3 CO 2, LiAsF 6, LiSbF 6, LiB 10 Cl 10, LiAlCl 4, LiCl , LiBr, LiB (C ₂ H ₅ ) ₄ , CF ₃ SO ₃ Li, CH ₃ SO ₃ Li, LiCF ₃ SO ₃ , LiC ₄ F ₉ SO ₃ , Li (CF ₃ SO ₂ ) ₂ N, lower aliphatic carboxylic Examples thereof include lithium acid.

The solvent for dissolving such an electrolyte (electrolyte solution solvent) is not particularly limited. Specific examples include carbonates such as propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate and vinylene carbonate; lactones such as γ-butyl lactone; trimethoxymethane, 1,2-dimethoxyethane, diethyl ether, 2 -Esters such as ethoxyethane, tetrahydrofuran and 2-methyltetrax; sulfoxides such as dimethylsulfoxide; oxolanes such as 1,3-dioxolane and 4-methyl-1,3-dioxolane; nitrogen-containing compounds such as acetonitrile and nitromethane Classes; organic acid esters such as methyl formate, methyl acetate, ethyl acetate, butyl acetate, methyl propionate, ethyl propionate; inorganic acid esters such as triethyl phosphate, dimethyl carbonate, diethyl carbonate; diglimes; triglimes; Sulfolans; oxazolidinones such as 3-methyl-2-oxazolidinone; sultons such as 1,3-propanesulton, 1,4-butanesulton, naphthalusulton, etc., which can be used alone or in admixture of two or more. .. When a gel-like electrolytic solution is used, a nitrile-based polymer, an acrylic-based polymer, a fluorine-based polymer, an alkylene oxide-based polymer, or the like can be added as a gelling agent.

In a non-aqueous electrolyte secondary battery, for example, a negative electrode and a positive electrode are overlapped with each other via a separator such as a polypropylene porous film, wound or folded according to the shape of the battery, placed in a battery container, and an electrolytic solution is injected. It can be manufactured by sealing it. The shape of the battery may be any of known coin type, button type, sheet type, cylindrical type, square type, flat type and the like.

The carbon dioxide gas absorber may be installed in the non-aqueous electrolyte secondary battery, for example, when the carbon dioxide gas absorber is in the form of a film, a film, or a sheet, it may be laminated and arranged together with the electrodes and the separator, and is in the form of fibers. Alternatively, in the case of powder or the like, it can be mixed with the electrode material or the separator material and arranged in the battery as a part of the constituent members of the electrode and the separator.

An electric double layer capacitor generally has a structure in which a polar electrode, an electrolytic solution, and a separator are mainly configured, and a separator is arranged between a pair of electrodes. The electric double layer capacitor of the present invention can be manufactured using known materials and techniques. As the polar electrode material, for example, activated carbon is preferably used in terms of capacitance. The carbon material used as a raw material for activated carbon is not particularly limited, and examples thereof include coal, coal pitch, petroleum pitch, thermosetting resins such as phenol, and coconut shells.

A known method can be applied to the production of the polar electrode. For example, commercially available substances known as binders such as polyvinylidene fluoride and polytetrafluoroethylene, and conductive materials such as carbon black are added up to about several% of the polar electrode material as needed. After kneading well, it can be molded into an electrode by putting it in a mold and press-molding it, or rolling it into a sheet and then punching it into a required shape. Further, the kneaded product may be applied to a current collector to serve as a coating electrode. At the time of electrode formation, if necessary, an organic compound such as alcohol or N-methylpyrrolidone, a solvent such as water, a dispersant, and various additives may be used. It is also possible to apply heat within a range that does not impair the effects of the present invention.

As the separator, a glass filter paper, a non-woven fabric such as polypropylene or nylon, or a porous film such as polytetrafluoroethylene can be used.

As the electrolyte, tetraethylammonium tetrafluoroborate, tetramethylammonium tetrafluoroborate and the like can be used. Solvents that dissolve the electrolyte and use it as the electrolytic solution include carbonates such as ethylene carbonate, dimethyl carbonate, diethyl carbonate and propylene carbonate, nitriles such as acetonitrile, lactones such as γ-butyrolactone and α-methyl-γ-butyrolactone. Sulfoxides such as dimethyl sulfoxide and amides such as dimethylformamide are used.

Each component constituting the electric double layer capacitor can have the same configuration as a known electric double layer capacitor except that the carbon dioxide gas absorber according to the present invention is used. For example, a current collecting member made of aluminum or the like. , Polarizing electrodes, separators, gaskets made of polypropylene, polyethylene, polyamide, polyamideimide, polybutylene, etc., and cases made of materials such as stainless steel are used.

The carbon dioxide absorber may be installed on the electric double layer capacitor, for example, when the carbon dioxide absorber is in the form of a film, a film, or a sheet, it may be laminated and arranged together with a polarizing electrode or a separator. Alternatively, in the case of powder or the like, it can be arranged in the battery as a part of the constituent members of the polarization electrode and the separator.

<Separation and recovery method of carbon dioxide gas>
In the method for separating and recovering carbon dioxide gas of the present invention, the carbon dioxide gas absorber of the present invention is brought into contact with a gas containing carbon dioxide gas to absorb the carbon dioxide gas, and the carbon dioxide gas absorber has absorbed the carbon dioxide gas. It includes separating and recovering carbon dioxide gas from a carbon dioxide gas absorber.
Specifically, for example, the carbon dioxide gas release temperature of the carbon dioxide gas absorber into the absorption tower in which the carbon dioxide gas absorber of the present invention having a film-like, film-like, sheet-like, fibrous or powdery form is installed. The carbon dioxide gas contained in the carbon dioxide gas-containing gas is supplied by supplying the carbon dioxide gas-containing gas controlled to the temperature below (for example, 100 ° C. or less) and passing the carbon dioxide gas-containing gas through the carbon dioxide gas absorber installed in the absorption tower. Is absorbed by the carbon dioxide gas absorber. The gas after the carbon dioxide gas absorber absorbs the carbon dioxide gas may be discharged to the outside of the absorption tower by a discharge port or the like provided in the absorption tower. Next, by heating the carbon dioxide gas absorber that has absorbed the carbon dioxide gas to a temperature equal to or higher than the carbon dioxide gas release temperature of the carbon dioxide gas absorber, the carbon dioxide gas absorbed from the carbon dioxide gas absorber can be separated and recovered. In the method for separating and recovering carbon dioxide gas of the present invention, by using a solid carbon dioxide gas absorber, the process from absorption of carbon dioxide gas to separation and recovery can be performed in one tower. For this reason, in general, carbon dioxide gas is absorbed in the presence of water in the absorption tower, and the absorbed carbon dioxide gas is separated and recovered in a regeneration tower different from the absorption tower, which is a conventional method for absorbing and separating and recovering carbon dioxide gas. It is more efficient in comparison and is also advantageous in that it does not require complicated equipment.

The contact between the carbon dioxide gas absorber and the carbon dioxide gas-containing gas is preferably performed at a temperature lower than the carbon dioxide gas release temperature of the carbon dioxide gas absorber, and more preferably a temperature about 50 to 80 ° C. lower than the carbon dioxide gas release temperature of the absorber. Contact with. Further, the heating for separating and recovering the carbon dioxide gas absorbed from the carbon dioxide gas absorber may be performed by directly heating, for example, by blowing steam or the like, or may be indirectly heated by a jacket or the like. The heating temperature is preferably equal to or higher than the carbon dioxide gas discharge temperature of the carbon dioxide gas absorber, and more preferably a temperature about 10 to 20 ° C. higher than the carbon dioxide gas discharge temperature. The separated carbon dioxide gas may be discharged from the absorption tower by a recovery discharge line and recovered. The carbon dioxide gas absorber after separating the carbon dioxide gas is repeatedly used as the carbon dioxide gas absorber.

The carbon dioxide gas-containing gas is not particularly limited, and examples thereof include exhaust gas from thermal power plants, ironworks, chemical plants, etc., biofermentation gas, natural gas, and the like. It is also suitable for absorbing carbon dioxide gas in the air by arranging it in a container for foods, pharmaceuticals, cosmetics, etc., a non-aqueous electrolyte storage battery, or the like.

Hereinafter, the present invention will be specifically described with reference to Examples, but these do not limit the scope of the present invention.

1. 1. Example 1
(1) Preparation of carbon dioxide gas absorber 1000 g of an aqueous solution of 10% by mass polyvinyl alcohol (manufactured by Kuraray, PVA-117, average degree of polymerization: 1700, degree of saponification: 98-99%) was added to a 5 L flask, and the mixture was stirred with a mechanical stirrer. did. Next, 100 g of polyethyleneimine (manufactured by Showa Kagaku, undiluted solution, weight average molecular weight Mw10000, amine ratio 1st grade: 2nd grade: 3rd grade = 35:35:30) was added, and stirring was continued at 25 ° C. for 3 hours to obtain a solid content of 18. A mixed solution of mass% was obtained. The obtained mixed solution was coated on a 100 μm polyethylene terephthalate (PET) film to a thickness of 500 μm, and then dried in a dryer at 80 ° C. for 30 minutes. The polyvinyl alcohol-polyethyleneimine mixed film was peeled off from the PET film to obtain a film-like carbon dioxide gas absorber. The film thickness of the mixed film was 60 μm.

(2) Measurement of Moisture Content The water content of the obtained carbon dioxide absorber was measured according to the following method.
After vacuum-drying 10 g of the sample for moisture content measurement at 105 ° C. for 6 hours and 140 ° C. for 3 hours, 1 g of the sample is weighed and heated to 140 ° C. by Karl Fischer (manufactured by Mitsubishi Chemical Analytech Co., Ltd.). The amount of moisture absorbed was measured below. The water content of the film-shaped carbon dioxide absorber obtained in (1) above was 1.2% by mass.

(3) Measurement of carbon dioxide release temperature 1 g of the film-shaped carbon dioxide gas absorber obtained in (1) above is put in a desiccator, 10 g of carbon dioxide is put in, and the mixture is stored at 25 ° C. for 1 hour and then taken out to obtain differential heat. The carbon dioxide emission temperature of the carbon dioxide absorber was measured using a thermogravimetric simultaneous measuring device: TG-DTA, manufactured by Seiko Instruments. As a result, it was confirmed that the heat weight decreased due to the release of adsorbed water around 100 ° C. and the heat weight decrease due to the release of carbon dioxide around 170 ° C.

(4) Measurement of carbon dioxide absorption amount Using a high-pressure gas adsorption amount measuring device: BELSORP (manufactured by Microtrac Bell), the carbon dioxide gas adsorption amount of the film-shaped carbon dioxide gas absorber obtained in (1) above is measured. did. The amount of carbon dioxide absorbed per 1 g of the carbon dioxide absorber was 297 mg.

2. 2. Example 2
Instead of adding 100 g of polyethyleneimine (manufactured by Showa Kagaku, undiluted solution, weight average molecular weight Mw10000, amine ratio 1st grade: 2nd grade: 3rd grade = 35:35:30), polyethyleneimine (manufactured by Showa Kagaku, undiluted solution, weight average molecular weight) Examples except that 50 g of Mw10000, amine ratio 1st grade: 2nd grade: 3rd grade = 35:35:30) and 50 g of polyallylamine (manufactured by Nitto Spinning Co., Ltd., undiluted solution, weight average molecular weight Mw15000 primary amine alone) were added. A film-shaped carbon dioxide gas absorber (thickness: 58 μm) was obtained by the same method as in 1.
The water content was 1.6% by mass, the carbon dioxide release temperature was 185 ° C., and the amount of carbon dioxide adsorbed was the amount of carbon dioxide absorbed per 1 g of the carbon dioxide absorber, which was measured by the same method as in Example 1. It was 336 mg.

3. 3. Example 3
Instead of adding 100 g of polyethyleneimine (manufactured by Showa Kagaku, undiluted solution, weight average molecular weight Mw10000, amine ratio 1st grade: 2nd grade: 3rd grade = 35:35:30), polyethyleneimine (manufactured by Showa Kagaku, undiluted solution, weight average molecular weight) Examples except that 25 g of Mw10000, amine ratio 1st grade: 2nd grade: 3rd grade = 35:35:30) and 75 g of polyallylamine (manufactured by Nitto Spinning Co., Ltd., undiluted solution, weight average molecular weight Mw15000 primary amine alone) were added. A film-shaped carbon dioxide gas absorber (thickness: 62 μm) was obtained by the same method as in 1.
The water content was 1.8% by mass, the carbon dioxide release temperature was 198 ° C., and the carbon dioxide absorption amount was 356 mg per 1 g of the carbon dioxide gas absorber, which was measured by the same method as in Example 1.

4. Example 4
Instead of adding 100 g of polyethyleneimine (manufactured by Showa Kagaku, undiluted solution, weight average molecular weight Mw10000, amine ratio 1st grade: 2nd grade: 3rd grade = 35:35:30), polydialylamine (manufactured by Nitto Boseki, weight average molecular weight Mw5000 2) A film-shaped carbon dioxide absorber (thickness: 62 μm) was obtained by the same method as in Example 1 except that 100 g of (classic amine alone) was added.
The water content measured by the same method as in Example 1 is. It was 1.4% by mass, the carbon dioxide emission temperature was 165 ° C., and the amount of carbon dioxide absorbed was 274 mg per 1 g of the carbon dioxide gas absorber.

5. Example 5
A film-like carbon dioxide absorber (thickness) by the same method as in Example 1 except that 1000 g of a 10% by mass starch (made by Wako Pure Chemical Industries, Ltd., derived from corn) aqueous solution was used instead of the 10% by mass polyvinyl alcohol aqueous solution. : 61 μm) was obtained.
The water content was 0.3% by mass, the carbon dioxide release temperature was 155 ° C., and the carbon dioxide absorption amount per 1 g of the carbon dioxide gas absorber was 257 mg, which was measured by the same method as in Example 1.

6. Example 6
A film-like carbon dioxide gas absorber (thickness: 60 μm) by the same method as in Example 1 except that 1000 g of a 10 mass% glucose (manufactured by Wako Pure Chemical Industries, Ltd.) aqueous solution was used instead of the 10 mass% polyvinyl alcohol aqueous solution. Got
The water content was 0.6% by mass, the carbon dioxide release temperature was 168 ° C., and the carbon dioxide absorption amount per 1 g of the carbon dioxide gas absorber was 290 mg, which was measured by the same method as in Example 1.

7. Comparative Example 1
Water was added to polyethyleneimine (manufactured by Showa Kagaku, undiluted solution, weight average molecular weight Mw10000, amine ratio 1st grade: 2nd grade: 3rd grade = 35:35:30) without adding polyvinyl alcohol, and the solid content was 18% by mass. A film-shaped carbon dioxide gas absorber (thickness: 60 μm) was obtained by the same method as in Example 1 except that an aqueous polyethyleneimine solution was obtained. The water content was 2.8% by mass, the carbon dioxide release temperature was 180 ° C., and the carbon dioxide absorption amount per 1 g of the carbon dioxide gas absorber was 119 mg, which was measured by the same method as in Example 1.

8. Comparative Example 2
Polyethylenimine (manufactured by Showa Kagaku, undiluted solution, weight average molecular weight Mw10000, amine ratio 1st grade: 2nd grade: 3rd grade = 35:35:30) and polyallylamine (manufactured by Nitto Spinning Co., Ltd., undiluted solution, weight average) without adding polyvinyl alcohol. A film was prepared by the same method as in Example 2 except that water was added to a mixture having a molecular weight of Mw15000 primary amine alone) at a mass ratio of 1: 1 to obtain an aqueous solution of polyethyleneimine and polyallylamine having a solid content of 18% by mass. A carbon dioxide gas absorber (thickness: 59 μm) was obtained. The water content was 3.6% by mass, the carbon dioxide release temperature was 185 ° C., and the carbon dioxide absorption amount per 1 g of the carbon dioxide gas absorber was 139 mg, which was measured by the same method as in Example 1.

9. Comparative Example 3
Polyethylenimine (manufactured by Showa Kagaku, undiluted solution, weight average molecular weight Mw10000, amine ratio 1st grade: 2nd grade: 3rd grade = 35:35:30) and polyallylamine (manufactured by Nitto Spinning Co., Ltd., undiluted solution, weight average) without adding polyvinyl alcohol. A film was formed by the same method as in Example 3 except that water was added to a mixture having a molecular weight of Mw15000 primary amine alone) at a mass ratio of 1: 3 to prepare a mixed aqueous solution of polyethyleneimine and polyallylamine having a solid content of 18% by mass. Carbon dioxide gas absorber (thickness: 62 μm) was obtained. The water content was 3.9% by mass, the carbon dioxide release temperature was 191 ° C., and the carbon dioxide absorption amount per 1 g of the carbon dioxide gas absorber was 147 mg, which was measured by the same method as in Example 1.

10. Comparative Example 4
Same as Example 3 except that water was added to 100 g of polydialylamine (manufactured by Nitto Boseki, weight average molecular weight Mw5000 secondary amine alone) without adding polyvinyl alcohol to obtain a polydialylamine aqueous solution having a solid content of 18% by mass. A film-like carbon dioxide absorber (thickness: 62 μm) was obtained by the above method. The water content was 2.9% by mass, the carbon dioxide release temperature was 164 ° C, and the carbon dioxide absorption amount per 1 g of the carbon dioxide gas absorber was 79 mg, which was measured by the same method as in Example 1.

11. Example 7
(1) Preparation of Carbonate Gas Absorber 1000 g of a 10 mass% polyvinyl alcohol (Kuraray, PVA-117, average degree of polymerization: 1700, saponification degree 98-99%) aqueous solution was added to a 5 L flask, and the mixture was stirred with a mechanical stirrer. .. Next, 100 g of polyethyleneimine (manufactured by Showa Kagaku, undiluted solution, weight average molecular weight Mw10000, amine ratio 1st grade: 2nd grade: 3rd grade = 35:35:30) was added, and stirring was continued at 25 ° C. for 3 hours to 18% by mass. A mixed solution of the above was obtained. The obtained mixed solution was coated on a 100 μm polyethylene terephthalate (PET) film to a thickness of 500 μm, and then dried in a dryer at 80 ° C. for 30 minutes. The polyvinyl alcohol-polyethyleneimine mixed film was peeled off from the PET film to obtain a film-like carbon dioxide gas absorber. The film thickness of the mixed film was 60 μm.

(2) Measurement of Moisture Content The water content of the obtained carbon dioxide absorber was measured according to the following method.
After vacuum-drying 10 g of the sample for moisture content measurement at 105 ° C. for 6 hours and 140 ° C. for 3 hours, 1 g of the sample is weighed in a glove box in an inert atmosphere, and Karl Fischer (Mitsubishi Chemical Analytical Analysis) is used in the dry chamber. It was heated to 140 ° C. (manufactured by Tech), and the amount of moisture absorbed was measured under a nitrogen stream. The water content of the film-shaped carbon dioxide absorber obtained in (1) above was 215 ppm.

(3) Measurement of carbon dioxide release temperature 1 g of the film-shaped carbon dioxide gas absorber obtained in (1) above is put in a desiccator, 10 g of carbon dioxide is put in, and the mixture is stored at 25 ° C. for 1 hour and then taken out to obtain differential heat. The carbon dioxide emission temperature of the carbon dioxide absorber was measured using a thermogravimetric simultaneous measuring device: TG-DTA, manufactured by Seiko Instruments. As a result, it was confirmed that the heat weight decreased due to the release of adsorbed water around 100 ° C. and the heat weight decrease due to the release of carbon dioxide around 170 ° C.

(4) Preparation of coin-type lithium secondary battery To prepare the slurry for the electrode, a 10 wt% aqueous solution of SBR as a binder for the negative electrode is added to 100 parts by weight of natural graphite (DMGS, BYD) as the active material for the negative electrode. As a result, 6.452 parts by weight and 1.075 parts by weight of Super-P (manufactured by Timcal Co., Ltd.) as a conductive auxiliary agent (conductivity-imparting agent) were put into a special container, and a planetary stirrer (ARE-250, Kneaded using (manufactured by Shinky). In order to adjust the slurry viscosity, water was added at the time of kneading and kneaded again to prepare a slurry for electrode coating. The composition ratio of the active material and the binder in the slurry is graphite powder: conductive auxiliary agent: binder composition = 100: 1.075: 6.452 as a solid content.

Using a bar coater (T101, manufactured by Matsuo Sangyo), coat the obtained slurry on the copper foil (C1100H, manufactured by UACJ) of the current collector, and put it in a hot air dryer (manufactured by Yamato Scientific Co., Ltd.) at 80 ° C. for 30 minutes. After primary drying, it was rolled using a roll press (manufactured by Hosen). Then, after punching as a battery electrode (φ14 mm), a coating electrode for a coin battery was produced by secondary drying under reduced pressure conditions at 120 ° C. for 3 hours.

The battery coating electrode obtained above was transferred to a glove box (manufactured by Miwa Seisakusho) in an argon gas atmosphere. A metallic lithium foil (thickness 0.2 mm, φ16 mm) was used for the positive electrode. Further, a polypropylene type (Cellguard # 2400, manufactured by Polypore) was used as the separator. The carbon dioxide absorber, the coating electrode, the separator, and the positive electrode were laminated in this order in the SUS case. As an electrolytic solution, a mixed solvent system (1M-LiPF ₆ , EC / EMC = 3) in which vinylene carbonate (VC) is added to ethylene carbonate (EC) of lithium hexafluorophosphate (LiPF ₆ ) and ethyl methyl carbonate (EMC). / 7 vol%, VC 2 wt%) was injected to prepare a coin battery (2032 type).

(5) Evaluation of charge / discharge performance The manufactured coin battery was subjected to a charge / discharge test using a charge / discharge tester (TOSCAT3100, manufactured by Toyo System). The coin battery is placed in a constant temperature bath at 25 ° C., and the battery is charged with a constant current of 0.1 C (about 0.5 mA / cm ² ) with respect to the amount of active material until it reaches 0 V with respect to the lithium potential. A constant voltage charge of 0 V was carried out up to a current of 0.02 mA. Next, a constant current discharge of 0.1 C (about 0.5 mA / cm ² ) was performed up to 1.5 V with respect to the lithium potential, and the capacity at this time was defined as the initial discharge capacity (mAh / g). After charging in the same manner, the battery was stored in a constant temperature bath at 60 ° C. for 100 hours, and the discharge capacity after storage at 60 ° C. was measured in the same manner as the initial discharge capacity. The discharge capacity retention rate was determined from the discharge capacity / initial discharge capacity ratio after storage at 60 ° C. The results are shown in Table 2.

12. Example 8
(1) Preparation of carbon dioxide gas absorber Instead of adding 100 g of polyethyleneimine (manufactured by Showa Kagaku, undiluted solution, weight average molecular weight Mw10000, amine ratio 1st grade: 2nd grade: 3rd grade = 35:35:30), polyethyleneimine (manufactured by Showa Chemical Co., Ltd.) Showa Chemical Co., Ltd., undiluted solution, weight average molecular weight Mw10000, amine ratio 1st grade: 2nd grade: 3rd grade = 35:35:30) and polyallylamine (manufactured by Nitto Spinning Co., Ltd., undiluted solution, weight average molecular weight Mw15000 primary amine alone) A film-shaped carbon dioxide gas absorber (thickness: 60 μm) was obtained by the same method as in Example 7 except that 50 g was added. The water content of the obtained carbon dioxide absorber was 238 ppm, and the carbon dioxide release temperature was 185 ° C.

(2) Preparation of Coin-type Lithium Secondary Battery A coin-type lithium secondary battery is produced from a film-shaped carbon dioxide gas absorber by the same method as in Example 7, and the discharge capacity retention rate is maintained by the same method as in Example 7. Asked. The results are shown in Table 2.

13. Example 9
(1) Preparation of carbon dioxide absorber Instead of adding 100 g of polyethyleneimine (manufactured by Showa Kagaku, weight average molecular weight Mw10000, amine ratio 1st grade: 2nd grade: 3rd grade = 35:35:30), polydialylamine (Nitto Spinning Co., Ltd.) A film-like carbon dioxide gas absorber (thickness: 60 μm) was obtained by the same method as in Example 1 except that 100 g of (Mw5000 secondary amine alone) having a weight average molecular weight was added. The water content of the obtained carbon dioxide absorber was 228 ppm, and the carbon dioxide release temperature was 165 ° C.

(2) Preparation of Coin-type Lithium Secondary Battery A coin-type lithium secondary battery is produced from a film-shaped carbon dioxide gas absorber by the same method as in Example 7, and the discharge capacity retention rate is maintained by the same method as in Example 7. Asked. The results are shown in Table 2.

14. Comparative Example 5
A coin-type lithium secondary battery was produced by the same method as in Example 7 except that the carbon dioxide absorber was not used, and the discharge capacity retention rate was determined by the same method as in Example 7. The results are shown in Table 2.

15. Example 10
(1) Preparation of Electric Double Layer Capacitor An electric double layer capacitor was prepared according to the following method using a carbon dioxide gas absorber prepared in the same manner as in Example 7.
Activated carbon is pulverized to a particle size of 5 to 20 μm to obtain powdered activated carbon, and the powdered activated carbon is 80% by weight, conductive carbon is 10% by weight, and polytetrafluoroethylene (Teflon (registered trademark) 6J, Mitsui / DuPont Chemical Co., Ltd.) is 10% by weight. The mixture consisting of% was kneaded. The obtained kneaded product was formed into a sheet having a thickness of 300 μm by roll rolling, punched into a circle having a diameter of 2 cm using a punching machine, and then dried under reduced pressure at 150 ° C. for 4 hours to obtain a sheet-shaped polar electrode. Made.

The obtained polar electrode is placed in a glove box with a dew point of -80 ° C or less, and a carbon dioxide gas absorber, a current collector, a polar electrode sheet, a polypropylene non-woven fabric, a polar electrode sheet, and a current collector are placed in a stainless steel case. After laminating in order, the polar electrode is impregnated with a propylene carbonate solution containing 1 mol of tetraethylammonium tetrafluoroborate, and an electric double-layer capacitor is crimped and sealed on the upper lid of a stainless steel case using a polypropylene insulating gasket. Was produced.

(2) Evaluation of charge / discharge performance For the obtained electric double layer capacitor, use an electric double layer capacitor evaluation device (manufactured by Hioki Denki) at room temperature up to a maximum voltage of 3.3 V, ² mA / cm ² per electrode surface area. It was charged with a constant current at 3.3 V for 30 minutes under a low voltage, and after the supplementary charge was completed, it was discharged with a constant current of ² mA / cm ² . The initial capacitance was determined by a fixed method from the discharge curve from 1.2V to 1.0V at that time. After the discharge, the battery was similarly charged to 3.3 V at 60 ° C. and stored for 100 hours. After storage, the battery was discharged in the same manner, and the capacitance retention rate was determined from the ratio with the initial capacitance. The results are shown in Table 3.

16. Example 11
An electric double layer capacitor was prepared by the same method as in Example 10 using the carbon dioxide gas absorber prepared in the same manner as in Example 8. The capacitance retention rate of the obtained electric double layer capacitor was measured by the same method as in Example 10. The results are shown in Table 3.

17. Example 12
An electric double layer capacitor was prepared by the same method as in Example 10 using the carbon dioxide gas absorber prepared in the same manner as in Example 9. The capacitance retention rate of the obtained electric double layer capacitor was measured by the same method as in Example 10. The results are shown in Table 3.

18. Comparative Example 6
An electric double layer capacitor was produced by the same method as in Example 10 except that a carbon dioxide absorber was not used, and the capacitance retention rate of the electric double layer capacitor was determined by the same method as in Example 10. The results are shown in Table 3.

Claims (10)

A carbon dioxide gas absorber composed of a mixture containing an amine-based polymer having an amino group in a repeating unit and an alcohol compound and having a water content of less than 10% by mass. The carbon dioxide absorber according to claim 1, wherein the carbon dioxide outgassing temperature is 100 ° C. or higher and 300 ° C. or lower. Claim 1 or 2 wherein the amine-based polymer is selected from the group consisting of polyethyleneimine, polyallylamine, polyacrylamide, polytetramethyleneimine, polyvinylamine, dicyandiamide-formalin condensate and dicyandiamide-alkylene (polyamine) condensate. The carbon dioxide absorber described. The carbon dioxide absorber according to any one of claims 1 to 3, wherein the alcohol compound is selected from the group consisting of monosaccharides, oligosaccharides, polysaccharides, polyvinyl alcohol and derivatives thereof, and polyphenols and derivatives thereof. The carbon dioxide absorber according to any one of claims 1 to 4, which is in the form of a film, a film, a sheet, a fiber, or a powder. The carbon dioxide absorber according to any one of claims 1 to 5, which has a water content of 500 ppm or less. A non-aqueous electrolyte storage battery comprising the carbon dioxide gas absorber according to claim 6. The non-aqueous electrolyte storage battery according to claim 7, which is a non-aqueous electrolyte secondary battery. The non-aqueous electrolyte storage battery according to claim 7, which is an electric double layer capacitor. The carbon dioxide gas absorber according to any one of claims 1 to 6 is brought into contact with a gas containing carbon dioxide gas to allow the carbon dioxide gas absorber to absorb the carbon dioxide gas, and the carbon dioxide gas absorber that has absorbed the carbon dioxide gas. A method for separating and recovering carbon dioxide gas, which comprises separating and recovering carbon dioxide gas from the gas.