JP4601273B2 - Non-aqueous solvent type secondary battery - Google Patents

Description

  The present invention relates to a non-aqueous solvent secondary battery, and more particularly to a non-aqueous solvent secondary battery excellent in cycle characteristics, quick charge characteristics, and rapid discharge characteristics.

  With the rapid spread of portable electronic devices, the required specifications for the batteries used for them are becoming stricter year by year, and in particular, small and thin, high capacity, excellent cycle characteristics, and stable performance are required. Yes. In the field of secondary batteries, lithium non-aqueous solvent secondary batteries, which have a higher energy density than other batteries, are attracting attention. The proportion of lithium non-aqueous solvent secondary batteries accounts for a significant increase in the secondary battery market. Is shown.

  This lithium non-aqueous solvent type secondary battery includes a negative electrode in which a negative electrode active material mixture is applied in a film form on both sides of a negative electrode core (current collector) made of an elongated sheet-like copper foil and the like, and an elongated sheet-like battery A separator made of a microporous polypropylene film or the like is placed between both sides of a positive electrode core made of aluminum foil or the like and coated with a positive electrode active material mixture in the form of a film, and the negative electrode and the positive electrode are insulated from each other by the separator. In the case of a rectangular battery, the wound electrode body is further crushed to form a flat shape, and a negative electrode lead and a positive electrode lead are respectively attached to predetermined portions of the negative electrode and the positive electrode. It has the structure which connected and accommodated in the exterior of a predetermined shape.

  The non-aqueous solvent of the non-aqueous electrolyte used for such a non-aqueous solvent secondary battery needs to have a high dielectric constant in order to ionize the electrolyte, and has an ionic conductivity in a wide temperature range. Because of the high necessity, carbonates such as propylene carbonate and ethylene carbonate, lactones such as γ-butyrolactone, and other organic solvents such as ethers, ketones and esters are used.

  However, if a carbonaceous material such as graphite or amorphous carbon, a siliconaceous material, or a metal oxide material is used as the negative electrode material, the organic solvent is reduced and decomposed on the electrode surface during the charge / discharge process, generating gas and generating side reactions. There has been a problem in that the negative electrode impedance increases due to the accumulation of objects and the like, resulting in a decrease in charge / discharge efficiency, deterioration in cycle characteristics, and the like.

  Therefore, conventionally, in order to suppress the reductive decomposition of the organic solvent, various compounds are added to the non-aqueous electrolyte so that the negative electrode active material does not directly react with the organic solvent. A technique for controlling a negative electrode surface coating (SEI: Solid Electrolyte Interface. Hereinafter referred to as “SEI surface coating”) is important. For example, in the following Patent Document 1, at least one selected from vinylene carbonate and derivatives thereof is added to a non-aqueous electrolyte solution as a non-aqueous electrolyte solution of a non-aqueous solvent-based secondary battery. Before the insertion of lithium into the negative electrode by the first charge, a passivation layer is formed on the negative electrode active material layer to function as a barrier that prevents the insertion of solvent molecules around lithium ions It is disclosed.

  For the same purpose, the following Patent Document 2 includes a non-aqueous electrolyte in which a vinyl ethylene carbonate compound is added as an additive, and the following Patent Document 3 includes a ketone added to the same patent. Document 4 contains vinyl ethylene carbonate, and further added at least one kind of vinylene carbonate, cyclic sulfonic acid or cyclic sulfate, and cyclic acid anhydride. Similarly, Patent Document 5 adds cyclic acid anhydride. Similarly, the following Patent Document 6 discloses the addition of a cyclic acid anhydride and a vinyl ethylene carbonate compound, respectively.

  However, the SEI surface coating obtained by adding the above-described additives disclosed in Patent Documents 1 to 6 below to the non-aqueous electrolyte solution can still only have a high resistance with low lithium ion conductivity. In other words, the negative electrode impedance is remarkably increased, so that the quick charge and rapid discharge performance is deteriorated.

JP 08-045545 A (claims, paragraphs [0009] to [0012], [0023] to [0036]) JP 2001-006729 A (claims, paragraphs [0006] to [0014]) JP 2001-202991 A (claims, paragraphs [0006] to [0009]) JP 2003-151623 A (claims, paragraphs [0008] to [0009], [0022] to [0031]) JP 2000-268859 A (claims, paragraphs [0007] to [0008]) JP 2002-352852 A (claims, paragraphs [0010] to [0013])

The present inventor has made various studies on the generation mechanism of the SEI surface coating described above, and as a result, when the cyclic acid anhydride is contained in the non-aqueous electrolyte, carbon dioxide is separately dissolved , and the cyclic acid anhydride is anhydrous. When succinic acid or diglycolic anhydride is contained at a specific ratio, the impedance of the SEI surface coating is reduced, and the cycle characteristics can be improved without reducing the rapid charge and rapid discharge performance. I found. The reason why such a result can be obtained is not clear at present, and it is necessary to wait for further research. Probably, the inorganic coating component mainly composed of lithium carbonate produced by reduction of carbon dioxide during charging is lithium ion. It is presumed that SEI film growth with excellent conductivity was promoted.

  Accordingly, an object of the present invention is to provide a non-aqueous solvent secondary battery excellent in cycle characteristics, quick charge characteristics, and rapid discharge characteristics by reducing the impedance of the SEI surface coating.

The above object of the present invention can be achieved by the following configurations. That is, the invention of the nonaqueous solvent secondary battery according to claim 1 of the present application has at least a positive electrode having a positive electrode material reversibly occluding and releasing lithium and a negative electrode material reversibly occluding and releasing lithium. In a non-aqueous solvent secondary battery comprising a negative electrode and a non-aqueous electrolyte, the non-aqueous electrolyte contains a cyclic acid anhydride and carbon dioxide gas is dissolved, and the cyclic acid anhydride is succinic anhydride. Or it is diglycolic anhydride and is contained in the said nonaqueous electrolyte solution in the ratio of 0.01-10 mass%, It is characterized by the above-mentioned.

In the non-aqueous solvent type secondary battery of the present invention, if the content of the cyclic acid anhydride is less than 0.01% by mass, the effect of addition of the acid anhydride is not substantially recognized, and 10% by mass. Exceeding this value is not preferable because the amount of dissolved electrolyte is reduced by that amount, the electrolyte concentration is lowered, and the electrical conductivity of the nonaqueous electrolytic solution is reduced. More desirably, the cyclic acid anhydride is in the range of 0.05% by mass to 5% by mass in the non-aqueous electrolyte.

The nonaqueous solvent (organic solvent) constituting the nonaqueous electrolytic solution that can be used in the nonaqueous solvent secondary battery of the present invention includes carbonates, lactones, ethers, esters, aromatic hydrocarbons, and the like. Among these, carbonates, lactones, ethers, ketones, esters and the like are preferable, and carbonates are more preferably used.

  Specific examples of carbonates include propylene carbonate, ethylene carbonate, butylene carbonate, γ-butyrolactone, γ-valerolactone, γ-dimethoxyethane, tetrahydrofuran, anisole, 1,4-dioxane, diethyl carbonate, and the like. Propylene carbonate and ethylene carbonate are preferably used from the viewpoint of increasing charge / discharge efficiency. Two or more of these solvents can be mixed and used.

The electrolyte constituting the nonaqueous electrolytic solution that can be used in non-aqueous solvent secondary battery of the present invention, lithium perchlorate (LiClO _4), lithium hexafluorophosphate (LiPF _6), lithium tetrafluoroborate ( LiBF ₄ ), lithium hexafluoroarsenate (LiAsF ₆ ), lithium trifluoromethylsulfonate (LiCF ₃ SO ₃ ), lithium bistrifluoromethylsulfonylimide [LiN (CF ₃ SO ₂ ) ₂ ] and the like can be mentioned. . Of these, LiPF ₆ and LiBF ₄ are preferably used, and the amount dissolved in the non-aqueous solvent is preferably 0.5 to 2.0 mol / l.

In addition, the positive electrode active material that can be used in the nonaqueous solvent secondary battery of the present invention includes LixMO ₂ (wherein M is at least one of Co, Ni, and Mn), a lithium transition metal composite oxide. LiCoO ₂ , LiNiO ₂ , LiNiCo _1-y O ₂ (y = 0.01 to 0.99), Li _0.5 MnO ₂ , LiMnO ₂ , LiCo _x Mn _y Ni _z O ₂ (x + y + z = 1) May be used singly or in combination.

Further, the negative electrode active material that can be used in the nonaqueous solvent secondary battery of the present invention is at least one selected from the group consisting of carbonaceous materials, siliconaceous materials, and metal oxides capable of occluding and releasing lithium. Mixtures of the above are used.

  In addition, when carbon dioxide is dissolved in a non-aqueous electrolyte containing a cyclic acid anhydride, it is desirable to keep the temperature of the non-aqueous electrolyte and the partial pressure of the carbon dioxide constant and to saturate by bubbling.

The invention according to claim 2 of the present application is the nonaqueous solvent secondary battery according to claim 1, wherein the carbon dioxide has a partial pressure of carbon dioxide of 1.01 × 10 ^{4 to} 5.07 ×. It is characterized by being contained by bubbling in a non-aqueous electrolyte at room temperature within a range of 10 ⁵ pa (0.1 to ⁵ atm).

  If the partial pressure of carbon dioxide gas during bubbling is too low, the amount dissolved in the non-aqueous electrolyte decreases, and it is difficult to obtain a sufficient effect. Since it is degassed violently when it is returned to, it becomes difficult to handle in the process.

The invention according to claim 3 of the present application is characterized in that, in the non-aqueous solvent secondary battery according to claim 1, the non-aqueous electrolyte is gelled.

  When the electrolyte is gelled, the negative electrode interface resistance increases because the polymer component adheres to the surface of the negative electrode active material. Therefore, the increase in the interfacial resistance due to the addition of the cyclic acid anhydride causes a significant deterioration in characteristics as compared with the nonaqueous solvent secondary battery using the liquid electrolyte. Therefore, the effect of dissolving the carbon dioxide gas as in the present invention is remarkable. is there.

The invention according to claim 4 of the present application is the nonaqueous solvent secondary battery according to claim 3 , wherein the content of the electrolyte in the gelled nonaqueous electrolyte is gelled. It is characterized by being 50 mass% or more and 99.5 mass% or less with respect to the total amount of the non-aqueous electrolyte solution.

   If the content of the electrolytic solution in the gelled non-aqueous electrolytic solution is too small, less than 50% by mass, the ionic conductivity is lowered and the high load discharge capacity is lowered. More preferably, it is 75 mass% or more with respect to the total amount of the gel electrolyte. Furthermore, when the content of the electrolytic solution exceeds 99.5% by mass, the mechanical strength of the gelled non-aqueous electrolytic solution cannot be obtained.

In the gel electrolyte that can be used in the nonaqueous solvent secondary battery of the present invention, the polymer that holds the electrolytic solution includes an alkylene oxide polymer and a fluorine-based polymer such as a polyvinylidene fluoride-hexafluoropropylene copolymer. Examples thereof include a polymer such as a polymer. A method for forming a gel electrolyte using such a polymer material can be obtained by immersing the electrolytic solution in a polymer such as an isocyanate cross-linked product of polyethylene oxide, polypropylene oxide, or polyalkylene oxide.

   In addition, a method of subjecting an electrolytic solution containing a polymerizable gelling agent to a polymerization treatment such as ultraviolet curing or thermosetting, or a method of cooling a solution obtained by dissolving a polymer that forms a gel electrolyte at room temperature at a high temperature. Are also preferably used. When using a polymerizable gelling agent-containing electrolyte, examples of the polymerizable gelling agent include those having an unsaturated double bond such as acryloyl group, methacryloyl group, vinyl group, allyl group, epoxy, oxetane, Examples thereof include those having a cationically polymerizable cyclic ether group such as formal.

   Specifically, acrylic acid, methyl acrylate, ethyl acrylate, ethoxyethyl acrylate, methoxyethyl acrylate, ethoxyethoxyethyl acrylate, polyethylene glycol monoacrylate, ethoxyethyl methacrylate, ethoxyethyl methacrylate, polyethylene glycol monomethacrylate, N, N- Diethylaminoethyl acrylate, glycidyl acrylate, allyl acrylate, acrylonitrile, diethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, polyalkylene glycol dimethacrylate , Polyalkylene glycol dimethacrylate, trimethylolpropane alkoxylate triacrylate, pentaerythritol alkoxylate triacrylate, pentaerythritol alkoxylate tetraacrylate and other monomers having an unsaturated double bond, methyl methacrylate and (3-ethyl-3 -Oxetanyl) methyl acrylate copolymer (molecular weight 400,000), cyclic ether group-containing compounds such as tetraethylene glycol bisoxetane, and the like.

   A monomer having an unsaturated bond can be polymerized by heat, ultraviolet light, electron beam, or the like, but a polymerization initiator may be added to the electrolyte solution in order to effectively advance the reaction. Examples of the polymerization initiator include organic compounds such as benzoyl peroxide, t-butyl peroxycumene, lauroyl peroxide, di-2-ethylhexyl peroxydicarbonate, t-butyl peroxypivalate, and t-hexyl peroxyisopropyl monocarbonate. Peroxides can be used.

Polymerization of the cyclic ether group-containing compound is initiated by heat or charge / discharge due to Li ⁺ or a small amount of H ⁺ in the electrolyte.

   On the other hand, a method of cooling a polymer that forms a gel electrolyte at room temperature at a high temperature is dissolved in an electrolyte solution. As such a polymer, a gel is formed with respect to the electrolyte solution and is stable as a battery material. Anything may be used. For example, polymers having a ring such as polyvinyl pyridine and poly-N-vinyl pyrrolidone; acrylic derivative polymers such as methyl polyacrylate and polyethyl acrylate; fluorine-based resins such as polyvinyl fluoride and polyvinylidene fluoride; polyacrylonitrile CN group-containing polymers such as polyvinylidene cyanide; polyvinyl alcohol polymers such as polyvinyl acetate and polyvinyl alcohol; halogen-containing polymers such as polyvinyl chloride and polyvinylidene chloride. Moreover, it can be used even if it is a mixture with said polymer | macromolecule, a modified body, a derivative | guide_body, a random copolymer, a graft copolymer, a block copolymer etc. The weight average molecular weight of these polymers is usually in the range of 10,000 to 5,000,000. When the molecular weight is low, it is difficult to form a gel. If the molecular weight is high, the viscosity becomes too high and handling becomes difficult.

The present invention contains a specific cyclic acid anhydride in the non-aqueous electrolyte and dissolves carbon dioxide gas, so that the impedance of the SEI film becomes very low. As described in detail below, the cycle characteristics, A non-aqueous solvent secondary battery excellent in rapid charge characteristics and rapid discharge characteristics can be obtained.

  BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the best mode for carrying out the present invention will be described in detail using examples and comparative examples. First, a specific method for producing a nonaqueous solvent secondary battery common to the examples and comparative examples will be described. Will be described.

<Preparation of positive electrode plate>
A positive electrode active material made of LiCoO _{2 is} a carbon-based conductive agent (for example, 5% by mass) such as acetylene black and graphite, and a binder (for example, 3% by mass) made of polyvinylidene fluoride (PVdF) is N-methyl. A material dissolved in an organic solvent made of pyrrolidone is mixed to obtain an active material slurry or an active material paste. These active material slurries or active material pastes, in the case of slurry using a die coater, a doctor blade, etc., in the case of paste, a positive electrode core (for example, an aluminum foil or aluminum mesh having a thickness of 20 μm) by a roller coating method or the like The positive electrode plate which apply | coated uniformly on both surfaces and apply | coated the active material layer is formed. Then, the positive electrode plate coated with the active material layer is passed through a dryer to remove and dry the organic solvent necessary for making the slurry or paste. After drying, the positive electrode plate is rolled with a roll press. The positive electrode plate has a thickness of 0.17 mm.

<Preparation of negative electrode plate>
A slurry or paste prepared by mixing a negative electrode active material made of natural graphite, a binder (for example, 3% by mass) made of polyvinylidene fluoride (PVdF) and an organic solvent made of N-methylpyrrolidone, etc. And These slurries or pastes, die coater in the case of the slurry using a doctor blade or the like, the negative electrode substrate in the case of a paste by a roller coating method (e.g., copper foil 20μm thick) evenly over both sides of the entire surface of The negative electrode plate which apply | coated and applied the active material layer is formed. Thereafter, the negative electrode plate coated with the active material layer is passed through a drier to remove the organic solvent that was necessary when making the slurry or paste and dry it. After drying, the dried negative electrode plate is rolled by a roll press to obtain a negative electrode plate having a thickness of 0.14 mm.

<Production of electrode body>
The positive electrode plate and the negative electrode plate prepared as described above are sandwiched with a microporous membrane (for example, a thickness of 0.025 mm) made of a polyolefin resin that is low in reactivity with an organic solvent and inexpensive, and The center lines in the width direction of each electrode plate are aligned and overlapped. Then, it winds with a winder and tapes the outermost periphery, and it is set as the spiral electrode body of an Example and a comparative example. Next, the electrode bodies produced as described above are inserted into the exterior bodies made of aluminum laminate, and the positive electrode current collecting tab and the negative electrode current collection tab extending from the electrode bodies are welded together with the exterior body.

<Preparation of electrolyte>
An electrolyte is prepared by dissolving in a solvent mixed at a mass ratio of ethylene carbonate (EC) / diethylene carbonate (DEC) = 30/70 at a ratio of 1.0M-LiPF ₆ and cyclic acid is added to the electrolyte. When the anhydride was added, the amount added was 1.0% by mass with respect to the mass of the electrolyte. Carbon dioxide was dissolved by bubbling (carbon dioxide partial pressure: 1.01 × 10 ⁵ Pa; 10 L / min-30 min) from the bottom of 3 L of the electrolyte kept at 23 ° C.

<Production of battery>
Next, necessary amounts of various electrolytes were injected from the opening of the outer package and sealed to prepare lithium ion secondary batteries having a design capacity of 750 mAh for all of the examples and comparative examples.

The cyclic acid anhydride used is
(A) Succinic anhydride (b) Methyl succinic anhydride (c) 5-Norbornene-2,3-dicarboxylic anhydride (d) Nonenyl succinic anhydride (e) Glutaric anhydride (f) Maleic anhydride (g) Di-anhydride Seven types of glycolic acid, in which the carbon dioxide gas was not dissolved in each case, were sequentially designated as Comparative Example 1 to Comparative Example 7, and in each case the carbon dioxide gas was dissolved in the order of Example 1 and Reference Examples 1 to 1. 5 and Example 2, and Comparative Example 8 in which no cyclic acid anhydride was added and carbon dioxide was not dissolved Comparative Example 8 in which no cyclic acid anhydride was added and carbon dioxide was dissolved It was set to 9.

<Charging / discharging conditions>
For each of the non-aqueous solvent secondary batteries of Examples 1 and 2, Reference Examples 1 to 5, and Comparative Examples 1 to 9 produced as described above, various charge / discharge conditions were performed under the following charge / discharge conditions. A test was conducted. The ambient temperature during the charge / discharge test is 25 ° C.

<Measurement of initial discharge capacity>
First, each battery is charged with a constant current of 1 It = 750 mA (1 C), and after the battery voltage reaches 4.2 V, it is charged with a constant voltage of 4.2 V for 3 hours, and then a constant current of 1 It. The battery was discharged until the battery voltage reached 2.75 V, and the discharge capacity at this time was determined as the initial discharge capacity.

<Measurement of cycle characteristics>
The cycle characteristics were measured by charging each battery whose initial charge / discharge capacity was measured at a constant current of 1 It until the battery voltage reached 4.2 V, then charging at a constant voltage of 4.2 V for 3 hours, and then 1 It of Discharging until the battery voltage reached 2.75 V at a constant current was taken as one cycle, and repeated until 300 cycles were reached, and the discharge capacity at 300 cycles was determined. And about each battery, capacity | capacitance residual rate (%) was calculated | required based on the following formulas. The results are shown in Table 1.
Capacity remaining rate (%) = (discharge capacity at 300 cycles / initial discharge capacity) × 100

<Quick chargeability>
Each battery whose initial charge / discharge capacity was measured was charged at a constant current of 3 It until the battery voltage reached 4.2 V, and the charge capacity at that time was determined as a CC (Constant Current) charge capacity. Thereafter, the battery was charged at a constant voltage of 4.2 V for 3 hours, and the total charge capacity was determined from the current value that had flowed up to this point. The results are summarized in Table 1.
CC charge rate (%) = (CC charge capacity / total charge capacity) × 100

<Rapid discharge characteristics>
Each battery whose initial charge / discharge capacity was measured was charged at a constant current of 1 It until the battery voltage reached 4.2 V, and then charged at a constant voltage of 4.2 V for 3 hours. Thereafter, the battery is discharged at a constant current of 3 It until the battery voltage reaches 2.75 V, and the discharge capacity at this time is obtained as a 3 It discharge capacity. For a similar battery, the battery voltage is 2.75 V at a constant current of 0.2 It. The discharge capacity at this time was determined as a 0.2 It discharge capacity, and the rapid discharge efficiency was determined by the following formula. The results are summarized in Table 1.
Rapid discharge efficiency (%) = (3 It discharge capacity / 0.2 It discharge capacity) × 100

From the results of Table 1, the following can be seen based on the results of the non-aqueous solvent secondary battery of Comparative Example 8 in which neither the cyclic acid anhydride nor carbon dioxide is contained in the non-aqueous electrolyte.
(1) The non-aqueous solvent secondary battery of Comparative Example 9 containing only carbon dioxide is slightly more than the non-aqueous solvent secondary battery of Comparative Example 8 in terms of cycle characteristics, quick charge characteristics, and rapid discharge characteristics. Are better.
(2) The non-aqueous solvent secondary batteries of Comparative Examples 1 to 7 that contain only cyclic acid anhydrides and do not contain carbon dioxide gas have cycle characteristics that are higher than those of the non-aqueous secondary battery of Comparative Example 8. Although excellent, quick charge characteristics and rapid discharge characteristics are inferior to those of the non-aqueous solvent secondary battery of Comparative Example 8.
(3) The non-aqueous solvent type secondary batteries of Example 1 and Reference Examples 1 to 5 and Example 2 containing both cyclic acid anhydride and carbon dioxide gas have the same cycle characteristics as those of Comparative Example 8. It is superior to the water-based secondary battery, and both the quick charge characteristics and the rapid discharge characteristics are comparable to those of the nonaqueous solvent-type secondary battery of Comparative Example 8. In particular, the results of Examples 1 and 2 using succinic anhydride or diglycolic anhydride as the cyclic acid anhydride were more than the results of Reference Examples 1 to 5 using other reduced acid anhydrides, and the cycle characteristic capacity remaining. Rate, rapid charge / discharge characteristics and discharge efficiency are excellent .

In addition, the non-aqueous solvent secondary battery of Example 1 , Reference Examples 1 to 5 and Example 2 has cycle characteristics as compared with the non-aqueous solvent secondary battery of Comparative Example 9 containing only carbon dioxide gas. Are excellent, and the rapid charge characteristics and rapid discharge characteristics are comparable. In addition, the nonaqueous solvent secondary batteries of Example 1 , Reference Examples 1 to 5 and Example 2 are respectively compared with the corresponding nonaqueous solvent secondary batteries of Comparative Examples 1 to 7 not containing carbon dioxide gas. Then, it can be seen that the cycle characteristics are slightly improved.

From the above, in the present invention, by including both succinic anhydride or diglycolic acid anhydride and carbon dioxide as the cyclic acid anhydride, compared with the conventional example in which only the cyclic acid anhydride is added. In addition, a non-aqueous solvent type secondary battery excellent in cycle characteristics, quick charge characteristics and rapid discharge characteristics can be obtained.

  Further, in Examples 1 and 2 above, only examples using a liquid non-aqueous electrolyte were shown, but the effect of the present invention is a phenomenon caused by SEI at the interface of the negative electrode, so it does not vary depending on the properties of the electrolyte. Therefore, it will be apparent to those skilled in the art that the same effect can be obtained even when the non-aqueous electrolyte is gelled.

Claims (4)

In a nonaqueous solvent secondary battery comprising at least a positive electrode having a positive electrode material that reversibly occludes / releases lithium, a negative electrode having a negative electrode material that reversibly occludes / releases lithium, and a nonaqueous electrolyte solution,
Including the cyclic acid anhydride in the non-aqueous electrolyte solution and dissolving carbon dioxide gas ,
The cyclic acid anhydride is succinic anhydride or diglycolic anhydride, and is contained in the nonaqueous electrolytic solution in a proportion of 0.01 to 10% by mass. battery. The carbon dioxide gas is contained by bubbling in a non-aqueous electrolyte at room temperature in the range of carbon dioxide partial pressure of 1.01 × 10 ^{4 to} 5.07 × 10 ⁵ pa. The non-aqueous solvent secondary battery according to claim 1.   The non-aqueous solvent secondary battery according to claim 1, wherein the non-aqueous electrolyte is gelled. The content of the electrolyte in the nonaqueous electrolytic solution is the gelation claims, characterized in that the total amount of the nonaqueous electrolytic solution is gelled at most 50 wt% 99.5 wt% Item 4. The nonaqueous solvent secondary battery according to Item 3 .