JP2011159596A - Secondary battery and method of manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a secondary battery capable of attaining high capacity by enlarging an area of a negative electrode, and a method of manufacturing the same. <P>SOLUTION: In the secondary battery 10, a positive electrode 11 and the negative electrode 12 are arranged through an electrolyte 15, charge and discharge of the secondary battery is performed by exchanging ions of alkaline metal or alkaline earth metal between both electrodes. The negative electrode 12 is formed under conditions that an active material layer including alkaline metal or alkaline earth metal is not formed on a collector 13 at the time of assembling the secondary battery 10, at least one of the positive electrode 11 and the electrolyte 15 contains ions of alkaline metal or alkaline earth metal. Furthermore, alkaline metal or alkaline earth metal is deposited on the collector 13 of the negative electrode at the time of charging. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a secondary battery in which a positive electrode and a negative electrode are arranged via an electrolyte, and charge and discharge are performed by exchanging ions of alkali metal or alkaline earth metal between the two electrodes, and a method for manufacturing the same. is there. In particular, the present invention relates to a secondary battery suitable for upsizing that can increase the negative electrode area and achieve high capacity.

  The secondary battery is used for power load leveling, emergency power supply, instantaneous power failure countermeasure, and the like. As one of such secondary batteries, a sodium-sulfur (NAS) battery is known. For example, in Patent Document 1, molten metal sodium, which is a negative electrode active material, and molten sulfur, which is a positive electrode active material, are arranged, and a gap between the two is separated by a β-alumina solid electrolyte that is selectively conductive to sodium ions. A NAS battery has been disclosed.

Moreover, a lithium ion battery is also known as another secondary battery. For example, Patent Document 2 discloses a lithium ion battery using metallic lithium as a negative electrode active material and lithium cobaltate (LiCoO ₂ ) as a positive electrode active material.

In recent years, magnesium ion batteries have been attracting attention and research and development have been promoted. For example, Patent Document 3 discloses a magnesium ion battery using metallic magnesium as a negative electrode active material and magnesium oxide (Mg _x CoO ₂ ) as a positive electrode active material.

  These secondary batteries charge and discharge by exchanging ions of alkali metals such as Na and Li or alkaline earth metals such as Mg between the positive electrode and the negative electrode through the electrolyte. A high energy density can be obtained by using an alkali metal or an alkaline earth metal for the negative electrode.

JP 2007-273297 A JP 2009-43535 A JP 2001-76720 A

  In the above-described conventional secondary battery, an alkali metal or alkaline earth is provided on a current collector such as a foil (plate) obtained by rolling an alkali metal or an alkaline earth metal on the negative electrode, or a foil (plate) made of Cu, Ni, or stainless steel. A material in which an active material layer is formed by vapor deposition of a similar metal by a vapor phase method (for example, a vacuum deposition method or a sputtering method) is used. However, in the conventional secondary battery, it is difficult to increase the area of the negative electrode, and there is a limit to improving the battery capacity.

  Alkali metals or alkaline earth metals such as Na, Li, and Mg react with moisture and oxygen in the atmosphere, and therefore must be handled in a dry inert gas. For this reason, it is necessary to perform rolling and vapor deposition in a box with controlled moisture content so that these metals do not come into contact with the atmosphere. Due to equipment limitations, the area is large (eg, 500 mm x 500 mm or more). It is difficult to produce a negative electrode. Therefore, the conventional secondary batteries are mainly small-sized batteries whose battery capacity is limited to the negative electrode area and whose battery capacity is small.

  Although the secondary battery can be used alone, it is common to connect a plurality of the secondary batteries as an assembled battery. Here, when the battery capacity per battery is small, it is necessary to use a large number of batteries in order to secure a predetermined capacity as a whole assembled battery. Since the number increases, there are problems in terms of productivity and cost. Therefore, a large secondary battery having a large negative electrode area and a large battery capacity may be advantageous from the viewpoint of productivity and cost.

  The present invention has been made in view of the above circumstances, and one of its purposes is to increase the negative electrode area and achieve a higher capacity, and a secondary battery suitable for upsizing, and its manufacture. It is to provide a method.

  When assembling the secondary battery, the present inventors made a negative electrode composed of a negative electrode current collector in which a negative electrode active material layer containing an alkali metal or an alkaline earth metal was not formed, and charged by charging after the battery was assembled. The above problem is solved by precipitating alkali metal or alkaline earth metal on the negative electrode current collector.

  In the secondary battery of the present invention, the positive electrode and the negative electrode are arranged via an electrolyte, and charge and discharge are performed by exchanging ions of alkali metal or alkaline earth metal between these electrodes. When the battery is assembled, the negative electrode is configured in a state where an active material layer containing an alkali metal or an alkaline earth metal is not formed on the current collector, and at least one of the positive electrode and the electrolyte is an alkali metal. Alternatively, alkaline earth metal ions are contained. In addition, an alkali metal or an alkaline earth metal is deposited on the negative electrode current collector during charging.

On the other hand, the method for manufacturing a secondary battery according to the present invention includes the following steps.
A step of preparing a positive electrode or an electrolyte containing alkali metal or alkaline earth metal ions.
A step of disposing a positive electrode and a negative electrode current collector through an electrolyte without forming a negative electrode active material layer containing an alkali metal or an alkaline earth metal on the negative electrode current collector.
A step of arranging a positive electrode and negative electrode current collector and an electrolyte and then charging to deposit an alkali metal or alkaline earth metal on the negative electrode current collector.

  According to the secondary battery of the present invention, when assembling a battery in which a positive electrode and negative electrode current collector and an electrolyte are arranged, the negative electrode has an active material layer containing an alkali metal or alkaline earth metal on the current collector. It is configured in a state where it is not formed. Therefore, as in the past, the active material layer is obtained by depositing alkali metal or alkaline earth metal on a foil (plate) obtained by rolling an alkali metal or alkaline earth metal on the negative electrode, or on a foil or plate-like current collector. It is not necessary to use what formed. Further, by charging / discharging after battery assembly, an alkali metal or alkaline earth metal can be reversibly deposited and dissolved on the negative electrode current collector. Therefore, it is possible to increase the size (large area) of the negative electrode, which has heretofore been difficult due to restrictions on equipment, and it is easy to achieve high capacity, which is suitable for increasing the size. Here, in the present invention, the alkali metal or alkaline earth metal includes precipitation in a solid state or a molten (liquid) state.

  As one form of the secondary battery of this invention, the form whose alkali metal is Na is mentioned.

  In the secondary battery of the present invention, the alkali metal or alkaline earth metal is not particularly limited, and examples thereof include Na and Li for alkali metals, and Mg and Ca for alkaline earth metals. When Na is selected, the battery is a sodium ion battery, when Li is selected, the battery is a lithium ion battery, when Mg is selected, the battery is a magnesium ion battery, and when Ca is selected, the battery is a calcium ion battery. Among them, Na is abundant in resources, inexpensive and stable in supply, and therefore suitable for upsizing.

  As one form of the secondary battery of this invention, the form whose electrolyte is molten salt is mentioned.

  In the secondary battery of the present invention, examples of the electrolyte include a molten salt, an organic electrolyte, and a solid electrolyte. Among them, the molten salt is suitable for high energy density because it is nonflammable, high in safety, and high in ion conductivity.

  As one form of the secondary battery of the present invention, at least a part of the electrolyte-side surface of the negative electrode current collector is Al, Cr, Fe, Ni, Cu, Mo, W, Pt and Au, and alloys and stainless steels thereof. The form currently formed with at least 1 type of these is mentioned.

  In the secondary battery of the present invention, as the negative electrode current collector, a metal material having good wettability with an alkali metal or alkaline earth metal and good conductivity can be suitably used. Examples of such metals include at least one of Al, Cr, Fe, Ni, Cu, Mo, W, Pt, and Au, alloys thereof, and stainless steel. For example, when the alkali metal is Na, it is preferable to select at least one of Al, Mo, W, Pt and Au, and alloys thereof. The negative electrode current collector may be entirely formed of the above metal alone, but may be formed by forming the above metal on the surface of the substrate. When using the above-mentioned metal formed on the surface of the substrate, at least a part of the surface on the electrolyte side is made of the above metal when the negative electrode current collector is used. Examples of the method for forming a metal on the substrate surface include vapor deposition or plating of a metal on the surface of the substrate, or pressure bonding or adhesion of a foil or plate metal.

  The secondary battery of the present invention and the method for manufacturing the secondary battery are suitable for increasing the size by increasing the area of the negative electrode and achieving high capacity.

It is a schematic cross section which shows an example of a structure of the secondary battery which concerns on this invention, (A) shows the state at the time of an assembly, (B) shows the state at the time of charge.

  Embodiments of the present invention will be described below.

[Secondary battery]
In a secondary battery 10 shown in FIG. 1, a positive electrode 11 and a negative electrode 12 are arranged via an electrolyte 15, and charge and discharge are performed by exchanging ions of alkali metal or alkaline earth metal between these electrodes. More specifically, the operating temperature of the battery is 250 ° C. or lower, preferably 200 ° C. or lower, more preferably 150 ° C. or lower, particularly preferably 100 ° C. or lower, and most preferably 80 ° C. or lower. In the case of a NAS battery, the operating temperature is as high as 300 to 350 ° C., so the heating energy consumed for operation is large. In contrast, if the operating temperature is as low as 250 ° C. or less, the heating energy required for battery operation can be saved. Specific examples include a molten salt battery using a molten salt as an electrolyte, a lithium ion battery, and the like. The molten salt battery is usually suitable for high energy density because the electrolyte is nonflammable and highly safe, and the electrolyte has high ionic conductivity. The lithium ion battery may be heated but can operate without heating. Hereinafter, the configuration of each battery will be described in more detail.

{Molten salt battery}
The molten salt battery described here has the same basic configuration as that shown in FIG. 1, and includes a positive electrode 11, a negative electrode 12, and an electrolyte 15 made of a molten salt. For the electrolyte 15, a separator impregnated with a molten salt may be used. These power generation elements are housed in a case (not shown).

(Positive electrode)
As the positive electrode 11, one containing a metal or a metal compound, a binder, and a conductive additive can be suitably used. As this metal or metal compound, those that intercalate one of alkali metals or alkaline earth metals are suitable. In particular, when the alkali metal is Na, a metal or metal compound represented by the following formula is preferable in that it has excellent charge / discharge cycle characteristics and a battery having a high energy density can be obtained.
NaxM1yM2zM3w Equation 1

In Formula 1, M1 represents Fe, Ti, Cr, Mn or V, M2 represents PO ₄ or S, and M3 represents F or O. X is a real number that satisfies the relationship 0 ≦ x ≦ 2, y is a real number that satisfies the relationship 0 ≦ y ≦ 1, z is a real number that satisfies the relationship 0 ≦ z ≦ 2, and w is 0 It is a real number that satisfies the relationship of ≦ w ≦ 3. The relationship x + y> 0 is satisfied, and the relationship z + w> 0 is satisfied. Specific examples of the positive electrode 11 include NaCrO ₂ , TiS ₂ , NaMnF ₃ , Na ₂ FePO ₄ F, NaVPO ₄ F, Na _0.44 MnO _{2 and the} like.

  As the binder, polytetrafluoroethylene (PTFE) can be suitably used. The content of the binder in the positive electrode 11 is preferably 40% by mass or less. In particular, 1% by mass or more and 10% by mass or less is more preferable. When the content of the binder is within the specified range, the metal or metal compound and the conductive additive can be more firmly fixed, and the conductivity of the positive electrode 11 can be easily made appropriate. This binder is not necessarily contained in the positive electrode 11.

  As the conductive assistant, carbon black such as ketjen black or acetylene black can be used. The content of the conductive additive in the positive electrode 11 is preferably 40% by mass or less. In particular, 5% by mass or more and 20% by mass or less is more preferable. If the content rate of a conductive support agent is the said regulation range, it is excellent in the cycling characteristics of charging / discharging, and it is easy to obtain a battery of high energy density. The conductive auxiliary agent may be added as appropriate according to the conductivity of the positive electrode, and is not essential.

  Further, the positive electrode 11 may include a positive electrode current collector. Examples of the method for producing the positive electrode include applying a solvent mixed with the above positive electrode material to the surface of the current collector, mixing the above positive electrode material, press-molding, and then firing. As the positive electrode current collector, for example, Al, Ni, stainless steel, or the like can be used.

(Negative electrode)
The negative electrode 12 is configured in a state where an active material layer containing an alkali metal or an alkaline earth metal is not formed on a current collector at the time of battery assembly. In this example, the negative electrode 12 includes only the negative electrode current collector 13 (see FIG. 1A). As the negative electrode current collector 13, a metal material having good wettability with an alkali metal or alkaline earth metal and having good conductivity can be suitably used.For example, Al, Cr, Fe, Ni, Cu, Mo, W, At least one of Pt and Au, alloys thereof and stainless steel can be used. In particular, when the alkali metal is Na, it is preferable to select at least one of Al, Mo, W, Pt and Au, and alloys thereof.

  In addition, the negative electrode 12 is charged with an alkali metal or alkaline earth metal ion (eg, Na ion) previously contained in at least one of the positive electrode 11 and the electrolyte 15 on the negative electrode current collector 13 by charging after battery assembly. By deposition, a negative electrode active material layer 14 is formed (see FIG. 1B).

  It is preferable to determine the vertical position of the negative electrode 12 in consideration of the relationship with the specific gravity of the electrolyte (molten salt) 15. For example, when the specific gravity of the negative electrode 12 during battery operation is smaller than the specific gravity of the electrolyte 15, the negative electrode 12 is placed on the top and the electrolyte 15 is on the bottom, and the specific gravity of the negative electrode 12 is larger than the specific gravity of the electrolyte 15. It is preferable that the negative electrode 12 is disposed below and the electrolyte 15 is disposed above. During operation of the battery, the negative electrode 12 (including the negative electrode current collector 13 and the deposited negative electrode active material layer 14) is in a solid state or a molten state, and the electrolyte 15 is a liquid (molten state) molten salt. If there is no separator to be used, when the negative electrode 12 having a small specific gravity falls below the electrolyte 15, the negative electrode 12 floats on the electrolyte 15. On the other hand, when the negative electrode 12 having a large specific gravity is above the electrolyte 15, the negative electrode 12 becomes an electrolyte. This is because it may sink below 15 and short-circuit with the positive electrode 11.

(Electrolytes)
As the electrolyte 15, one that can be used as a molten salt at 250 ° C. or lower, preferably 200 ° C. or lower, more preferably 150 ° C. or lower, particularly preferably 100 ° C. or lower, and most preferably 80 ° C. or lower can be suitably used. Furthermore, it is preferable that each of the electrodes 11, 12, particularly those which become a molten salt below the melting point of the deposited alkali metal or alkaline earth metal (negative electrode active material layer 14). By using such a molten salt with a low melting point for the electrolyte 15, the operating temperature of the battery can be lowered, and as a result, the heating energy required for operation can be greatly reduced compared to the NAS battery, and the electrode Can be operated in a state maintained in a solid state. Specifically, a molten salt containing an anion represented by the following formula 2 and a metal cation can be suitably used. The metal cation includes at least one of alkali metal cations and at least one of alkaline earth metal cations.

  In Formula 2, R1 and R2 each independently represent a fluorine atom or a fluoroalkyl group. R1 and R2 may be the same or different.

As a specific example of the anion, at least one of a bisfluorosulfonylimide ion (FSI ⁻ ) in which R1 and R2 are F and a bistrifluoromethylsulfonylimide ion (TFSI ⁻ ) in which R1 and R2 are CF ₃ is used preferable.

As a single salt of molten salt MFSI (M is one of alkali metals or alkaline earth metals), LiFSI, NaFSI, KFSI, RbFSI, CsFSI, Be (FSI) ₂ , Mg (FSI) ₂ , Ca (FSI) ₂ , Sr (FSI) ₂ or Ba (FSI) ₂ may be mentioned. Further, as a single salt of molten salt MTFSI, LiTFSI, NaTFSI, KTFSI, RbTFSI, CsTFSI, Be (TFSI) ₂ , Mg (TFSI) ₂ , Ca (TFSI) ₂ , Sr (TFSI) ₂ or Ba (TFSI) ₂ Is mentioned. These single salts may be used alone or as a mixture of two or more.

  In particular, a binary molten salt (NaFSI-KFSI) composed of a mixture of NaFSI and KFSI can have a melting point of 57 ° C. When the alkali metal is Na, the melting point of Na (about 98 ° C) The electrolyte (molten salt) 15 can be operated in a molten state at the following temperature.

  The molar ratio of Na cation to K cation in NaFSI-KFSI molten salt ((number of moles of K cation) / (number of moles of Na cation + number of moles of K cation)) is preferably 0.4 or more and 0.7 or less, 0.5 More preferably, it is 0.6 or less. With this molar ratio, the melting point is easily adjusted to 90 ° C. or lower, and the operating temperature is easily set to a low temperature of 90 ° C. or lower.

  The electrolyte 15 made of a molten salt may contain an organic cation. In this case, the conductivity of the electrolyte can be increased, and the operating temperature of the battery tends to be decreased. Examples of organic cations include alkylimidazole cations such as 1-ethyl-3-methylimidazolium cation, alkylpyrrolidinium cations such as N-ethyl-N-methylpyrrolidinium cation, and 1-methyl-pyridinium cation. A quaternary ammonium cation such as an alkylpyridinium cation or a trimethylhexylammonium cation can be used.

(Other)
The electrolyte 15 made of a molten salt may be used by impregnating a separator. As the separator, a material that is stable with respect to the electrolyte, such as a glass mesh, can be suitably used. When assembling the battery, the electrolyte 15 may be impregnated into the separator in a molten state, and the separator (electrolyte 15) may be disposed between the positive electrode 11 and the negative electrode current collector 13. During battery operation, the electrolyte 15 is heated to a molten salt. Moreover, you may provide the elastic material which provides press-contact force between both electrodes as needed. For example, the elastic material may be disposed so as to apply pressure in the stacking direction of the power generation elements. As the elastic material, for example, a disc spring, a leaf spring, a compression spring, or the like can be used.

  When the battery is manufactured, the positive electrode 11 or the electrolyte 15 containing alkali metal or alkaline earth metal ions is prepared. Then, after the positive electrode 11 and the negative electrode current collector 13 are disposed via the electrolyte 15, they are finally housed in a case (not shown). At this time, the negative electrode current collector 13 is not formed with a negative electrode active material layer containing an alkali metal or an alkaline earth metal. Further, the negative electrode active material layer 14 is formed by depositing alkali metal or alkaline earth metal on the negative electrode current collector 13 by charging after the battery is assembled.

{Lithium ion battery}
A lithium ion battery includes a positive electrode, a negative electrode, and an electrolyte interposed between the two electrodes. A lithium ion battery is a secondary battery that charges and discharges by exchanging Li ions, which are alkali metals, between a positive electrode and a negative electrode through an electrolyte. This lithium ion battery can operate without heating. Each component is as follows.

(Positive electrode)
As the positive electrode, a material containing a positive electrode active material, a binder, and a conductive additive can be suitably used. Examples of the positive electrode active material include lithium oxides such as lithium cobaltate (LiCoO ₂ ), lithium nickelate (LiNiO ₂ ), lithium manganate (LiMn ₂ O ₄ ), and olivine-type lithium iron phosphate (LiFePO ₄ ). Metal oxides such as manganese oxide (MnO ₂ ) can be used. Examples of the binder include polyvinylidene fluoride (PVdF), polytetrafluoroethylene, ethylene-propylene-diene copolymer, fluorine-based rubber, carboxymethyl cellulose, fluoroolefin copolymer cross-linked polymer, polyvinyl alcohol, and polyacrylic acid. Polyimide or the like can be used. As the solvent for dissolving the binder, for example, N-methylpyrrolidone such as N-methyl-2-pyrrolidone or an organic solvent such as acetone can be used. As the conductive assistant, carbon black such as ketjen black or acetylene black can be used.

(Negative electrode)
The negative electrode is configured in a state where a negative electrode active material layer containing Li is not formed on the negative electrode current collector at the time of battery assembly. For example, the negative electrode is composed of only the negative electrode current collector. As the negative electrode current collector, for example, at least one of Cr, Fe, Ni, Cu, alloys thereof, and stainless steel can be used. Further, the negative electrode is charged after the battery is assembled, so that Li ions previously contained in at least one of the positive electrode and the electrolyte are deposited on the negative electrode current collector, whereby a negative electrode active material layer is formed.

(Electrolytes)
An organic electrolyte or a solid electrolyte can be used as the electrolyte.

Examples of the organic electrolyte include those obtained by adding a lithium salt to an organic solvent. As the organic solvent, cyclic carbonate or chain carbonate can be used. Examples of the cyclic carbonate include ethylene carbonate (EC), vinylene carbonate (VC), propylene carbonate (PC), butylene carbonate (BC), and the like. Examples of the chain carbonate include dimethyl carbonate (DMC), methyl ethyl carbonate (MEC), and diethyl carbonate (DEC). In particular, ethylene carbonate (EC) or vinylene carbonate (VC) is suitable. As the lithium salt, LiPF ₆ , LiBF ₄ , LiClO ₄ , LiTFSI, LiBETI, or the like can be used, and two or more of these lithium salts may be used in combination.

As the solid electrolyte, a sulfide-based solid electrolyte containing Li ₂ S, or an oxide-based solid electrolyte such as Li ₃ PO ₄ or LiPON can be used. Sulfide-based solid electrolytes are preferable in that they exhibit higher Li ion conductivity than oxide-based solid electrolytes. Specific sulfide-based solid electrolytes include Li ₂ S-P ₂ S ₅ system, Li ₂ S-SiS ₂ system, Li ₂ S-B ₂ S ₃ system, etc., and also P ₂ O ₅ and Li _{2 3} PO ₄ may be added. Among them, a sulfide-based solid electrolyte containing Li ₂ S and P ₂ S ₅ is preferable because it exhibits high Li ion conductivity.

(Other)
When using an organic electrolyte, a separator is interposed between the positive and negative electrodes. As this separator, for example, a polyolefin nonwoven fabric can be used. The positive electrode may be provided with a positive electrode current collector. As the positive electrode current collector, for example, Al, Ni, stainless steel, or the like can be used.

<Example 1>
A molten salt battery having the basic configuration shown in FIG. 1 was produced and a charge / discharge test was performed. As the electrolyte, NaFSI-KFSI molten salt (NaFSI: 0.45 mol%, KFSI: 0.55 mol%) containing Na ions of alkali metal was used. The melting point of this molten salt was 57 ° C. This molten salt was impregnated into a porous glass cloth having a thickness of 80 μm serving as a separator. On the other hand, NaCrO ₂ was used for the positive electrode and Ni was used for the negative electrode current collector. Then, a glass cloth impregnated with a molten salt was disposed between the positive electrode and the negative electrode current collector, and the assembly was stored in a coin-type battery case. A more detailed manufacturing procedure of the positive electrode is as follows. NaCrO ₂ serving as a positive electrode active material, PTFE serving as a binder, and acetylene black serving as a conductive auxiliary agent are kneaded at a mass ratio of 80: 5: 15, respectively, and this kneaded product is placed on an Al mesh (positive electrode current collector). It was prepared by pressure bonding to.

After the battery was assembled, a charge / discharge test was performed under the conditions of operating temperature: 80 ° C., charge start voltage: 2.5 V, discharge start voltage: 3.5 V, and current density: 0.6 mA / cm ² with the battery heated. As a result, the capacity of the battery was 75 mAh / g.

<Modification>
In the embodiment described above, the case where the negative electrode current collector at the time of battery assembly is formed of a single metal material has been described as an example. However, the negative electrode current collector has the above-described negative electrode current collector material on the surface of the substrate. You may use what formed. In this case, when the negative electrode current collector is used, at least a part of the surface on the electrolyte side is formed of the negative electrode current collector material. For example, foil or plate-like stainless steel is adopted as the base material, and the negative electrode current collector material other than stainless steel is formed on the surface of the base material.

  Note that the present invention is not limited to the above-described embodiment, and can be modified as appropriate without departing from the gist of the present invention. For example, in addition to alkali metals such as Na and Li, alkaline earth metals such as Mg and Ca may be used. In that case, the positive electrode material, the negative electrode current collector material, and the electrolyte may be appropriately changed.

  The secondary battery of the present invention and the manufacturing method thereof can be used as, for example, power load leveling such as wind power generation and solar power generation, an emergency power source, an instantaneous power failure countermeasure, a power source for an electric vehicle, etc. It is expected to be applied as a power source for equipment.

10 Secondary battery
11 Positive electrode
12 Negative electrode
13 Negative electrode current collector 14 Negative electrode active material layer (Na)
15 Electrolyte (molten salt)

Claims (5)

A secondary battery in which a positive electrode and a negative electrode are disposed via an electrolyte, and charge and discharge are performed by exchanging ions of alkali metal or alkaline earth metal between the two electrodes,
When assembling this battery,
The negative electrode is configured in a state where an active material layer containing the alkali metal or the alkaline earth metal is not formed on a current collector,
At least one of the positive electrode and the electrolyte contains ions of the alkali metal or the alkaline earth metal,
The secondary battery, wherein the alkali metal or the alkaline earth metal is deposited on the current collector of the negative electrode during charging.   The secondary battery according to claim 1, wherein the alkali metal is Na.   The secondary battery according to claim 1, wherein the electrolyte is a molten salt.   At least a part of the surface of the current collector on the electrolyte side is made of at least one of Al, Cr, Fe, Ni, Cu, Mo, W, Pt, and Au, alloys thereof, and stainless steel. The secondary battery as described in any one of Claims 1-3 characterized by the above-mentioned. A method for producing a secondary battery that performs charge and discharge by exchanging alkali metal or alkaline earth metal ions between a positive electrode and a negative electrode via an electrolyte,
Preparing the positive electrode or the electrolyte containing ions of the alkali metal or the alkaline earth metal;
Disposing the positive electrode and the negative electrode current collector through the electrolyte in a state where the negative electrode active material layer containing the alkali metal or the alkaline earth metal is not formed on the negative electrode current collector; ,
Arranging the positive electrode, the negative electrode current collector and the electrolyte, and then charging to deposit the alkali metal or the alkaline earth metal on the negative electrode current collector;
A method for producing a secondary battery, comprising:

Images