JP2017059366A - Secondary battery and electrolytic solution for secondary battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an inexpensive secondary battery, which has a high charging capacity, operates even at an atmospheric temperature, and works according to a novel energy-saving principle; and an electrolytic solution for such a secondary battery.SOLUTION: A secondary battery 1 according to the present invention comprises: a positive electrode 11 including a metal B as a positive electrode active material; a negative electrode 12; and an electrolytic solution 13. The electrolytic solution 13 contains an electrolyte. The electrolyte includes an ionic compound MX (where M is a metal ion substance; and X is an anion substance). The electrolytic solution 13 contains a compound stronger than a compound BX produced by the anion substance X in combination with an ion substance of the metal B, which is the positive electrode active material in Lewis acidity to the anion substance X constituting the ionic compound MX.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a secondary battery and an electrolytic solution such as a secondary battery, and relates to a secondary battery that operates based on a new charge / discharge reaction, and an electrolytic solution used in the secondary battery.

  Secondary batteries are used in various electronic devices such as portable devices, notebook computers, and portable devices. In particular, a lithium ion battery has a high energy density and a high voltage, and there is no so-called memory effect because the battery capacity gradually decreases when charged before being completely discharged during charging and discharging. It is often used as a power source for electronic devices.

Currently, as a measure to prevent global warming, efforts are being made to reduce CO ₂ emissions on a global scale. Under such circumstances, there is an urgent need to develop and popularize next-generation clean energy vehicles such as plug-in hybrid vehicles and electric vehicles that have low dependence on petroleum and can contribute to CO ₂ reduction. For example, lithium ion batteries are also expected as a driving force for such next-generation clean energy vehicles.

  Specifically, the lithium ion battery includes a positive electrode, a negative electrode, a separator, and a nonaqueous electrolytic solution (see, for example, Patent Document 1). The positive electrode is configured such that a mixture layer containing a positive electrode active material, a binder, and a conductive agent is provided on a current collector such as an aluminum foil. The negative electrode is configured by providing a current collector such as a copper foil with a mixture layer containing a negative electrode active material, a binder, and a conductive agent. Lithium transition metal composite oxides such as lithium cobaltate and lithium nickelate are used as the positive electrode active material, and graphite and various alloy materials are used as the negative electrode active material. In a lithium ion battery, during charging, lithium ions contained in the positive electrode active material are released (desorbed) from the positive electrode and inserted in the negative electrode. On the other hand, the reverse movement occurs during discharge. In the lithium ion battery, electric energy is created by repeating occlusion / release of lithium ions between the positive electrode and the negative electrode.

  However, the lithium transition metal composite oxide used in such a lithium ion battery is a special compound and has a drawback of being expensive.

  On the other hand, molten salt batteries such as zebra batteries have been proposed as secondary batteries other than lithium ion batteries. The zebra battery has a positive electrode made of nickel (Ni) and a negative electrode made of molten sodium (Na), and uses sodium aluminum chloride (melting point: about 160 ° C.) as an electrolyte and operates at a temperature of about 250 ° C.

  However, such a molten salt battery does not operate at room temperature and is not sufficient as an energy-saving secondary battery.

  In addition, as secondary batteries, techniques such as Patent Documents 2 to 4 have been proposed.

JP 2006-310010 A International Publication No. 2013/108309 International Publication No. 2010/073978 JP 2007-200966 A

  An object of the present invention is to provide a secondary battery that is inexpensive, has a high charge capacity, operates at room temperature, and operates on a new energy-saving principle, and an electrolyte for the secondary battery.

  (1) 1st invention of this invention is equipped with the positive electrode containing the metal B as a positive electrode active material, a negative electrode, and electrolyte solution, The said electrolyte solution contains electrolyte, and ionic compound MX ( M: metal ionic substance, X: anionic substance), and the electrolytic solution contains the anionic substance X and the positive electrode active material with respect to the anionic substance X constituting the ionic compound MX. A secondary battery comprising a compound having a Lewis acidity stronger than that of the compound BX in which the ionic substance of the metal B is bonded.

  (2) A second invention of the present invention includes a positive electrode containing metal B as a positive electrode active material, a negative electrode, and an electrolytic solution, and the electrolytic solution contains an electrolyte, and the electrolyte contains an ionic compound MX ( M: metal ion substance, X: anion substance), and the electrolyte solution contains an aluminum compound.

(3) According to a third aspect of the present invention, in the first or second aspect, the electrolytic solution further includes TFSI ⁻ (bistrifluoromethanesulfonylimide ion) or FSI ⁻ (bisfluorosulfonylimide ion). Secondary battery.

  (4) According to a fourth aspect of the present invention, in any one of the first to third aspects, the ionic compound MX is dissolved in the electrolytic solution, or as a solid in the electrolytic solution. It is a secondary battery that exists.

  (5) A fifth invention of the present invention is the secondary battery according to any one of the first to fourth inventions, wherein the negative electrode is made of a material that reduces and metalizes the metal ion substance M. is there.

  (6) According to a sixth aspect of the present invention, in any one of the first to fifth aspects, the standard electrode potential of the metal constituting the positive electrode active material and the metal constituting the negative electrode is the ionicity. The secondary battery is larger than the standard electrode potential of the metal ion substance M constituting the compound MX.

  (7) According to a seventh aspect of the present invention, in any one of the first to sixth aspects, at least a part of the positive electrode or a surface of the positive electrode opposite to the electrolyte side is electrically conductive. It is a secondary battery provided with a substance.

  (8) According to an eighth aspect of the present invention, in any one of the first to seventh aspects, the metal ion substance M constituting the ionic compound MX is lithium, sodium, potassium, magnesium, calcium, and aluminum. The secondary battery is any one selected from the following.

  (9) According to a ninth aspect of the present invention, in any one of the first to eighth aspects, (I) during charging, the anionic substance X dissociated from the ionic compound MX and the positive electrode active material are ionized. When the metal ionic substance B is bonded at the positive electrode, a compound precipitate BX is generated, and the metal ionic substance M dissociated from the ionic compound MX is reduced at the negative electrode, whereby the negative electrode collector The metal deposit is deposited on the electric body, and (II) upon discharge, the anionic substance X is ionized from the compound precipitate BX generated by the charging and returns to the electrolyte, and the compound precipitate The ionic substance of metal B is ionized from BX and returned to the metal by being reduced at the positive electrode, and the metal ionic substance M is formed from the metal precipitate deposited on the negative electrode current collector by the charging. Apart back into the electrolyte, a secondary battery.

(10) A tenth aspect of the present invention includes a positive electrode containing a metal as a positive electrode active material, a negative electrode, and an electrolytic solution, and the electrolytic solution contains an electrolyte, and the electrolyte contains an ionic compound MX (M : Metal ion substance, X: anion substance), and the electrolyte contains TFSI ⁻ (bistrifluoromethanesulfonylimide ion) or FSI ⁻ (bisfluorosulfonylimide ion). This is a featured secondary battery.

  (11) An eleventh aspect of the present invention is an electrolytic solution used in a secondary battery composed of a positive electrode containing metal B as a positive electrode active material, a negative electrode, and an electrolytic solution, which contains an electrolyte, The electrolyte contains an ionic compound MX (M: metal ionic substance, X: anionic substance), and the anionic substance X and the anionic substance X constituting the ionic compound MX. An electrolyte solution for a secondary battery comprising a compound having Lewis acidity stronger than that of a compound BX in which an ionic substance of metal B as a positive electrode active material is bonded.

  (12) The twelfth aspect of the present invention is an electrolytic solution used for a secondary battery composed of a positive electrode containing a metal as a positive electrode active material, a negative electrode, and an electrolytic solution, containing an electrolyte, The electrolyte contains an ionic compound MX (M: metal ion substance, X: anionic substance) and is an electrolyte for a secondary battery characterized by containing an aluminum compound.

(13) The thirteenth invention of the present invention is the secondary battery according to the eleventh or twelfth invention, further comprising TFSI ⁻ (bistrifluoromethanesulfonylimide ion) or FSI ⁻ (bisfluorosulfonylimide ion). Electrolytic solution.

  (14) In a fourteenth aspect of the present invention, in any one of the eleventh to thirteenth aspects, the metal ion substance M constituting the ionic compound MX is lithium, sodium, potassium, magnesium, calcium, and aluminum. And the electrolytic solution is a non-aqueous electrolytic solution for a secondary battery.

(15) The fifteenth aspect of the present invention is an electrolytic solution used for a secondary battery composed of a positive electrode containing a metal as a positive electrode active material, a negative electrode, and an electrolytic solution, containing an electrolyte, The electrolyte contains an ionic compound MX (M: metal ion substance, X: anion substance) and TFSI ⁻ (bistrifluoromethanesulfonylimide ion) or FSI ⁻ (bisfluorosulfonylimide ion). It is the electrolyte solution for secondary batteries characterized by having.

  According to the present invention, it is possible to provide a novel secondary battery that is inexpensive, has a high charge capacity, operates at room temperature, and saves energy, and operates on a new principle, and an electrolyte for the secondary battery. .

It is a figure for demonstrating the structure and operating principle of the secondary battery which concern on this invention. It is a figure which shows an example of a structure of the secondary battery which concerns on this invention. It is a figure which shows an example of the other structure of the secondary battery which concerns on this invention. It is a figure which shows an example of the other structure of the secondary battery which concerns on this invention. When the AlCl ₃ was contained in the electrolytic solution is a diagram for explaining an auxiliary effect of reaction with the ionic compound MX during charging and discharging reactions.

  Hereinafter, specific embodiments of the present invention will be described. In addition, this invention is not limited to the following embodiment, A various change is possible in the range which does not change the summary of this invention.

<1. Secondary battery>
The secondary battery according to the present invention includes a positive electrode containing metal B as a positive electrode active material, a negative electrode, and an electrolytic solution. The electrolytic solution contains an electrolyte, and the electrolyte contains an ionic compound MX (M : Metal ion substance, X: anion substance). In this secondary battery, the anionic substance X and the ionic substance of metal B as the positive electrode active material are contained in the electrolytic solution with respect to the anionic substance X constituting the ionic compound MX of the electrolyte. A compound having Lewis acidity stronger than the bound compound BX is included.

Specifically, for example, in a secondary battery, when the positive electrode includes copper (Cu) as a positive electrode active material and LiCl (M: Li, X: Cl) as an ionic compound MX that is an electrolyte. A compound having Lewis acidity stronger than the compound CuCl with respect to Cl which is an anionic substance constituting the ionic compound MX is contained in the electrolytic solution. Examples of such a compound having Lewis acidity include aluminum compounds such as AlCl ₃ .

  In the present specification, “metal” means a single metal and an alloy, and those single metals and alloys doped with other elements are included.

  Specifically, FIG. 1 is a schematic configuration diagram showing an example of the configuration of the secondary battery according to the present invention. The secondary battery 1 includes a positive electrode 11, a negative electrode 12, and an electrolyte solution 13.

  The positive electrode 11 is formed in a sheet shape as shown in FIG. 1, for example, and is composed of a positive electrode current collector (not shown) and a positive electrode active material bonded to the positive electrode current collector. Note that the positive electrode active material includes metal B.

  Similarly, the negative electrode 12 is formed in a sheet shape as shown in FIG. 1, and is made of, for example, a negative electrode current collector. Note that. In the secondary battery 1, the negative electrode 12 may not include the negative electrode active material. By not including the negative electrode active material, the negative electrode 12 can be thinned, and the size of the secondary battery 1 can be further reduced, and the energy density can be increased.

  The electrolytic solution 13 includes an electrolyte and a solvent that dissolves the electrolyte. In the secondary battery 1, the electrolyte contains an ionic compound MX (M: metal ion substance, X: anion substance). In the electrolytic solution 13, Lewis is stronger than the compound BX in which the anionic substance X constituting the ionic compound MX is combined with the ionic substance of the metal B as the positive electrode active material. A compound having acidity (hereinafter sometimes abbreviated as “Lewis acidic compound”) is included.

  In the secondary battery 1 having such a configuration, for example, as shown in FIGS. 1 to 4, a charge and discharge reaction occurs, and the reaction is activated to produce electric energy.

That is, (I) at the time of charging, the anion substance X dissociated from the ionic compound MX and the ionic substance of the metal B ionized from the positive electrode active material contained in the positive electrode 11 are combined at the positive electrode 11, thereby forming a compound precipitate. BX generates. At the same, the dissociated metal ion material from ionic compound MX (positive ion material) M, by being reduced at the negative electrode 12, the metal deposit M _d.

On the other hand, at the time of (II) discharge, the anionic substance X is ionized from the compound precipitate BX generated at the positive electrode 11 by charging and returns to the electrolytic solution 13, and the metal B ionic substance is converted from the compound precipitate BX. The dissociated metal ion substance that has dissociated is returned to the metal B by being reduced by the positive electrode 11. On the other hand, metal deposit M _d precipitated generated at the negative electrode 12 by charging, anionic substance on the anode 12 without returning metal ion material M back into the electrolyte 13, or into the electrolyte 13 by ionization Combines with X to return to ionic compound MX.

  In the secondary battery 1 according to the present invention, charging and discharging are performed by such a new reaction mechanism without using an expensive active material. A part of the compound precipitate BX may be dissolved.

  At this time, in the secondary battery 1 according to the present invention, since the Lewis acid compound is contained in the electrolytic solution 13, the B component is ionized from the combined precipitate BX generated on the positive electrode 11 by charging. Dissolving in the liquid can be effectively prevented, and a high charge capacity can be maintained.

In the secondary battery 1, TFSI ⁻ (bistrifluoromethanesulfonylimide ion) or FSI ⁻ (bisfluorosulfonylimide ion) can be further contained in the electrolytic solution 13. These anions are dissolved in the solvent at a high concentration and efficiently consume the solvent component in the electrolytic solution 13. Therefore, by dissolving such anions in the electrolytic solution 13, the solvent component can be reduced, and the field where the B component is ionized and eluted from the combined precipitate BX generated at the positive electrode 11 can be eliminated. By such an action, elution of the B component from the compound precipitate BX can be more effectively prevented.

  Below, each structure of the secondary battery 1 is demonstrated more concretely.

<2. Positive electrode>
[Configuration of positive electrode]
The positive electrode 11 includes a positive electrode active material. The positive electrode active material is provided by being bonded to, for example, a sheet-like positive electrode current collector or by being applied to the positive electrode current collector. In addition, the positive electrode 11 itself may have a current collector and an active material.

  The positive electrode 11 contains the metal B as a positive electrode active material. The standard electrode potential of the metal B is larger than the standard electrode potential of the metal ion substance M constituting the ionic compound MX contained in the electrolyte, and does not spontaneously elute in the electrolyte solution 13. Specifically, as such a metal B, nickel (Ni) having a standard electrode potential of about −0.25 V or a metal nobler than the nickel (standard electrode potential of −0.25 V or more) is preferably mentioned. . For example, nickel (Ni, -0.25V), copper (Cu, + 0.340V), silver (Ag, + 0.799V), platinum (Pt, + 1.188V), gold (Au, + 1.520V), etc. It is done. Among these, nickel and copper are preferable from the viewpoint of cost and the like.

  When the positive electrode current collector is provided in the positive electrode 11, a material made of a material that does not cause an electrode reaction can be applied. Examples of such a positive electrode current collector include metals, conductive polymers, carbon, and the like, which are more precious than the metal B contained in the positive electrode active material. The positive electrode current collector is joined to the above-described positive electrode active material to constitute the positive electrode 11. In addition, a joining means and a joining aspect with a positive electrode active material are not specifically limited.

  The shape of the positive electrode 11 is not particularly limited, and may be, for example, a sheet shape or a granular shape, but is preferably a sheet shape. Here, the sheet shape does not limit the thickness, hardness, width, length, etc., for example, it means that it is formed into a rectangular shape having an arbitrary thickness with a metal foil, A layer can be formed. Moreover, it is not restricted to foil shape like metal foil, A film | membrane shape, a film shape, plate shape, etc. are also contained in the sheet-like concept. The positive electrode 11 may be porous. Further, the size and thickness of the positive electrode 11 are not particularly limited, and can be appropriately determined according to the desired size of the secondary battery 1.

  Further, a conductive material may be provided on at least a part of the positive electrode 11 or on the surface of the positive electrode 11 opposite to the electrolyte solution 13 side as shown in FIG. In the configuration illustrated in FIG. 4, the conductive material provided on the positive electrode 11 is described as “conductive material 15”. This conductive substance is provided so as to be in contact with the positive electrode 1 and acts like a current collector to supplement the current collecting function when most of the positive electrode 1 is used for the reaction. In particular, it can be suitably used when nickel or copper is used as the metal B contained in the positive electrode active material.

  The conductive substance may be provided on the entire surface (one surface) opposite to the electrolyte solution 13 side of the positive electrode 11 or may be provided on a part of the one surface. In particular, from the viewpoint of increasing the field where the ionic compound MX contained in the electrolyte in the electrolyte solution 13 and the metal B contained in the positive electrode active material directly react and fulfill the function as a current collector, It is preferable to be provided. For example, FIG. 4 shows an example in which the sheet-like conductive material 15 is provided on one side of the sheet-like positive electrode 11 in a laminated manner. As another example, although not shown, a large number of particles constituting the positive electrode 11 and a large number of particles of the conductive material may be mixed to form a sheet as a whole. Thus, a conductive material may be provided on at least a part of the positive electrode 11.

  The conductive substance is not particularly limited, and examples thereof include carbon such as acetylene black, ketjen black and graphite, a conductive polymer such as polyaniline, and a metal such as gold. This conductive substance is formed by mixing in a solvent such as NMP (N-methyl-2-pyrrolidone) containing a resin binder such as polyvinylidene fluoride to form a conductive paste, and applying the conductive paste to the positive electrode 11. Can do. Examples of the solvent include NMP, MEK (methyl ethyl ketone), IPA (isopropyl alcohol), water, and the like. The obtained conductive paste is applied on the positive electrode 11 and then dried to volatilize and remove all or most of it. be able to. Note that the conductive paste may contain a binder component that does not reduce the conductivity so much, and examples of the binder component include polyvinylidene fluoride, polyethylene oxide, and polyvinyl alcohol.

[Reaction mechanism at the positive electrode]
In the positive electrode 11, during charging, as shown in FIGS. 1 and 2, the anionic substance X (for example, “Cl ⁻ ”) dissociated from the ionic compound MX (for example, “LiCl”) in the electrolytic solution 13, and the positive electrode 11. The ionic substance of metal B (for example, “Cu”) contained in the positive electrode active material is combined, and a compound precipitate BX (for example, “CuCl”) is generated on the positive electrode 11. That is, in the secondary battery 1, the ionic substance of the metal B combines with the anionic substance X to become the compound precipitate BX at the positive electrode 11, and the charged state is maintained by holding the compound precipitate BX on the positive electrode 11. . Therefore, the charged state is maintained for a long time by the ionic substance of the metal B. FIG. 2 shows an example when LiCl is used as the ionic compound MX.

For example, as shown in FIG. 2, when the metal B is Cu and the anionic substance X is Cl ⁻ , CuCl (copper chloride) or CuCl ₂ (cupric chloride) is added to the positive electrode 11 as the compound precipitate BX. Generate. Further, when the metal B is Ni and the anionic substance X is Cl ⁻ , NiCl ₂ (nickel chloride) is generated on the positive electrode 11 as the compound precipitate BX. And the produced | generated compound precipitate BX copper chloride and nickel chloride are hold | maintained as the compound precipitate BX by the effect | action of the copper or nickel which is the metal B, and a charged state is maintained.

  The compound precipitate BX such as copper chloride or nickel chloride generated on the positive electrode 11 may be partially or wholly dissolved in the electrolytic solution 13 while maintaining a charged state. By dissolving the compound precipitate BX in the electrolytic solution 13, the progress of the discharge reaction can be accelerated.

On the other hand, at the time of discharging, as shown in FIGS. 1 and 2, the anionic substance X (for example, “Cl ⁻ ”) is ionized and jumped out from the compound precipitate BX (for example, “CuCl”) generated in the positive electrode 11, Return to the electrolyte 13. Further, the ionic substance of the metal B is ionized from the compound precipitate BX (for example, “CuCl”), and the ionized substance of the metal B (for example, “Cu ion”) is reduced at the positive electrode 11 to be a metal (for example, “Cu”). with return to the metal ion material M which is ionized from metal deposit M _d generated is reduced with the negative electrode 12 (e.g., "Li") is returned into the electrolytic solution 13.

  In the positive electrode 11, a charging reaction and a discharging reaction occur by a new reaction mechanism different from the conventional one.

<3. Negative electrode>
[Configuration of negative electrode]
The negative electrode 12 is composed of at least a negative electrode current collector. The negative electrode 12 may include a negative electrode current collector and a negative electrode active material.

Negative electrode current collector constituting the negative electrode 12 does not naturally eluted into the electrolyte solution 13, it is precipitated as a metal deposit M _d by a reduction reaction of the metal ion material M of the ionic compound MX contained in the electrolyte 13 It is made of a material that can be used. The standard electrode potential of such a negative electrode current collector is larger than the standard electrode potential of the metal ion substance M constituting the ionic compound MX and does not spontaneously elute in the electrolyte solution 13.

  Specifically, the negative electrode current collector is made of nickel (Ni) having a standard electrode potential of −0.25 V or a metal that is nobler than the nickel (standard electrode potential is −0.25 V or more). For example, metals such as nickel (Ni, -0.25V), copper (Cu, + 0.340V), silver (Ag, + 0.799V), platinum (Pt, + 1.188V), gold (Au, + 1.520V) Among them, those made of nickel and copper are preferable from the viewpoint of cost and the like.

In the negative electrode 12, the metal ion material M dissociated from ionic compound MX at the time of charge would metal ion material M is generated deposited on the negative electrode current collector as metal deposit M _d generated by reduction . In this regard, as in conventional lithium ion batteries, for example, a negative electrode active material such as carbon is included, and lithium ions released from the positive electrode active material by charging are stored in the negative active material carbon in an ionic state It is different from the embodiment. Note that “storage” means that the metal ion substance is not a metal, that is, becomes a compound in an ionic state.

  The shape of the negative electrode 12 is not particularly limited, and may be, for example, a sheet shape or a granular shape, but is preferably a sheet shape. The negative electrode 12 may be porous. Further, the size and thickness of the negative electrode 12 are not particularly limited, and can be appropriately determined according to the desired size of the secondary battery 1.

[Reaction mechanism at the negative electrode]
In the negative electrode 12, at the time of charging, as shown in FIGS. 1 and 2, the metal ion substance M (for example, “Li”) is ionized from the ionic compound MX (for example, “LiCl”) in the electrolytic solution 13 to form metal ions ( For example, “Li ions”), and the metal ions are reduced at the negative electrode 12 and deposited on the negative electrode 12 as a metal precipitate M _d (for example, “metal Li”).

  For example, as shown in FIG. 2, when the negative electrode 12 is Cu and the metal ion material M constituting the ionic compound MX is Li, the Li ions are reduced on the Cu electrode (negative electrode 12) to be metallized. Then, it becomes metal lithium (metal Li) and is deposited on the negative electrode current collector. Moreover, when the negative electrode 12 is Ni and the metal ion substance which comprises the ionic compound MX is Li, the Li ion is reduced on a Ni electrode (negative electrode 12), and precipitates as metal Li.

On the other hand, during discharge, the metal deposit M _d (for example, “metal Li”) deposited on the negative electrode 12 is eluted as metal ions (for example, “Li ion”) into the electrolyte solution 13 and ionized from the positive electrode 11. It combines with the anion (eg, “Cl ion”) that has jumped out to return to the ionic compound MX (eg, “LiCl”).

  In the negative electrode 12, a charging reaction and a discharging reaction occur by such a new reaction mechanism different from the conventional one.

Here, a metal M ′ of the same kind as the metal deposit M _d (for example, “metal Li”) may be placed in advance on the negative electrode 12 before charging as a solid. By disposing the solid metal M ′ in this way, when the amount of precipitation of the metal ion substance M on the negative electrode 12 at the time of charging, in particular, the initial charging is insufficient, the metal M ′ is compensated. be able to.

  Moreover, as shown in FIG. 3, the electrolyte 14 may be provided in the negative electrode 12 as a solid. Preferable electrolyte provided as a solid includes, for example, sodium chloride, potassium chloride, magnesium chloride, and sodium chloride is particularly preferable. In many cases, these electrolytes are electrically insulating, and are preferably mixed with a conductive material such as carbon particles.

For example, when a secondary battery is configured by using AlCl ₃ dissolved in a mixed solvent such as propylene carbonate or ethylene carbonate as an electrolytic solution, these electrolytes (for example, “NaCl”) 14 provided on the negative electrode 12 are: At the time of charging, Na ions as the metal ion substance M are deposited on the negative electrode 12 as metal Na (metal precipitate M _d ), and at the time of discharging, the deposited Na returns to the electrolyte compound as NaCl. At the same time, Cl ions as the anionic substance X are released into the electrolytic solution 13 during charging, react with the metal B on the positive electrode 11 side to form a compound precipitate BX (for example, “CuCl”), and during discharging. , released dissociate from CuCl in the electrolytic solution 13, returns to the sodium chloride reacts with the metal Na is a metal deposit M _d are deposited on the negative electrode 12.

  Thus, by providing the solid electrolyte 14 on the negative electrode 12, the electrolyte 14 comes to behave as described above, so that the metal ion substance M (for example, “Na”) constituting the electrolyte is the negative electrode 12. It will stop moving and dendrite generation can be suppressed. This increases safety and improves life.

  The solid electrolyte 14 is preferably provided with a thickness of 0.01 mm to 0.5 mm. If the thickness of the electrolyte 14 is less than 0.01 mm, it may be difficult to obtain a sufficient capacity due to being too thin. On the other hand, if the thickness exceeds 0.5 mm, the reaction may be slow. Further, the solid electrolyte 14 can be provided on the negative electrode 12 by various film forming methods.

<4. Electrolyte>
The electrolytic solution 13 contains an electrolyte and a solvent that dissolves the electrolyte. Further, the electrolyte contains an ionic compound MX (M: metal ion substance, X: anion substance). Even when the ionic compound MX is provided adjacent to the positive electrode 11 or the negative electrode 12 as a solid as described above, it is an electrolyte contained in the electrolytic solution 13.

The ionic compound MX causes a charging reaction and a discharging reaction based on the above-described mechanism. For example, as the metal ion substance M constituting the ionic compound MX, lithium (Li), sodium (Na), potassium (K), magnesium (Mg), calcium (Ca), aluminum (Al), cobalt (Co) And any one selected from zinc (Zn) and the like. Other metal ion substances M not listed here may be used as long as they exhibit the same behavior as these metal ion substances M. Examples of the anionic substance X include chlorine (Cl), fluorine (F), bromine (Br), iodine (I), PF ₆ , TFSI (trifluoromethanesulfonylimide), BF _{4 and the} like.

Specific examples of the ionic compound MX include inorganic lithium salts such as LiCl, LiClO ₄ , LiBF ₄ , LiPF ₆ , LiAsF ₆ , and LiBr, LiB (C ₆ H ₅ ) ₄ , LiN (SO ₃ CF ₃ ) ₂ , LiC (SO ₂ CF ₃ ) ₃ , LiOSO ₂ CF ₃ , LiOSO ₂ C ₂ F ₅ , LiOSO ₂ C ₄ F ₉ , LiOSO ₂ C ₅ F ₁₁ , LiOSO ₂ C ₆ F ₁₃ , and LiOSO ₂ C ₇ F _15, etc. The organic lithium salt can be mentioned.

  In the secondary battery 1 according to the present invention, a Lewis acidic compound is contained in the electrolytic solution 13 together with the ionic compound MX. Specifically, a compound having a Lewis acidity stronger than that of the compound BX in which the anionic substance X constituting the ionic compound MX is combined with the ionic substance of the metal B as the positive electrode active material. It is included.

Such a Lewis acidic compound acts to assist the reaction of the ionic compound MX during the charge / discharge reaction. Specifically, the Lewis acidic compound is determined by the relationship between the metal B as the positive electrode active material and the compound precipitate BX in which the ionic compound MX is bonded to the anionic material X. For example, AlCl ₃ , CuCl, ZnCl _{2 and the} like.

FIG. 5 is a diagram for explaining the auxiliary action of the reaction with the ionic compound MX during the charge / discharge reaction when AlCl ₃ is contained in the electrolytic solution 13 as a Lewis acidic compound. In this example, copper (Cu) is used as the metal B as the positive electrode active material, LiCl (M: Li, X: Cl) is used as the ionic compound MX as the electrolyte, and the positive electrode 11 is charged by the above-described mechanism. In this case, CuCl is produced as the compound precipitate BX.

That is, as described above, during charging, LiCl, which is the ionic compound MX, is dissociated into Li ⁺ and Cl ^−, and Li ⁺ is deposited on the negative electrode 12 as metal Li by the reaction of Li ⁺ → Li. , Cl ⁻ is combined with Cu, which is a metal of the positive electrode active material, and is accumulated in the positive electrode 11 as a combined precipitate of CuCl. On the other hand, during discharge, the deposited metal Li is eluted as Li ⁺ and Cl ⁻ is ejected from CuCl accumulated in the positive electrode 11. Note that Cu ⁺ → Cu. However, LiCl, which is the ionic compound MX, behaves as a Lewis base in an organic solvent, whereas CuCl deposited on the positive electrode 11 is a Lewis acid, so that both react to become Li ⁺ and CuCl ₂ ⁻ , and Cu Is easily dissolved from the positive electrode 11.

On the negative electrode 12 side, Li⇔Li ⁺ reaction occurs, and the amount of Li accumulated in the negative electrode 12 becomes equal to the charge capacity. However, Cu is ionized (CuCl ₂ ⁻ ) from the CuCl generated in the positive electrode 11 and thus in the electrolytic solution 13. When elution occurs, the Cu ions migrate to the negative electrode 12 and a reaction occurs in which the deposited metal Li is replaced by Cu. Then, as the amount of accumulated Li decreases, the charge capacity decreases, and the portion that should have been charged cannot be discharged. Moreover, the accumulation of Cu in the negative electrode 12 causes a short circuit.

At this time, by containing a Lewis acidic compound in the electrolytic solution 13, it is possible to effectively prevent elution of CuCl which is a compound precipitate. That is, in the example shown in FIG. 5, by adding AlCl ₃ as a Lewis acidic compound in the electrolytic solution 13, the contained AlCl ₃ is a compound precipitate of the positive electrode 11 with respect to LiCl acting as a Lewis base. It reacts preferentially over CuCl. That is, AlCl ₃ becomes a reaction medium with LiCl, which is a Lewis base. Then, while the reaction between LiCl and AlCl ₃ produces AlCl ₄ ⁻ , the reaction of the compound precipitate CuCl of the positive electrode 11 is suppressed, and as a result, the elution of Cu ions into the electrolytic solution 13 is suppressed. Is done. Thereby, a reduction in charge capacity can be prevented.

Moreover, it is preferable that the electrolyte solution 13 further contains an anion of TFSI ⁻ (bistrifluoromethanesulfonylimide ion) or FSI ⁻ (bisfluorosulfonylimide ion). These anions can be dissolved in a solvent at a high concentration, and efficiently consume the solvent component in the electrolytic solution 13. Therefore, by dissolving these anions in the electrolytic solution 13, the B component (Cu) is converted from the compound precipitate BX (for example, “CuCl”) generated at the positive electrode 11 due to a decrease in the solvent component in the electrolytic solution 13. Ionization and elution can be prevented more firmly.

That is, as described with reference to FIG. 5, LiCl, which is the ionic compound MX, behaves as a Lewis base in an organic solvent, whereas CuCl deposited on the positive electrode 11 is a Lewis acid, so that both react. Li ⁺ and CuCl ₂ ^— , and Cu may be dissolved into the electrolytic solution 13. At this time, if there is no solvent for dissolving Cu ions in the electrolytic solution 13, the elution is suppressed. As described above, since TFSI ⁻ (bistrifluoromethanesulfonylimide ion) or FSI ⁻ (bisfluorosulfonylimide ion) is an anion dissolved in a solvent component at a high concentration, it becomes a medium for Cl to elute. The solvent component is also consumed. Thus, elution of Cu can be effectively suppressed by containing the anion mentioned above in the electrolyte solution 13.

  Examples of the solvent include cyclic esters, chain esters, cyclic ethers, and chain ethers. Specific examples include γ-butyrolactone, cyclohexanone, tetrahydrofuran, crown ether, ethylene carbonate, propylene carbonate, and ethylene glycol dimethyl ether. These solvents may be used alone or in combination of two or more.

  In addition, when the ionic compound MX which is an electrolyte is an ionic liquid, the electrolyte solution 13 does not necessarily contain a solvent.

  The blending ratio of the ionic compound MX and the solvent constituting the electrolytic solution 13 is not particularly limited, but when the total amount is 100% by mass, the ionic compound MX is preferably blended at 30% by mass or more. More preferably, it is blended at a ratio of at least mass%. By mixing the electrolyte solution 13 at such a ratio, good charge / discharge can be realized.

  In addition, you may circulate electrolyte solution like the electrolyte solution which comprises a redox flow battery. By circulating the electrolyte, the battery capacity and battery life can be increased. The electrolytic solution may be a gel such as a polymer gel by mixing a gelling agent such as a polymer. According to the gel electrolyte, the fluidity is lowered, so that the seepage from the outer container or the like can be suppressed and the short circuit between the positive electrode 11 and the negative electrode 12 can be prevented, and the safety of the battery can be improved. it can.

  Further, as shown in FIG. 3, when the electrolyte is a solid electrolyte 14 provided in the negative electrode 12, examples of preferable electrolytes include sodium chloride, potassium chloride, and magnesium chloride as described above. In particular, sodium chloride is preferred. Moreover, as a solvent in the electrolyte solution 13 at this time, it is preferable that they are propylene carbonate, ethylene carbonate, and diethylene carbonate. In addition, the solid electrolyte preferably contains a conductive substance such as carbon or a conductive polymer as long as the action thereof is not hindered, thereby increasing the speed of charging and discharging. .

  FIG. 3 shows an example in which a solid electrolyte 14 is provided on the negative electrode 12, but the solid electrolyte is similarly provided on the positive electrode 11 or in the electrolytic solution 13. May be. Moreover, it can also provide on a separator, an exterior container, etc. As described above, the solid electrolyte can be provided at a location where the solid battery is in contact with the solvent constituting the electrolytic solution inside the secondary battery. Specifically, in the place where the solid electrolyte is arranged, in order to shorten the charge / discharge time, the metal ion substance M constituting the ionic compound MX which is the electrolyte contained in the electrolytic solution 13 is in a solvent. It can be determined in consideration of the moving speed and the moving speed of the anionic substance X in the solvent. For example, when the moving speed of the metal ion substance M in the solvent is slower than the moving speed of the anionic substance X in the solvent, the distance between the negative electrode 12 or the distance between the solid electrolyte and the negative electrode 12 is increased. It can be provided at a location in the battery where the distance is shorter than the distance between the solid electrolyte and the positive electrode 11. Further, when the moving speed of the anionic substance X in the solvent is slower than the moving speed of the metal ion substance M in the solvent, the distance between the positive electrode 11 and the distance between the solid electrolyte and the positive electrode 11 is increased. It can be provided at a location in the battery where the distance is shorter than the distance between the solid electrolyte and the negative electrode 12.

  As described above, the secondary battery 1 according to the present invention is a secondary battery (storage battery) that includes the ionic compound MX as an electrolyte in the electrolyte solution 13 and generates electric energy by generating the above-described new charge / discharge mechanism. is there. Specifically, for example, a metal ion salt such as LiCl is used as the ionic compound MX, and charging and discharging are performed based on dissociation between Li ions and Cl ions. At this time, the metal B as the positive electrode active material such as copper functions to fix the dissociated Cl ions in order to maintain the charged state. Various metal salts can be applied to the secondary battery 1 operating with such a charge / discharge mechanism, and the battery can be made cheaper than those using an expensive positive electrode active material as in the past.

  In the secondary battery 1, the electrolyte solution 13 contains a Lewis acidic compound. As a result, it is possible to effectively prevent the compound precipitates in the positive electrode 11 from eluting and the charge capacity from decreasing, and the battery capacity can be improved.

<4. Other configurations>
The secondary battery 1 may be configured to increase the voltage and current by stacking a plurality of single cell structures constituted by the positive electrode 11, the negative electrode 12, and the electrolytic solution 13 described above. For example, a single cell structure can be laminated by sandwiching a separator therebetween. Specifically, the laminate of the positive electrode 11, the separator (not shown), and the negative electrode 12 may be accommodated in the outer container while remaining in a plate shape, or is accommodated in the outer container in a spirally wound state. May be.

  Further, lead wires (not shown) are connected to the positive electrode 11 and the negative electrode 12, respectively. The lead wire connected to the positive electrode 11 is usually connected to the positive electrode terminal of the outer container, and the lead wire connected to the negative electrode 12 is usually connected to the negative electrode terminal of the outer container.

  The separator has a function of dissociating the positive electrode 11 and the negative electrode 12, and is not particularly limited as the separator, and a conventionally known separator can be appropriately selected and used in the field of secondary batteries. In addition, a separator is not an essential structure, For example, it can also be set as the aspect which does not use a separator by using gel-like electrolyte solution.

  Moreover, you may use the solid electrolyte etc. which are generally used as a diaphragm. Such a diaphragm can effectively prevent a short circuit of the battery and can improve safety.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples of the present invention, but the present invention is not limited to the following examples.

[Example 1]
LiCl is used as the electrolyte, AlCl ₃ is used as the Al source in the electrolyte, and copper foil (negative electrode current collector) / separator / copper foil (positive electrode active material) / nickel foil (positive electrode current collector) in this order A two-pole soft package cell that was laminated together was assembled.

  Specifically, a nickel foil (thickness 8 μm) was used as a positive electrode current collector, and a copper foil (thickness 10 μm) as a positive electrode active material was bonded to the nickel foil. Further, a copper foil (thickness: 10 μm) was used as a negative electrode current collector. A negative electrode active material was not used. Moreover, the nonwoven fabric (Nippon Vilene Co., Ltd. make, OA-0711) was used as a separator.

  Lithium chloride (LiCl) was used as the electrolyte, and an electrolyte containing the electrolyte was prepared in a glove box filled with argon gas. That is, first, 30 parts by mass of aluminum chloride, 40 parts by mass of EC (ethylene carbonate) and 30 parts by mass of PC (propylene carbonate) were prepared, mixed, and stirred at 30 ° C. for 24 hours. Next, 30 parts by weight of lithium chloride was mixed with 70 parts by weight of the liquid to prepare an electrolytic solution.

  A soft package cell was assembled from the positive electrode, negative electrode, and electrolyte solution thus prepared (copper foil (negative electrode current collector) / separator / copper foil (positive electrode active material) / nickel foil (positive electrode current collector)). . The size of the electrode was 4 cm square, the separator was 5 cm square, and the injection volume was 0.5 g. The liquid injection operation during cell assembly was also performed in a glove box filled with argon gas.

  The assembled soft package cell was subjected to a charge test and a discharge test. Charging was performed to a voltage of 4.3 V under a constant current control of 5 mA. Thereafter, there was a pause for 300 seconds. Subsequently, the battery was discharged to 0 V under 5 mA constant current control.

  As a result, the battery was charged at a charging voltage of about 3.1V, and discharged at a discharging voltage of about 2.6V. From the X-ray diffraction (XRD) measurement, the precipitate deposited on the negative electrode (negative electrode current collector) upon completion of charging was metallic lithium, and the precipitate deposited on the positive electrode nickel current collector was copper chloride (CuCl). there were. Furthermore, when the subsequent discharge was completed, lithium chloride was confirmed on the negative electrode current collector, and lithium chloride and copper were confirmed on the positive electrode current collector.

  This means that the lithium chloride electrolyte is divided into lithium ions and chlorine ions during charging, and the chlorine ions combine with copper ions on the positive electrode side to become copper chloride, while the lithium ions are reduced at the negative electrode. It is shown that it was deposited as metallic lithium on the negative electrode. Moreover, the reverse reaction occurs at the time of discharge, and it returns to lithium chloride.

[Example 2]
In Example 2, a soft package cell was assembled in the same manner as in Example 1 except that NaCl was used instead of LiCl as the electrolyte.

  The assembled soft package cell was subjected to a charge test and a discharge test. Charging was performed to a voltage of 4.0 V under a constant current control of 5 mA. Thereafter, there was a pause for 300 seconds. Subsequently, the battery was discharged to 0 V under 5 mA constant current control.

  As a result, the battery was charged at a charging voltage of about 3.1V, and discharged at a discharging voltage of about 2.6V. From the XRD measurement, the deposit deposited on the negative electrode (negative electrode current collector) upon completion of charging was metallic sodium, and the deposit deposited on the nickel current collector of the positive electrode was copper chloride (CuCl). Furthermore, when the subsequent discharge was completed, sodium chloride was confirmed on the negative electrode current collector, and sodium chloride and copper were confirmed on the positive electrode current collector.

  This is because sodium chloride, which is an electrolyte, is divided into sodium ions and chlorine ions during charging, and chlorine ions combine with copper ions on the positive electrode side to become copper chloride, while sodium ions are reduced at the negative electrode. It is shown that it was deposited as metallic sodium on the negative electrode. Moreover, the reverse reaction occurs at the time of discharge, and returns to sodium chloride.

[Example 3]
LiCl is used as an electrolyte, and AlCl ₃ and lithium bis (trifluoromethanesulfonyl) imide are contained as an Al source in the electrolytic solution. Copper foil (negative electrode current collector) / separator / copper foil (positive electrode active material) / A two-pole type soft package cell in which nickel foils (positive electrode current collector) were laminated in this order was assembled.

  Specifically, a nickel foil (thickness 8 μm) was used as a positive electrode current collector, and a copper foil (thickness 10 μm) as a positive electrode active material was bonded to the nickel foil. Further, a copper foil (thickness: 10 μm) was used as a negative electrode current collector. A negative electrode active material was not used. Moreover, the nonwoven fabric (Nippon Vilene Co., Ltd. make, OA-0711) was used as a separator.

  Lithium chloride (LiCl) was used as the electrolyte, and an electrolyte containing the electrolyte was prepared in a glove box filled with argon gas. That is, first, 10 parts by mass of aluminum chloride, 30 parts by mass of EC (ethylene carbonate), 30 parts by mass of PC (propylene carbonate), and 30 parts by mass of lithium bis (trifluoromethanesulfonyl) imide were prepared, and 30 parts by mixing them. Stir at 24 ° C. for 24 hours. Next, 30 parts by weight of lithium chloride was mixed with 70 parts by weight of the liquid to prepare an electrolytic solution.

  A soft package cell was assembled from the positive electrode, negative electrode, and electrolyte solution thus prepared (copper foil (negative electrode current collector) / separator / copper foil (positive electrode active material) / nickel foil (positive electrode current collector)). . The size of the electrode was 4 cm square, the separator was 5 cm square, and the injection volume was 0.5 g. The liquid injection operation during cell assembly was also performed in a glove box filled with argon gas.

  The assembled soft package cell was subjected to a charge test and a discharge test. Charging was performed to a voltage of 4.3 V under a constant current control of 5 mA. Thereafter, there was a pause for 300 seconds. Subsequently, the battery was discharged to 0 V under 5 mA constant current control.

  As a result, the battery was charged at a charging voltage of about 3.1V, and discharged at a discharging voltage of about 2.6V. From the X-ray diffraction (XRD) measurement, the precipitate deposited on the negative electrode (negative electrode current collector) upon completion of charging was metallic lithium, and the precipitate deposited on the positive electrode nickel current collector was copper chloride (CuCl). there were. Furthermore, when the subsequent discharge was completed, lithium chloride was confirmed on the negative electrode current collector, and lithium chloride and copper were confirmed on the positive electrode current collector.

  This means that the lithium chloride electrolyte is divided into lithium ions and chlorine ions during charging, and the chlorine ions combine with copper ions on the positive electrode side to become copper chloride, while the lithium ions are reduced at the negative electrode. It is shown that it was deposited as metallic lithium on the negative electrode. Moreover, the reverse reaction occurs at the time of discharge, and it returns to lithium chloride.

DESCRIPTION OF SYMBOLS 1 Secondary battery 11 Positive electrode 12 Negative electrode 13 Electrolytic solution 14 Electrolyte (solid electrolyte)
15 Conductive material

Claims (15)

A positive electrode containing metal B as a positive electrode active material, a negative electrode, and an electrolyte solution,
The electrolytic solution contains an electrolyte, and the electrolyte contains an ionic compound MX (M: metal ion substance, X: anion substance),
In the electrolytic solution, Lewis acidity stronger than the compound BX in which the anionic substance X and the ionic substance of the metal B as the positive electrode active material are combined with the anionic substance X constituting the ionic compound MX. The secondary battery characterized by including the compound which has these. A positive electrode containing a metal as a positive electrode active material, a negative electrode, and an electrolyte solution,
The electrolytic solution contains an electrolyte, and the electrolyte contains an ionic compound MX (M: metal ion substance, X: anion substance),
The secondary battery, wherein the electrolytic solution contains an aluminum compound. The secondary battery according to claim 1, wherein the electrolytic solution further contains TFSI ⁻ (bistrifluoromethanesulfonylimide ion) or FSI ⁻ (bisfluorosulfonylimide ion). 4. The secondary battery according to claim 1, wherein the ionic compound MX is dissolved in the electrolytic solution or is present as a solid in the electrolytic solution. 5. 5. The secondary battery according to claim 1, wherein the negative electrode has a configuration made of a material that reduces and metalizes the metal ion substance M. 6. The standard electrode potential of each of the metal constituting the positive electrode active material and the metal constituting the negative electrode is larger than the standard electrode potential of the metal ion material M constituting the ionic compound MX. The secondary battery according to claim 1. 7. The secondary battery according to claim 1, wherein a conductive substance is provided on at least a part of the positive electrode or a surface of the positive electrode opposite to the electrolyte solution side. The secondary battery according to any one of claims 1 to 7, wherein the metal ion substance M constituting the ionic compound MX is any one selected from lithium, sodium, potassium, magnesium, calcium, and aluminum. At the time of charging, the anion substance X dissociated from the ionic compound MX and the ionic substance of metal B ionized from the positive electrode active material are combined at the positive electrode, whereby a compound precipitate BX is generated and the ions When the metal ion substance M dissociated from the conductive compound MX is reduced at the negative electrode, the metal deposit is deposited on the negative electrode current collector,
At the time of discharging, the anionic substance X is ionized from the compound precipitate BX generated by the charging and returns to the electrolyte, and the ionic substance of metal B is ionized from the compound precipitate BX and reduced at the positive electrode. The metal ion substance M is ionized from the metal deposit deposited on the negative electrode current collector by the charging and returned to the electrolyte while being returned to the metal by being charged. Secondary battery described in 1. A positive electrode containing a metal as a positive electrode active material, a negative electrode, and an electrolyte solution,
The electrolytic solution contains an electrolyte, and the electrolyte contains an ionic compound MX (M: metal ion substance, X: anion substance),
Wherein the electrolytic solution, TFSI - ^{(bis-trifluoromethanesulfonyl} imide ion) or FSI - secondary battery characterized in that it contains ^{(bisfluorosulfonylimide} ions). An electrolytic solution used for a secondary battery composed of a positive electrode containing metal B as a positive electrode active material, a negative electrode, and an electrolytic solution,
An electrolyte, the electrolyte contains an ionic compound MX (M: metal ion substance, X: anion substance),
A compound having a Lewis acidity stronger than the compound BX in which the anionic substance X constituting the ionic compound MX is combined with the ionic substance of the metal B as the positive electrode active material is included. An electrolyte for a secondary battery. An electrolytic solution used for a secondary battery composed of a positive electrode containing a metal as a positive electrode active material, a negative electrode, and an electrolytic solution,
An electrolyte, the electrolyte contains an ionic compound MX (M: metal ion substance, X: anion substance),
An electrolytic solution for a secondary battery, comprising an aluminum compound. TFSI - ^{(bis-trifluoromethanesulfonyl} imide ion) or FSI - ^{(bisfluorosulfonylimide} ions) electrolyte solution for a secondary battery according to claim 11 or 12 is further included. The metal ion substance M constituting the ionic compound MX is any one selected from lithium, sodium, potassium, magnesium, calcium, and aluminum,
The electrolyte solution for a secondary battery according to any one of claims 11 to 13, wherein the electrolyte solution is a non-aqueous electrolyte solution. An electrolytic solution used for a secondary battery composed of a positive electrode containing a metal as a positive electrode active material, a negative electrode, and an electrolytic solution,
An electrolyte, the electrolyte contains an ionic compound MX (M: metal ion substance, X: anion substance),
TFSI - ^{(bis-trifluoromethanesulfonyl} imide ion) or FSI - ^{(bisfluorosulfonylimide} ions) electrolyte solution for a secondary battery, characterized in that it contains.

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