JP2014011110A - Nonaqueous electrolyte secondary battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a nonaqueous electrolyte secondary battery in which durability performance can be enhanced by restoring the battery capacity, even if repetition of charge and discharge of the nonaqueous electrolyte secondary battery inevitably leads to deterioration of battery capacity.SOLUTION: A nonaqueous electrolyte secondary battery (B, B) includes a positive electrode (1, 10, 100) having a positive electrode collector (12) and a positive electrode active material layer (11) disposed on the positive electrode collector, a negative electrode (2) disposed to face the positive electrode and having a negative electrode collector (22) and a negative electrode active material layer (21) disposed on the negative electrode collector, and an electrolyte (3) interposed between the positive electrode and negative electrode. An electron supply compound layer (13) containing a compound for supplying electrons irreversibly with an oxidation potential more noble than the positive electrode active material is disposed on a surface (12b) of the positive electrode collector not facing the negative electrode.

Description

  The present invention relates to a non-aqueous electrolyte secondary battery.

  With the recent spread of portable electronic devices such as portable personal computers and handy video cameras, non-aqueous electrolyte secondary batteries having high voltage and high energy density are widely used as power sources. From the viewpoint of environmental problems, electric vehicles and hybrid vehicles using electric power as a part of power have been put into practical use.

  Among these non-aqueous electrolyte secondary batteries, lithium ion secondary batteries using lithium-containing metal oxides for the positive electrode and carbon materials for the negative electrode are used in various electronic devices as secondary batteries having high energy density. Has been. Further, lithium ion secondary batteries are expected to have higher performance such as higher energy density.

  As an electricity storage device that achieves this high performance, Patent Document 1 discloses that in a lithium ion secondary battery, metallic lithium that functions as a lithium ion supply layer is formed on one surface of a negative electrode current collector of a stacked electrode unit. The thing of the arrangement | positioning arranged is disclosed.

JP 2008-123826 A

  However, the method of arranging metallic lithium in advance is limited to the supply of lithium ions at the initial stage of use in which metallic lithium is dissolved in the electrolyte. In the charge and discharge after the second cycle, the current collection structure in the active material layer is deteriorated and lithium is consumed due to irreversible side reactions, and the lithium in the battery is gradually inactivated. Therefore, the conventional method has a problem that it is possible to temporarily increase the capacity, but the battery capacity cannot be deteriorated over time.

  Moreover, there was also a problem that the energy density of the battery was lowered by dissolving metallic lithium in the electrolytic solution.

  The present invention has been completed in view of the above circumstances, and even if the battery capacity is inevitably deteriorated while the non-aqueous electrolyte secondary battery is repeatedly charged and discharged, the battery capacity is recovered at that time and is durable. It is an object to provide a non-aqueous electrolyte secondary battery capable of enhancing performance.

  In order to solve the above-mentioned problems, the present inventors have studied the non-aqueous electrolyte battery, and as a result, have reached the present invention.

  The non-aqueous electrolyte secondary battery of the present invention according to claim 1 is disposed to face a positive electrode having a positive electrode current collector and a positive electrode active material layer disposed on the positive electrode current collector, In a non-aqueous electrolyte secondary battery comprising: a negative electrode current collector; a negative electrode having a negative electrode active material layer disposed on the negative electrode current collector; and an electrolyte solution interposed between the positive electrode and the negative electrode. The positive electrode is characterized in that an electron supply compound for irreversibly supplying electrons is disposed on a surface of the positive electrode current collector that is not opposed to the negative electrode.

  The positive electrode has an electron supply compound that irreversibly supplies electrons, and the electrons supplied by the electron supply compound by charging cause a reaction with ions in the electrolytic solution. That is, in the positive electrode, not only the electrode reaction in the positive electrode active material but also the electron supply compound causes a reaction. In particular, when the electron supply compound undergoes a reaction of supplying electrons by charging, ions in the electrolytic solution can be fixed to the positive electrode or the negative electrode active material.

  In addition, the electron supply compound is disposed on the surface of the positive electrode that is not opposed to the negative electrode. This indicates that the electron supply compound is not disposed on the surface of the positive electrode facing the negative electrode. The electron supply compound itself is different from the positive electrode active material and does not cause an electrode reaction. In the secondary battery, the opposite surfaces of the positive and negative electrodes are the surfaces that most generate the supply of ions in the electrolytic solution. When a compound different from the electrode active material is disposed on the surfaces facing each other, the amount of the electrode active material contributing to the electrode reaction is reduced, and as a result, the characteristics of the secondary battery (for example, battery capacity and energy density) are reduced. Give rise to

  As in the present invention, the electron supply compound is disposed on the surface of the positive electrode that is not opposed to the negative electrode, so that the electron supply compound is disposed on the positive electrode without causing deterioration in battery performance. The effect of that.

  In the present invention, the positive electrode and the negative electrode disposed to face each other may be in a state in which ions in the electrolytic solution can move between both electrodes in the opposed state, and a separator may be disposed between both electrodes. .

  In the nonaqueous electrolyte secondary battery of the present invention, the electron supply compound preferably has a noble oxidation potential as compared with the positive electrode active material.

  In the non-aqueous electrolyte secondary battery of the present invention, when the positive electrode active material becomes an oxidation potential, an oxidation reaction, that is, an electrode reaction proceeds. And since an electron supply compound has a noble oxidation potential than a positive electrode active material, when the potential at the time of charge of the positive electrode of a non-aqueous electrolyte secondary battery is a potential at which the positive electrode active material causes an electrode reaction The reaction of the electron supply compound has not started. That is, when the potential of the positive electrode is at the oxidation potential of the positive electrode active material, the original electrode reaction proceeds at the positive electrode, and the ions originally fixed in the positive electrode active material are released into the electrolyte as electrons are released. It is in a state.

  When the potential of the positive electrode is higher than the oxidation potential at which the electrode reaction originally proceeds, and the noble potential at which the electron supply compound supplies electrons, the electron supply reaction of the electron supply compound occurs. The ions in the electrolytic solution are reduced by the supplied electrons and fixed in the positive electrode or negative electrode active material. The immobilized ions can cause an electrode reaction. In the state where the potential of the positive electrode is at a noble potential that causes an electron supply reaction, the oxidation potential of the positive electrode active material is passed in the process of reaching the noble potential, and the oxidation reaction is completed.

  In other words, when the electron supply compound causes an electron supply reaction, ions are already included in the negative electrode, and ions fixed by the electron supply reaction can also contribute to the electrode reaction, so that the battery capacity is high. Become. Accordingly, the capacity can be recovered by supplying active ions derived from the electron supply compound even in a state in which inactivation of ions is unavoidable due to deterioration of the positive electrode active material or the like.

  Specifically, when the potential of the positive electrode increases during charging, first, the oxidation potential of the positive electrode active material is reached, and ions are released from the positive electrode active material while releasing electrons to the external circuit. At the same time, the negative electrode receives electrons and the electrode reaction proceeds. And the ion of the maximum amount of substance which should finish electrode reaction from a positive electrode will detach | leave, and charge will be completed. In a general non-aqueous electrolyte secondary battery, the maximum substance amount of ions determines the battery capacity used for discharge.

  And in the non-aqueous electrolyte secondary battery of this invention, if charge is further advanced and the electric potential of a positive electrode is made high after completion of charge, the electron supply compound will reach the oxidation potential which supplies an electron. The supplied electrons reach the negative electrode through an external circuit, and reduce ions in the electrolytic solution on the negative electrode active material surface or in the active material. The reduced ions are included around the negative electrode active material and in the crystal structure thereof, so that the battery capacity can be expressed. That is, in the nonaqueous electrolyte secondary battery of the present invention, the electron supply compound supplies electrons, so that the amount of electrode reaction that occurs can be increased, and the battery capacity can be increased as compared to before supply of electrons.

  In addition, the electron supply compound layer of the nonaqueous electrolyte secondary battery of the present invention preferably has a specific surface area larger than that of the positive electrode active material layer. Here, the electron supply compound layer is a layered member containing an electron supply compound disposed on the surface not facing the negative electrode.

  In general, in the oxidation-reduction reaction between a solid electron supply compound and ions in a liquid electrolyte, the activity of the surface of the solid is important, the surface area is directly linked to the activity, and the specific surface area is larger. The function as an electron supply compound (reducing agent) is good. Therefore, it is possible to expect the above-described high recovery capacity of the battery capacity.

  In addition, depending on the electron supply compound, the electrolyte solution may be reduced and decomposed to generate an irreversible by-product, or the electron supply compound itself may be decomposed in accordance with a reaction for reducing the partner. In general, a porous conductive carbon material having a large specific surface area decomposes itself so that a so-called immobile film is not formed and ions are not easily stored in the layer structure. Suitable for guiding and fixing to a substance.

  In this case, even if the active electron supply compound is partially lost, the specific surface area of the electron supply compound layer is secured so as to compensate for this, so that the electron supply compound can The effect distributed can be maintained.

  Furthermore, in the non-aqueous electrolyte secondary battery of the present invention, the positive electrode has a positive electrode active material layer disposed on one surface of the plate-shaped positive electrode current collector facing the negative electrode, and the other surface has an electron. A feed compound layer is preferably provided.

  In this configuration, the positive electrode can be plate-shaped, and the energy density of the secondary battery can be increased. At this time, the negative electrode preferably has a similar plate shape in which a negative electrode active material layer is disposed on the surface of the plate-shaped negative electrode current collector.

  Furthermore, the plate-like positive electrode having the electron supply compound disposed so as to be opposed can be the same size as the conventional positive electrode. That is, the nonaqueous electrolyte secondary battery of the present invention can be implemented simply by replacing the conventional plate-like positive electrode.

  The positive electrode active material layer disposed on one surface is preferably disposed on the entire surface of one surface. Further, the electron supply compound layer disposed on the other surface is also preferably disposed on the entire surface of the other surface. Here, the entire surface of the current collector on which the active material layer and the electron supply compound layer are formed refers to the entire surface of the area where the active material layer can be formed on the surface of the plate-shaped current collector.

  Further, it is preferable to form a through-hole through which ions contained in the electrolytic solution pass in the positive electrode having the positive electrode active material layer and the electron supply compound layer, and in particular, ions from the electron supply compound layer side to the positive electrode active material layer side. Moves and is supplied to the positive electrode or negative electrode active material. That is, more electrode reactions can be caused.

  The nonaqueous electrolyte secondary battery of the present invention may be a stacked secondary battery in which positive electrodes and negative electrodes are alternately stacked in a state where the positive electrode is formed on at least one end in the stacking direction. In this case, the positive electrode is formed on at least one end in the stacking direction, whereby the electron supply compound can be arranged on the end face of the end. Here, when the stacked secondary battery is formed, the structure other than the positive electrode that forms at least one end in the stacking direction, that is, the positive electrode sandwiched between the negative electrodes is the same as the conventional stacked secondary battery. Similarly, it is preferable to have a positive electrode active material layer on both surfaces in the stacking direction.

  The non-aqueous electrolyte secondary battery of the present invention can have the same configuration as a conventionally known non-aqueous electrolyte secondary battery except for the configuration described above.

  The type of the nonaqueous electrolyte secondary battery of the present invention is not limited as long as it is a secondary battery known as a nonaqueous electrolyte secondary battery. The non-aqueous electrolyte secondary battery of the present invention is preferably a lithium ion secondary battery in which lithium ions are contained in the non-aqueous electrolyte.

  In addition, the conventional method of arranging metallic lithium on the negative electrode is limited to the supply of active lithium ions at the beginning of use in which metallic lithium dissolves, but the present invention recovers the battery capacity even after durable use of the battery. , Can improve the durability performance.

  In the prior art, metallic lithium is disposed, but when dissolved in the electrolyte, the portion where the lithium is present becomes a gap. If it does so, a clearance gap will be made in a battery, the movement distance of ion will become long, and will cause an increase in internal resistance. Further, when the electrode is displaced due to vibration or the like, problems such as (physically) damage to the electrode active material occur.

  On the other hand, in the present invention, since the electron supply compound remains, such electrode displacement does not occur. That is, the above problem does not occur.

  Furthermore, since metallic lithium itself is an active material that is highly dangerous in terms of water prohibition, strong basicity, short circuit thermal runaway, and the like, it is safer than batteries that directly handle metallic lithium.

The positive electrode potential of a lithium ion secondary battery B _1, and a diagram schematically illustrating the change in battery voltage. The internal structure of the lithium ion secondary battery B ₁ is an embodiment of the present invention is a cross-sectional view schematically showing. It is a sectional view showing the structure of a lithium ion secondary battery B ₂ prepared in Example. It is the graph which showed the cycle change of the capacity | capacitance maintenance factor of the battery of an Example and a comparative example.

(Operation and effect of electron supply compounds)
Hereinafter, as an example of the non-aqueous electrolyte secondary battery according to the present invention, the action and effect of the electron supply compound in the lithium ion secondary battery B ₁ (see FIG. 2) of the present embodiment to be described later will be described. As will be described later, in the lithium ion secondary battery B _{1 of the} present embodiment, LiFePO ₄ (lithium iron phosphate) is used as the positive electrode active material, and styrene butadiene rubber (hereinafter referred to as SBR) is used as the electron supply compound. Acetylene black is used as the negative electrode active material and graphite.

Assembling a lithium ion secondary battery B _1, the initial charge (first charge), first performs a constant current. As the charging proceeds, the potential of the positive electrode increases, and the potential of the positive electrode 10 in the outer layer reaches the oxidation potential Rm of LiFePO ₄ . After reaching the charge end voltage Vm corresponding to the oxidation potential Rm, it is charged at a constant voltage with the charge end voltage Vm as necessary and fully charged.

After fully charged, the lithium-ion secondary battery B ₁ represents subjected to use, electrical energy is consumed by the connected load, the discharge progresses and reaches a predetermined discharge termination voltage. Here, for example, the initial discharge capacity can be obtained by setting one cycle from the start of the initial charge to the full charge and from the full charge to the end of the discharge.

  After charging is started again, the discharge capacity can be obtained in the same manner every time one cycle of charge / discharge is completed, and the capacity maintenance rate based on the initial discharge capacity can be calculated. The discharge capacity can be obtained by a predetermined known method.

  Then, while the above charge / discharge is repeated at a voltage not lower than the discharge end voltage and lower than the charge end voltage Vm, some of the lithium ions in the battery to be electrode-reacted are inevitably inactivated and the battery capacity decreases. Thus, the capacity retention rate gradually decreases as the number of cycles increases.

Then, when the capacity maintenance rate becomes equal to or lower than the predetermined value, the charge end voltage of the next cycle is set to be increased from Vm to Vr. The end-of-charge voltage Vr is a voltage that can secure the oxidation potential Rr at which the SBR disposed on the positive electrode 10 of the outer layer starts the electron supply reaction. Further, the oxidation potential Rr is a potential nobler than the oxidation potential Rm of LiFePO ₄ .

Further, in the cycle in which the capacity retention rate of the lithium ion secondary battery B ₁ is maintained at a predetermined value or higher, the potential of the positive electrode 10 in the outer layer is maintained without exceeding the oxidation potential Rm of LiFePO ₄ . Therefore, side reaction with the electrolyte solution is promoted and lithium is irreversibly consumed, or the current collecting structure of LiFePO ₄ becomes unstable with the release of lithium. As a result, eventually LiFePO ₄ is The problem of overcharging more than expected, such as being disassembled, is suppressed.

When constant-current charging is started with the end-of-charge voltage set to Vr, the potential of the positive electrode 10 on the outer layer rises as the amount of charge increases, and first reaches the vicinity of the oxidation potential Rm of LiFePO ₄ as shown in FIG. To do. At this time, LiFePO ₄ causes an electrode reaction in which lithium fixed in the layer structure is released together with electrons.

When charging is advanced after the electrode reaction of LiFePO ₄ is completed, the potential of the positive electrode 10 of the outer layer further increases and reaches the vicinity of the oxidation potential Rr. At this time, the SBR supplies electrons, and the negative electrode active material layer 21 receives the electrons via an external circuit. The lithium ions in the electrolytic solution are reduced by the electrons and intercalated in the negative electrode active material layer 21.

  At this time, the lithium ions to be reduced can easily move to the negative electrode active material layer 21 through the through holes 12 c, the positive electrode active material layer 11, and the separator 7. Then, the lithium intercalated in the negative electrode active material layer 21 becomes deintercalable lithium. That is, due to the intercalated lithium, the negative electrode active material contains more lithium, thus increasing the battery capacity. In addition, since the electron supply compound layer 13 contains acetylene black together with SBR, the conductivity is enhanced and the activity of the electron supply reaction is enhanced.

Thus, in the lithium ion secondary battery B ₁ , when the oxidation potential Rr of the electron supply compound is reached, the original electrode reaction of LiFePO ₄ is completed, and an electrode reaction is caused in a larger amount of lithium. The battery capacity can be increased compared to before the supply of electrons.

After the potential of the positive electrode 10 of the outer layer reaches the vicinity of the oxidation potential Rr, constant voltage charging is performed at the charge end voltage Vr as necessary. In lithium ion secondary batteries B _1, in the state in which the electron donor compound has stopped the supply of electrons, it is preferable that the potential of the positive electrode is lowered to a lower oxidation potential Rm than the oxidation potential Rr of SBR. In a state where the supply of electrons from the electron supply compound is completed and the potential of the positive electrode is maintained at the oxidation potential Rr, an overcharge state occurs and the above-described problems occur.

Further, as described above, in the first half cycle in which the capacity of the lithium ion secondary battery B ₁ is maintained within a certain range, the potential of the positive electrode 1 is charged in a state between Q ₁ and Q _{2 in} FIG. Since the discharge is repeated, the problem of overcharging is suppressed. In the present invention, depending on conditions such as the number of times of charging / discharging of the battery and usage time, the capacity can be effectively recovered by specializing when the inevitable decrease in battery capacity is incurred.

In addition, although SBR has been described in the above description as a compound that irreversibly supplies electrons at an oxidation potential Rr that is higher than the oxidation potential Rm of LiFePO ₄ , other compounds may be used as described later. That is, the electron supply compound layer 13 may contain two or more types of electron supply compounds having different oxidation potentials.

When the outer layer electrode 10 includes the electron supply compound layer 13 containing two or more types of electron supply compounds having different oxidation potentials, the respective oxidation potentials Rr ₁ , Rr ₂ ,... Rr _m (where m is an integer) Thus, the end-of-charge voltage can be set in accordance with the oxidation potential of each of which is greater than the oxidation potential Rm of LiFePO ₄ . Specifically, when the capacity maintenance rate decreases to a predetermined value during repeated use of charge / discharge at the initial charge end voltage Vm, the charge end voltage is _first raised to Vr ₁ to perform charging. After that, charging / discharging is repeated and used, and when the capacity retention rate decreases again to a predetermined value, charging is further performed by further increasing the charge end voltage to Vr ₂ and repeating this m times. Can do.

  In addition, a charging method for calculating and using the capacity retention rate as a threshold value for determining when to increase the charge end voltage from Vm to Vr in correspondence with the oxidation potential Rr of SBR has been described. The present invention is not limited to this example, and other indicators can be used. For example, electrons may be supplied by comparing the measured battery capacity value with a threshold value. Further, when the number of charge / discharge times reaches a predetermined number, electrons may be supplied.

  Further, in the above embodiment, electrons are supplied after repeated charge / discharge and the battery capacity is reduced. However, the lithium ion secondary battery of the present invention may supply electrons at the first charge. In this case, the initial capacity of the secondary battery is increased.

Incidentally, the lithium ion secondary battery B ₁ represents the potential of the positive electrode 10 of the outer layer is used in a state where the oxidation potential of the positive electrode active material Rm (between Q _1, Q ₂ in FIG. 1). The electron supply compound of the present invention is a compound that irreversibly supplies electrons. Therefore, under the condition that the lithium-ion secondary battery B ₁ is used, SBR and acetylene black of the electron donor compound layer 13 does not contribute to the reaction (and battery performance) of the battery.

In the present embodiment, the positive electrode active material layer 11 and the electron supply compound layer 13 are arranged on both surfaces of the plate-like positive electrode current collector 12 of the positive electrode 10 of the outer layer. Therefore, compared with the case where an active material layer in which SBR and acetylene black are mixed in a composite material containing LiFePO ₄ is formed, the positive electrode active material layer 11 does not contain an electron supply compound that does not contribute to the charge / discharge reaction. The capacity of the material layer is increased and the energy density is improved.

Further, the LiFePO ₄ composite and the graphite composite can be applied to the entire surfaces of the positive and negative current collectors 12 and 22, respectively, and the electron supply compound composite is also applied to the entire surface of the positive electrode current collector 12 in the same manner. The positive and negative current collectors 12 and 22 are both formed in the same plate shape. Therefore, it is possible to secure the maximum reaction area of each active material and compound.

Furthermore, since the electrode unit U has a structure in which the same plate-shaped positive electrode 1 and negative electrode 2 are alternately arranged and laminated, from the viewpoint of electrode arrangement, while ensuring the electron supply function of the electron supply compound, LiFePO ₄ and graphite Each positive and negative active material can contribute to the electrode reaction without waste. Therefore, the energy density of the battery can be increased.

  Moreover, the positive electrode 10 of the outer layer which has the electron supply compound layer 13 is arrange | positioned at the up-and-down both ends of the electrode unit U which laminated | stacked the positive electrode 100 and the negative electrode 2 alternately, and the said electron supply compound layer 13 does not oppose a negative electrode. It is arranged on the other surface 12b.

In the above-described configuration, the same plate-shaped outer layer positive electrode 10 is laminated and inserted into both ends of the same electrode unit including the positive electrode and the negative electrode that do not have the conventional electron supply compound layer 13. the machining of the lithium ion secondary battery B ₁ of the present embodiment easily. In addition, the process which substitutes the positive electrode active material layer 11 of the other surface of the positive electrode which does not have the electron supply compound layer 13 with the electron supply compound layer 13 is also possible.

Further, since the electron supply compound layer 13 is not disposed on the surface facing the negative electrode 2, the negative electrode active material layers 21 of all the negative electrodes 2 are either the positive electrode 100 of the inner layer or the positive electrode 10 of the outer layer. It faces the surface on which the layer 11 is disposed. SBR and acetylene black itself does not result in different electrode react with LiFePO ₄ because they are not disposed in the surface facing the negative electrode 2. Therefore, the function of the electron supply compound can be exhibited without causing a decrease in battery performance. In other words, the surfaces of the positive and negative electrodes facing each other are the surfaces where the transfer of lithium ions in the electrolyte solution occurs most. When an electron supply compound different from the electrode active material is disposed, the amount of the electrode active material contributing to the electrode reaction is reduced. Although it may decrease, this can be avoided.

Furthermore, when an active material mixture in which an electron supply compound is mixed is used, for example, the internal resistance may not be sufficiently reduced due to the characteristics of one active material, or the battery performance may be reduced. , LiFePO ₄ , SBR and acetylene black are separately arranged on both sides of the positive electrode current collector, so that these adverse effects on the positive electrode can be avoided.

Also, in the lithium ion secondary battery B _1, unlike the configuration that arranged metal lithium is dissolved, the electron supply compound layer 13 containing an electron donor compound be repeatedly charged and discharged is left as it is. Therefore, since no gap is generated in the electrode or the battery, it is possible to avoid problems such as an increase in internal resistance and physical damage caused by the electrode being displaced due to vibration or the like.

(Description of Lithium Ion Secondary Battery B ₁ of Embodiment)
Hereinafter, a specific configuration of the lithium ion secondary battery B _{1 according to} an embodiment of the present invention will be described. As shown schematically in Figure 2, the lithium ion secondary battery B ₁ represents a structure that houses together with an electrolyte a stacked electrode unit U into the battery container (not shown).

  The electrode unit U has a configuration in which a predetermined number of plate-like positive electrodes 1 and negative electrodes 2 are alternately stacked with separators 7 in a state where the active material layers 11 and 21 face each other. In the electrode unit U, positive and negative electrodes 1 and 10 are formed at upper and lower ends along the stacking direction L. That is, when the number of the negative electrodes 2 is n, the number of the positive electrodes 1 is n + 1. The positive electrode 1 includes an outer layer positive electrode 10 disposed on each of both ends and an inner layer positive electrode 100 other than the outer layer positive electrode 10.

  The positive electrode 100 of each inner layer has a configuration in which the positive electrode active material layer 11 is disposed on each of both surfaces of a plate-like positive electrode current collector 12, and has a plate shape with a predetermined thickness as a whole positive electrode. The positive electrode active material layer 11 contains a positive electrode active material described later. Each negative electrode 2 has a plate shape similar to that of the positive electrode, and similarly includes a negative electrode current collector 22 and negative electrode active material layers 21 disposed on both sides thereof. The negative electrode active material layer 21 contains a negative electrode active material to be described later. In the electrode unit U, the positive electrode 100 and the negative electrode 2 of the inner layer are laminated in a state where the active material layers 11 and 21 face each other.

  The positive electrode 10 of the outer layer forming both ends has the same plate shape as the positive electrode 100 of the inner layer, and the positive electrode active material layer 11 is formed on one surface 12a of the positive electrode current collector 12 and the other surface 12b. Is a configuration in which an electron supply compound layer 13 is disposed. The electron supply compound layer 13 contains an electron supply compound described later. The outer layer positive electrode 10 is disposed such that one surface 12 a on which the positive electrode active material layer 11 is disposed faces the negative electrode 2. That is, the other surface 12 b on which the electron supply compound layer 13 is disposed is disposed without facing the negative electrode 2.

  The positive electrode current collector 12 in the positive electrode 10 of the outer layer is formed with a large number of through holes 12c having a predetermined diameter. This is because lithium ions in the electrolyte solution in the vicinity of the electron supply compound layer 13 pass through the positive electrode current collector 12 and can easily reach the back surface on which the positive electrode active material layer 11 is disposed.

Further, each positive electrode current collector 12 is electrically connected to the positive electrode terminal 41, and each negative electrode current collector 22 is electrically connected to the negative electrode terminal 51. Incidentally, the positive electrode terminal 41 and the negative electrode terminal 51 is connected to the charge and discharge state of the lithium ion secondary battery B ₁ to properly controllable secondary battery system.

  The positive electrode current collector 12 and the negative electrode current collector 22 are made of a conductive material formed in a foil shape. The conductive material is not particularly limited, and a current collector made of a conventionally known material can be used. For example, aluminum, stainless steel, copper, nickel, or the like can be used. In the present embodiment, an aluminum foil is used for the positive electrode current collector 12 and a copper foil is used for the negative electrode current collector 22.

  The positive electrode active material layer is composed of a positive electrode active material mixture containing a positive electrode active material such as a metal sulfide, metal oxide, or polymer compound capable of inserting and extracting lithium ions. The positive electrode active material mixture is formed by mixing a positive electrode active material, a binder, a conductive material, a solvent, and the like into a paste, and the positive electrode active material layer 11 includes the positive electrode active material mixture as a positive electrode current collector. 12 is a coating layer formed on the surface of 12 by applying and drying. The coating layer may be compressed by a press or the like after drying.

  Examples of the binder include polyvinylidene fluoride (hereinafter referred to as PVDF), polytetrafluoroethylene, EPDM, SBR, nitrile butadiene rubber (hereinafter referred to as NBR), and the like. As the conductive material, ketjen black, acetylene black, carbon black, graphite or the like is used. As the solvent, carbonates are used.

  Among the substances that can be the positive electrode active material, lithium metal composite oxide is used as the metal oxide, and examples of the metal include cobalt, nickel, manganese, iron, zinc, chromium, titanium, and silicon. The above metal elements or nonmetallic elements such as phosphorus and boron are applicable. In addition, it is desirable to select a lithium composite oxide such as a lithium / iron composite oxide, a lithium / cobalt composite oxide, or a lithium / nickel oxide according to required characteristics such as high potential, high capacity, and durability.

The positive electrode active material layer 11 of this embodiment is formed of a positive electrode active material mixture containing 80 parts by mass of LiFePO ₄ as a positive electrode active material, 10 parts by mass of the PVDF, and 10 parts by mass of acetylene black. . The positive electrode active material layer 11 is formed on both surfaces of the positive electrode current collector 12 of the inner layer positive electrode 100 and on one side of the positive electrode 10 of each pair of outer layers and on one surface 12a facing the negative electrode 2. It is arranged.

  And the electron supply compound layer 13 of this embodiment is formed with the compound compound material which mixed the electron supply compound, the binder, the electrically conductive material, the solvent, etc. like the positive electrode active material layer 11, and made it into paste form, This is a coating layer formed by applying and drying the compound mixture on the surface of the positive electrode current collector 12. The coating layer may be compressed by a press or the like after drying.

  Here, as the electron supply compound contained in the electron supply compound layer 13, a compound capable of supplying electrons by being oxidized within the range of the charging potential applied from the secondary battery system is used.

First, a compound that is oxidized at a noble potential is preferable to a positive electrode active material. In the present embodiment, the LiFePO ₄ contained in the positive electrode active material layer 11 has a more noble oxidation potential based on the oxidation potential when the lithium ions are released (= electrons are released = oxidized) during charging. Any compound can be used as long as it can supply electrons. This is because, during charging, lithium intercalation of the electron supply compound is performed at the negative electrode at an oxidation potential nobler than the normal positive electrode potential. In the present embodiment, SBR is used, which is particularly preferable. However, the present invention is not limited to this, and examples of other electron supply compounds that can supply electrons at a more noble oxidation potential than LiFePO ₄ include polyacrylic acid, polyaniline, polyurethane, and silicone.

  Furthermore, an electron supply compound that can make the specific surface area of the electron supply compound layer larger than that of the positive electrode active material layer is preferable. This is to increase the activity of the compound surface and ensure the reducing function as an electron donating compound. In this embodiment, acetylene black is used and is particularly preferable. However, it is not limited to this, and activated carbon, ketjen black and the like can be exemplified.

  The electron supply compound layer 13 of this embodiment is formed from a compound mixture containing 50 parts by mass of SBR and 50 parts by mass of acetylene black as an electron supply compound. The electron supply compound layer 13 is disposed on the other surface 12b that does not face the negative electrode 2 of the positive electrode current collector 12 of the positive electrode 10 of each pair of outer layers.

  The negative electrode active material is not particularly limited, and a conventionally known negative electrode active material can be used. For example, a compound capable of inserting and extracting lithium ions, or a combination of these compounds can be used. Examples of the compound capable of inserting and extracting lithium ions include metal materials such as lithium, alloy materials containing silicon and tin, graphite, coke, organic polymer compounds, and carbon materials such as amorphous carbon. These compounds can be used not only independently as an active material but also as a mixture of a plurality of types.

  Similarly to the positive electrode active material layer described above, the negative electrode active material layer 21 is formed of a negative electrode active material mixture containing a negative electrode active material, a binder, and the like, and the negative electrode active material mixture is formed on the surface of the negative electrode current collector 22. It is the coating layer formed by apply | coating and drying. The coating layer may be compressed by a press or the like after drying. In addition, when using metallic lithium as a negative electrode active material, it can form by crimping | bonding metallic lithium to the surface of the electrical power collector which consists of metals, such as copper.

  The negative electrode active material layer 21 of the present embodiment contains 98 parts by mass of graphite as a negative electrode active material, 1 part by mass of SBR as a binder, and 1 part by mass of carboxymethyl cellulose (hereinafter referred to as CMC) as a solvent. It is formed from a material mixture.

  The electrolytic solution is not particularly limited, and may be any path when lithium ions move from the positive (negative) electrode to the negative (positive) electrode, and a conventionally known electrolytic solution can be used. For example, a solution in which an electrolyte salt is dissolved in a solvent, an ionic liquid that is liquid itself, a solution in which an electrolyte salt is further dissolved in the ionic liquid, and the like are applicable. The “electrolyte” in the present specification includes not only the above liquid form but also a known solid or gel electrolyte. In this embodiment, it can be set as the electrolyte solution which consists of an aprotic organic solvent containing lithium salt.

  As the organic solvent, those usually used for non-aqueous electrolytes can be used singly or in combination of two or more, but a cyclic carbonate compound, a cyclic ester compound, a sulfone or sulfoxide compound, a chain carbonate compound, a chain It is preferable to contain 1 or more types chosen from the group which consists of a linear or cyclic ether compound and a chain | strand-shaped ester compound. In particular, it is preferable to contain at least one cyclic carbonate compound and one chain carbonate compound.

  Specifically, as the cyclic carbonate compound, ethylene carbonate, propylene carbonate, vinylene carbonate, 1,2-butylene carbonate, isobutylene carbonate, etc., and as the chain carbonate compound, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, ethyl -N-butyl carbonate, methyl-t-butyl carbonate, etc. are mentioned.

The type of electrolyte salt is not particularly limited, but an inorganic salt selected from LiPF ₆ , LiBF ₄ , LiClO ₄ and LiAsF ₆ , derivatives of these inorganic salts, LiSO ₃ CF ₃ , LiC (SO ₂ CF ₃ ) ₃ , an organic salt selected from LiN (SO ₂ CF ₃ ) ₂ , LiN (SO ₂ C ₂ F ₅ ) _2, LiN (SO ₂ CF ₃ ) (SO ₂ C ₄ F ₉ ), and the like, and their organic It is desirable to be at least one of salt derivatives. The concentration of the electrolyte salt is not particularly limited, and is preferably selected appropriately in consideration of the types of the electrolyte salt and the organic solvent depending on the use. The electrolyte salt is preferably dissolved in the organic solvent so that the concentration in the electrolytic solution is 0.1 to 3.0 mol / liter, particularly 0.5 to 2.0 mol / liter.

In addition, the ionic liquid is not particularly limited as long as it is an ionic liquid that is usually used for an electrolyte of a lithium ion secondary battery. For example, the cation component may be 1-methyl-3-ethyl having high conductivity. Examples include an imidazolium cation and a dimethylethylmethoxyammonium cation, and examples of the anion component include BF ₄ ⁻ and LiN (SO ₂ C ₂ F ₅ ) ₂ ^— .

  The separator 7 plays a role of electrically insulating the positive electrode and the negative electrode and holding the electrolytic solution. For example, a porous synthetic resin film, particularly a polyolefin polymer (polyethylene, polypropylene) porous film may be used. The separator is preferably larger than the positive electrode and the negative electrode in order to ensure insulation between the positive electrode and the negative electrode.

(Explanation of components of lithium ion secondary battery)
Hereinafter, the components of the non-electrolytic water secondary battery such as the above-described lithium ion secondary battery B ₁ will be described in detail particularly regarding the positive electrode.

  The positive electrode has a positive electrode current collector and a positive electrode active material layer integrated therewith. The positive electrode active material layer is a slurry obtained by suspending and mixing a positive electrode active material mixture composed of an active material, a conductive agent, and a binder formed into a powder, granular, short fiber, etc. in an appropriate solvent. It can be produced by applying the product to one or both sides of the positive electrode current collector and drying.

  The positive electrode active material is not particularly limited as long as it can reversibly occlude / release light metal ions such as lithium ions, and various conventionally known oxides, sulfides, lithium-containing oxides, and conductive materials. A polymer or the like is used.

Specific examples of the positive electrode active material include the following materials. LiFePO ₄ , LiMnPO ₄ , Li ₂ MnSiO ₄ , Li ₂ Mn _x Fe _(1-x) SiO ₄ , MnO ₂ , TiS ₂ , TiS ₃ , MoS ₃ , FeS ₂ , Li _(1-x) MnO ₂ , Li _{( 1-x)} Mn ₂ O ₄ , Li _(1-x) CoO ₂ , Li _(1-x) NiO ₂ , LiV ₂ O ₃ , V ₂ O ₅ , polyaniline, polyparaphenylene, polyphenylene sulfide, polyphenylene oxide, polythiophene , Polypyrrole, and derivatives thereof, stable radical compounds. “X” represents a number from 0 to 1.

The metal oxide compound may be a material obtained by adding or replacing a transition metal such as Li, Mg, Al, or Co, Ti, Nb, or Cr. Of these, not only lithium-metal composite oxides can be used alone, but also a plurality of these can be mixed and used. Among these, the lithium-metal composite oxide is preferably at least one of a lithium manganese-containing composite oxide having a layered structure or a spinel structure, a lithium nickel-containing composite oxide, and a lithium cobalt-containing composite oxide. In the non-aqueous electrolyte secondary battery of the present invention, it is most preferable to use a polyanion type material such as LiFePO ₄ as the positive electrode active material.

  And an electron supply compound should just be a compound which can supply an electron irreversibly with a positive electrode. Therefore, after the completion of charging, the electron supply compound does not return to the discharge state while the positive electrode falls from the high potential to the reduction potential of the positive electrode active material and returns to the discharge state. That is, in the potential range where the positive electrode active material undergoes electrode reaction, the electron supply compound is maintained in a charged state and does not contribute to the reaction. Therefore, it is possible to avoid the consumption of the site in which the ions in the crystal structure of the positive electrode active material are accommodated due to the reduction reaction of the electron supply compound during use or discharge of the battery. Therefore, the amount of lithium substance (discharge battery capacity) that is directly intercalated from the negative electrode to the positive electrode is ensured.

  The ability to supply electrons irreversibly can be determined by the oxidation-reduction current when a potential is applied in a cyclic voltammetry test (hereinafter referred to as CV test).

  In addition, the electron supply compound is preferably a compound that has a potential outside the range of the positive electrode potential assumed when a normal battery is used, and can supply electrons with an oxidation potential more noble than the positive electrode active material. Moreover, it is most preferable that a compound that can make the specific surface area of the electron supply compound layer larger than that of the positive electrode active material layer is contained.

Here, in general, LiFePO ₄ can reduce the original charge / discharge voltage as compared with other practical positive electrode active materials, and even if the charge pressure is increased, the heat of the battery may be increased. The advantage is that it is stable. Therefore, even if the electrode reaction of LiFePO ₄ is combined with the reaction of a compound that supplies electrons at a more noble potential, it is easy to ensure the reliability of the battery. Further, as described above, the use durability of the battery can be improved in terms of securing the capacity by arranging the electron supply compound. Therefore, the battery according to the present invention has a long product life and is suitable as a battery for in-vehicle use that requires high reliability.

  The negative electrode can be produced in the same manner as the positive electrode. As the negative electrode active material, a compound that occludes lithium ions during charging and desorbs during discharging can be used. The active material is not particularly limited in its material configuration, and a known material and configuration can be used. Specific examples of the active material have been described above, and materials that exhibit a capacity such as graphite can be specifically mentioned. More specifically, a simple substance of a group 4B metal element or a semi-metal element in the short-period periodic table Alternatively, an alloy such as silicon or tin can be used.

The electrode unit is formed by laminating the positive electrode and the negative electrode alternately while facing each other. In the lithium ion secondary battery B _{1 of the} present embodiment, the stacked outer layer electrodes at both upper and lower end portions are positive electrodes, and have a positive electrode active material layer and an electron supply compound layer that are different on both sides, and an electron supply compound Although the example which is distribute | arranged to the outer layer which does not oppose a negative electrode was shown, the structure of this invention is not restricted to this. The electrode unit is not limited to the laminated type, and for example, an electrode including one positive electrode and one negative electrode each provided with a positive electrode active material layer and an electron supply compound layer may be used. Moreover, the positive electrode provided with the electron supply compound layer does not necessarily have to be disposed in the outer layer.

In the lithium ion secondary battery B ₁ described above, the outer layer positive electrodes 10 and 10 are arranged at both ends in the stacking direction L of the electrode unit U, but the outer layer positive electrode 10 is arranged only at one end, and the other The end may be configured such that the negative electrode 2 is disposed.

Also, in the lithium ion secondary battery B _1, when accommodating the electrode unit U in the battery container (not shown) may be arranged member for restricting contact between the battery container and the electrode unit U. An example of this member is a separator.

It has been described lithium-ion secondary battery B ₁ as the present embodiment, the metal ions according to the present invention, if those that may become ions Ninaeru the electric conductivity in the electrolytic solution is not limited to lithium. The non-aqueous electrolyte secondary battery of the present invention includes other elements as required in addition to the above elements. The shape of the non-aqueous electrolyte secondary battery of the present invention is not particularly limited, and can be used as a battery having various shapes such as a coin shape, a cylindrical shape, and a square shape. Also, the case of the non-aqueous electrolyte secondary battery of the present invention is not limited, but various forms of batteries such as a metal or resin case that can retain its outer shape, a soft case such as a laminate pack, etc. Can be used as

  The manufacturing method of the non-aqueous electrolyte secondary battery of the present invention is not limited, and can be manufactured in the same manner as a conventionally known method for manufacturing a non-aqueous electrolyte secondary battery.

Hereinafter, the present invention will be described using examples. As an example of a non-aqueous electrolyte secondary battery of the present invention to prepare a lithium ion secondary battery B ₂ coin. The following examples show one embodiment in which the present invention is specifically implemented, and the present invention is not limited to the following examples.

(Example)
(Positive electrode)
(Preparation of LiFePO ₄ composite material)
80 parts by mass of LiFePO ₄ as a positive electrode active material, 10 parts by mass of PVDF as a binder, and 10 parts by mass of acetylene black as a conductive material are mixed, and an appropriate amount of N-methyl-2-pyrrolidone is added and kneaded to form LiFePO _4. A paste-like positive electrode active material mixture was obtained.

(Preparation of electron supply compound compound material)
50 parts by mass of SBR (manufactured by Nippon Zeon Co., Ltd.) and 50 parts by mass of acetylene black are mixed, and an appropriate amount of N-methyl-2-pyrrolidone is added and kneaded to combine the SBR and acetylene black paste-like electron supply compound. The material was obtained.

(Preparation of positive electrode)
The obtained paste-like positive electrode active material mixture was applied to one surface of a positive electrode current collector made of 100 mesh aluminum mesh, dried, and subjected to a pressing step to produce a positive electrode active material layer.

  The obtained paste-like electron supply compound mixture was applied to the other surface of the positive electrode current collector and dried, and an electron supply compound layer was formed through a pressing step.

(Preparation of negative electrode)
(Production of graphite mixture)
98 parts by weight of graphite as a negative electrode active material, 1 part by weight of SBR as a binder, and 1 part by weight of CMC as a dispersant are mixed, and an appropriate amount of N-methyl-2-pyrrolidone is added and kneaded to form a paste of graphite. The negative electrode active material mixture was obtained.

  The obtained paste-like negative electrode active material mixture was applied to a negative electrode current collector made of a copper thin film having a thickness of 10 μm, dried and pressed to obtain a negative electrode plate.

(Preparation of electrolyte)
Nonaqueous solvent electrolyte in which LiPF ₆ is added at a concentration of 1.0 mol / L to an organic solvent in which ethylene carbonate (EC) and diethyl carbonate (DEC) are mixed at a volume ratio of 7: 3. Was used.

(Production of coin-type battery)
The cross-sectional view of a coin type battery B ₂ produced is shown in FIG. The same / similar numbers are assigned to the same / similar configurations as the above-described embodiment.

  As the positive electrode 1 and the negative electrode 2, the above positive electrode and negative electrode were used, respectively. As the electrolytic solution 3, the prepared electrolytic solution was used.

The separator 7 using a polyethylene porous film having a thickness of 25μm, respectively, A coin-type battery was produced B _2. The positive electrode 1 has a positive electrode current collector 12 in which a through hole 12 c is formed, and the negative electrode 2 has a negative electrode current collector 22. In the drawing, 21 is a negative electrode active material layer, 11 is a positive electrode active material layer formed on one surface 12a of the positive electrode current collector 12, and 13 is an electron supply compound similarly formed on the other surface 12a. Indicates the layer.

  These power generation elements were housed in a stainless steel case (consisting of a positive electrode case 42 and a negative electrode case 52). Here, in the positive electrode 1, the positive electrode active material layer 11 and the electron supply compound layer 13 are respectively arranged on one surface 12 a of the positive electrode current collector 12 facing the negative electrode 2 and on the other surface 12 b not facing each other. It is stored as is. Moreover, the positive electrode case 42 and the negative electrode case 52 serve as a positive electrode terminal and a negative electrode terminal. A gasket 6 made of polypropylene is interposed between the positive electrode case 42 and the negative electrode case 52 to ensure sealing and insulation between the positive electrode case 42 and the negative electrode case 52.

(CV test)
A CV test was conducted to confirm in advance that SBR and acetylene black used as electron supply compounds irreversibly supply electrons and that SBR has a noble oxidation potential than LiFePO ₄ .

First, using the positive electrode active material layer of the example, the electrode potential was swept from 2.0 V to 4.3 V and then returned to 2.0 V again. The scanning speed was 0.01 V / second. An oxidation peak corresponding to the lithium elimination reaction of LiFePO ₄ was observed near 3.4 V, and a reduction peak corresponding to the lithium occlusion reaction was confirmed near 3.3 V.

  On the other hand, a CV test was conducted in the same manner as described above using the electron supply compound layer of the example. An oxidation peak in which SBR supplies (releases) electrons in the vicinity of 4.1 V was confirmed. A reduction peak could not be confirmed.

(Measurement of specific surface area)
The specific surface areas of the positive electrode active material layer and the electron supply compound layer were measured with AUTOSORB-1 manufactured by Quantum Chrome Instruments. ^They were 20, 40 (m ² / g), respectively.

(Evaluation of cycle characteristics)
The evaluation of the prepared capacity characteristics of the lithium secondary battery B _2, were fully charged by constant current charging until the 3.6V at 0.3C equivalent constant current value. Thereafter, the fully charged lithium ion secondary battery B _2, until the discharge end voltage 2.0 V, and the initial discharge capacity to measure the discharge capacity when discharged at a constant current value corresponding 0.3 C. In addition, the measurement of charging / discharging and discharge capacity was performed in 25 degreeC atmosphere.

  In the next 1 to 10 times after the first charge / discharge, the battery was fully charged by charging at a constant current value corresponding to a charge current of 0.3 C until reaching a charge end voltage of 3.6 V.

  After that, charging is performed so that a constant current equivalent to 0.3 C and a constant voltage charging are maintained for 10 hours from a voltage 3.6 V at full charge to a charge end voltage 4.3 V for 10 hours. It was. During this time, SBR supplies electrons, and lithium ions are intercalated into the negative electrode active material layer 21.

  In the next 11th to 20th times, the battery was fully charged by charging at a constant current value corresponding to a charge current of 0.3 C until reaching a charge end voltage of 3.6 V. Then, a cycle of discharging at a constant current value corresponding to 0.3 C was repeated from the charge end voltage of 3.6 V to the discharge end voltage of 2.0 V.

  The discharge capacity of each time in the 1st to 20th charge / discharge was measured in the same manner as the first time, and the capacity retention rate was calculated and shown in FIG. In FIG. 4, the capacity retention rate was obtained by the following formula with the initial discharge capacity being 100.

Capacity maintenance rate (%) = [(discharge capacity in each cycle) / (initial discharge capacity)] × 100
(Comparative example)
(Production of coin-type battery)
Using only the positive electrode active material layer 11 using LiFePO ₄ as the positive electrode active material, it was applied to both surfaces 12a and 12b of the positive electrode current collector 12, dried, and pressed to obtain a positive electrode 1 ′.

  A battery was produced in the same manner as in the example except that the positive electrode 1 ′ was used.

(Evaluation of cycle characteristics)
The initial discharge capacity was determined under the same conditions and method as in the examples.

  In all the first to twentieth cycles after the first charge / discharge, except that the same charge end voltage is 3.6 V, the test is performed in the same manner as in the examples, the discharge capacity at each time is measured, and the capacity maintenance rate is This is shown in FIG.

As shown in FIG. 4, the battery B ₂ of the example including the positive electrode 1 having the positive electrode active material layer 11 and the electron supply compound layer 13 maintains the capacity in the 11th to 20th cycles after increasing the end-of-charge voltage. It was confirmed that the battery was excellent in the characteristics. In addition, after the 10th cycle in which the capacity retention rate was less than 60% was completed, a suitable capacity recovery was recognized by increasing the charge end voltage.

  In addition, the effect in said Example is acquired irrespective of a composition of an electrode. For this reason, a present Example is not restrict | limited by the composition ratio of the material which comprises an electrode.

B ₁ and B ₂ : Lithium ion secondary battery U: Electrode unit 1: Positive electrode 10: Positive electrode of outer layer 11: Positive electrode active material layer 12: Positive electrode current collector 12a: One side 12b: Other side 13: Electron supply compound layer 2 : Negative electrode 21: Negative electrode active material layer 22: Negative electrode current collector 3: Electrolytic solution

Claims (6)

A positive electrode (1, 10, 100) having a positive electrode current collector (12) and a positive electrode active material layer (11) disposed on the positive electrode current collector;
A negative electrode (2) disposed opposite to the positive electrode and having a negative electrode current collector (22) and a negative electrode active material layer (21) disposed on the negative electrode current collector;
An electrolyte solution (3) interposed between the positive electrode and the negative electrode;
In a non-aqueous electrolyte secondary battery (B ₁ , B ₂ ) comprising:
The positive electrode (1, 10) is characterized in that an electron supply compound for irreversibly supplying electrons is disposed on a surface (12b) of the positive electrode current collector that is not opposed to the negative electrode. Non-aqueous electrolyte secondary battery.   The non-aqueous electrolyte secondary battery according to claim 1, wherein the electron supply compound is a compound having an oxidation potential nobler than that of the positive electrode active material.   The non-aqueous electrolyte secondary battery according to claim 1 or 2, wherein the electron supply compound layer (13) containing an electron supply compound has a specific surface area larger than that of the positive electrode active material layer.   The positive electrode (1, 10) is a plate-like surface of the positive electrode current collector, the positive electrode active material layer is disposed on one surface (12a) facing the negative electrode, and the other surface (12b). The non-aqueous electrolyte secondary battery according to claim 1, wherein the electron supply compound layer is disposed.   The nonaqueous electrolytic solution according to any one of claims 1 to 4, wherein the positive electrode having the positive electrode active material layer and the electron supply compound layer has a through hole (12c) through which ions contained in the electrolytic solution pass. Secondary battery.   The nonaqueous electrolysis according to any one of claims 1 to 5, wherein the positive electrode and the negative electrode are alternately laminated in a state in which the positive electrode (10) is formed at least one end in the laminating direction (L). Liquid secondary battery.

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