JP6031774B2 - Secondary battery, negative electrode current collector, electronic device and electric vehicle - Google Patents

Description

  The present technology relates to a secondary battery, a negative electrode current collector, an electronic device, and an electric vehicle. More specifically, the present technology relates to a secondary battery, a negative electrode current collector, an electronic device using the secondary battery, and an electric vehicle.

  In a lithium ion secondary battery, a Cu film is used as a negative electrode current collector. Cu is a material in which Li is difficult to alloy and the diffusion and disappearance of Li are relatively small. In addition, Ti, Ni, and the like are known as materials that are difficult to alloy with Li.

  However, in these metal materials, it is also known that Li is actually diffused minutely. This is noticeable in the thin film battery of the Li-free negative electrode. (For example, refer nonpatent literature 1) In this thin film battery of a Li-free negative electrode, Li metal precipitates between a negative electrode collector and a solid electrolyte, and this functions as a negative electrode active material. The discharge capacity is obtained by returning all Li metal deposited at the time of discharge to the positive electrode active material. However, since the battery capacity is this deposited Li itself, the battery gradually disappears when the deposited Li diffuses into the negative electrode current collector and disappears. Capacity goes down. For this reason, a current collector configuration is required in which Li does not disappear into the negative electrode current collector.

  On the other hand, an effect of attracting Li into the metal due to a potential difference between the potential of the current collector metal and the potential of Li is also generally known. Only when Li passes through the current collector metal and reaches the opposite surface, and Li is covered on both surfaces of the current collector metal, the potential balance becomes stable and stable. At that time, when the negative electrode current collector is exposed to moisture through the atmosphere or the like, Li reacts gradually and is lost. Thus, when Li and current collector metals other than Li are in contact, Li diffuses and disappears.

B. J. Neudecker et al., “Lithium-Free Thin-Film Battery with In Situ Plated Li Anode”, J. Electrochem. Soc., 147, 517-523 (2000) (Experimental)

  Secondary batteries are required to have a current collector configuration that suppresses diffusion of an electrode reactant such as Li in the negative electrode current collector.

  Accordingly, an object of the present technology is to provide a secondary battery, a negative electrode current collector, an electronic device, and an electric vehicle that can suppress diffusion of an electrode reactant in the negative electrode current collector.

In order to solve the above-described problem, the present technology includes a positive electrode, a negative electrode including a negative electrode current collector, and an electrolyte, and the negative electrode current collector is made of a first metal material and has conductivity. A negative electrode current collector, a second metal material that is the same as or different from the first metal material, and has conductivity, a first negative electrode current collector, and a second negative electrode current collector. be between the collector includes at least lithium, and, viewed contains a block area consisting of material capable of leaving and occluding lithium ions, the electrode reactant is a secondary battery is a lithium.

The present technology includes a first negative electrode current collector made of a first metal material and having conductivity, and a second negative electrode made of a second metal material that is the same as or different from the first metal material and has conductivity. A current collector and a block region between the first negative electrode current collector and the second negative electrode current collector, the block region being made of a material containing at least lithium and capable of desorbing and occluding lithium ions; seen including, electrode reactant is a negative electrode current collector for a secondary battery is a lithium.

  The present technology is an electronic device or an electric vehicle using the above-described secondary battery.

  In the present technology, the negative electrode current collector has a configuration including a block region that suppresses movement of the electrode reactant. With this configuration, diffusion of the electrode reactant in the negative electrode current collector can be suppressed.

  According to the present technology, it is possible to suppress the diffusion of the electrode reactant in the negative electrode current collector.

FIG. 1A is a plan view showing a configuration of a solid electrolyte secondary battery of the present technology. FIG. 1B is a cross-sectional view showing a cross section taken along line XX in FIG. 1A. 1C is a cross-sectional view showing a cross section taken along line YY of FIG. 1A. FIG. 2A is a plan view showing the configuration of the solid electrolyte secondary battery of the present technology. 2B is a cross-sectional view showing a cross section taken along line XX of FIG. 2A. 2C is a cross-sectional view showing a cross section taken along line YY of FIG. 1A. FIG. 3 is a cross-sectional view illustrating a configuration example of the secondary battery of the present technology. FIG. 4 is an enlarged cross-sectional view showing a part of the spirally wound electrode body shown in FIG. FIG. 5 is a block diagram illustrating a configuration example of the battery pack of the present technology. FIG. 6 is a schematic diagram illustrating an example applied to a residential power storage system using the secondary battery of the present technology. FIG. 7 is a schematic diagram schematically illustrating an example of a configuration of a hybrid vehicle that employs a series hybrid system to which the present technology is applied. FIG. 8 is a graph in which the utilization rate is plotted against the number of cycles for Example 1. FIG. 9 is a graph plotting the utilization rate against the number of cycles for Comparative Example 1. FIG. 10 is an SEM image obtained by observing the surface of the negative electrode current collector of Comparative Example 1. FIG. 11 is a photograph showing the surface state of the negative electrode current collector of Comparative Example 1.

Hereinafter, embodiments of the present technology will be described with reference to the drawings. The description will be given in the following order.
1. First embodiment (first example of thin-film solid electrolyte secondary battery)
2. Second embodiment (second example of thin-film solid electrolyte secondary battery)
3. Third Embodiment (Example of Cylindrical Nonaqueous Electrolyte Secondary Battery)
4). Fourth embodiment (battery pack)
5. Fifth embodiment (electronic device, electric vehicle, power storage device, etc.)
6). Other embodiment (modification)

1. First Embodiment A solid electrolyte secondary battery according to a first embodiment of the present technology will be described. 1A to 1C show a configuration of a solid electrolyte secondary battery according to a first embodiment of the present technology. FIG. 1A is a plan view of a solid electrolyte secondary battery. FIG. 1B is a cross-sectional view showing a cross section taken along line XX in FIG. 1A. 1C is a cross-sectional view showing a cross section taken along line YY of FIG. 1A. This solid electrolyte secondary battery is, for example, a secondary battery that can be charged and discharged. This solid electrolyte secondary battery is, for example, a lithium secondary battery in which lithium, which is a reactant in an electrode reaction (hereinafter referred to as an electrode reactant), moves between a positive electrode and a negative electrode with charge / discharge. In the present technology, lithium secondary batteries including those in which lithium is deposited at the negative electrode during charging are used. The solid electrolyte secondary battery is a thin film type solid electrolyte secondary battery in which battery constituent members such as a positive electrode, a negative electrode, and a solid electrolyte are formed of a thin film.

  As shown in FIG. 1A to FIG. 1C, in this solid electrolyte secondary battery, an inorganic insulating film 20 is formed on a substrate 10 that is a base material, and on the inorganic insulating film 20, a positive current collector film 30 and The positive electrode active material film 40, the solid electrolyte film 50, the first negative electrode side current collector film 60a, the block layer 60c, and the second negative electrode side current collector film 60b are stacked in this order. Have a body. An entire protective film 80 made of, for example, an ultraviolet curable resin is formed so as to cover the entire laminate. Note that the inorganic insulating film 20 may be formed on the entire protective film 80. This solid electrolytic secondary battery includes a positive electrode side layer, a negative electrode side layer, and a solid electrolyte layer between the positive electrode side layer and the negative electrode side layer. In this solid electrolyte secondary battery, the positive electrode side layer is on the positive electrode side of the solid electrolyte layer with the solid electrolyte layer as a boundary. In the example shown in FIGS. 1A to 1C, the positive electrode side layer includes, for example, a positive electrode active material film 40 that is a positive electrode active material layer and a positive electrode side current collector that are on the positive electrode side of the solid electrolyte film 50 that is a solid electrolyte layer. And positive electrode side current collector film 30 as a layer. In this solid electrolyte secondary battery, the negative electrode side layer is on the negative electrode side of the solid electrolyte layer with the solid electrolyte layer as a boundary. In the example shown in FIGS. 1A to 1C, the negative electrode side layer includes, for example, a first negative electrode side current collector film 60 a that is a negative electrode side current collector layer located on the negative electrode side from the solid electrolyte film 50 that is a solid electrolyte layer; It includes a block layer 60c and a second negative electrode current collector film 60b.

(substrate)
Examples of the substrate 10 include a polycarbonate (PC) resin substrate, a fluororesin substrate, a polyethylene terephthalate (PET) substrate, a polybutylene terephthalate (PBT) substrate, a polyimide (PI) substrate, a polyamide (PA) substrate, and a polysulfone (PSF) substrate. Polyethersulfone (PES) substrate, polyphenylene sulfide (PPS) substrate, polyetheretherketone (PEEK) substrate, polyethylene naphthalate (PEN), cycloolefin polymer (COP) and the like can be used. The material of this substrate is not particularly limited, but a substrate having low moisture absorption and moisture resistance is more preferable.

(Positive electrode side current collector film 30)
As a material constituting the positive electrode side current collector film 30, Cu, Mg, Ti, Fe, Co, Ni, Zn, Al, Ge, In, Au, Pt, Ag, Pd, or any of these may be used. Including alloys can be used.

(Positive electrode active material film 40)
The positive electrode active material constituting the positive electrode active material film 40 may be any material that can easily release and occlude lithium ions and can release and occlude many lithium ions in the positive electrode active material film. A material having a high potential and a small electrochemical equivalent is preferable. For example, an oxide or a phosphoric acid compound containing at least one of Mn, Co, Fe, P, Ni, Si, and Cr and Li, or a sulfur compound can be given. Specifically, for example, lithium manganese oxides such as LiMnO ₂ (lithium manganate), LiMn ₂ O ₄ and Li ₂ Mn ₂ O ₄ , lithium such as LiCoO ₂ (lithium cobaltate) and LiCo ₂ O ₄ Cobalt oxide, lithium-nickel oxide such as LiNiO ₂ (lithium nickelate), LiNi ₂ O ₄ , lithium-manganese-cobalt oxide such as LiMnCoO ₄ , Li ₂ MnCoO ₄ , Li ₄ Ti ₅ O ₁₂ , LiTi ₂ Li-titanium oxide such as O ₄ , LiFePO ₄ (lithium iron phosphate), titanium sulfide (TiS ₂ ), molybdenum sulfide (MoS ₂ ), iron sulfide (FeS, FeS ₂ ), copper sulfide (CuS) and nickel sulfide (Ni ₃ S _2), bismuth oxide (Bi ₂ O _3), lead-acid bismuth _{(Bi 2 Pb 2 O 5)} , copper oxide ( uO), vanadium oxide (V ₆ O _13), niobium selenide (NbSe _3), and the like. Moreover, it is also possible to mix and use these. In consideration of film formability, battery cycle stability, and potential, a lithium composite oxide having Co or Mn and Li such as LiCoO ₂ and LiMnO ₂ is preferable.

  The positive electrode active material film 40 may be composed of an amorphous lithium phosphate compound. For example, the positive electrode active material film 40 is composed of an amorphous lithium phosphate compound containing Li, P, and any element M1 and O selected from Ni, Co, Mn, Au, Ag, and Pd.

This lithium phosphate compound has the following excellent characteristics as a positive electrode active material. That is, it has a high potential with respect to the pair Li ⁺ / Li. The potential flatness is excellent, that is, the potential fluctuation accompanying the composition change is small. Since the composition ratio of lithium is large, the capacity is high. High electrical conductivity. Since there is no collapse of the crystal structure due to repeated charge / discharge unlike the crystalline positive electrode active material, the charge / discharge cycle characteristics are also excellent. Further, since it can be formed without an anneal, the process can be simplified, the yield can be improved, and the resin substrate can be used.

  The positive electrode active material film 40 may be composed of, for example, a lithium phosphate compound represented by the formula (1) as the lithium phosphate compound as described above.

Formula (1)
Li _x Ni _y PO _z
(Wherein x represents the composition ratio of lithium, y represents the composition ratio of nickel, z represents the composition ratio of oxygen, x is 0 <x <8.0, and y is 2.0 ≦ y. ≦ 10, z represents the composition ratio of oxygen, and z is a ratio in which oxygen is stably contained according to the composition ratio of Ni and P.)

In the formula (1), the range of the lithium composition ratio x is preferably 0 <x <8.
The upper limit of the lithium composition ratio x is not particularly limited, but the limit at which the potential is maintained is the upper limit value of the lithium composition ratio x. In the confirmed range, the composition ratio x of lithium is preferably less than 8. The range of the lithium composition ratio x is more preferably 1.0 ≦ x <8. This is because when the composition ratio x of lithium is less than 1.0, the impedance is large and charging / discharging cannot be performed.

  In the formula (1), the range of the Ni composition ratio y is preferably 2.0 ≦ y ≦ 10.0 from the viewpoint of obtaining a sufficient charge / discharge capacity. For example, when the composition ratio y of Ni is less than 2.0, the charge / discharge capacity is rapidly reduced. The upper limit of the Ni composition ratio y is not particularly limited, but when the Ni composition ratio y exceeds 4, the charge / discharge capacity gradually decreases. Taking about half of the maximum capacity as a guide, the Ni composition ratio y is preferably 10 or less. If there are advantages in terms of durability, ion conductivity, etc., the composition ratio may exceed 10.0 at the expense of charge / discharge capacity.

  In the formula (1), the composition ratio z of oxygen is a ratio that is stably included according to the composition ratio of Ni and the composition ratio of P.

  The positive electrode active material film 40 may be made of a lithium phosphate compound represented by Formula (2) in an amorphous state.

Formula (2)
Li _x Cu _y PO ₄
(In the formula, x represents the composition ratio of lithium, and y represents the composition ratio of copper.)

The lithium composite oxide represented by the formula (2) in an amorphous state has the following excellent characteristics as a positive electrode active material. That is, it has a high potential with respect to the pair Li ⁺ / Li. The potential flatness is excellent, that is, the potential fluctuation accompanying the composition change is small. Since the composition ratio of lithium is large, the capacity is high. High electrical conductivity. Since there is no collapse of the crystal structure due to repeated charge / discharge unlike the crystalline positive electrode active material, the charge / discharge cycle characteristics are also excellent. Further, since it can be formed without an anneal, the process can be simplified, the yield can be improved, and the resin substrate can be used.

  In the lithium phosphate compound represented by the formula (2), the range of the lithium composition ratio x may be, for example, 0.5 ≦ x <7.0 and 5 <x <7.0.

  In the lithium phosphate compound represented by the formula (2), the range of the copper composition ratio y is preferably 1.0 ≦ y ≦ 4.0 from the viewpoint of obtaining a sufficient charge / discharge capacity. In particular, when the copper composition ratio y is less than 1.0, the charge / discharge capacity decreases rapidly. The upper limit of the copper composition ratio y is not particularly limited, but when the composition ratio y exceeds 3, the charge / discharge capacity gradually decreases. As a guide, about half of the maximum capacity is 4 or less. However, if there are advantages in terms of durability, ion conductivity, etc., it is possible to make the composition 4 or more at the expense of charge / discharge capacity. In the lithium phosphate compound represented by the formula (2), the lower limit of the copper composition ratio y is more preferably 2.2 ≦ y from the viewpoint of obtaining good charge / discharge cycle characteristics.

  The composition of the lithium phosphate compound constituting the positive electrode active material film 40 is determined as follows, for example. A single-layer film similar to the positive electrode active material film 40 is formed on quartz glass under the same film formation conditions as the positive electrode active material film 40. And the composition analysis of this single layer film is performed by X-ray photoelectron spectroscopy (X-ray photoelectron spectroscopy (XPS); X-ray photoelectron spectroscopy).

Incidentally, in a secondary battery, it is indispensable to increase the capacity of the positive electrode active material in order to improve the energy density. For example, as a high-capacity positive electrode active material used for a lithium ion secondary battery or the like, a metal composite oxide (for example, Li _x CoO ₂ , Li _x NiO ₂ , roughly divided into a rock salt type layered structure and a spinel type structure) Li _x Mn ₂ O _{4 and the} like), and thereby, the capacity is increased.

However, since these positive electrode active materials have a crystal structure, the structure collapses with the number of cycles, and the internal impedance is high, so it is difficult to increase the number of reaction electrons. In the case of Li _x Mn ₂ O ₄ categorized as a spinel structure, volume expansion / contraction due to yarn teller ions (Mn ³⁺ ) occurs when 1 <X <2 if excessive Li is contained in the active material. Thus, it is known that the potential decreases. (For example, see JM Tarascan, J. Electrochem. Soc, 138, 2864 (1991), T. Ohzuku, J. Electrochem. Soc, 137, 769 (1990))

  On the other hand, the positive electrode active material of the present technology can be charged and discharged in an amorphous state, can relieve volume expansion and contraction due to insertion and desorption of Li, and can suppress structural changes. Moreover, since the positive electrode active material of this technique can contain Li in a wide range like the positive electrode active material of said Formula (1) and Formula (2), for example, high capacity | capacitance is possible. For example, in Formula (1), it can contain to less than lithium composition ratio x = 8, and in Formula (2), it can contain to less than lithium composition ratio x = 7.

In an all solid state secondary battery, since it is necessary to deposit a current collector, a positive electrode active material, an electrolyte, and a negative electrode, it is essential to reduce interface resistance and internal resistance of the positive electrode active material. The interface resistance is reduced as Li ion path formation contributes and Li ion diffusion is easier. Although the main solution is to improve the ionic conductivity of the electrolyte, interface control such as surface uniformity and adhesion of each layer also leads to improved characteristics. The internal resistance of the positive electrode active material cannot be increased unless the internal impedance is lowered. In the case of an all solid state secondary battery, since the film thickness is proportional to the battery capacity, the positive electrode active material must be formed thick. Therefore, reducing the impedance inside the positive electrode leads to an increase in capacity. It has been found that the positive electrode active material of the present technology has lower internal impedance than LiCoO ₂ having a layered structure.

  The positive electrode active material film 40 includes at least one element selected from Li, P, Ni, Co, Mn, Au, Ag, and Pd, and any element M1 selected from Ni, Co, Mn, Au, Ag, Pd, and Cu. It may be composed of an amorphous lithium phosphate compound containing a seed element M2 (where M1 ≠ M2) and O. Such a lithium phosphate compound can obtain a positive electrode active material with more excellent characteristics by, for example, appropriately selecting the element M1 and the element M2. For example, when the positive electrode active material film 40 is composed of an amorphous lithium phosphate compound containing Li, P, Ni (element M1), Cu (element M2), and O, the charge / discharge cycle characteristics are further improved. can do. For example, when the positive electrode active material film 40 is made of an amorphous lithium phosphate compound containing Li, P, Ni (element M1), Pd (element M2), and O, the capacity can be further improved and the charge can be improved. The discharge cycle characteristics can be further improved. For example, when the positive electrode active material film 40 is composed of an amorphous lithium phosphate compound containing Li, P, Ni (element M1), Au (element M2), and O, the charge / discharge cycle characteristics are further improved. can do.

  The positive electrode active material film 40 includes at least one element selected from Li, P, Ni, Co, Mn, Au, Ag, and Pd, and any element M1 selected from Ni, Co, Mn, Au, Ag, Pd, and Cu. Seed element M2 (where M1 ≠ M2) and B, Mg, Al, Si, Ti, V, Cr, Fe, Zn, Ga, Ge, Nb, Mo, In, Sn, Sb, Te, W, Os , Bi, Gd, Tb, Dy, Hf, Ta, Zr, and may be composed of an amorphous lithium phosphate compound containing at least one additional element M3 and O selected from Zr.

  The positive electrode active material film 40 includes any element M1 ′ selected from Li, P, Ni, Co, Mn, Au, Ag, Pd, and Cu, Mg, Al, Si, Ti, V, Cr, Fe, Contains at least one additive element M3 and O selected from Zn, Ga, Ge, Nb, Mo, In, Sn, Sb, Te, W, Os, Bi, Gd, Tb, Dy, Hf, Ta, and Zr It may be composed of an amorphous lithium phosphate compound.

  Even if the additive element M3 is contained only in the lithium phosphate compound, the lithium phosphate compound cannot be used as the positive electrode active material. That is, when the positive electrode active material film 40 is composed of an amorphous lithium phosphate compound containing Li, P, only the additive element M3, and O, the battery is not driven. On the other hand, when the additive element M3 is contained in the lithium phosphate compound together with the element M1 and the element M2 (M1 ≠ M2) or the element M1 ′, the lithium phosphate compound can be used as a positive electrode active material, and further added element Depending on the selection of the species, the properties as the positive electrode active material can be improved. That is, even when the positive electrode active material film 40 is formed by adding the additive element M3 to the lithium phosphate compound together with the element M1 and the element M2 (M1 ≠ M2) or the element M1 ', the battery driving is not affected. Further, in the case where the positive electrode active material film 40 is configured by adding the additive element M3 to the lithium phosphate compound together with the element M1 and the element M2 (M1 ≠ M2) or the element M1 ′, depending on the selection of the element type to be added, There are effects such as improvement of capacity and cycle characteristics and reduction of internal impedance.

Examples of preferable additive element M3 include the following. That is, in general, ion conduction is considered to facilitate movement of ions by disturbing a structure including conductivity. In fact, it is known that the solid electrolyte of Li ₃ PO ₄ is increased in ionic conductivity by doping nitrogen and partially replacing it like Li ₃ PO _3.7 N _0.3 . On the other hand, in the case of a crystal material, the ion conduction path is formed with a structure (crystal) that is as uniform as possible. It has been. Therefore, there is a common aspect in terms of increasing the number of paths through which lithium can easily move inside the solid electrolyte, and materials that have improved ionic conductivity with crystalline materials are often effective even with amorphous materials. It is conceivable that the additive (additive element) of the material with improved sapphire is also effective for the amorphous positive electrode active material (amorphous lithium phosphorylated compound) of the present technology. Lithium oxide solid electrolyte materials, which are crystalline materials with improved ionic conductivity, include Li _0.5 La _0.5 TiO ₃ , Li _3.5 Zn, in addition to Li _1.3 Al _0.3 Ti _1.7 (PO ₄ ) ₃ (LATP). _There are many materials such as _0.35 GeO ₄ . Therefore, the additive elements of these materials, Al, Ti, La, Zn, Ge, and other Si, V, W, Ga, Ta, Zr, Cr, and Pd, are also ion-conductive in the amorphous positive electrode active material of the present technology. It is possible to improve the characteristics such as degree, and to be effective.

  For example, when the positive electrode active material film 40 is composed of an amorphous lithium phosphate compound containing Li, P, Ni (element M1 ′), at least one of Al and Ti (additive element M3), and O. Can reduce internal impedance and provide excellent high rate discharge characteristics. By reducing the internal impedance, the potential change during high-speed discharge is reduced, and a battery with a higher potential can be realized. Furthermore, since the internal impedance is low, the ratio of discharge energy to charge energy (discharge energy / charge energy) approaches 1, so that energy loss is reduced and energy efficiency is increased, and Joule heat at the time of charge and discharge is also increased. The effect of suppressing heat generation is expected due to the decrease in the temperature.

  The positive electrode active material film 40 does not include a crystalline phase and is a completely amorphous single-phase thin film. It can be confirmed that the positive electrode active material film 40 is an amorphous single phase by observing a cross section with a transmission electron microscope (TEM). That is, when the cross section of the positive electrode active material film 40 is observed with a transmission electron microscope (TEM), a state in which no crystal grains are present can be confirmed in the TEM image. It can also be confirmed from an electron diffraction image.

(Solid electrolyte membrane)
As a material constituting the solid electrolyte membrane 50, lithium phosphate (Li ₃ PO ₄ ), Li ₃ PO _4-x N _{x in} which nitrogen is added to lithium phosphate (Li ₃ PO ₄ ) (generally called LiPON) _{have.), Li x B 2 O} 3-y N y, Li 4 SiO 4 -Li 3 PO 4, Li 4 may be used such as SiO ₄ -Li ₃ VO _4. The subscripts x (x> 0) and y (y> 0)) used in the compound indicate the composition ratio of the elements in the formula.

(Lithium excess layer)
In this solid electrolyte secondary battery, the negative electrode active material is generated on the negative electrode side together with charging without forming the negative electrode active material layer. What is generated on the negative electrode side is a layer (Li excessive layer) that contains Li metal and / or Li excessively generated between the first negative electrode side current collector film 60 a and the solid electrolyte film 50. While using this excessively deposited Li (Li excess layer) as a negative electrode active material, it has high durability against repeated charge and discharge without impairing charge and discharge characteristics.

(Negative electrode current collector film)
The negative electrode side current collector film 60 includes, for example, a first negative electrode side current collector film 60a, a second negative electrode side current collector film 60b, a first negative electrode side current collector film 60a, and a second negative electrode. And a blocking layer 60c between the side current collector film 60b.

(First negative electrode side current collector film)
Examples of the material constituting the first negative electrode side current collector film 60a include Cu, Mg, Ti, Fe, Co, Ni, Zn, Al, Ge, In, Au, Pt, Ag, Pd, and the like. Alloys containing either can be used.

(Second negative electrode side current collector film)
Examples of the material constituting the second negative electrode side current collector film 60b include Cu, Mg, Ti, Fe, Co, Ni, Zn, Al, Ge, In, Au, Pt, Ag, Pd, or the like. Alloys containing either can be used. In addition, the material which comprises the 1st negative electrode side collector film 60a, and the material which comprises the 2nd negative electrode side collector film 60b may be the same, or may differ.

(Block layer)
The block layer 60c is a block region that is formed inside the negative electrode current collector film 60 and inhibits lithium migration. By forming the block layer 60c inside the negative electrode current collector film 60, lithium can be prevented from diffusing.

  The block layer 60c is made of, for example, a lithium ion conductor and an electrically conductive material. Examples of such a material include a positive electrode active material used for a lithium secondary battery. Examples of such a positive electrode active material include the same positive electrode active material as the material constituting the positive electrode active material film 40 described above. Since the block layer 60c is covered with the negative electrode side current collector film 60, the block layer 60c is formed so as not to be exposed to the atmosphere or an electrolyte. Thereby, while the conductivity of the current collector is maintained, the amount of lithium can be maintained or replenished with respect to the ingress of lithium, which contributes to the improvement of the durability of repeated charging and discharging of the lithium secondary battery. In addition, also when using the negative electrode active material material used for a lithium secondary battery as a material of the block layer 60c, it is possible to store Li, maintaining the electrical conductivity of a collector similarly, but in this case Has a large storage capacity of Li, and since Li is not contained in the initial stage, a loss of taking in diffused Li becomes large. Therefore, it is preferable to use the positive electrode active material used for the lithium secondary battery as the material of the block 60c.

  In this solid electrolyte secondary battery, Li metal deposited between the negative electrode side current collector film 60 and the solid electrolyte film 50 functions as a negative electrode active material. At the time of discharge, the capacity can be obtained by returning all the deposited Li metal to the positive electrode active material. However, since the battery capacity is the deposited Li itself, the deposited Li diffuses into the negative electrode current collector film 60 and disappears. As a result, the battery capacity gradually decreases. On the other hand, in the present technology, by forming the block layer 60c in the negative electrode side current collector film 60, lithium is prevented from diffusing into the negative electrode side current collector film 60 and disappearing, A decrease in battery capacity due to repeated charge and discharge can be suppressed.

  The negative electrode side current collector film 60 is formed by, for example, forming a thin film made of a positive electrode active material as a block layer 60c on the first negative electrode side current collector film 60a made of the above-described metal material, and by forming a thin film such as a sputtering method. In addition, the second negative electrode side current collector film 60b made of the above-described metal material can be further formed thereon. Instead of at least one of the first negative electrode side current collector film 60a and the second negative electrode side current collector film 60b, a metal foil (metal film) may be used. In the configuration in which the block layer 60c is sandwiched between the first negative electrode side current collector film 60a and the second negative electrode side current collector film 60b, the block layer 60c made of the positive electrode active material is electrically conductive. Therefore, the potential between the negative electrode side current collector film 60 divided into two layers (the first negative electrode side current collector film 60a and the second negative electrode side current collector film 60b) is considered to be the same. . That is, the block layer 60c sandwiched between the first negative electrode side current collector film 60a and the second negative electrode side current collector film 60b has no potential applied to one, and the block layer 60c (that is, the positive electrode active layer) Lithium does not move from the material) and deposit on either negative electrode current collector film.

(Inorganic insulating film 20)
The material constituting the inorganic insulating film 20 may be any material that can form a film having low moisture absorption and moisture resistance. As such a material, an oxide or nitride or sulfide of Si, Cr, Zr, Al, Ta, Ti, Mn, Mg, Zn, or a mixture thereof can be used. More specifically, Si ₃ N ₄ , SiO ₂ , Cr ₂ O ₃ , ZrO ₂ , Al ₂ O ₃ , TaO ₂ , TiO ₂ , Mn ₂ O ₃ , MgO, ZnS, or a mixture thereof is used. To do.

(Method for manufacturing solid electrolyte secondary battery)
The above-described solid electrolyte secondary battery is manufactured, for example, as follows. First, the inorganic insulating film 20 is formed on the substrate 10. Next, on the inorganic insulating film 20, the positive electrode side current collector film 30, the positive electrode active material film 40, the solid electrolyte film 50, the first negative electrode side current collector film 60a, the block layer 60c, and the second negative electrode side current collector. The electric conductor film 60b is sequentially formed, whereby a stacked body is formed. Next, an entire protective film 80 made of, for example, an ultraviolet curable resin is formed on the substrate 10 so as to cover the entire laminate and the inorganic insulating film 20. Through the above series of steps, the solid electrolyte secondary battery according to the first embodiment of the present technology can be manufactured.

(Thin film formation method)
The inorganic insulating film 20, the positive electrode side current collector film 30, the positive electrode active material film 40, the solid electrolyte film 50, the first negative electrode side current collector film 60a, the block layer 60c, and the second negative electrode side current collector film 60b. A forming method will be described.

  Each thin film can be formed by a vapor phase method such as a PVD (Physical Vapor Deposition) method or a CVD (Chemical Vapor Deposition) method. Moreover, it can form by liquid phase methods, such as electroplating, electroless plating, the apply | coating method, and a sol-gel method. Further, it can be formed by a solid phase method such as an SPE (solid phase epitaxy) method or an LB (Langmuir-Blodgett) method.

  The PVD method is a method in which a thin film raw material to be thinned is once evaporated and vaporized by energy such as heat or plasma to form a thin film on a substrate. Examples of the PVD method include a vacuum deposition method, a sputtering method, an ion plating method, an MBE (molecular beam epitaxy) method, and a laser ablation method.

  In the CVD method, energy such as heat, light, and plasma is applied to the constituent material of a thin film supplied as a gas to form decomposition, reaction, and intermediate products of source gas molecules, and adsorption and reaction on the substrate surface. This is a method of depositing a thin film through separation.

  Examples of the CVD method include thermal CVD method, MOCVD (Metal Organic Chemical Chemical Vapor Deposition) method, RF plasma CVD method, photo CVD method, laser CVD method, LPE (Liquid Phase Epitaxy) method and the like. Can be mentioned.

  It is easy for those skilled in the art to form a thin film having a desired configuration by the above-described thin film forming method. For example, the inorganic insulating film 20, the positive electrode side current collector film 30, the positive electrode active material film 40, the solid electrolyte film 50, the first negative electrode side current collector film 60 a, the block layer 60 c, the second thin film forming method are used. It is easy for those skilled in the art to form the negative electrode side current collector film 60b. That is, a person skilled in the art appropriately selects an inorganic insulating film 20, a positive electrode side current collector film 30, a positive electrode active material film 40, a solid electrolyte film having a desired configuration by appropriately selecting a thin film raw material, a thin film forming method, thin film forming conditions, and the like. 50, the 1st negative electrode side collector film 60a, the block layer 60c, and the 2nd negative electrode side collector film 60b can be formed easily.

2. Second Embodiment A solid electrolyte secondary battery according to a second embodiment of the present technology will be described. 2A to 2C show the configuration of the solid electrolyte secondary battery according to the second embodiment of the present technology. FIG. 2A is a plan view of the solid electrolyte secondary battery. 2B is a cross-sectional view showing a cross-section along the line XX in FIG. 2A. 2C is a cross-sectional view showing a cross section taken along line YY of FIG. 2A. This solid electrolyte secondary battery is a secondary battery that can be charged and discharged, for example. This solid electrolyte secondary battery is, for example, a lithium secondary battery in which lithium, which is an electrode reactant, moves between a positive electrode and a negative electrode with charge / discharge. The solid electrolyte secondary battery is, for example, a thin film type solid electrolyte secondary battery in which battery constituent members such as a positive electrode, a negative electrode, and a solid electrolyte are formed of a thin film.

  In this solid electrolyte secondary battery, an inorganic insulating film 20 is formed on a substrate 10 that is a base material, and a positive current collector film 30, a positive electrode active material film 40, and a solid electrolyte film 50 are formed on the inorganic insulating film 20. The negative electrode active material film 70, the first negative electrode side current collector film 60a, the block layer 60c, and the second negative electrode side current collector film 60b are stacked in this order. An overall protective film 80 made of, for example, an ultraviolet curable resin is formed so as to cover the entire laminate and the inorganic insulating film 20. Note that the inorganic insulating film 20 may be formed on the entire protective film 80. This solid electrolytic battery includes a positive electrode side layer, a negative electrode side layer, and a solid electrolyte layer between the positive electrode side layer and the negative electrode side layer. In this solid electrolyte secondary battery, the positive electrode side layer is on the positive electrode side of the solid electrolyte layer with the solid electrolyte layer as a boundary. In the example shown in FIGS. 2A to 2C, the positive electrode side layer includes, for example, a positive electrode active material film 40 that is a positive electrode active material layer and a positive electrode side current collector that are on the positive electrode side of the solid electrolyte film 50 that is a solid electrolyte layer. And positive electrode side current collector film 30 as a layer. In this solid electrolyte secondary battery, the negative electrode side layer is on the negative electrode side of the solid electrolyte layer with the solid electrolyte layer as a boundary. In the example shown in FIGS. 2A to 2C, the negative electrode side layer includes, for example, a negative electrode active material film 70 that is closer to the negative electrode than the solid electrolyte film 50 that is a solid electrolyte layer, and a negative electrode side current collector that is a negative electrode side current collector layer. Body membrane 60.

  Substrate 10, inorganic insulating film 20, positive electrode side current collector film 30, positive electrode active material film 40, solid electrolyte film 50, first negative electrode side current collector film 60a, block layer 60c, second negative electrode side current collector Since the film 60b and the entire protective film 80 are the same as those in the first embodiment, detailed description thereof is omitted. The negative electrode active material film 70 has the following configuration.

(Negative electrode active material film)
The material constituting the negative electrode active material film 70 may be any material as long as it can easily occlude and release lithium ions and can occlude and release many lithium ions in the negative electrode active material film 70. As such materials, Sn, Si, Al, Ge, Sb, Ag, Ga, In, Fe, Co, Ni, Ti, Mn, Ca, Ba, La, Zr, Ce, Cu, Mg, Sr, Cr, A material containing at least one of Mo, Nb, V, and Zn, for example, an oxide containing the above-described element can be used. These materials such as oxides can also be mixed and used.

Specifically, the material of the negative electrode active material film 70 is, for example, a silicon-manganese alloy (Si-Mn), a silicon-cobalt alloy (Si-Co), a silicon-nickel alloy (Si-Ni), or niobium pentoxide (Nb). ₂ O ₅ ), vanadium pentoxide (V ₂ O ₅ ), titanium oxide (TiO ₂ ), indium oxide (In ₂ O ₃ ), zinc oxide (ZnO), tin oxide (SnO ₂ ), nickel oxide (NiO), Added indium oxide (ITO) to which Sn is added, zinc oxide (AZO) to which Al is added, zinc oxide (GZO) to which Ga is added, tin oxide (ATO) to which Sn is added, and F (fluorine) Tin oxide (FTO) and the like. Moreover, these can also be mixed and used. Further, Li metal may be used as a material constituting the negative electrode active material film 70.

(Method for manufacturing solid electrolyte secondary battery)
The above-described solid electrolyte secondary battery is manufactured, for example, as follows.

  First, the inorganic insulating film 20 is formed on the substrate 10. Next, on the inorganic insulating film 20, a positive electrode side current collector film 30, a positive electrode active material film 40, a solid electrolyte film 50, a negative electrode active material film 70, a first negative electrode side current collector film 60a, a block layer 60c, The second negative electrode current collector film 60b is sequentially formed, whereby a stacked body is formed. Next, an entire protective film 80 made of, for example, an ultraviolet curable resin is formed on the substrate 10 so as to cover the entire laminate and the inorganic insulating film 20. Through the above series of steps, the solid electrolyte secondary battery according to the second embodiment of the present technology can be manufactured.

3. Third embodiment (cylindrical lithium secondary battery)
(Battery configuration)
A nonaqueous electrolyte secondary battery according to a third embodiment of the present technology will be described with reference to FIGS. 3 and 4. FIG. 3 shows a cross-sectional configuration of a nonaqueous electrolyte secondary battery according to the third embodiment of the present technology. FIG. 4 shows an enlarged part of the spirally wound electrode body 100 shown in FIG. This nonaqueous electrolyte secondary battery is, for example, a nonaqueous electrolyte secondary battery that can be charged and discharged. The nonaqueous electrolyte secondary battery is, for example, a lithium secondary battery in which lithium, which is an electrode reactant, moves between the positive electrode and the negative electrode with charge / discharge.

  This non-aqueous electrolyte secondary battery mainly includes a wound electrode body 100 in which a positive electrode 101 and a negative electrode 102 are laminated and wound via a separator 103 inside a substantially hollow cylindrical battery can 91, and a pair. The insulating plates 92 and 93 are accommodated. The battery structure using the cylindrical battery can 91 is called a cylindrical type.

  The battery can 91 has, for example, a hollow structure in which one end is closed and the other end is opened, and is made of iron (Fe), aluminum (Al), or an alloy thereof. When the battery can 91 is made of iron, for example, nickel (Ni) or the like may be plated on the surface of the battery can 91. The pair of insulating plates 92 and 93 are arranged so as to sandwich the wound electrode body 100 from above and below and to extend perpendicularly to the wound peripheral surface.

  A battery lid 94, a safety valve mechanism 95 and a heat sensitive resistance element (Positive Temperature Coefficient: PTC element) 96 are caulked through a gasket 97 at the open end of the battery can 91, and the battery can 91 is hermetically sealed. ing. The battery lid 94 is made of the same material as the battery can 91, for example. The safety valve mechanism 95 and the thermal resistance element 96 are provided inside the battery lid 94. The safety valve mechanism 95 is electrically connected to the battery lid 94 via the heat sensitive resistance element 96. In the safety valve mechanism 95, when the internal pressure becomes a certain level or more due to an internal short circuit or external heating, the disk plate 95A is reversed and the electric power between the battery lid 94 and the wound electrode body 100 is reversed. Connection is cut off. The heat-sensitive resistance element 96 prevents abnormal heat generation due to a large current by increasing the resistance (limiting the current) as the temperature rises. The gasket 97 is made of, for example, an insulating material, and for example, asphalt is applied to the surface thereof.

  The wound electrode body 100 is obtained by laminating and winding a positive electrode 101 and a negative electrode 102 with a separator 103 interposed therebetween. A center pin 104 may be inserted in the center of the wound electrode body 100. In the wound electrode body 100, a positive electrode lead 105 made of aluminum or the like is connected to the positive electrode 101, and a negative electrode lead 106 made of nickel or the like is connected to the negative electrode 102. The positive electrode lead 105 is welded to the safety valve mechanism 95 and electrically connected to the battery lid 94, and the negative electrode lead 106 is welded to the battery can 91 and electrically connected thereto.

(Positive electrode)
In the positive electrode 101, for example, a positive electrode active material layer 101B is provided on both surfaces of a positive electrode current collector 101A having a pair of surfaces. However, the positive electrode active material layer 101B may be provided only on one surface of the positive electrode current collector 101A.

  The positive electrode current collector 101A is made of, for example, a metal material such as Al, Ni, or SUS.

  The positive electrode active material layer 101B contains one or more positive electrode active material materials capable of occluding and releasing lithium as a positive electrode active material, and a binder or a conductive material as necessary. Other materials such as agents may be included.

  As the positive electrode active material capable of inserting and extracting lithium, the same material as in the first embodiment can be used.

  Examples of the binder include synthetic rubbers such as styrene butadiene rubber, fluorine rubber or ethylene propylene diene, and polymer materials such as polyvinylidene fluoride. These may be used alone or in combination of two or more.

  Examples of the conductive agent include carbon materials such as graphite and carbon black. These may be used alone or in combination of two or more. Note that the conductive agent may be a metal material or a conductive polymer as long as it is a conductive material.

(Negative electrode)
In the negative electrode 102, for example, a negative electrode active material layer 102B is provided on both surfaces of a negative electrode current collector 102A having a pair of surfaces. However, the negative electrode active material layer 102B may be provided only on one surface of the negative electrode current collector 102A.

  The negative electrode current collector 102A is a block between the first negative electrode current collector 102a, the second negative electrode current collector 102b, and the first negative electrode current collector 102a and the second negative electrode current collector 102b. Layer 102c. The first negative electrode current collector 102a and the second negative electrode current collector 102b are made of a foil-like metal material such as Cu, Ni, or SUS, for example. The materials of the first negative electrode current collector 102a and the second negative electrode current collector 102b may be the same or different. The block layer 102c is the same as the block layer 60c of the first embodiment.

  The negative electrode active material layer 102B includes one or more negative electrode materials capable of inserting and extracting lithium as a negative electrode active material, and a binder, a conductive agent, and the like as necessary. Other materials may be included. In this negative electrode active material layer 102B, for example, the chargeable capacity of the negative electrode material is larger than the discharge capacity of the positive electrode 101 in order to prevent unintentional precipitation of lithium metal during charging and discharging. Is preferred. Note that the same binder and conductive agent as those described for the positive electrode 101 can be used.

  Examples of the negative electrode material capable of inserting and extracting lithium include a carbon material. Examples of the carbon material include non-graphitizable carbon, graphitizable carbon, artificial graphite such as MCMB (mesocarbon microbeads), natural graphite, pyrolytic carbons, cokes, graphites, and glassy carbons. Organic polymer compound fired bodies, carbon blacks, carbon fibers or activated carbon. Among these, examples of coke include pitch coke, needle coke, and petroleum coke. An organic polymer compound fired body refers to a carbonized material obtained by firing a polymer material such as phenol resin or furan resin at an appropriate temperature, and part of it is non-graphitizable carbon or graphitizable carbon. Some are classified as:

  As the negative electrode material capable of inserting and extracting lithium in addition to the carbon material described above, for example, it can store and release lithium and constitute at least one of a metal element and a metalloid element The material which has as an element is mentioned. This is because a high energy density can be obtained. Such a negative electrode material may be a single element, an alloy or a compound of a metal element or a metalloid element, and may have one or two or more phases thereof at least in part. The “alloy” in the present technology includes an alloy containing one or more metal elements and one or more metalloid elements in addition to an alloy composed of two or more metal elements. Further, the “alloy” may contain a nonmetallic element. This structure includes a solid solution, a eutectic (eutectic mixture), an intermetallic compound, or one in which two or more of them coexist.

  Examples of the metal element or metalloid element described above include a metal element or metalloid element capable of forming an alloy with lithium. Specifically, magnesium (Mg), boron (B), aluminum (Al), gallium (Ga), indium (In), silicon (Si), germanium (Ge), tin (Sn), lead (Pb), Examples thereof include bismuth (Bi), cadmium (Cd), silver (Ag), zinc (Zn), hafnium (Hf), zirconium (Zr), yttrium (Y), palladium (Pd), and platinum (Pt). Among these, at least one of silicon and tin is preferable, and silicon is more preferable. This is because a high energy density can be obtained because the ability to occlude and release lithium is large.

  Examples of the negative electrode material having at least one of silicon and tin include at least a part of a simple substance, an alloy or a compound of silicon, a simple substance, an alloy or a compound of tin, or one or more phases thereof. The material which has in is mentioned.

  As an alloy of silicon, for example, as a second constituent element other than silicon, tin (Sn), nickel (Ni), copper (Cu), iron (Fe), cobalt (Co), manganese (Mn), zinc ( One containing at least one of the group consisting of Zn), indium (In), silver (Ag), titanium (Ti), germanium (Ge), bismuth (Bi), antimony (Sb) and chromium (Cr) Can be mentioned. Examples of tin alloys include silicon (Si), nickel (Ni), copper (Cu), iron (Fe), cobalt (Co), and manganese (Mn) as second constituent elements other than tin (Sn). , Zinc (Zn), indium (In), silver (Ag), titanium (Ti), germanium (Ge), bismuth (Bi), antimony (Sb) and chromium (Cr). Including.

  Examples of the tin compound or the silicon compound include those containing oxygen (O) or carbon (C), and include the second constituent element described above in addition to tin (Sn) or silicon (Si). You may go out.

  In particular, as a negative electrode material containing at least one of silicon (Si) and tin (Sn), for example, tin (Sn) is used as the first constituent element, and in addition to the tin (Sn), the second configuration What contains an element and a 3rd structural element is preferable. Of course, this negative electrode material may be used together with the negative electrode material described above. The second constituent element is cobalt (Co), iron (Fe), magnesium (Mg), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), nickel (Ni), copper (Cu ), Zinc (Zn), gallium (Ga), zirconium (Zr), niobium (Nb), molybdenum (Mo), silver (Ag), indium (In), cerium (Ce), hafnium (Hf), tantalum (Ta) ), Tungsten (W), bismuth (Bi), and silicon (Si). The third constituent element is at least one selected from the group consisting of boron (B), carbon (C), aluminum (Al), and phosphorus (P). This is because the cycle characteristics are improved by including the second element and the third element.

  Further, examples of the negative electrode material capable of inserting and extracting lithium include metal oxides or polymer compounds capable of inserting and extracting lithium. Examples of the metal oxide include lithium titanate, iron oxide, ruthenium oxide, and molybdenum oxide. Examples of the polymer compound include polyacetylene, polyaniline, and polypyrrole.

  The negative electrode material capable of inserting and extracting lithium may be other than the above. Moreover, 2 or more types of said negative electrode materials may be mixed by arbitrary combinations.

  The negative electrode active material layer 102B may be formed by any of, for example, a gas phase method, a liquid phase method, a thermal spray method, a firing method, or a coating method, or a combination of two or more thereof.

  In addition, as a vapor phase method, for example, physical deposition method or chemical deposition method, specifically, vacuum deposition method, sputtering method, ion plating method, laser ablation method, thermal chemical vapor deposition (CVD; Chemical Vapor Deposition) Or plasma chemical vapor deposition. As the liquid phase method, a known method such as electroplating or electroless plating can be used. The firing method is, for example, a method in which a particulate negative electrode active material is mixed with a binder and dispersed in a solvent and then heat treated at a temperature higher than the melting point of the binder. A known method can also be used for the firing method, for example, an atmospheric firing method, a reactive firing method, or a hot press firing method.

(Separator)
The separator 103 separates the positive electrode 101 and the negative electrode 102 and allows lithium ions to pass through while preventing a short circuit of current caused by contact between the two electrodes. The separator 103 is made of, for example, a porous film made of a synthetic resin such as polytetrafluoroethylene, polypropylene, or polyethylene, or a porous film made of ceramic, and these two or more kinds of porous films are laminated. It may be what was done. The separator 103 is impregnated with an electrolytic solution that is a liquid electrolyte.

(Electrolyte)
The electrolytic solution includes a solvent and an electrolyte salt. This electrolytic solution is a liquid electrolyte, for example, a nonaqueous electrolytic solution in which an electrolyte salt is dissolved in a nonaqueous solvent.

(solvent)
Solvents include ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, γ-butyrolactone, γ-valerolactone, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, Tetrahydropyran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, 1,3-dioxane, 1,4-dioxane, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl butyrate, isobutyric acid Methyl, methyl trimethylacetate, ethyl trimethylacetate, acetonitrile, glutaronitrile, adiponitrile, methoxyacetonitrile, 3-methoxypropionitrile, N, N-dimethylformamide, N-methylpyrrolidinone, N-methyloxazo Non-aqueous solvents such as ridinone, N, N′-dimethylimidazolidinone, nitromethane, nitroethane, sulfolane, trimethyl phosphate, or dimethyl sulfoxide.

  These exemplified solvents may be used alone or in combination of two or more. Among these other solvents, at least one selected from the group consisting of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate is preferable. In this case, a high viscosity (high dielectric constant) solvent such as ethylene carbonate or propylene carbonate (for example, a relative dielectric constant ε ≧ 30) and a low viscosity solvent such as dimethyl carbonate, ethyl methyl carbonate or diethyl carbonate (for example, viscosity) ≦ 1 mPa · s) is more preferable. This is because the dissociation property of the electrolyte salt and the ion mobility are improved.

(Electrolyte salt)
As the electrolyte salt, for example, any one or more of light metal salts such as lithium salt can be used.

Examples of the lithium salt include lithium hexafluorophosphate (LiPF ₆ ), lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium tetraphenylborate (LiB (C ₆ H ₅ ) ₄ ), lithium methanesulfonate (LiCH ₃ SO ₃ ), lithium trifluoromethanesulfonate (LiCF ₃ SO ₃ ), lithium tetrachloroaluminate (LiAlCl ₄ ), dilithium hexafluorosilicate (Li ₂ SiF ₆ ), Examples include lithium chloride (LiCl) and lithium bromide (LiBr). These exemplified electrolyte salts may be used in appropriate combination.

(Battery manufacturing method)
This nonaqueous electrolyte secondary battery is manufactured by the following manufacturing method, for example.

(Manufacture of positive electrode)
First, the positive electrode 101 is manufactured. First, a positive electrode active material, a binder, and a conductive agent are mixed to form a positive electrode mixture, and then dispersed in an organic solvent to obtain a paste-like positive electrode mixture slurry. Subsequently, the positive electrode mixture slurry is uniformly applied to both surfaces of the positive electrode current collector 101A by a doctor blade or a bar coater and dried. Finally, the positive electrode active material layer 101B is formed by compression molding the coating film with a roll press or the like while heating as necessary. In this case, compression molding may be repeated a plurality of times.

(Manufacture of negative electrode)
Next, the negative electrode 102 is produced. First, a negative electrode material, a binder, and a conductive agent as necessary are mixed to form a negative electrode mixture, which is then dispersed in an organic solvent to obtain a paste-like negative electrode mixture slurry. Subsequently, the negative electrode mixture slurry is uniformly applied to both surfaces of the negative electrode current collector 102A by a doctor blade or a bar coater and dried. Finally, the negative electrode active material layer 102B is formed by compressing and molding the coating film with a roll press or the like while heating as necessary.

(Battery assembly)
The non-aqueous electrolyte secondary battery is assembled as follows. First, the positive electrode lead 105 is attached to the positive electrode current collector 101A by welding or the like, and the negative electrode lead 106 is attached to the negative electrode current collector 102A by welding or the like. Subsequently, the positive electrode 101 and the negative electrode 102 are laminated and wound through the separator 103 to produce the wound electrode body 100, and then the center pin 104 is inserted into the winding center. Subsequently, the spirally wound electrode body 100 is housed in the battery can 91 while being sandwiched between the pair of insulating plates 92 and 93, the tip of the positive electrode lead 105 is welded to the safety valve mechanism 95, and the tip of the negative electrode lead 106 is attached. The battery can 91 is welded.

  Subsequently, the above-described electrolytic solution is injected into the battery can 91 and impregnated in the separator 103. Finally, the battery lid 94, the safety valve mechanism 95, and the heat sensitive resistance element 96 are fixed to the opening end portion of the battery can 91 by caulking through the gasket 97. Thereby, the nonaqueous electrolyte secondary battery shown in FIGS. 3 and 4 is completed.

4). Fourth embodiment (example of battery pack)
FIG. 5 is a block diagram illustrating a circuit configuration example when a nonaqueous electrolyte secondary battery of the present technology (hereinafter appropriately referred to as a secondary battery) is applied to a battery pack. The battery pack includes a switch unit 304 including an assembled battery 301, an exterior, a charge control switch 302a, and a discharge control switch 303a, a current detection resistor 307, a temperature detection element 308, and a control unit 310.

  In addition, the battery pack includes a positive electrode terminal 321 and a negative electrode terminal 322. During charging, the positive electrode terminal 321 and the negative electrode terminal 322 are connected to the positive electrode terminal and the negative electrode terminal of the charger, respectively, and charging is performed. Further, when the electronic device is used, the positive electrode terminal 321 and the negative electrode terminal 322 are connected to the positive electrode terminal and the negative electrode terminal of the electronic device, respectively, and discharge is performed.

  The assembled battery 301 is formed by connecting a plurality of secondary batteries 301a in series and / or in parallel. The secondary battery 301a is a secondary battery of the present technology. In addition, in FIG. 5, the case where six secondary batteries 301a are connected in two parallel three series (2P3S) is shown as an example, but in addition, n parallel m series (n and m are integers) Any connection method may be used.

  The switch unit 304 includes a charge control switch 302a and a diode 302b, and a discharge control switch 303a and a diode 303b, and is controlled by the control unit 310. The diode 302b has a reverse polarity with respect to the charging current flowing from the positive terminal 321 in the direction of the assembled battery 301 and the forward polarity with respect to the discharging current flowing from the negative terminal 322 in the direction of the assembled battery 301. The diode 303b has a forward polarity with respect to the charging current and a reverse polarity with respect to the discharging current. In the example, the switch portion is provided on the + side, but may be provided on the − side.

  The charge control switch 302 a is turned off when the battery voltage becomes the overcharge detection voltage, and is controlled by the charge / discharge control unit so that the charge current does not flow in the current path of the assembled battery 301. After the charge control switch is turned off, only discharging is possible through the diode 302b. Further, it is turned off when a large current flows during charging, and is controlled by the control unit 310 so that the charging current flowing in the current path of the assembled battery 301 is cut off.

  The discharge control switch 303a is turned off when the battery voltage becomes the overdischarge detection voltage, and is controlled by the control unit 310 so that the discharge current does not flow through the current path of the assembled battery 301. After the discharge control switch 303a is turned off, only charging is possible via the diode 303b. Further, it is turned off when a large current flows during discharging, and is controlled by the control unit 310 so as to cut off the discharging current flowing in the current path of the assembled battery 301.

  The temperature detection element 308 is, for example, a thermistor, is provided in the vicinity of the assembled battery 301, measures the temperature of the 301 assembled battery 301, and supplies the measured temperature to the control unit 310. The voltage detection unit 311 measures the voltage of the assembled battery 301 and each secondary battery 301a constituting the assembled battery 301, performs A / D conversion on the measured voltage, and supplies the voltage to the control unit 310. The current measurement unit 313 measures the current using the current detection resistor 307 and supplies this measurement current to the control unit 310.

  The switch control unit 314 controls the charge control switch 302a and the discharge control switch 303a of the switch unit 304 based on the voltage and current input from the voltage detection unit 311 and the current measurement unit 313. The switch control unit 314 sends a control signal to the switch unit 304 when any voltage of the secondary battery 301a falls below the overcharge detection voltage or overdischarge detection voltage, or when a large current flows suddenly. By sending, overcharge, overdischarge, and overcurrent charge / discharge are prevented.

  Here, for example, when the secondary battery is a lithium ion secondary battery, the overcharge detection voltage is determined to be 4.20 V ± 0.05 V, for example, and the overdischarge detection voltage is determined to be 2.4 V ± 0.1 V, for example. .

  As the charge / discharge switch, for example, a semiconductor switch such as a MOSFET can be used. In this case, the parasitic diode of the MOSFET functions as the diodes 302b and 303b. When a P-channel FET is used as the charge / discharge switch, the switch control unit 314 supplies control signals DO and CO to the gates of the charge control switch 302a and the discharge control switch 303a, respectively. When the charge control switch 302a and the discharge control switch 303a are P-channel type, they are turned on by a gate potential that is lower than the source potential by a predetermined value or more. That is, in normal charging and discharging operations, the control signals CO and DO are set to the low level, and the charging control switch 302a and the discharging control switch 303a are turned on.

  For example, during overcharge or overdischarge, the control signals CO and DO are set to a high level, and the charge control switch 302a and the discharge control switch 303a are turned off.

  The memory 317 includes a RAM and a ROM, and includes, for example, an EPROM (Erasable Programmable Read Only Memory) that is a nonvolatile memory. In the memory 317, the numerical value calculated by the control unit 310, the internal resistance value of the battery in the initial state of each secondary battery 301a measured in the manufacturing process, and the like are stored in advance, and can be appropriately rewritten. . (Also, by storing the full charge capacity of the secondary battery 301a, for example, the remaining capacity can be calculated together with the control unit 310.

  The temperature detection unit 318 measures the temperature using the temperature detection element 308, performs charge / discharge control during abnormal heat generation, and performs correction in the calculation of the remaining capacity.

5. Fifth Embodiment The nonaqueous electrolyte secondary battery and the battery pack using the same described above can be used for mounting or supplying electric power to devices such as electronic devices, electric vehicles, and power storage devices.

  Examples of electronic devices include notebook computers, PDAs (personal digital assistants), mobile phones, cordless phones, video movies, digital still cameras, electronic books, electronic dictionaries, music players, radios, headphones, game consoles, navigation systems, Memory card, pacemaker, hearing aid, electric tool, electric shaver, refrigerator, air conditioner, TV, stereo, water heater, microwave oven, dishwasher, washing machine, dryer, lighting equipment, toys, medical equipment, robots, road conditioners, traffic lights Etc.

  In addition, examples of the electric vehicle include a railway vehicle, a golf cart, an electric cart, an electric vehicle (including a hybrid vehicle), and the like, and these are used as a driving power source or an auxiliary power source.

  Examples of the power storage device include a power storage power source for buildings such as houses or power generation facilities.

  Below, the specific example of the electrical storage system using the electrical storage apparatus to which the nonaqueous electrolyte secondary battery of this technique mentioned above is applied among the application examples mentioned above is demonstrated.

  This power storage system has the following configuration, for example. The first power storage system is a power storage system in which a power storage device is charged by a power generation device that generates power from renewable energy. The second power storage system is a power storage system that includes a power storage device and supplies power to an electronic device connected to the power storage device. The third power storage system is an electronic device that is supplied with power from the power storage device. These power storage systems are implemented as a system for efficiently supplying power in cooperation with an external power supply network.

  Further, the fourth power storage system includes an electric vehicle having a conversion device that receives power supplied from the power storage device and converts the power into a driving force of the vehicle, and a control device that performs information processing related to vehicle control based on information related to the power storage device. It is. The fifth power storage system is a power system that includes a power information transmission / reception unit that transmits / receives signals to / from other devices via a network, and performs charge / discharge control of the power storage device described above based on information received by the transmission / reception unit. . The sixth power storage system is a power system that receives power from the power storage device described above or supplies power from the power generation device or the power network to the power storage device. Hereinafter, the power storage system will be described.

(5-1) Power Storage System in a House as an Application Example An example in which a power storage device using the nonaqueous electrolyte secondary battery of the present technology is applied to a power storage system for a house will be described with reference to FIG. For example, in a power storage system 400 for a house 401, power is stored from a centralized power system 402 such as a thermal power generation 402a, a nuclear power generation 402b, and a hydroelectric power generation 402c through a power network 409, an information network 412, a smart meter 407, a power hub 408, and the like. Supplied to the device 403. At the same time, power is supplied to the power storage device 403 from an independent power source such as the home power generation device 404. The electric power supplied to the power storage device 403 is stored. Electric power used in the house 401 is supplied using the power storage device 403. The same power storage system can be used not only for the house 401 but also for buildings.

  The house 401 is provided with a power generation device 404, a power consumption device 405, a power storage device 403, a control device 410 that controls each device, a smart meter 407, and a sensor 411 that acquires various types of information. Each device is connected by a power network 409 and an information network 412. A solar cell, a fuel cell, or the like is used as the power generation device 404, and the generated power is supplied to the power consumption device 405 and / or the power storage device 403. The power consuming device 405 is a refrigerator 405a, an air conditioner 405b, a television receiver 405c, a bath 405d, and the like. Furthermore, the electric power consumption device 405 includes an electric vehicle 406. The electric vehicle 406 is an electric vehicle 406a, a hybrid car 406b, and an electric motorcycle 406c.

  The nonaqueous electrolyte secondary battery of the present technology is applied to the power storage device 403. The nonaqueous electrolyte secondary battery of the present technology may be configured by, for example, the above-described lithium ion secondary battery. The smart meter 407 has a function of measuring the usage amount of commercial power and transmitting the measured usage amount to an electric power company. The power network 409 may be any one or a combination of DC power supply, AC power supply, and non-contact power supply.

  The various sensors 411 are, for example, human sensors, illuminance sensors, object detection sensors, power consumption sensors, vibration sensors, contact sensors, temperature sensors, infrared sensors, and the like. Information acquired by various sensors 411 is transmitted to the control device 410. Based on the information from the sensor 411, the weather condition, the condition of the person, and the like can be grasped, and the power consumption device 405 can be automatically controlled to minimize the energy consumption. Furthermore, the control device 410 can transmit information regarding the house 401 to an external power company or the like via the Internet.

  The power hub 408 performs processing such as branching of power lines and DC / AC conversion. The communication method of the information network 412 connected to the control device 410 includes a method using a communication interface such as UART (Universal Asynchronous Receiver-Transceiver), wireless communication such as Bluetooth, ZigBee, and Wi-Fi. There is a method of using a sensor network according to the standard. The Bluetooth method is applied to multimedia communication and can perform one-to-many connection communication. ZigBee uses the physical layer of IEEE (Institute of Electrical and Electronics Engineers) 802.15.4. IEEE 802.15.4 is the name of a short-range wireless network standard called PAN (Personal Area Network) or W (Wireless) PAN.

  The control device 410 is connected to an external server 413. The server 413 may be managed by any one of the house 401, the power company, and the service provider. The information transmitted and received by the server 413 is, for example, information related to power consumption information, life pattern information, power charges, weather information, natural disaster information, and power transactions. These pieces of information may be transmitted / received from a power consuming device (for example, a television receiver) in the home, or may be transmitted / received from a device outside the home (for example, a mobile phone). Such information may be displayed on a device having a display function, such as a television receiver, a mobile phone, or a PDA (Personal Digital Assistants).

  A control device 410 that controls each unit includes a CPU (Central Processing Unit), a RAM (Random Access Memory), a ROM (Read Only Memory), and the like, and is stored in the power storage device 403 in this example. The control device 410 is connected to the power storage device 403, the home power generation device 404, the power consumption device 405, various sensors 411, the server 413 and the information network 412, and adjusts, for example, the amount of commercial power used and the amount of power generation. It has a function. In addition, you may provide the function etc. which carry out an electric power transaction in an electric power market.

  As described above, electric power can be stored not only in the centralized power system 402 such as the thermal power 402a, the nuclear power 402b, and the hydraulic power 402c but also in the power storage device 403 in the power generation device 404 (solar power generation, wind power generation). it can. Therefore, even if the generated power of the home power generation device 404 fluctuates, it is possible to perform control such that the amount of power sent to the outside is constant or discharged as much as necessary. For example, the power obtained by solar power generation is stored in the power storage device 403, and the nighttime power at a low charge is stored in the power storage device 403 at night, and the power stored by the power storage device 403 is discharged during a high daytime charge. You can also use it.

  In this example, the example in which the control device 410 is stored in the power storage device 403 has been described. However, the control device 410 may be stored in the smart meter 407 or may be configured independently. Furthermore, the power storage system 400 may be used for a plurality of homes in an apartment house, or may be used for a plurality of detached houses.

(5-2) Power Storage System in Vehicle as Application Example An example in which the present technology is applied to a power storage system for a vehicle will be described with reference to FIG. FIG. 7 schematically shows an example of the configuration of a hybrid vehicle that employs a series hybrid system to which the present technology is applied. A series hybrid system is a car that runs on an electric power driving force conversion device using electric power generated by a generator driven by an engine or electric power once stored in a battery.

  The hybrid vehicle 500 includes an engine 501, a generator 502, a power driving force conversion device 503, driving wheels 504 a, driving wheels 504 b, wheels 505 a, wheels 505 b, a battery 508, a vehicle control device 509, various sensors 510, and a charging port 511. Is installed. The nonaqueous electrolyte secondary battery of the present technology described above is applied to the battery 508.

  The hybrid vehicle 500 travels using the power driving force conversion device 503 as a power source. An example of the power / driving force conversion device 503 is a motor. The electric power / driving force converter 503 is operated by the electric power of the battery 508, and the rotational force of the electric power / driving force converter 503 is transmitted to the driving wheels 504a and 504b. In addition, by using DC-AC (DC-AC) or reverse conversion (AC-DC conversion) at a required place, the power driving force conversion device 503 can be applied to either an AC motor or a DC motor. The various sensors 510 control the engine speed through the vehicle control device 509 and control the opening (throttle opening) of a throttle valve (not shown). Various sensors 510 include a speed sensor, an acceleration sensor, an engine speed sensor, and the like.

  The rotational force of the engine 501 is transmitted to the generator 502, and the electric power generated by the generator 502 by the rotational force can be stored in the battery 508.

  When the hybrid vehicle 500 decelerates by a braking mechanism (not shown), the resistance force at the time of deceleration is applied as a rotational force to the electric power driving force conversion device 503, and the regenerative electric power generated by the electric power driving force conversion device 503 by this rotational force becomes the battery 508. Accumulated in.

  The battery 508 is connected to an external power source of the hybrid vehicle 500, so that the battery 508 can receive power from the external power source using the charging port 511 as an input port and store the received power.

  Although not shown, an information processing device that performs information processing related to vehicle control based on information related to the secondary battery may be provided. As such an information processing apparatus, for example, there is an information processing apparatus that displays a remaining battery level based on information on the remaining battery level.

  In addition, the above demonstrated as an example the series hybrid vehicle which drive | works with a motor using the electric power generated with the generator driven by an engine, or the electric power once stored in the battery. However, the present technology is also effective for a parallel hybrid vehicle in which the engine and motor outputs are both driving sources, and the system is switched between the three modes of driving with only the engine, driving with the motor, and engine and motor. Applicable. Furthermore, the present technology can be effectively applied to a so-called electric vehicle that travels only by a drive motor without using an engine.

  Hereinafter, the present technology will be specifically described by way of examples. However, the present technology is not limited only to these examples.

<Example 1>
A solid electrolyte secondary battery having the configuration shown in FIGS. 1A to 1C was produced. A polycarbonate (PC) substrate having a thickness of 1.1 mm was used as the substrate 10. SiN was deposited on the substrate 10 as the inorganic insulating film 20.

A metal mask is disposed on the inorganic insulating film 20, and the positive electrode side current collector film 30, the positive electrode active material film 40, the solid electrolyte film 50, the first negative electrode side current collector film 60a, and the block layer 60c are disposed in predetermined regions. Then, the second negative electrode side current collector film 60b was formed in this order to form a laminate. Specifically, the positive electrode side current collector film 30 is a Ti film, the positive electrode active material film 40 is a Li _x Ni _y PO _z film, the solid electrolyte film 50 is a Li ₃ PO _4-x N _x film, and the first negative electrode side collector layer Ni film as 60a, Li _x Ni _y PO _z film as the blocking layer 60c, to form a Ni film as the second negative electrode side current collector film 60b. Note that the subscripts x (x> 0), y (y> 0), and z (z> 0)) used in the compound indicate the composition ratio of the elements in the formula.

  The film forming conditions of the inorganic insulating film 20 and each thin film constituting the laminate were as follows. The substrate 10 was formed without heating the substrate.

(Inorganic insulating film 20)
The inorganic insulating film 20 was formed using the following sputtering apparatus and film forming conditions.
Sputtering device (C-3103, manufactured by Anelva)
Target composition: Si
Target size: Φ6 inch Sputtering gas: Ar 60 sccm, N ₂ 30 sccm, 0.11 Pa
Sputtering power: 1500W (DC)
Film thickness: 50nm

(Positive electrode side current collector film 30)
The positive electrode side current collector film 30 was formed using the following sputtering apparatus and film forming conditions.
Sputtering device (ULVAC, SMO-01 special type)
Target composition: Ti
Target size: Φ4 inch sputtering gas: Ar 70 sccm, 0.45 Pa
Sputtering power: 1000 W (DC)
Film thickness: 100nm

(Positive electrode active material film 40)
The positive electrode active material film was formed using the following sputtering apparatus and film formation conditions.
Sputtering device (ULVAC, SMO-01 special type)
Target composition: Cosputtering target of Li ₃ PO ₄ and Ni Size: Φ4 inch Sputtering gas: Ar (80%) + O ₂ (20%) 20 sccm, 0.20 Pa
Sputtering power: Li ₃ PO ₄ 600 W (RF), Ni 150 W (DC)
Film thickness: 400nm

(Solid electrolyte membrane 50)
The solid electrolyte membrane 50 was formed using the following sputtering apparatus and film formation conditions.
Sputtering device (ULVAC, SMO-01 special type)
Target composition: Li ₃ PO ₄
Target size: Φ4 inch sputtering gas: Ar20 sccm + N ₂ 20 sccm, 0.26 Pa
Sputtering power: 600W (RF)
Film thickness: 400nm

(Negative electrode side current collector film 60; (first negative electrode side current collector film 60a / block layer 60c / second negative electrode side current collector film 60b)

(First negative electrode side current collector film)
The first negative electrode current collector film 60a was formed using the following sputtering apparatus and film formation conditions.
Sputtering device (ULVAC, SMO-01 special type)
Target composition: Ni
Target size: Φ4 inch sputtering gas: Ar 70 sccm, 0.46 Pa
Sputtering power: Ni 250W (DC)
Film thickness: 100nm

(Block layer)
The Li _x Ni _y PO _z film as the block layer 60c was formed using the following sputtering apparatus and film formation conditions.
Sputtering device (ULVAC, SMO-01 special type)
Target composition: Cosputtering target of Li ₃ PO ₄ and Ni Size: Φ4 inch Sputtering gas: Ar (80%) + O ₂ (20%) 20 sccm, 0.20 Pa
Sputtering power: Li ₃ PO ₄ 600 W (RF), Ni 150 W (DC)
Film thickness: 130nm

(Second negative electrode side current collector film)
The second negative electrode current collector film 60b was formed using the following sputtering apparatus and film formation conditions.
Sputtering device (ULVAC, SMO-01 special type)
Target composition: Ni
Target size: Φ4 inch sputtering gas: Ar 70 sccm, 0.46 Pa
Sputtering power: Ni 250W (DC)
Film thickness: 100nm

  Finally, the whole protective film 80 was formed using an ultraviolet curable resin (manufactured by Sony Chemical & Information Device, model number SK3200), and an inorganic insulating film was further formed on the whole protective film 80. Thus, the thin film type solid electrolyte secondary battery of Example 1 was obtained. That is, a thin film type solid electrolyte secondary battery having the following film configuration was obtained.

(Membrane structure of thin-film solid electrolyte secondary battery)
Polycarbonate substrate / SiN (50 nm) / Ti (100 nm) / Li _x Ni _y PO _z (400 nm) / Li ₃ PO _4−x N _x (400 nm) / Ni (100 nm) / Li _x Ni _y PO _z (130 nm) / Ni (100 nm) / UV curable resin (20 μm) / SiN (50 nm)

<Comparative Example 1>
In place of the first negative electrode side current collector film 60a / block layer 60c / second negative electrode side current collector film 60b as described below, a negative electrode side current collector film consisting of one Ni film layer was formed. In the same manner as in Example 1, a thin film type solid electrolyte secondary battery of Comparative Example 1 was obtained.

(Negative electrode current collector film)
The negative electrode side current collector film was formed twice by the following sputtering apparatus and film formation conditions.
(First film formation)
Sputtering device (ULVAC, SMO-01 special type)
Target composition: Ni
Target size: Φ4 inch sputtering gas: Ar 70 sccm, 0.46 Pa
Sputtering power: Ni 250W (DC)
Film thickness: 100nm
(Second film formation)
Sputtering device (ULVAC, SMO-01 special type)
Target composition: Ni
Target size: Φ4 inch sputtering gas: Ar 70 sccm, 0.46 Pa
Sputtering power: Ni 250W (DC)
Film thickness: 100nm

(Membrane structure of thin-film solid electrolyte secondary battery)
The film configuration of the thin-film solid electrolyte secondary battery of Comparative Example 1 is as follows.
Polycarbonate substrate / SiN (50 nm) / Ti (100 nm) / Li _x Ni _y PO _z (400 nm) / Li ₃ PO _4−x N _x (400 nm) / Ni (200 nm) / UV curable resin (20 μm) / SiN (50 nm) )

(Charge / discharge test)
About Example 1 and Comparative Example 1, the charging / discharging test which repeats charging / discharging on the following conditions was done.
Charging: charging current 100 μA, CV at 5.0 V, charging stop current 50 μA, OCV standby time after charging 2 minutes,
Discharge: discharge current 100 μA, cut-off voltage 2.0 V, OCV standby time after discharge 2 minutes

  FIG. 8 shows a graph in which the utilization rate (Utilization) is plotted against the number of cycles for Example 1. Note that the utilization rate generally indicates a percentage of capacity with respect to the theoretical capacity calculated from the positive electrode active material film, but here, as an equivalent numerical value, the percentage of capacity based on the initial charge / discharge capacity is used. . FIG. 9 shows a graph in which the utilization rate is plotted against the number of cycles for Comparative Example 1. 8 and 9, a line c is a graph for charging, and a line d is a graph for discharging.

(SEM observation)
For Example 1 and Comparative Example 1, the surface of the Ni current collector (negative electrode side current collector) was observed by SEM (Scanning Electron Microscope) after one charge and discharge in vacuum. In FIG. 10, the SEM image about this comparative example 1 is shown.

  In Example 1, it was known that Ni used for the negative electrode side current collector easily permeated Li, and it was predicted that there was a problem in durability. Thus, in the charge / discharge test of Example 1, a capacity of 80% or more was maintained after 50 cycles of charge / discharge.

  In the charge / discharge test in Comparative Example 1, the capacity rapidly deteriorated due to charge / discharge of about 20 cycles, and the battery almost did not function after about 40 cycles. This result is because the battery is not short-circuited but the amount of Li is reduced and the battery capacity is deteriorated.

  As shown by arrows q1 to q4 in FIG. 10, in the SEM image obtained by observing the surface of the Ni current collector (negative electrode side current collector), a spot can be confirmed, and when XPS measurement is performed on this spot portion, Li is detected. It was done. That is, in Comparative Example 1, Li was diffused on the Ni current collector after one charge / discharge. On the other hand, in Example 1, after one charge / discharge, the stain as seen in Comparative Example 1 could not be confirmed, and after one charge / discharge, Li diffusion could not be confirmed on the Ni current collector. . Moreover, as shown by the arrow p in FIG. 11, in the battery of Comparative Example 1, the surface state after 60 cycles was a state in which the surface of the negative electrode current collector metal was scattered by light. On the other hand, in the battery of Example 1, the metallic luster of the negative electrode current collector metal was maintained at the same number of cycles. Therefore, the difference in the surface state after 60 cycles between the battery of Comparative Example 1 and the battery of Example 1 was clear. In Comparative Example 1, the surface state of the negative electrode side current collector after 60 cycles is considered to be a trace of Li diffusing and reacting with the current collector. That is, it is clear that Li is suppressed from diffusing in the negative electrode side current collector film by the configuration of Example 1 (a configuration in which the block layer is in the negative electrode side current collector film).

6). Other Embodiments The present technology is not limited to the above-described embodiments of the present technology, and various modifications and applications can be made without departing from the gist of the present technology.

  For example, the configurations, methods, steps, shapes, materials, numerical values, and the like given in the above-described embodiments and examples are merely examples, and different configurations, methods, steps, shapes, materials, and numerical values are necessary as necessary. Etc. may be used.

  In addition, the configurations, methods, processes, shapes, materials, numerical values, and the like of the above-described embodiments and examples can be combined with each other without departing from the gist of the present technology.

  For example, in the embodiments and examples, a battery using lithium as an electrode reactant has been described, but other alkali metals such as sodium (Na) or potassium (K), or alkaline earth such as magnesium or calcium (Ca). The present technology can also be applied to batteries using other light metals such as similar metals or aluminum.

  For example, the membrane configuration of the solid electrolyte secondary battery is not limited to that described above. For example, in the first to second embodiments, the inorganic insulating film may be omitted. In the first embodiment, a protective film may be formed between the negative electrode current collector film 60 and the solid electrolyte film 50. This protective film may be made of, for example, the same material as the positive electrode active material constituting the positive electrode active material film 40.

  For example, in the above-described embodiments and examples, the negative electrode side current collector film 60 includes the block layer 60c between the first negative electrode side current collector film 60a and the second negative electrode side current collector film 60b. Although having the structure, the negative electrode side current collector film 60 is not limited to this configuration. For example, the negative electrode side current collector film 60 may have a structure in which a first negative electrode side current collector film 60a and a block layer 60c are laminated in this order from the solid electrolyte film side. Even in this case, diffusion and disappearance of lithium in the negative electrode current collector film 60 are suppressed by the block layer 60c.

  Alternatively, a plurality of stacked bodies may be sequentially stacked, electrically connected in series, and covered with the entire protective film 80. Further, a plurality of stacked bodies may be formed side by side on the substrate, electrically connected in parallel or in series, and covered with the entire protective film 80.

  For example, the structure of the solid electrolyte secondary battery is not limited to the above-described example. For example, the present invention can also be applied to a solid electrolyte secondary battery having a structure in which a conductive material is used for the substrate 10 and the positive collector film 30 is omitted. Moreover, each member which comprises a solid electrolyte secondary battery may not be a thin film form. For example, the positive electrode current collector film 30 may be replaced with a metal plate, a metal foil, or the like made of a positive electrode current collector material. The negative electrode side current collector film 60 may be replaced with a metal plate, a metal foil, or the like made of a negative electrode current collector material.

This technique can take the following composition.
[1]
A positive electrode;
A negative electrode including a negative electrode current collector;
With electrolyte,
The negative electrode current collector is a secondary battery including a block region that suppresses movement of an electrode reactant.
[2]
The secondary battery according to [1], wherein the electrode reactant is lithium.
[3]
The secondary battery according to any one of [1] to [2], wherein the electrolyte is a solid electrolyte.
[4]
The positive electrode is a positive electrode layer,
The negative electrode is a negative electrode layer,
The negative electrode current collector is a negative electrode current collector layer,
The secondary battery according to [3], wherein the solid electrolyte is a solid electrolyte layer.
[5]
The negative electrode current collector layer is
A first negative electrode current collector layer;
A second negative electrode current collector layer;
The secondary battery according to [4], including a block layer that is the block region.
[6]
The secondary battery according to [5], wherein the block layer is between the first negative electrode current collector layer and the second negative electrode current collector layer.
[7]
The secondary battery according to any one of [4] to [6], wherein a lithium excess layer is formed on the negative electrode side of the solid electrolyte layer by charging.
[8]
The said block area | region is a secondary battery in any one of [1]-[7] containing the material which has electrical conductivity and lithium ion conductivity.
[9]
The secondary battery according to [8], wherein the material having electrical conductivity and lithium ion conductivity is a positive electrode active material.
[10]
The secondary battery according to any one of [5] to [9], wherein the first negative electrode current collector layer and the second negative electrode current collector layer are made of the same material or different materials.
[11]
Further comprising a substrate,
The secondary battery according to any one of [4] to [10], wherein a laminate including the positive electrode layer, the negative electrode layer, and the solid electrolyte layer is formed on the base material.
[12]
The positive electrode layer includes the positive electrode current collector layer and the positive electrode active material layer,
The secondary battery according to any one of [4] to [11], wherein each layer constituting the positive electrode layer, each layer constituting the negative electrode layer, and at least one of the solid electrolyte layers is formed as a thin film. .
[13]
A negative electrode current collector including a block region that suppresses movement of an electrode reactant.
[14]
Having the secondary battery according to [1],
An electronic device that receives power from the secondary battery.
[15]
A secondary battery according to [1];
A conversion device that receives supply of electric power from the secondary battery and converts it into driving force of the vehicle;
An electric vehicle having a control device that performs information processing related to vehicle control based on information related to the secondary battery.

  DESCRIPTION OF SYMBOLS 10 ... Board | substrate, 20 ... Inorganic insulating film, 30 ... Positive electrode side collector film, 40 ... Positive electrode active material film | membrane, 50 ... Solid electrolyte membrane, 60 ... Negative electrode side collector Body film, 60a ... first negative electrode side current collector film, 60b ... second negative electrode side current collector film, 60c ... block layer, 70 ... negative electrode active material film, 80 ...・ Overall protective film, 91 ... battery can, 92, 93 ... insulating plate, 94 ... battery cover, 95 ... safety valve mechanism, 95A ... disk plate, 96 ... heat resistance element 97 ... gasket, 100 ... wound electrode body, 101 ... positive electrode, 101A ... positive electrode current collector, 101B ... positive electrode active material layer, 102 ... negative electrode, 102A ... Negative electrode current collector, 102a ... first negative electrode current collector layer, 102b ... second negative electrode current collector layer, 102c ... blocking layer, 02B ... negative electrode active material layer, 103 ... separator, 104 ... center pin, 105 ... positive electrode lead, 106 ... negative electrode lead, 301 ... assembled battery, 301a ... secondary battery , 302 ... Charge control switch, 302a ... Charge control switch, 302b ... Diode, 303a ... Discharge control switch, 303b ... Diode, 304 ... Switch unit, 307 ... Current detection Resistance, 308 ... Temperature detection element, 310 ... Control unit, 311 ... Voltage detection unit, 313 ... Current measurement unit, 314 ... Switch control unit, 317 ... Memory, 318 ... Temperature detection unit, 321... Positive terminal, 322... Negative terminal, 400... Power storage system, 401 .. residence, 402 .. centralized power system, 402a. Electricity, 402b ... Nuclear power generation, 402c ... Hydroelectric power generation, 403 ... Power storage device, 404 ... Power generation device, 405 ... Power consumption device, 405a ... Refrigerator, 405b ... Air conditioning device 405c ... TV receiver, 405d ... bath, 406 ... electric vehicle, 406a ... electric car, 406b ... hybrid car, 406c ... electric bike, 407 ... smart meter 408 ... Power hub, 409 ... Power network, 410 ... Control device, 411 ... Sensor, 412 ... Information network, 413 ... Server, 500 ... Hybrid vehicle, 501 ... Engine, 502 ... Generator, 503 ... Electric power / driving force converter, 504a ... Drive wheel, 504b ... Drive wheel, 505a ... Wheel, 505b ... Wheel, 508 ... Battery, 509 ... Vehicle control device, 510 ... Various sensors, 511 ... Charging port

Claims (12)

A positive electrode;
A negative electrode including a negative electrode current collector;
With electrolyte,
The negative electrode current collector is
A first negative electrode current collector made of a first metal material and having conductivity;
A second negative electrode current collector made of a second metal material which is the same as or different from the first metal material and has conductivity;
A block region between the first negative electrode current collector and the second negative electrode current collector, including at least lithium and made of a material capable of releasing and occluding lithium ions;
A secondary battery in which the electrode reactant is lithium.   The secondary battery according to claim 1, wherein the electrolyte is a solid electrolyte. The positive electrode is a positive electrode layer,
The negative electrode is a negative electrode layer,
The negative electrode current collector is a negative electrode current collector layer,
The first negative electrode current collector is a first negative electrode current collector layer,
The second negative electrode current collector is a second negative electrode current collector layer,
The block area is a block layer,
The secondary battery according to claim 2, wherein the solid electrolyte is a solid electrolyte layer.   The secondary battery according to claim 3, wherein a lithium excess layer is formed on the negative electrode side of the solid electrolyte layer by charging.   The secondary battery according to any one of claims 1 to 4, wherein the material containing at least lithium and capable of releasing and occluding lithium ions is a positive electrode active material. The positive electrode active material is
Any element M1 selected from Li, P and Ni, Co, Mn, Au, Ag, Pd, and at least one element M2 selected from Ni, Co, Mn, Au, Ag, Pd, Cu (provided that M1 ≠ M2, and an amorphous lithium phosphate compound containing O,
Or
Any element M1 selected from Li, P and Ni, Co, Mn, Au, Ag, Pd, and at least one element M2 selected from Ni, Co, Mn, Au, Ag, Pd, Cu (provided that M1 ≠ M2, and B, Mg, Al, Si, Ti, V, Cr, Fe, Zn, Ga, Ge, Nb, Mo, In, Sn, Sb, Te, W, Os, Bi, Gd, Tb, An amorphous lithium phosphate compound containing at least one additive element M3 and O selected from Dy, Hf, Ta, and Zr;
Or
Any element M1 ′ selected from Li, P, Ni, Co, Mn, Au, Ag, Pd, Cu and B, Mg, Al, Si, Ti, V, Cr, Fe, Zn, Ga, Ge, Nb Lithium phosphate in an amorphous state containing at least one additional element M3 and O selected from Mo, In, Sn, Sb, Te, W, Os, Bi, Gd, Tb, Dy, Hf, Ta, and Zr The secondary battery according to claim 5, which is a compound. The secondary battery according to claim 5, wherein the positive electrode active material is a lithium phosphate compound represented by Formula (1) or Formula (2) in an amorphous state.
Formula (1)
Li _x Ni _y PO _z
(Wherein x represents the composition ratio of lithium, y represents the composition ratio of nickel, z represents the composition ratio of oxygen, x is 0 <x <8.0, and y is 2.0 ≦ y. ≦ 10 z is a ratio in which oxygen is stably contained according to the composition ratio of Ni and P.)
Formula (2)
Li _x Cu _y PO ₄
(Wherein x represents the composition ratio of lithium, y represents the composition ratio of copper, x is 0.5 ≦ x <7.0, and y is 1.0 ≦ y ≦ 4.0. ) Further comprising a substrate,
The secondary battery according to claim 3, wherein a laminate including the positive electrode layer, the negative electrode layer, and the solid electrolyte layer is formed on the base material.   The secondary battery according to claim 3, wherein the positive electrode layer includes a positive electrode current collector layer and a positive electrode active material layer. A first negative electrode current collector made of a first metal material and having conductivity;
A second negative electrode current collector made of a second metal material which is the same as or different from the first metal material and has conductivity;
A block region between the first negative electrode current collector and the second negative electrode current collector, including at least lithium and made of a material capable of releasing and occluding lithium ions;
A negative electrode current collector for a secondary battery, wherein the electrode reactant is lithium. Having the secondary battery according to any one of claims 1 to 9,
An electronic device that receives power from the secondary battery. The secondary battery according to any one of claims 1 to 9,
A conversion device that receives supply of electric power from the secondary battery and converts it into driving force of the vehicle;
An electric vehicle having a control device that performs information processing related to vehicle control based on information related to the secondary battery.