JP6704295B2 - All-solid-state lithium secondary battery and manufacturing method thereof - Google Patents

Description

The present invention relates to a highly practical all-solid-state lithium secondary battery using a hydride-based solid electrolyte and a method for manufacturing the same.

In recent years, with the development of portable electronic devices such as mobile phones and notebook personal computers, and the practical use of electric vehicles, small and lightweight secondary batteries with high capacity and high energy density have been required. Is coming.

Currently, non-aqueous secondary batteries that can meet this demand, particularly lithium ion secondary batteries, use lithium-containing composite oxides such as lithium cobalt oxide (LiCoO ₂ ) and lithium nickel oxide (LiNiO ₂ ) as a positive electrode active material. Graphite or the like is used as the negative electrode active material, and an organic electrolytic solution containing an organic solvent and a lithium salt is used as the non-aqueous electrolyte. With the further development of non-aqueous secondary battery application equipment, further long life, high capacity, and high energy density of non-aqueous secondary batteries are required, as well as long life and high There is also a strong demand for safety and reliability of non-aqueous secondary batteries with increased capacity and higher energy density.

However, the organic electrolyte used in lithium-ion secondary batteries contains an organic solvent that is a flammable substance, so when an abnormal situation such as a short circuit occurs in the battery, the organic electrolyte heats up abnormally. there is a possibility. Further, with the recent trend toward higher energy densities of non-aqueous secondary batteries and the increasing trend of the amount of organic solvent in the organic electrolyte, further safety and reliability of non-aqueous secondary batteries are required.

Under the circumstances as described above, attention is paid to an all-solid-state lithium secondary battery that does not use an organic solvent. The all-solid-state lithium secondary battery uses a molded body of a solid electrolyte that does not use an organic solvent, instead of a conventional organic solvent-based electrolyte, and there is no fear of abnormal heat generation of the solid electrolyte, and high safety is achieved. I have it.

On the other hand, since the solid electrolyte molded body is brittle, it has poor workability, and it is difficult to make the solid electrolyte into a thin film and to have a large area. Therefore, the handleability of the solid electrolyte at the time of battery production is poor, and the molded body of the solid electrolyte becomes thick, so that the lithium ion conductivity of the solid electrolyte becomes low, and there is a problem that the battery performance deteriorates.

In order to solve these problems, various studies have been made as described in Patent Documents 1 to 5, for example.

JP, 2007-273436, A JP, 2005-353309, A International publication WO2009/139382 pamphlet JP-A-01-115069 JP, 2008-103258, A

Patent Document 1 proposes an all-solid-state battery using a sulfide-based solid electrolyte having high lithium ion conductivity, which is highly promising for practical use. In Patent Document 1, in order to provide a solid electrolyte sheet that prevents electric short-circuiting of electrodes and operates stably, spherical silica having a diameter of 100 μm, which is an inorganic particle, is used as a spacer for forming a sulfide-based solid electrolyte layer, a fluororesin fiber, or the like. Are dispersed and used. However, the sulfide-based solid electrolyte is limited in working environment and usable solvent, and there is a possibility that a toxic gas such as H ₂ S may be generated due to cleavage of the trial environment and cell exterior material. Therefore, when forming the sulfide-based solid electrolyte layer, it is difficult to solvent-disperse the spacer particles or fibers in the sulfide-based solid electrolyte without generating a toxic gas. In addition, the sulfide-based solid electrolyte is flexible, and the addition of spacer particles and fibers does not affect the mechanical strength of the electrolyte layer and the mechanical strength of the laminated body. Is difficult, and the battery cell size is as small as about 0.8 cm ² .

Similarly, Patent Document 2 proposes an all-solid-state battery using a sulfide-based solid electrolyte. In Patent Document 2, in order to provide a battery element structure capable of obtaining a highly safe and highly reliable bulk type all-solid-state lithium battery further excellent in mechanical strength, an intermediate layer is provided between a negative electrode layer and a sulfide-based solid electrolyte. A conductive mesh is formed between the intermediate layer and the sulfide-based solid electrolyte. By filling the periphery of the electrode filler in the mesh with an electrolyte material, it is possible to prevent a short circuit between the positive and negative electrodes, but since it is a conductive mesh, there is a risk of short circuits between the positive and negative electrodes due to mesh burrs and the like. .. Further, as in Patent Document 1, the sulfide-based solid electrolyte may generate H ₂ S, and the battery size is a small area of about 0.8 cm ² .

Patent Document 3 proposes an all-solid-state battery using a hydride-based solid electrolyte having high lithium ion conductivity. In Patent Document 3, high ionic conductivity is realized by adding an alkali metal compound to a hydride-based solid electrolyte. However, the hydride-based solid electrolyte layer used is still low in mechanical strength, and it is difficult to make the hydride-based solid electrolyte layer thin and have a large area, and the battery size is as small as about 0.8 cm ^2. Is becoming

Patent Document 4 proposes a method of manufacturing a solid electrolyte sheet by applying a solid electrolyte ink to a nonwoven fabric by spraying. Patent Document 5 proposes a solid electrolyte sheet in which a nonwoven fabric is filled with a solid electrolyte glass ceramics. However, in Patent Documents 4 and 5, it is not possible to sufficiently impregnate a base material having a curved path such as a non-woven fabric with a solid electrolyte, the conduction path of the solid electrolyte is cut, and the lithium ion conductivity is reduced. There is a risk.

The all-solid-state lithium secondary battery of the present invention is an all-solid-state lithium secondary battery including a positive electrode, a negative electrode, and a solid electrolyte layer arranged between the positive electrode and the negative electrode, wherein the solid electrolyte layer is , Including a hydride-based solid electrolyte,
At least one of the positive electrode and the negative electrode includes a conductive porous base material and active material particles filled in the conductive porous base material.

Further, the method for producing the all-solid-state lithium secondary battery of the present invention is a method for producing the all-solid-state lithium secondary battery of the present invention, which comprises a step of filling active material particles in a conductive porous substrate by a dry method. It is characterized by including.

According to the present invention, it is possible to provide an all-solid-state lithium secondary battery with high capacity, high energy density, and high safety by using a solid electrolyte capable of increasing the area and generating no toxic gas. it can.

FIG. 1 is a plan view showing an example of a solid electrolyte layer used in the present invention. FIG. 2 is a plan view showing another example of the solid electrolyte layer used in the present invention. FIG. 3 is a diagram showing the relationship between the thickness of the compact and the pressing pressure.

(All-solid-state lithium secondary battery of the present invention)
The all-solid lithium secondary battery of the present invention comprises a positive electrode, a negative electrode, and a solid electrolyte layer disposed between the positive electrode and the negative electrode, the solid electrolyte layer contains a hydride-based solid electrolyte, At least one of the positive electrode and the negative electrode is characterized by including a conductive porous base material and active material particles filled in the conductive porous base material.

In the all-solid-state lithium secondary battery of the present invention, since the active material particles are provided with the positive electrode or the negative electrode formed by filling the conductive porous substrate, the strength of the electrode holding the solid electrolyte layer is improved, It is possible to increase the area of the solid electrolyte layer. More specifically, the size of the main surface of the solid electrolyte layer can be 1.0 cm ² or more. As a result, an all-solid-state lithium secondary battery with high capacity and high energy density can be provided.

Moreover, since the solid electrolyte layer contains the hydride-based solid electrolyte, no toxic gas is generated even when the hydride-based solid electrolyte comes into contact with the outside air containing water.

The conductive porous substrate preferably has straight pores. This improves the filling property of the active material particles in the conductive porous substrate.

Moreover, in the all-solid-state lithium secondary battery of the present invention, the solid electrolyte layer further includes an insulating porous substrate, and the hydride-based solid electrolyte is filled in the insulating porous substrate. Is preferred. As a result, the strength of the solid electrolyte layer is improved, and the solid electrolyte layer can have a larger area.

Further, the insulating porous substrate preferably has straight pores. This improves the filling property of the hydride-based solid electrolyte into the insulating porous substrate.

Hereinafter, embodiments of the all-solid-state lithium secondary battery of the present invention will be described. In the solid electrolyte layer of the following embodiment, an insulating porous substrate is shown filled with a solid electrolyte, but at least one of the positive electrode and the negative electrode is provided with a conductive porous substrate filled with active material particles. Then, the solid electrolyte layer does not have to include the insulating porous substrate. In this case, since the solid electrolyte layer does not include an insulating porous base material that hinders ion conduction, the load characteristics of the battery can be improved. On the other hand, in order to increase the strength of the solid electrolyte layer and further improve the reliability of the battery, a conductive porous substrate is used for at least one of the positive electrode and the negative electrode, and an insulating porous substrate is used for the solid electrolyte layer. It is preferable to use.

<Solid electrolyte layer>
FIG. 1 is a plan view showing an example of the solid electrolyte layer used in the present invention, and FIG. 2 is a plan view showing another example of the solid electrolyte layer used in the present invention.

In FIG. 1, the solid electrolyte layer 10 includes an insulating porous base material 11 and a solid electrolyte 12 filled in a straight pore 11 a having a square opening portion of the insulating porous base material 11.

The solid electrolyte 12 is formed of a hydride-based solid electrolyte, and the hydride-based solid electrolyte is filled in the straight pores 11a of the insulating porous substrate 11 by being pressed to fill the straight pores 11a. It is fixed. Therefore, the mechanical strength of the solid electrolyte layer 10 can be improved, the solid electrolyte 12 is not damaged even if the solid electrolyte layer 10 has a large area, and the solid electrolyte 12 falls off from the insulating porous substrate 11. It can also be prevented. Further, by disposing the solid electrolyte layer 10 between the positive electrode and the negative electrode, it is possible to prevent a short circuit between the positive electrode and the negative electrode while maintaining lithium ion conductivity between the positive electrode and the negative electrode.

Further, in FIG. 2, the solid electrolyte layer 20 includes an insulating porous base material 21 and a solid electrolyte 22 filled in the straight pores 21a having circular opening portions of the insulating porous base material 21. There is. The solid electrolyte 22 is also formed of a hydride-based solid electrolyte, and the hydride-based solid electrolyte is filled in the straight pores 21a of the insulating porous base material 21 by being pressed to fill the straight pores 21a. It is fixed. The solid electrolyte layer 20 shown in FIG. 2 can also exhibit the same actions and effects as the solid electrolyte layer 10 shown in FIG.

The hydride-based solid electrolyte is not particularly limited as long as it has lithium ion conductivity, and includes, for example, LiBH ₄ , LiAlH ₄ , Li ₃ AlH ₆ , LiBH(Et) ₃ , LiBH(s-Bu) _{3. , LiNH 2, Li 2 NH,} Li [OC (CH _{3) 3] 3 AlH, Li (OCH 3)} 3 AlH, Li (OC 2 H 5) 3 H, the molar ratio of LiBH ₄ and LiI is 1: 1 A solid electrolyte of ˜20:1 (LiBH ₄ :LiI=3:1, LiBH ₄ :LiI=7:1, etc.), Li ₂ B ₁₂ H ₁₂ etc. can be used. Among these, it is desirable to use a solid electrolyte in which the molar ratio of LiBH ₄ and LiI is 1:1 to 20:1, and particularly, the molar ratio of LiBH ₄ and LiI, which has high lithium ion conductivity, is 3: It is desirable to use one solid electrolyte. The solid electrolyte having a molar ratio of LiBH ₄ and LiI of 1:1 to 20:1 is a mixture of LiBH ₄ and LiI, and the obtained mixture is 50° C. or higher, preferably 150° C. or higher, and particularly preferably. It can be produced by heating to 250° C. or higher to melt or sinter, and then cooling.

The above hydride-based solid electrolytes may be used alone or in combination of two or more. The form of the hydride-based solid electrolyte is preferably in the form of particles from the viewpoint of filling the insulating porous substrate, but may be in a form other than the form of particles. When two or more hydride-based solid electrolytes are used in combination, the solid electrolytes may be mixed in the form of particles, or the solid electrolytes may be mixed at the molecular level. You may laminate|stack and use each solid electrolyte in layers.

The shape of the open pores of the straight pores of the insulating porous substrate is not limited to a square or a circle, and may be, for example, a rectangle, a rhombus, an oval, or the like. The form of the insulating porous base material is not particularly limited, and an insulating thin plate or a base material provided with a large number of apertures in a thin film may be used, and the thin plate may be cut and pulled on both sides. Although an expanded base material may be used, it is preferable to use a reticulated base material from the viewpoint of improving the filling property of the filling material. When the reticulated substrate is used, the wire diameter of the reticulation can be 10 to 300 μm, and from the viewpoint of improving the strength of the reticulated substrate, it is preferably 20 to 200 μm.

The open pore diameter of the straight pores is preferably 40 μm or more and 500 μm or less, and more preferably 100 μm or more and 250 μm or less. If the pore size is too large, the strength of the solid electrolyte layer tends to decrease, and if the pore size is too small, the filling property of the hydride-based solid electrolyte into the insulating porous substrate tends to decrease. It is in. In the present invention, the straight pore is viewed in plan from the thickness direction, and the maximum diameter of the circle inscribed in the opening is defined as the opening diameter of the straight pore. For example, when the shape of the opening portion of the straight pore is square, the length of one side of the square is the diameter of the opening of the straight pore.

The material of the insulating porous substrate is not particularly limited as long as it does not react with lithium metal and has an insulating property, and for example, a resin material such as polyethylene terephthalate, polyamide, polyarylate, or polyamideimide is used. be able to.

The thickness of the insulating porous base material is not particularly limited and can be, for example, 10 μm or more and 100 μm or less, and ensures the mechanical strength of the insulating porous base material and prevents an increase in the electric resistance of the base material. From the viewpoint of achieving a balance with

When the hydride-based solid electrolyte is used in the form of particles, its average particle size is preferably 4% or less of the open pore size of the straight pores of the insulating porous substrate. This improves the filling property of the hydride-based solid electrolyte into the insulating porous substrate and the moldability of the solid electrolyte layer. The lower limit of the average particle diameter of the hydride-based solid electrolyte is not particularly limited, but may be 0.07% or more with respect to the open pore diameter of the straight pores of the insulating porous substrate.

1 and 2, the insulating porous substrate having straight pores is used, but the insulating porous substrate is not limited to those having straight pores as long as it can be filled with a hydride-based solid electrolyte. Alternatively, other porous structured substrates can be used.

Since the solid electrolyte layer used in the present invention has a large mechanical strength, the size of the main surface thereof can be 1.0 cm ² or more, and the thickness of the solid electrolyte layer is usually the above-mentioned insulating layer. The same as the thickness of the porous base material. As a result, an all-solid-state lithium secondary battery with high capacity and high energy density can be provided.

<Positive electrode>
The positive electrode is not particularly limited as long as it is a positive electrode used in a conventionally known lithium ion secondary battery, that is, a positive electrode containing an active material capable of absorbing and releasing Li ions. For example, as the positive electrode active material, LiM _x Mn _2-x O ₄ (where M is Li, B, Mg, Ca, Sr, Ba, Ti, V, Cr, Fe, Co, Ni, Cu, Al, Spinel type lithium manganese represented by 0.01≦x≦0.5), which is at least one element selected from the group consisting of Sn, Sb, In, Nb, Mo, W, Y, Ru, and Rh. Complex oxide, Li _x Mn _(1-yx) Ni _y M _z O _{(2-k) Fl} (where M is Co, Mg, Al, B, Ti, V, Cr, Fe, Cu, Zn, It is at least one element selected from the group consisting of Zr, Mo, Sn, Ca, Sr and W, and 0.8≦x≦1.2, 0<y<0.5, 0≦z≦0. 5, k+l<1, −0.1≦k≦0.2, 0≦l≦0.1), a layered compound, LiCo _1-x M _x O ₂ (where M is Al, Mg, At least one element selected from the group consisting of Ti, Zr, Fe, Ni, Cu, Zn, Ga, Ge, Nb, Mo, Sn, Sb, and Ba, represented by 0≦x≦0.5) Lithium cobalt composite oxide, LiNi _1-x M _x O ₂ (where M is Al, Mg, Ti, Zr, Fe, Co, Cu, Zn, Ga, Ge, Nb, Mo, Sn, Sb and At least one element selected from the group consisting of Ba and a lithium nickel composite oxide represented by 0≦x≦0.5, LiM _1-x N _x PO ₄ (where M is Fe, At least one element selected from the group consisting of Mn and Co, N being a group consisting of Al, Mg, Ti, Zr, Ni, Cu, Zn, Ga, Ge, Nb, Mo, Sn, Sb and Ba. An olivine-type composite oxide represented by 0≦x≦0.5), a lithium titanium composite oxide represented by Li ₄ Ti ₅ O ₁₂ , and the like, which are at least one element selected from Only one of these may be used, or two or more may be used in combination.

The positive electrode may have a structure in which a positive electrode mixture layer containing the positive electrode active material and a conductive additive or a binder is formed on one side or both sides of a current collector.

As the binder of the positive electrode, for example, a fluororesin such as polyvinylidene fluoride (PVDF) can be used, and as the conductive auxiliary agent of the positive electrode, for example, a carbon material such as carbon black can be used. An electrolyte may be used.

Further, as the current collector of the positive electrode, a foil of metal such as aluminum, punching metal, net, expanded metal or the like may be used, but in the present invention, a conductive porous substrate such as a net-structure substrate is particularly used. Is preferred.

More specifically, it is preferable that the positive electrode includes the conductive porous base material and positive electrode active material particles filled in the conductive porous base material. Thereby, the strength of the positive electrode holding the solid electrolyte layer described above is improved, and the area of the solid electrolyte layer can be increased. Further, the conductive porous substrate preferably has straight pores. This improves the filling property of the positive electrode active material particles in the conductive porous substrate.

The shape of the opening of the straight pore of the conductive porous substrate is not particularly limited, and may be, for example, a square, a circle, a rectangle, a rhombus, an oval, or the like.

The open pore diameter of the straight pores is preferably 40 μm or more and 500 μm or less, and more preferably 100 μm or more and 250 μm or less. If the opening diameter is too large, the strength of the positive electrode tends to decrease, and if the opening diameter is too small, the filling property of the positive electrode active material particles into the conductive porous substrate tends to decrease. The definition of the opening diameter of the straight pore is as described above.

The material of the conductive porous substrate is not particularly limited as long as it has a certain degree of strength and conductivity, and for example, a metal material such as copper, nickel or stainless steel can be used.

The thickness of the conductive porous substrate is not particularly limited, and can be, for example, 10 μm or more and 300 μm or less, and ensures the mechanical strength of the conductive porous substrate and prevents an increase in the electrical resistance of the substrate. From the viewpoint of achieving a balance with

The average particle size of the positive electrode active material particles is preferably 4% or less with respect to the open pore size of the straight pores of the conductive porous substrate. This improves the filling property of the positive electrode active material particles in the conductive porous substrate and the moldability of the positive electrode. The lower limit of the average particle diameter of the positive electrode active material particles is not particularly limited, but may be 0.07% or more with respect to the open pore diameter of the straight pores of the conductive porous substrate.

Since the positive electrode has a large mechanical strength, the size of the main surface thereof can be 1.0 cm ² or more, which makes it possible to provide an all-solid-state lithium secondary battery with high capacity and high energy density.

<Negative electrode>
The negative electrode is not particularly limited as long as it is a negative electrode used in a conventionally known lithium ion secondary battery, that is, a negative electrode containing an active material capable of absorbing and releasing Li ions. For example, as negative electrode active materials, graphite, pyrolytic carbons, cokes, glassy carbons, organic polymer compound fired bodies, mesocarbon microbeads (MCMB), carbon capable of absorbing and releasing lithium such as carbon fibers One kind or a mixture of two or more kinds of base materials is used. Further, a simple substance containing an element such as Si, Sn, Ge, Bi, Sb, or In, a compound and an alloy thereof, a lithium-containing nitride or a lithium-containing oxide, or a compound that can be charged and discharged at a low voltage close to that of lithium metal, or lithium. Metals and lithium/aluminum alloys can also be used as the negative electrode active material.

For the negative electrode, a negative electrode mixture obtained by appropriately adding a conductive auxiliary agent (a carbon material such as carbon black, a solid electrolyte, etc.), a binder such as PVDF, etc. to the negative electrode active material is formed using a current collector as a core material ( A negative electrode material mixture layer), a foil of the above-mentioned various alloys or a lithium metal, or a laminate of a negative electrode material layer on a current collector is used.

When using a current collector for the negative electrode, as the current collector, a foil made of copper or nickel, a punching metal, a net, an expanded metal or the like may be used. It is preferable to use a porous base material.

More specifically, the negative electrode preferably includes the conductive porous base material and negative electrode active material particles filled in the conductive porous base material. As a result, the strength of the negative electrode holding the solid electrolyte layer described above is improved, and the area of the solid electrolyte layer can be increased. Further, the conductive porous substrate preferably has straight pores. This improves the filling property of the negative electrode active material particles in the conductive porous substrate.

The shape of the opening of the straight pore of the conductive porous substrate is not particularly limited, and may be, for example, a square, a circle, a rectangle, a rhombus, an oval, or the like.

The open pore diameter of the straight pores is preferably 40 μm or more and 500 μm or less, and more preferably 100 μm or more and 250 μm or less. If the opening diameter is too large, the strength of the negative electrode tends to decrease, and if the opening diameter is too small, the filling property of the negative electrode active material particles into the conductive porous substrate tends to decrease. The definition of the opening diameter of the straight pore is as described above.

The material of the conductive porous substrate is not particularly limited as long as it has a certain degree of strength and conductivity, and for example, a metal material such as copper, nickel or stainless steel can be used.

The thickness of the conductive porous substrate is not particularly limited, and can be, for example, 10 μm or more and 300 μm or less, and ensures the mechanical strength of the conductive porous substrate and prevents an increase in the electrical resistance of the substrate. From the viewpoint of achieving a balance with

The average particle diameter of the negative electrode active material particles is preferably 4% or less of the open pore diameter of the straight pores of the conductive porous substrate. This improves the filling property of the negative electrode active material particles into the conductive porous substrate and the formability of the negative electrode. The lower limit of the average particle diameter of the negative electrode active material particles is not particularly limited, but may be 0.07% or more with respect to the open pore diameter of the straight pores of the conductive porous substrate.

Since the negative electrode has a large mechanical strength, the size of the main surface thereof can be 1.0 cm ² or more, which makes it possible to provide an all-solid-state lithium secondary battery with high capacity and high energy density.

<Electrode body>
The positive electrode and the negative electrode can be used in the form of a laminated electrode body in which the above-mentioned solid electrolyte layer of the present invention is laminated, or a wound electrode body in which the laminated electrode body is further wound.

(Method of manufacturing all-solid-state lithium secondary battery of the present invention)
Next, a method for manufacturing the all-solid-state lithium secondary battery of the present invention will be described. A preferred embodiment of the method for producing an all-solid-state lithium secondary battery of the present invention comprises a step of dry-filling a conductive porous substrate with active material particles as a method for producing an electrode. Thereby, the strength of the electrode holding the solid electrolyte layer is improved, and the area of the solid electrolyte layer can be increased. The specific method of dry-filling the active material particles into the conductive porous substrate is not particularly limited, and, for example, the active material particles are charged into the openings of the conductive porous substrate and pressurized. Examples of the method include molding. The method for producing the all-solid-state lithium secondary battery of the present invention is not limited to the above method, and the slurry of the active material particles is poured into the open pores of the conductive porous substrate, and pressure molding is performed after drying. The method of doing so may be used.

In addition, in the method for producing the electrode, it is preferable that the conductive porous substrate is filled with the hydride-based solid electrolyte together with the active material particles. This can improve the conductivity of the electrode.

Next, the method for producing the positive electrode used in the present invention will be described more specifically. The method for producing the positive electrode used in the present invention is not particularly limited, and includes, for example, a positive electrode active material, a binder, and a conductive auxiliary agent, a positive electrode mixture-containing paste obtained by dispersing a solvent such as N-methyl-2-pyrrolidone (NMP), or It can be manufactured by preparing a slurry, applying the slurry to one or both surfaces of a current collector, drying the slurry, and then subjecting it to a calendar treatment, if necessary. Further, when the conductive porous substrate is used for the current collector, it is preferable to include a step of filling the conductive porous substrate with the positive electrode active material in a dry manner. The specific method of dry-filling the positive electrode active material into the conductive porous substrate is not particularly limited.

Next, the method for producing the negative electrode used in the present invention will be described more specifically. The manufacturing method of the negative electrode used in the present invention is not particularly limited, and, for example, a negative electrode active material and a binder, and further a conductive auxiliary agent if necessary, are dispersed in a solvent such as N-methyl-2-pyrrolidone (NMP) or water. The negative electrode mixture-containing paste or slurry thus prepared is prepared, and the paste or slurry is applied to one side or both sides of the current collector, dried, and then subjected to a calendaring process if necessary, whereby the production can be performed. Further, when the above-mentioned conductive porous substrate is used for the current collector, it is desirable to include a step of filling the conductive porous substrate with the negative electrode active material in a dry method. The specific method of dry-filling the negative electrode active material into the conductive porous substrate is not particularly limited.

From the viewpoint of improving the mechanical strength of the electrode body, it is preferable that the positive electrode and the negative electrode are laminated together with the solid electrolyte layer and integrally pressure-molded.

Further, the method for producing an all-solid-state lithium secondary battery of the present invention preferably further comprises, as a method for producing a solid electrolyte layer, a step of dryly filling an insulating porous substrate with a hydride-based solid electrolyte. As a result, the strength of the solid electrolyte layer is improved, and the solid electrolyte layer can have a larger area. The specific method of dry-filling the insulating hydride-based solid electrolyte into the insulating porous base material is not particularly limited. For example, the hydride-based solid electrolyte is added to the open pores of the insulating porous base material. Then, the method of pressure molding may be used.

The method for producing the solid electrolyte layer may be a method in which a slurry containing a hydride-based solid electrolyte is poured into an insulating porous substrate, dried and then pressure-molded. As a method for pouring the slurry, a coating method such as a screen printing method, a doctor blade method or a dipping method can be adopted. The slurry is prepared by adding the hydride-based solid electrolyte to a solvent and mixing. However, it is necessary to select a solvent that does not easily deteriorate the hydride-based solid electrolyte as the solvent. In particular, hydride-based solid electrolytes use depolarization due to minute water, so use non-polar aprotic solvents represented by hydrocarbon solvents such as hexane, heptane, octane, nonane, decane, decalin, toluene and xylene. Preferably. Further, fluorine-based solvents such as "Bertrel" (registered trademark) manufactured by Mitsui DuPont Fluorochemicals, "Zeorora" (registered trademark) manufactured by Nippon Zeon, "Novec" (registered trademark) manufactured by Sumitomo 3M, A non-aqueous organic solvent such as dichloromethane, diethyl ether or the like can be used.

The hydride-based solid electrolyte is relatively flexible as compared with the oxide solid electrolyte, by pressure molding the powder, it is possible to easily pellet molding, it is also possible to stack the molded product Therefore, as a method for filling the insulating porous substrate with the hydride-based solid electrolyte, in order to prevent deliquescent of the solid electrolyte due to the water content, a dry process is used, and the hydride-based solid electrolyte is insulated from the insulating layer. It is more preferable to use a method in which the porous base material is charged into the open pores and pressure-molded.

Hereinafter, the present invention will be described in detail based on examples. However, the following examples do not limit the present invention.

(Example 1)
<Preparation of positive electrode layer>
First, 31.7 parts by mass of Li ₄ Ti ₅ O ₁₂ having an average particle diameter of 2 μm, which is a positive electrode active material, and 7.0 parts by mass of acetylene black, which is a conductive additive, were synthesized by heating at 320° C. , LiBH ₄ and LiI in a molar ratio of 3:1 and a hydride solid electrolyte: 61.3 parts by mass were mixed and well kneaded to prepare a positive electrode mixed powder.

Next, a circular stainless steel mesh (opening diameter: 400 μm, thickness: 100 μm, diameter: 16 mm) manufactured by Daiwa Metal Co., Ltd. was prepared as a conductive porous substrate. Subsequently, the stainless steel mesh was placed in a powder molding die having a diameter of 16 mm, 80.4 mg of the positive electrode mixed powder was further placed, and pressure molding was performed using a press machine at a pressure gauge display value of 1500 kg to obtain a thickness of 268 μm. A positive electrode layer having an area of 2 cm ² and a density of 1.5 g/cm ³ was produced.

<Preparation of solid electrolyte layer>
Next, a circular polyester mesh (opening diameter: 124 μm, thickness: 72 μm, diameter: 16 mm) manufactured by Taiyo Wire Mesh Co., Ltd. was placed on the positive electrode layer in the powder molding die, and as a hydride-based solid electrolyte, 70 mg of a solid electrolyte having a molar ratio of LiBH ₄ and LiI of 3:1, which was synthesized by heating at 320° C., was charged, and pressure molding was performed using a press machine at a pressure gauge display value of 1500 kg, and the positive electrode layer A solid electrolyte layer having a thickness of 200 μm, an area of 2 cm ² and a density of 1.5 g/cm ³ was formed on the above.

<Preparation of negative electrode layer>
Next, a circular Li metal having a diameter of 16 mm and a thickness of 0.2 mm was placed on the solid electrolyte layer in the powder molding die, and a circular stainless mesh (opening diameter: 400 μm) manufactured by Daiwa Metal Co., Ltd. , Thickness: 100 μm, diameter: 16 mm), and pressure molding was performed with a press machine at a pressure gauge display value of 1500 kg to produce a negative electrode layer on the solid electrolyte layer.

<Preparation of electrode/electrolyte laminate>
Finally, pressure molding was further performed using the above press machine at a pressure gauge display value of 6000 kg, and then the layers were bonded by heating at 140° C. for 2 hours to bond the positive electrode layer, the solid electrolyte layer, and the negative electrode layer. An electrode/electrolyte laminate having a main surface area of 2 cm ² composed of 3 layers was prepared.

<Battery assembly>
The obtained electrode/electrolyte laminate was inserted into a stainless steel 2016 type outer can and sealed to produce an all-solid-state lithium ion battery.

(Example 2)
<Preparation of positive electrode layer>
First, 31.7 parts by mass of Li ₄ Ti ₅ O ₁₂ having an average particle size of 2 μm which is a positive electrode active material, 7.0 parts by mass of acetylene black which is a conductive additive, and the solid electrolyte used in Example 1. : 61.3 parts by mass and thoroughly kneaded to prepare a positive electrode mixed powder.

Next, a circular stainless steel foil (thickness: 50 μm, diameter: 16 mm) was prepared as a current collector. Subsequently, the stainless foil was placed in a powder molding die having a diameter of 16 mm, 80.4 mg of the positive electrode mixed powder was further placed, and pressure molding was performed using a press machine at a pressure gauge display value of 1500 kg to obtain a thickness of 268 μm. A positive electrode layer having an area of 2 cm ² and a density of 1.5 g/cm ³ was produced.

An all-solid-state lithium-ion battery was produced in the same manner as in Example 1 except that the above positive electrode layer was used.

(Example 3)
<Preparation of positive electrode layer and solid electrolyte layer>
In the same manner as in Example 1, a solid electrolyte layer was produced on the positive electrode layer.

<Preparation of negative electrode layer>
Next, a circular Li metal having a diameter of 16 mm and a thickness of 0.2 mm was placed on the solid electrolyte layer in the powder molding die, and a circular stainless foil (thickness: 50 μm, diameter: 16 mm) was further placed thereon. The negative electrode layer was placed on the solid electrolyte layer by pressure-molding using a press machine at a pressure gauge reading of 1500 kg.

An all-solid-state lithium-ion battery was produced in the same manner as in Example 1 except that the positive electrode layer, the solid electrolyte layer, and the negative electrode layer were used.

(Example 4)
<Preparation of positive electrode layer>
A positive electrode layer was prepared in the same manner as in Example 1.

<Preparation of solid electrolyte layer>
Next, 70 mg of the solid electrolyte used in Example 1 was placed on the positive electrode layer in the powder molding die, and pressure molding was performed using a press machine at a pressure gauge display value of 1500 kg to obtain the positive electrode layer of the positive electrode layer. A solid electrolyte layer having a thickness of 200 μm, an area of 2 cm ² and a density of 1.5 g/cm ³ was formed on the above.

<Preparation of negative electrode layer>
A negative electrode layer was prepared in the same manner as in Example 1.

An all-solid-state lithium-ion battery was produced in the same manner as in Example 1 except that the positive electrode layer, the solid electrolyte layer, and the negative electrode layer were used.

(Example 5)
<Preparation of positive electrode layer>
First, 31.7 parts by mass of Li ₄ Ti ₅ O ₁₂ having an average particle size of 2 μm which is a positive electrode active material, 7.0 parts by mass of acetylene black which is a conductive additive, and the solid electrolyte used in Example 1. : 61.3 parts by mass and thoroughly kneaded to prepare a positive electrode mixed powder.

Next, a circular stainless steel foil (thickness: 50 μm, diameter: 16 mm) was prepared as a current collector. Subsequently, the stainless foil was placed in a powder molding die having a diameter of 16 mm, 80.4 mg of the positive electrode mixed powder was further placed, and pressure molding was performed using a press machine at a pressure gauge display value of 1500 kg to obtain a thickness of 268 μm. A positive electrode layer having an area of 2 cm ² and a density of 1.5 g/cm ³ was produced.

<Preparation of solid electrolyte layer>
Next, 70 mg of the solid electrolyte used in Example 1 was placed on the positive electrode layer in the powder molding die, and pressure molding was performed using a press machine at a pressure gauge display value of 1500 kg to obtain the positive electrode layer. A solid electrolyte layer having a thickness of 200 μm, an area of 2 cm ² and a density of 1.5 g/cm ³ was formed on the above.

<Preparation of negative electrode layer>
A negative electrode layer was prepared in the same manner as in Example 1.

An all-solid-state lithium-ion battery was produced in the same manner as in Example 1 except that the positive electrode layer, the solid electrolyte layer, and the negative electrode layer were used.

(Example 6)
<Preparation of positive electrode layer>
A positive electrode layer was prepared in the same manner as in Example 1.

<Preparation of solid electrolyte layer>
Then, a circular stainless steel mesh (opening diameter: 400 μm, thickness: 100 μm, diameter: 16 mm) manufactured by Daiwa Metal Co., Ltd. was placed on the main surface of the positive electrode layer in the powder molding die, and used in Example 1. 70 mg of solid electrolyte was charged, and pressure molding was performed using a press machine at a pressure gauge reading of 1500 kg, and a solid electrolyte layer having a thickness of 200 μm, an area of 2 cm ² , and a density of 1.5 g/cm ³ was formed on the positive electrode layer. Was produced.

<Preparation of negative electrode layer>
A negative electrode layer was prepared in the same manner as in Example 1.

An all-solid-state lithium-ion battery was produced in the same manner as in Example 1 except that the positive electrode layer, the solid electrolyte layer, and the negative electrode layer were used.

(Example 7)
<Preparation of positive electrode layer>
A positive electrode layer was prepared in the same manner as in Example 1.

<Preparation of solid electrolyte layer>
Next, 40 parts by mass of a polyhedron-shaped boehmite synthetic product (aspect ratio: 1.4, D50: 0.63 μm), which are inorganic particles, and 60 parts by mass of the solid electrolyte used in Example 1 were mixed, The mixture was thoroughly kneaded to prepare a solid electrolyte mixed powder. Subsequently, 70 mg of the solid electrolyte mixed powder was placed on the positive electrode layer in the powder molding die, and pressure molding was performed using a pressing machine at a pressure gauge display value of 1500 kg, and on the positive electrode layer, A solid electrolyte layer having a thickness of 200 μm, an area of 2 cm ² and a density of 1.5 g/cm ³ was prepared.

<Preparation of negative electrode layer>
A negative electrode layer was prepared in the same manner as in Example 1.

An all-solid-state lithium-ion battery was produced in the same manner as in Example 1 except that the positive electrode layer, the solid electrolyte layer, and the negative electrode layer were used.

(Comparative Example 1)
<Preparation of positive electrode layer>
First, 31.7 parts by mass of Li ₄ Ti ₅ O ₁₂ having an average particle size of 2 μm which is a positive electrode active material, acetylene black which is a conductive additive: 7.0 parts by mass, and 7Li which is a sulfide-based solid electrolyte. ₂ S-3P ₂ S ₅ :61.3 parts by mass was mixed and well kneaded to prepare a positive electrode mixed powder.

Next, a circular stainless steel mesh (opening diameter: 400 μm, thickness: 100 μm, diameter: 16 mm) manufactured by Daiwa Metal Co., Ltd. was prepared as a conductive porous substrate. Subsequently, the stainless steel mesh was placed in a powder molding die having a diameter of 16 mm, 80.4 mg of the positive electrode mixed powder was further placed, and pressure molding was performed using a press machine at a pressure gauge display value of 1500 kg to obtain a thickness of 268 μm. A positive electrode layer having an area of 2 cm ² and a density of 1.5 g/cm ³ was produced.

<Preparation of solid electrolyte layer>
Next, a circular polyester mesh (opening diameter: 124 μm, thickness: 72 μm, diameter: 16 mm) manufactured by Taiyo Wire Net Co., Ltd. was placed on the main surface of the positive electrode layer in the powder molding die to form a sulfide-based solid electrolyte. 7 Li ₂ S-3P ₂ S ₅ which is No. ₇ was charged and pressure-molded using a press machine at a pressure gauge display value of 1500 kg, and the thickness of the positive electrode layer was 200 μm, the area was 2 cm ² , and the density was 1. A solid electrolyte layer of 5 g/cm ³ was prepared.

<Preparation of negative electrode layer>
A negative electrode layer was prepared in the same manner as in Example 1.

An all-solid-state lithium-ion battery was produced in the same manner as in Example 1 except that the positive electrode layer, the solid electrolyte layer, and the negative electrode layer were used.

(Comparative example 2)
<Preparation of positive electrode layer>
First, 31.7 parts by mass of Li ₄ Ti ₅ O ₁₂ having an average particle size of 2 μm which is a positive electrode active material, 7.0 parts by mass of acetylene black which is a conductive additive, and the solid electrolyte used in Example 1. : 61.3 parts by mass and thoroughly kneaded to prepare a positive electrode mixed powder.

Next, a circular stainless steel foil (thickness: 50 μm, diameter: 16 mm) was prepared as a current collector. Subsequently, the stainless foil was placed in a powder molding die having a diameter of 16 mm, 80.4 mg of the positive electrode mixed powder was further placed, and pressure molding was performed using a press machine at a pressure gauge display value of 1500 kg to obtain a thickness of 268 μm. A positive electrode layer having an area of 2 cm ² and a density of 1.5 g/cm ³ was produced.

<Preparation of solid electrolyte layer>
Next, 70 mg of the solid electrolyte used in Example 1 was placed on the positive electrode layer in the powder molding die, and pressure molding was performed using a press machine at a pressure gauge display value of 1500 kg to obtain the positive electrode layer. A solid electrolyte layer having a thickness of 200 μm, an area of 2 cm ² and a density of 1.5 g/cm ³ was formed on the above.

<Preparation of negative electrode layer>
Next, a circular Li metal having a diameter of 16 mm and a thickness of 0.2 mm was placed on the solid electrolyte layer in the powder molding die, and a circular stainless steel foil (thickness: 50 μm, diameter: 16 mm) was further placed thereon. Was placed, and pressure molding was performed using a pressing machine at a pressure gauge display value of 1500 kg to produce a negative electrode layer on the solid electrolyte layer.

An all-solid-state lithium-ion battery was produced in the same manner as in Example 1 except that the positive electrode layer, the solid electrolyte layer, and the negative electrode layer were used.

The following tests were performed using the batteries of Examples 1 to 7 and Comparative Examples 1 and 2 to evaluate the battery characteristics.

<Charge/discharge test>
The manufactured battery was discharged at a constant current of 0.14 mA at 120° C. until the battery voltage reached 1.0 V, and then charged at a constant current of 0.14 mA until the battery voltage became 2.0 V. This series of operations was set as one cycle, repeated up to two cycles, and the discharge capacity at the second cycle was measured to obtain the standard battery capacity at 120°C. However, the battery of Comparative Example 2 could not be charged and discharged under the above conditions, and the standard battery capacity at 120° C. was 0.

<Load characteristic test>
The batteries of Examples 1 to 7 and Comparative Example 1 were discharged at a constant current of 0.72 mA at 120° C. until the battery voltage reached 1.0 V, and then at a constant current of 0.72 mA and a battery voltage of 2. It was charged until it reached 0V. This series of operations was set as one cycle, repeated up to two cycles, and the discharge capacity at the second cycle was measured to obtain the high-rate battery capacity. Further, the charged battery was cooled to room temperature and discharged at room temperature with a constant current of 1 μA until the battery voltage reached 1.0 V, and the discharge capacity was measured to be the room temperature battery capacity. The load characteristics were evaluated from these capacities.

The test results are shown in Table 1 together with the electrode constitution and the solid electrolyte constitution.

As shown in Table 1, in the batteries of Examples 1 to 7 in which at least one of the positive electrode and the negative electrode was formed using a conductive porous substrate, it was possible to sufficiently secure the strength of the electrode/electrolyte laminate. It has been confirmed that the battery has a sufficient charge/discharge function as a battery. In particular, in the batteries of Examples 4 and 5 in which the solid electrolyte layer was configured without using the porous base material or the insulating particles that would be a factor that inhibits ionic conduction in the solid electrolyte layer, the utilization rate of the active material of the electrode and the Compared to the batteries of Examples 1 to 3, Example 6 and Example 7 in which the solid electrolyte layer has an improved ionic conductivity and the solid electrolyte layer is formed by using the above-mentioned porous substrate or insulating particles, the standard battery capacity is higher. And a load characteristic was excellent.

The following tests were further conducted using the batteries of Examples 1 to 7 and Comparative Examples 1 and 2 to evaluate the battery characteristics.

<Drop test>
With respect to the batteries of Examples 1 to 7 and Comparative Example 1, the above charging/discharging test was performed for 3 cycles, and the charged battery was dropped onto the concrete surface from a height of 1.6 m 30 times, and then charged again under the same conditions. After discharging, the total discharge capacity at the 5th cycle was determined. Further, with respect to the battery of Comparative Example 2, since charging/discharging at a constant current of 0.14 mA could not be performed, the current value of the constant current for charging and discharging was changed to 0.07 mA, and the charging/discharging cycle was performed. A drop test was conducted in the same manner as above.

The above test was conducted on 10 batteries each, and as a result of the above test, it was determined that an internal short circuit occurred when the discharge capacity after the drop test was lower than the discharge capacity before the drop test by 0.5% or more. ..

<Crush test>
The produced battery was crushed until it was bent and crushed, the exterior body was cleaved, and the solid electrolyte inside was exposed to air. Whether or not H ₂ S gas was generated at that time was confirmed with a gas detector tube.

The test results are shown in Table 2. Regarding the drop test, when the number of batteries having an internal short circuit was 0, it was ⊚, when it was 1 to 4, it was ◯, when it was 5 to 8, it was Δ, and 9 to 10 batteries. If there was, it was represented by x.

As is clear from Table 2, in the batteries of Examples 1 to 7 in which at least one of the positive electrode and the negative electrode was configured using the conductive porous substrate, the conductive porous substrate was used for both the positive electrode and the negative electrode. The occurrence of short circuit could be reduced as compared to the battery of Comparative Example 2 which was not used. Further, by forming the solid electrolyte in the solid electrolyte layer with a hydride-based solid electrolyte, generation of H ₂ S gas was not observed, and a highly safe battery could be constructed. In particular, in the batteries of Examples 1 to 3 in which the solid electrolyte layer was formed by using the insulating porous base material, the strength of the electrode/electrolyte laminate was further improved, a short circuit did not occur, and a battery having excellent reliability was obtained. Could be configured. However, in Example 6 as well, although the solid electrolyte layer was formed using the porous base material as in Examples 1 to 3, since a conductive stainless mesh was used, a short circuit occurred in some batteries. ..

On the other hand, in Comparative Example 1, since the solid electrolyte in the solid electrolyte layer was composed of the sulfide-based solid electrolyte, generation of H ₂ S gas was observed in the crushing test, and the conductive porous material was used for both the positive electrode and the negative electrode. In Comparative Example 2 in which no base material was used, the strength of the electrode/electrolyte laminate was insufficient, resulting in a short circuit in all batteries.

<Study of relationship between average particle size of filler particles and pore size of porous substrate>
The relationship between the average particle size of the hydride-based solid electrolyte particles, the positive electrode active material particles, and the negative electrode active material particles and the pore size of the porous substrate was examined. In the following, the above relationship was examined using positive electrode active material particles as the representative filling particles from the above-mentioned three kinds of filling particles.

Specifically, a stainless steel mesh sheet having square openings (opening diameter: 0.3 mm) as straight pores is punched out into a circle with a diameter of 16 mm, and left standing inside a molding machine with a diameter of 16 mm. A powder of a positive electrode active material (lithium titanate: Li ₄ Ti ₅ O ₁₂ ) having a total amount of 100 mg was filled from above, and a press body was manufactured by changing a press pressure, and the thickness of the molded body was measured and filled. The filling property of the material particles into the porous substrate (mesh sheet) was evaluated. Further, the strength and moldability of the molded product were evaluated based on the occurrence of chipping, cracking, deformation, etc. when the molded product was taken out from the molding machine. As the positive electrode active material powder, four types of particles having an average particle diameter of 0.2 μm, 7 μm, 10 μm, and 20 μm were used.

The above results are shown in FIG. FIG. 3 is a diagram showing the relationship between the thickness of the compact and the pressing pressure. It can be seen from FIG. 3 that when the pressing pressure is increased, the thickness of the molded body is gradually reduced and the packing density of the positive electrode active material particles in the mesh sheet is increased. After that, when the pressing pressure is further increased, the net-like sheet is deformed, and it becomes impossible to reduce the thickness of the molded body and it is impossible to increase the packing density. In addition, as the average particle diameter of the positive electrode active material powder increases, the range of press pressure at which the compact density at which the packing density is considered to be the highest is around 300 μm is narrowed, which makes it difficult to form the compact. I understand. Therefore, it can be seen from FIG. 3 that the average particle diameter of the filler particles is preferably less than 20 μm. Here, the ratio of the average particle size of the filler particles to the open pore size of the straight pores of the reticulated sheet (average particle size/open pore size ratio) was calculated to be 6.7% when the average particle size was 20 μm. When the average particle diameter is 10 μm, it is 3.3%, when the average particle diameter is 7 μm, it is 2.3%, and when the average particle diameter is 0.2 μm, it is 0.07%. From this result, the average particle diameter of the filler particles is preferably 4% or less, more preferably 2% or less, and most preferably 1 with respect to the open pore diameter of the straight pores of the porous substrate. It can be seen that it is less than or equal to %.

<Examination of the size of the open pore diameter of the straight pore of the porous substrate>
Then, in the same manner as described above, a positive electrode active material (lithium titanate: Li ₄ Ti ₅ O ₁₂₎ having an average particle diameter of 0.13 μm to 7 μm was used using a stainless steel mesh sheet having an opening diameter of 38 μm to 1 mm. ), and the moldability was evaluated as follows. The results are shown in Table 3. In Table 3, the following evaluation of moldability and the average particle diameter/opening diameter ratio (%) showing the filling property of the molded product are also shown.
Evaluation A: When the moldability of the molded product is high Evaluation B: When the moldability of the molded product is slightly inferior Evaluation C: When the moldability of the molded product is low

From Table 3, if the open pore size is too large, the strength of the molded product cannot be increased even if the average particle size of the filler particles is reduced, and the moldability is deteriorated. On the other hand, if the open pore size is too small, the filler particles cannot be filled even if the average particle diameter of the filler particles is reduced, and the moldability deteriorates. From the above results, it is understood that the open pore diameter of the straight pores of the porous substrate is preferably 40 μm or more and 500 μm or less, and more preferably 100 μm or more and 250 μm or less.

The all-solid-state lithium secondary battery of the present invention can realize a battery with high capacity, high energy density, and high safety by using a solid electrolyte that can have a large area and does not generate toxic gas. Can be preferably used for power supply of various devices such as electronic devices (particularly portable electronic devices such as mobile phones and laptop personal computers), power supply systems, vehicles (electric vehicles, electric bicycles, etc.), etc.

Claims (10)

A positive electrode, a negative electrode, an all-solid lithium secondary battery comprising a solid electrolyte layer disposed between the positive electrode and the negative electrode,
The solid electrolyte layer comprises an insulating porous substrate and said insulating porous hydride system is filled to a substrate a solid electrolyte,
At least one of the positive electrode and the negative electrode includes a conductive porous base material and active material particles filled in the conductive porous base material, the all-solid-state lithium secondary battery. The all-solid-state lithium secondary battery according to claim 1, wherein the conductive porous substrate has straight pores. The average particle diameter of the active material particles filled in the conductive porous substrate is 4% or less of the open pore diameter of the straight pores of the conductive porous substrate. All-solid-state lithium secondary battery. The all-solid-state lithium secondary battery according to claim 2 or 3, wherein the open pore diameter of the straight pores of the conductive porous substrate is 40 µm or more and 500 µm or less. The all-solid-state lithium secondary battery according to any one of claims 1 to 4, wherein the insulating porous substrate has straight pores. The hydride-based solid electrolyte has a particulate form, and the average particle size of the hydride-based solid electrolyte is 4% or less with respect to the open pore size of the straight pores of the insulating porous substrate. The all-solid-state lithium secondary battery according to claim 5 . The all-solid-state lithium secondary battery according to claim 5 or 6 , wherein the opening diameter of the straight pores of the insulating porous substrate is 40 µm or more and 500 µm or less. A method of manufacturing all-solid lithium secondary battery according to any one of claims 1 to 7
A method for manufacturing an all-solid-state lithium secondary battery, comprising a step of filling active material particles in a conductive porous substrate in a dry manner. The method for manufacturing an all-solid lithium secondary battery according to claim 8 , wherein the conductive porous substrate is filled with a hydride-based solid electrolyte together with the active material particles. The method for producing an all-solid-state lithium secondary battery according to claim 8 or 9 , further comprising a step of dryly filling the insulating porous substrate with a hydride-based solid electrolyte.

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