Solid-state battery

Abstract

This solid-state battery comprises a positive electrode (20), a negative electrode (30), and a solid electrolyte layer (10) sandwiched between the positive electrode (20) and the negative electrode (30). The negative electrode (30) contains Li or an Li–M alloy. M is one or more elements selected from the group consisting of Si, Sn, Zn, Mg, Ag, and Al. The solid electrolyte layer (10) contains a solid electrolyte containing Li, Zr, SO3, and X. X is one or more elements selected from the group consisting of F, Cl, Br, and I.

Description

solid state battery

[0001] This disclosure relates to a solid-state battery. This application claims priority under Japanese Patent Application No. 2024-158934, filed in Japan on September 13, 2024, the contents of which are incorporated herein by reference.

[0002] With the remarkable advancements in electronics technology, portable electronic devices are becoming smaller, lighter, thinner, and more multifunctional. Batteries, which power these devices, are also in high demand for smaller size, lighter weight, thinner design, improved reliability, and enhanced safety. Solid-state batteries, which use solid electrolytes, are attracting attention because they are safer than lithium-ion secondary batteries that use liquid electrolytes.

[0003] Solid electrolytes include oxide-based solid electrolytes, sulfide-based solid electrolytes, complex hydride-based solid electrolytes, and halide-based solid electrolytes.

[0004] For example, Patent Document 1 discloses a halide-based solid electrolyte containing Li, M, O, X, and A.

[0005] International Publication No. 2022 / 091565 (A)

[0006] Batteries degrade in performance with repeated charging and discharging. Cycle characteristics indicate the degree of degradation during charging and discharging, and batteries with excellent cycle characteristics are in demand. Furthermore, batteries are prone to degradation during high-temperature operation. Solid-state batteries that exhibit excellent cycle characteristics even in high-temperature environments are needed.

[0007] This disclosure has been made in view of the above-mentioned issues and aims to provide a solid-state battery that exhibits excellent cycle characteristics even in high-temperature environments.

[0008] To solve the above problems, the following means are provided.

[0009] A solid-state battery according to the first embodiment comprises a positive electrode, a negative electrode, and a solid electrolyte layer sandwiched between the positive electrode and the negative electrode. The negative electrode contains Li or a Li-M alloy, where M is one or more elements selected from the group consisting of Si, Sn, Zn, Mg, Ag, and Al. The solid electrolyte layer contains Li, Zr, and SO ３It includes a solid electrolyte containing Li and X. The X is one or more elements selected from the group consisting of F, Cl, Br, and I.

[0010] The solid battery according to the above aspect may further include an intermediate layer. The intermediate layer is between the negative electrode and the solid electrolyte layer. The intermediate layer contains the Li and the X.

[0011] The solid battery according to the above aspect may further include an intermediate layer. The intermediate layer is between the negative electrode and the solid electrolyte layer. The thickness of the intermediate layer is 1 nm or more and 200 nm or less.

[0012] In the solid battery according to the above aspect, the solid electrolyte layer may have a molar ratio of S to Zr of 0.20 or more and 3.0 or less, and a molar ratio of X to Zr of 2.0 or more and 10.0 or less.

[0013] In the solid battery according to the above aspect, the solid electrolyte is Li ａ Zr ｂ E ｃ (SO ３ ) ｄ G ｅ X ｆ ... It may be represented by (1). In formula (1), E is at least one element selected from the group consisting of Na, K, Ba, Ca, Mg, Al, Y, Sr, La, Sc, In, Yb, Hf, Ce, Gd, Dy, Ta, Nb, and W, and G is OH, BO ２ , BO ３ , BO ４ , B ３ O ６ , B ４ O ７ , CO ３ , NO ３ , AlO ２ , SiO ３ , SiO ４ , Si ２ O ７ , Si ３ O ９ , Si ４ O １１ , Si ６ O １８ , PO ３ , PO ４ , P ２ O７ , P ３ O １０ , SO ４ , SO ５ , S ２ O ３ , S ２ O ４ , S ２ O ５ , S ２ O ６ , S ２ O ７ , S ２ O ８ , SO ３ , SOF ２ F ２ , BF ４ , PF ６ , BOB, (COO) ２ , N, AlCl ４ , CF ３ SO ３ , CH ３ COO, CF ３ COO, OOC-(CH ２ ) ２ , OOC-CH-COO, OOC-CH(OH)-CH(OH)-COO, OOC-CH(OH)-CH ２ -COO, C ２ H ６ SO ５ , OOC-CH=CH-COO (maleate), OOC-CH=CH-COO (fumarate), C(OH)(CH ３ COOH) ２ COO, AsO ２ , BiO ４ , CrO ４ , MnO ４ , PtF ４ , PtCl ６ , PtBr ６ , PtI ６ , PtI ６ , SbO ４ , SeO ４ , TeO ４It is at least one group selected from the group consisting of , HCOO, and O, where a satisfies 0.5 ≤ a < 6.0, b satisfies 0.2 < b < 1.0, c satisfies 0 ≤ c < 1.0, d satisfies 0.1 < d < 5.0, e satisfies 0 ≤ e ≤ 1.0, and f satisfies 3.0 < f ≤ 6.1.

[0014] In the solid-state battery according to the above embodiment, the solid electrolyte may further contain lithium sulfite particles.

[0015] In the solid-state battery according to the above embodiment, the negative electrode may further contain graphite, silicon, zinc, or silver.

[0016] In the solid-state battery according to the above embodiment, the negative electrode may further include the solid electrolyte.

[0017] In the solid-state battery according to the above embodiment, the positive electrode may further include the solid electrolyte.

[0018] The solid-state battery according to the above embodiment exhibits excellent cycle characteristics in high-temperature environments.

[0019] This is a schematic cross-sectional view of the solid-state battery according to this embodiment. This is an enlarged view of a characteristic part of the power generation element according to the first modified example.

[0020] This embodiment will now be described in detail with reference to the drawings as appropriate. The drawings used in the following description may be enlarged for convenience to clearly illustrate the features of this embodiment, and the dimensional ratios of each component may differ from those of the actual components. The materials, dimensions, etc., exemplified in the following description are examples only, and this disclosure is not limited to them. It is possible to modify and implement these examples as appropriate without altering the essence of the invention.

[0021] "Solid-state battery" Figure 1 is a schematic cross-sectional view of a solid-state battery 100 according to this embodiment. The solid-state battery 100 shown in Figure 1 comprises a power generation element 40 and an outer casing 50. The outer casing 50 covers the periphery of the power generation element 40. The power generation element 40 is connected to the outside by a pair of terminals 60 and 62 connected to the power generation element 40. Although Figure 1 shows a stacked battery, a wound-type battery may also be used. The solid-state battery 100 can be used, for example, in laminated batteries, prismatic batteries, cylindrical batteries, coin-type batteries, button-type batteries, etc.

[0022] <Power Generation Element> The power generation element 40 comprises a solid electrolyte layer 10, a positive electrode 20, and a negative electrode 30. The power generation element 40 charges or discharges through the exchange of ions via the solid electrolyte layer 10 and electrons via an external circuit between the positive electrode 20 and the negative electrode 30.

[0023] (Solid Electrolyte Layer) The solid electrolyte layer 10 is sandwiched between the positive electrode 20 and the negative electrode 30. The solid electrolyte layer 10 contains a solid electrolyte that can move ions by an externally applied voltage. For example, the solid electrolyte conducts lithium ions and inhibits electron movement.

[0024] Solid electrolytes include, for example, Li, Zr, and SO2. ３ It includes and X. X is a halogen element, one or more elements selected from the group consisting of F, Cl, Br, and I. The solid electrolyte is, for example, a halide solid electrolyte containing a halogen element. The solid electrolyte is SO ３ Including this substance can suppress the reduction of Zr and the decomposition of the solid electrolyte, even when using a low-potential negative electrode.

[0025] In a solid electrolyte, the molar ratio of S to Zr is, for example, 0.2 to 3.0. The molar ratio of S to Zr may also be, for example, 0.2 to less than 1.0, or 0.2 to 0.5. When the molar ratio of Zr is high, even if some of the Zr in the solid electrolyte is reduced, the framework of the solid electrolyte can be maintained, and the decrease in ionic conductivity at the interface can be suppressed, thus suppressing the deterioration of cycle characteristics. The molar ratio of S to Zr may also be, for example, greater than 1.0 and less than or equal to 3.0, or 1.5 to 3.0. When the molar ratio of S is high, excess S may form a film containing LiS between the solid electrolyte layer 10 and the negative electrode 30, suppressing the deterioration of the cycle characteristics of the solid battery 100.

[0026] Furthermore, in solid electrolytes, the molar ratio of element X to element Zr is, for example, between 2.0 and 10.0.

[0027] The molar ratio of constituent elements in a solid electrolyte can be determined by compositional analysis using area analysis with scanning electron microscopy energy-dispersive X-ray spectroscopy (SEM-EDX). However, since lithium (Li) is difficult to analyze with EDX, its composition can be analyzed using electron energy loss spectroscopy (EELS) or Auger electron spectroscopy (AES).

[0028] Solid electrolytes include, for example, Li ａ Zr ｂ E ｃ (SO ３ ) ｄ G ｅ X ｆ ...It may also be represented by (1).

[0029] In formula (1), a represents the composition ratio of Li in the compound represented by formula (1). In formula (1), a satisfies 0.5 ≤ a < 6.0. Preferably, a satisfies 1.0 ≤ a ≤ 3.0, and more preferably 1.5 ≤ a ≤ 2.5. In the solid electrolyte represented by formula (1), when a satisfies 0.5 ≤ a < 6.0, the amount of Li contained in the compound becomes appropriate, and the ionic conductivity of the solid electrolyte increases.

[0030] In formula (1), b is the composition ratio of Zr in the compound represented by formula (1). Zr is an element that forms the skeleton of the halide-based solid electrolyte represented by formula (1). It is more preferable that b satisfies 0.2 < b < 1.0. Zr is an element with a relatively high density compared to other elements contained in formula (1). A solid battery containing a solid electrolyte that satisfies b < 1.0 has a low solid electrolyte density and a large capacity.

[0031] In formula (1), E is at least one element selected from the group consisting of Na, K, Ba, Ca, Mg, Al, Y, Sr, La, Sc, In, Yb, Hf, Ce, Gd, Dy, Ta, Nb, W, and Fe. E is an element that forms the skeleton of the halide-based solid electrolyte represented by formula (1) together with Zr. The compound of formula (1) may not contain E. E, for example, substitutes for a part of the sites where Zr is accommodated in the halide-based solid electrolyte.

[0032] In formula (1), c is the composition ratio of E in the compound represented by formula (1). c satisfies 0 < c < 1.0, and it is more preferable that c satisfies 0.6 ≤ c.

[0033] In formula (1), SO ３ is sulfite ion and is substituted for a part of halogen X. SO ３ improves the reduction resistance of the solid electrolyte. d is the composition ratio of sulfite ion in the compound represented by formula (1). d satisfies 0.1 < d < 5.0, and it is preferable that d satisfies 0.2 ≤ d ≤ 3.0.

[0034] In formula (1), G is substituted for a part of halogen X. The compound of formula (1) may not contain G. G, for example, is OH, BO ２ , BO ３ , BO ４ , B ３ O ６ , B ４ O ７ , CO ３ , NO ３ , AlO ２ , SiO ３ , SiO ４ , Si ２ O ７ , Si３ O ９ 、Si ４ O １１ 、Si ６ O １８ 、PO ３ 、PO ４ 、P ２ O ７ 、P ３ O １０ 、SO ４ 、SO ５ 、S ２ O ３ 、S ２ O ４ 、S ２ O ５ 、S ２ O ６ 、S ２ O ７ 、S ２ O ８ 、SO ３ F、SO ２ F ２ 、BF ４ 、PF ６ 、BOB、(COO) ２ 、N、AlCl ４ 、CF ３ SO ３ 、CH ３ COO、CF ３ COO、OOC-(CH ２ ) ２ -COO、OOC-CH ２ -COO、OOC-CH(OH)-CH(OH)-COO、OOC-CH(OH)-CH ２ -COO、C ６ H ５ SO ３ 、OOC-CH=CH-COO(maleate)、OOC-CH=CH-COO(fumarate)、C(OH)(CH ２ ​​​​​​​​​​​​​​​​​​​​​​​４ It is at least one group selected from the group consisting of , HCOO, and O.

[0035] G is O, PF ６ S ｙ O ｘ F ｚ , P ｙ O ｘ F ｚ ,OH,(COO) ２ CO ３ It is preferable to include any of the following selected from the group consisting of S. ｙ O ｘ F ｚ For example, SO ４ SO ５ S ２ O ３ S ２ O ４ S ２ O ５ S ２ O ６ S ２ O ７ S ２ O ８ SO ３ F, SO ２ F ２ S ｙ O ｘ F ｚ SO ４ S ２ O ３ It is preferable that this is the case. ｙ O ｘ F ｚ In this case, x satisfies 2 ≤ x ≤ 8, y satisfies 1 ≤ y ≤ 3, and z satisfies 0 ≤ z < 6. ｙ O ｘ F ｚ For example, PO ３ , PO ４ , P ２ O ７ , P ３ O １０ , PO ２ F ２ , PO ２ F, PO ３ It is F. ｙ O ｘ F ｚ , PO ３ , PO４ It is preferable that this is the case. P ｙ O ｘ F ｚ In this case, x satisfies 2 ≤ x ≤ 8, y satisfies 1 ≤ y ≤ 3, and z satisfies 0 ≤ z < 6.

[0036] When a halogen-based solid electrolyte contains G, E ions become less easily reduced, and the solid electrolyte becomes less susceptible to reductive decomposition. Solid electrolytes containing G have a wide potential window on the reduction side and are less easily reduced.

[0037] In formula (1), e represents the composition ratio of G in the compound represented by formula (1). e is 0 ≤ e ≤ 1.0, preferably 0.1 ≤ e, and more preferably 0.5 ≤ e. Solid electrolytes containing G within this range have a wide potential window on the reducing side and are less susceptible to reductive decomposition. If the G content is high, the ionic conductivity of the solid electrolyte decreases.

[0038] In formula (1), X is a halogen. X is an essential atom of the solid electrolyte. X is one or more atoms selected from the group consisting of Cl, F, Br, and I. It is preferable that X contains Cl. X has a large ionic radius per valence. The halide solid electrolyte represented by formula (1) has high ionic conductivity and allows lithium ions to flow easily by containing X. Furthermore, the halide solid electrolyte represented by formula (1) has high ionic conductivity and excellent oxidation resistance and reduction resistance by containing Cl as X.

[0039] In formula (1), f represents the composition ratio of X in the compound represented by formula (1). f satisfies the condition 3.0 < f ≤ 6.1. When f satisfies 3.0 < f, the strength of the pellets increases when the solid electrolyte is pressure-molded into pellets. Also, when f satisfies 3.0 < f, the ionic conductivity of the solid electrolyte increases. Furthermore, it is preferable that f ≤ 5.0. This is to avoid a deficiency of G due to an increase in the X content, which would narrow the potential window of the solid electrolyte.

[0040] The solid electrolyte represented by formula (1) is, for example, Li ２ ZrSO ３ Cl ４ Li ２ ZrSO３ Cl ２ F ２ , Li ２ Zrki ３ Cl ２ Br ２ , Li ２ Zhr(Sị) ３ ) ０．５ (SOO) ４ ) ０．５ Cl ４ , Li ２．５ Zhr(Sị) ３ ) ０．５ (PO ４ ) ０．５ Cl ４ , Li １．５ Zhr(Sị) ３ ) ０．５ (PO ３ ) ０．５ Cl ４ , Li ２ Zhr(Sị) ３ ) ０．２ (SOO) ４ ) ０．８ Cl ４ , Li ２．５ Zhr(Sị) ３ ) ０．２ (PO ４ ) ０．８ Cl ４ , Li １．５ Zhr(Sị) ３ ) ０．２ (PO ３ ) ０．８ Cl ４ , Li ２ Zr ０．５ W ０．５ SO ３ Cl ５ , Li ２ Zr ０．５ That ０．５ SO ３ Cl ４．５ , Li ２ Zr ０．５ Nb ０．５ SO ３ Cl ４．５ , Li ２ Zr ０．５ Hf ０．５ SO ３ Cl ４．０ , Li ２ Zr ０．５ Yes０．５ SO ３ Cl ３．５ , Li ２ Zr ０．５ La ０．５ SO ３ Cl ３．５ , Li ２ Zr ０．５ Al ０．５ SO ３ Cl ３．５ , Li ２ Zr ０．５ I ０．５ SO ３ Cl ３．５ , Li ２ Zr ０．５ Sc ０．５ SO ３ Cl ３．５ , Li ２ Zr ０．５ Dy ０．５ SO ３ Cl ３．５ , Li ２ Zr ０．５ Gd ０．５ SO ３ Cl ３．５ , Li ２ Zr ０．５ Yb ０．５ SO ３ Cl ３．５ , Li ２ Zr ０．５ Y ０．５ SO ３ Cl ３．５ , Li ２ Zr ０．５ Zn ０．５ SO ３ Cl ３．０ , Li ２ Zr ０．５ Ba ０．５ SO ３ Cl ３．０ , Li ２ Zr ０．５ Ca ０．５ SO ３ Cl ３．０ , Li ２ Zr ０．５ Sr ０．５ SO ３ Cl ３．０ , Li ２ Zr ０．５ Mg ０．５ SO３ Cl ３．０ Li ２ Zr ０．５ Na ０．５ SO ３ Cl ３．０ Li ２ Zr ０．５ K ０．５ SO ３ Cl ３．０ That is the case.

[0041] The solid electrolyte may be in the form of a powder (particles) or a sintered body formed by sintering powder. The solid electrolyte may also be a molded body formed by compressing powder, a molded body formed by molding a mixture of powder and a binder, or a coating film formed by applying a paint containing powder, binder, and solvent, and then heating to remove the solvent. The main structure of the solid electrolyte may be amorphous, crystalline, or a mixture of amorphous and crystalline materials. The crystal system of a crystalline solid electrolyte may be triclinic, monoclinic, orthorhombic (orthorhombic), tetragonal, hexagonal, or cubic. Furthermore, if G contains O, the metal element M'' (Zr and M') in the solid electrolyte may be oxide nanoparticles M''O ｘ It may also exist in the form (0 < x < 3).

[0042] The solid electrolyte layer 10 may contain other substances in addition to the solid electrolyte. For example, the solid electrolyte layer 10 may further contain lithium sulfite particles. The particle size of the lithium sulfite particles is preferably 0.005 μm or more and less than 10 μm, and more preferably 0.01 μm or more and less than 1.0 μm. The lithium sulfite particles can be identified by scanning electron microscopy energy-dispersive X-ray spectroscopy (SEM-EDX), transmission electron microscopy energy-dispersive X-ray spectroscopy (TEM-EDX), compositional analysis using surface analysis of EELS, electron diffraction (ED), etc. For example, if in the compositional analysis of EDX, S and O elements are detected at 90 wt% or more, the composition ratio expressed as O / S is 2.0 or more and less than 4.0, and Li is detected by EELS, etc., then that region can be determined to be lithium sulfite particles. When the solid electrolyte layer 10 contains lithium sulfite particles, a high-quality coating (SEI) is formed at the interface between the solid electrolyte layer and the negative electrode, further improving reduction resistance.

[0043] (Positive electrode) The positive electrode 20 has, for example, a plate-shaped (foil-shaped) positive electrode current collector 22 and a positive electrode active material layer 24 (see Figure 1). The positive electrode active material layer 24 is in contact with at least one surface of the positive electrode current collector 22.

[0044] The positive electrode current collector 22 can be made of an electronically conductive material that is resistant to oxidation during charging and corrosion. Examples of materials for the positive electrode current collector 22 include metals such as aluminum, stainless steel, nickel, and titanium, and conductive resins. The positive electrode current collector 22 may also be in the form of powder, foil, punched, or expanded material.

[0045] The positive electrode active material layer 24 includes, for example, a positive electrode active material. The positive electrode active material is not particularly limited as long as it is capable of reversibly carrying out intercalation and deintercalation of lithium ions, and any positive electrode active material used in known solid-state batteries can be used. Examples of positive electrode active materials include lithium-containing metal oxides and lithium-containing metal phosphorus oxides.

[0046] Lithium-containing metal oxides include, for example, lithium cobalt oxide (LiCoO2). ２ ), lithium nickelate (LiNiO ２ ), lithium manganese spinel (LiMn ２ O ４ ), and general formula: LiNi ｘ Co ｙ Mn ｚ O ２ A composite metal oxide represented by (x + y + z = 1), lithium vanadium compound (LiVOPO) ４ Li ３ V ２ (PO ４ ) ３ ), olivine-type LiMPO ４ (wherein M represents at least one selected from Co, Ni, Mn, and Fe), lithium titanate (Li ４ Ti ５ O １２ ) etc.

[0047] Furthermore, the positive electrode active material may not contain lithium. Examples of such positive electrode active materials include lithium-free metal oxides (MnO２ , V ２ O ５ (etc.), lithium-free metal sulfides (MoS ２ (etc.), lithium-free fluoride (FeF ３ VF ３ Examples include the following. When using a positive electrode active material that does not contain lithium, the negative electrode is doped with lithium ions beforehand, or a negative electrode containing lithium ions is used.

[0048] The positive electrode active material layer 24 may contain a solid electrolyte, a conductive additive, and a binder in addition to the positive electrode active material. The solid electrolyte contained in the positive electrode active material layer 24 may be the same as, for example, the halide-based solid electrolyte contained in the solid electrolyte layer 10. If the solid electrolytes contained in the solid electrolyte layer 10 and the positive electrode 20 are the same, the manufacture of the solid battery 100 is easy. The solid electrolyte contained in the positive electrode active material layer 24 may be different from, for example, the solid electrolyte contained in the solid electrolyte layer 10.

[0049] The content of the solid electrolyte in the positive electrode active material layer 24 is not particularly limited, but is preferably 1% by mass or more and 50% by mass or less, and more preferably 5% by mass or more and 30% by mass or less, based on the total mass of the positive electrode active material, solid electrolyte, conductive additive and binder.

[0050] The binder binds the positive electrode active material, solid electrolyte, and conductive additive together within the positive electrode active material layer 24, and firmly adheres the positive electrode active material layer 24 to the positive electrode current collector 22. The positive electrode active material layer 24 preferably contains the binder. The binder preferably has oxidation resistance and good adhesion.

[0051] Examples of binders used in the positive electrode active material layer 24 include polyvinylidene fluoride (PVDF) or its copolymer, polytetrafluoroethylene (PTFE), polyamide (PA), polyimide (PI), polyamideimide (PAI), polybenzimidazole (PBI), polyethersulfone (PES), polyacrylic acid (PA) and its copolymers, metal ion crosslinked polyacrylic acid (PA) and its copolymers, polypropylene (PP) grafted with maleic anhydride, polyethylene (PE) grafted with maleic anhydride, or mixtures thereof. Among these, PVDF is particularly preferred as the binder.

[0052] The binder content in the positive electrode active material layer 24 is not particularly limited, but is preferably 0.3% by mass or more and 10% by mass or less, and more preferably 0.3% by mass or more and 5% by mass or less, based on the total mass of the positive electrode active material, solid electrolyte, conductive additive and binder. If the amount of binder is too small, it tends not to be possible to form a positive electrode 20 with sufficient adhesive strength. Since general binders are electrochemically inert and do not contribute to the discharge capacity, if the amount of binder is too large, it tends not to be possible to obtain a solid battery 100 with sufficient volume or mass energy density.

[0053] The conductive additive improves the electronic conductivity of the positive electrode active material layer 24. Known conductive additives can be used. Examples of conductive additives include carbon materials such as carbon black, graphite, carbon nanotubes, and graphene; metals such as aluminum, copper, nickel, stainless steel, iron, and amorphous metals; conductive oxides such as ITO; or mixtures thereof. The conductive additive may be in powder or fiber form.

[0054] The content of the conductive additive in the positive electrode active material layer 24 is not particularly limited. Based on the total mass of the positive electrode active material, solid electrolyte, conductive additive, and binder, the mass ratio of the conductive additive is preferably 0.5% by mass or more and 20% by mass or less, and more preferably 1% by mass or more and 5% by mass or less.

[0055] (Negative electrode) The negative electrode 30 has, for example, a negative electrode current collector 32 and a negative electrode active material layer 34 (see Figure 1). The negative electrode active material layer 34 is in contact with the negative electrode current collector 32. The negative electrode active material layer 34 is located between the negative electrode current collector 32 and the solid electrolyte layer 10. Here, we illustrate the case where the negative electrode 30 has a two-layer configuration consisting of a negative electrode current collector 32 and a negative electrode active material layer 34, but the negative electrode 30 may also be a single layer in which the conductor constituting the negative electrode current collector 32 and the negative electrode active material constituting the negative electrode active material layer 34 are mixed, or it may consist only of a negative electrode active material layer 34 containing the negative electrode active material.

[0056] The negative electrode current collector 32 only needs to be electrically conductive. The negative electrode current collector 32 can be, for example, a metal such as copper, aluminum, nickel, stainless steel, or iron, or a conductive resin. The negative electrode current collector 32 may also be in the form of powder, foil, punched, or expanded material.

[0057] The negative electrode active material layer 34 includes, for example, a negative electrode active material. The negative electrode active material reversibly facilitates the intercalation and release of lithium ions, and the insertion and deintercalation of lithium ions.

[0058] The negative electrode active material is, for example, elemental Li or a Li-M alloy in the discharge state (State of Charge (SOC) is 0%). For example, it is difficult to distinguish between a Li-Si alloy and a Si negative electrode compounded with Li in the charged state. Defining the composition of the negative electrode active material in the discharge state makes it easier to identify the elements that make up the negative electrode active material.

[0059] M is one or more elements selected from the group consisting of Si, Sn, Zn, Mg, Ag, and Al. It is more preferable that M is one or more elements selected from the group consisting of Si, Sn, and Mg, and even more preferable that M is Si. Li-Si alloys are, for example, Li ２２ Si ５ It may include Li １２ Si ５It may also include [the following]. Here, it is not necessary to prove that Li and M are clearly compounded in the Li-M alloy. For example, if Li and M are confirmed when the negative electrode 30 is compositionally analyzed, it can be assumed that it exists as a Li-M alloy. Here, the compositional analysis of M can be performed by EDX, EELS, AES, etc., and the compositional analysis of Li can be performed by EELS, AES, etc. The Li-M alloy may be crystalline or amorphous.

[0060] The weight ratio of Li or Li-M alloy is 50 wt% or more, preferably 70 wt% or more, more preferably 85 wt% or more, even more preferably 95 wt% or more, and particularly preferably 100 wt%. Here, the weight ratio of Li or Li-M alloy is the weight ratio of Li or Li-M alloy to the entire negative electrode 30 when the negative electrode 30 is a single layer, and is the weight ratio of Li or Li-M alloy to the negative electrode active material layer 34 when the negative electrode 30 is divided into a negative electrode current collector 32 and a negative electrode active material layer 34.

[0061] The negative electrode 30, which contains Li or Li-M alloy in a high weight ratio, undergoes significant expansion and contraction during charging and discharging of the solid-state battery 100, making it prone to volume changes. Volume changes in the negative electrode 30 can cause delamination at the interface between the negative electrode 30 and the solid electrolyte layer 10, leading to a decrease in cycle performance. The negative electrode 30, which contains Li or Li-M alloy in a high weight ratio, has a low potential. A low-potential negative electrode can induce reduction of Zr, potentially decomposing the solid electrolyte. The solid-state battery 100 according to this embodiment exhibits excellent cycle performance even when the negative electrode 30 contains Li or Li-M alloy.

[0062] The molar ratio of Li to M (Li / M) in the negative electrode 30 is, for example, 0.1 or more, more preferably 0.5 or more, more preferably 1.0 or more, and even more preferably 1.2 or more. Li / M may also be, for example, 4.4 or less. If Li / M is less than 0.1, the electronic conductivity of the negative electrode 30 decreases, and the output of the solid battery 100 decreases. If Li / M is 0.5 or more, the alloy becomes softer, and the strain generated at the interface between the negative electrode 30 and the solid electrolyte layer 10 due to volume changes during charging and discharging can be reduced.

[0063] Here, the molar ratio of Li to M is determined in the discharge state (state of charge (SOC) is 0%). Since the negative electrode current collector 32 does not contain Li and M, the molar ratio of Li to M can be measured for the entire negative electrode 30, whether the negative electrode 30 is single-layered or double-layered. The molar ratio of Li to M is determined as an average within the negative electrode 30, and the molar ratio of Li to M may differ depending on the location within the negative electrode 30. The molar ratio of Li and M can be measured, for example, using an inductive plasma mass spectrometer (ICP-MS), EELS, or AES. When performing ICP-MS analysis, a portion of the negative electrode 30 is taken from the solid-state battery 100, and the composition ratio of Li to M within the negative electrode 30 is measured. When performing compositional analysis with EELS or AES, the cross-section of the negative electrode is analyzed, and the composition ratio of Li to M is measured.

[0064] If the negative electrode 30 consists of a single layer, the thickness of the negative electrode 30 may be, for example, 10 μm or more and 70 μm or less. If the negative electrode 30 consists of two layers, the thickness of the negative electrode active material layer 34 may be, for example, 10 μm or more and 70 μm or less. The thinner the negative electrode 30 or the negative electrode active material layer 34, the larger the rate of volume change during charging and discharging, and the less sufficient the strain generated at the interface between the negative electrode 30 and the solid electrolyte layer 10 may be. The thicker the negative electrode 30 or the negative electrode active material layer 34, the lower the electron and ion conductivity of the negative electrode 30, and the lower the output of the solid battery 100.

[0065] The negative electrode active material layer 34 may contain negative electrode active materials other than Li or Li-M alloy. The negative electrode active material layer 34 may contain, for example, one or more selected from graphite, silicon, tin, zinc, silver, and lithium titanate. The negative electrode active material layer 34 may contain, for example, graphite or silicon.

[0066] The negative electrode active material layer 34 may contain a solid electrolyte, a conductive additive, and a binder in addition to the negative electrode active material. The solid electrolyte contained in the negative electrode active material layer 34 may be, for example, the solid electrolyte described above. If the solid electrolytes contained in the solid electrolyte layer 10, the positive electrode 20, and the negative electrode 30 are the same, the manufacture of the solid battery 100 is easy. The solid electrolyte contained in the negative electrode active material layer 34 may be different from, for example, the solid electrolyte contained in the solid electrolyte layer 10.

[0067] The materials and mass ratios of the binder and conductive additive contained in the negative electrode 30 are the same as those of the binder and conductive additive contained in the positive electrode 20.

[0068] Up to this point, an example of a negative electrode 30 has been shown in which a negative electrode active material layer 34 containing Li or Li-M is provided from the time of manufacture, but the negative electrode 30 is not limited to this case. The negative electrode 30 may be a so-called anode-free negative electrode, for example, in which Li is deposited during charging and Li is dissolved during discharge. An anode-free negative electrode does not have a layer corresponding to the negative electrode active material layer 34 at the time of manufacture. In an anode-free negative electrode, Li is deposited during charging, and Li functions as the negative electrode active material layer 34. For example, the negative electrode 30 may not contain Li or Li-M at the time of the first discharge, but Li may be deposited during charging. For example, the negative electrode 30 may contain Si, Zn, etc. at the time of the first discharge (SOC = 0%), and Li may be deposited on the negative electrode 30 during charging (Li-Si or Li-Zn may be confirmed).

[0069] (Intermediate Layer) Figure 2 is an enlarged view of a characteristic part of the power generation element according to the first modified example. The power generation element according to the first modified example differs from the power generation element 40 described above in that it has an intermediate layer 70 between the solid electrolyte layer 10 and the negative electrode 30. The intermediate layer 70 can be confirmed using a transmission electron microscope (TEM). If a layer with a different composition from the solid electrolyte layer 10 and the negative electrode 30 can be confirmed with a TEM, this layer is the intermediate layer 70.

[0070] As shown in Figure 2, an intermediate layer 70 may be present between the solid electrolyte layer 10 and the negative electrode 30. The intermediate layer 70 may contain, for example, Li and X. The intermediate layer 70 may contain two or more compositions. The X contained in the intermediate layer 70 is the same halogen element contained in the solid electrolyte layer 10. The X contained in the intermediate layer 70 may be two or more elements. The intermediate layer 70 may contain, for example, LiCl and LiF, or LiCl and LiBr. The intermediate layer 70 may also contain elements other than Li and X. For example, in addition to LiX, the intermediate layer 70 may contain Li ２ S, Li ２ It may include O.

[0071] The thickness of the intermediate layer 70 is, for example, 1 nm to 200 nm, preferably 1 nm to 100 nm, more preferably 1 nm to 50 nm, and even more preferably 1 nm to 10 nm. The intermediate layer 70 prevents direct contact between the solid electrolyte and the negative electrode and suppresses the reductive decomposition of the solid electrolyte. On the other hand, if the intermediate layer 70 is too thick, the ionic conductivity will decrease.

[0072] <Outer Body> The outer body 50 houses the power generation element 40 inside. The outer body 50 prevents moisture and other elements from entering the interior from the outside. The outer body 50 has, for example, a metal foil 52 and a resin layer 54 laminated on each surface of the metal foil 52, as shown in Figure 1. The outer body 50 is a metal laminate film in which the metal foil 52 is coated on both sides with the resin layer 54.

[0073] The metal foil 52 is, for example, aluminum foil or stainless steel foil. The resin layer 54 can be, for example, a resin film such as polypropylene. The materials constituting the resin layer 54 may be different on the inside and outside. For example, a polymer with a high melting point, such as polyethylene terephthalate (PET) or polyamide (PA), can be used as the outer material, while polyethylene (PE) or polypropylene (PP) can be used as the inner material.

[0074] <Terminals> Terminals 60 and 62 are connected to the negative electrode 30 and the positive electrode 20, respectively. Terminal 62, connected to the positive electrode 20, is the positive terminal, and terminal 60, connected to the negative electrode 30, is the negative terminal. Terminals 60 and 62 are responsible for electrical connections to the outside. Terminals 60 and 62 are made of conductive materials such as aluminum, nickel, and copper. The connection method may be welding or screw fastening. It is preferable to protect terminals 60 and 62 with insulating tape to prevent short circuits.

[0075] (Method for manufacturing a solid battery) The solid electrolyte layer 10 is made of, for example, Li, Zr, and SO on a film. ３ It is obtained by applying a paste containing and X and drying it. The paste is, for example, ZrCl ４ and Li ２ SO ３ It is a result of a mechanical reaction between two things.

[0076] The positive electrode 20 is manufactured by applying a paste containing positive electrode active material onto the positive electrode current collector 22 and drying it to form a positive electrode active material layer 24. The above-mentioned solid electrolyte may be added to the paste containing positive electrode active material.

[0077] Next, the negative electrode 30 is prepared. The negative electrode is manufactured by applying a paste containing the negative electrode active material onto the negative electrode current collector 32 and drying it to form a negative electrode active material layer 34. The above-mentioned solid electrolyte may be added to the paste containing the negative electrode active material.

[0078] Next, the negative electrode 30 is placed on the side of the solid electrolyte layer 10 where the first solid electrolyte layer 11 is formed, and the positive electrode 20 is placed on the side of the solid electrolyte layer 10 where the second solid electrolyte layer 12 is formed, and then pressed. Through this procedure, the power generation element 40 of the solid battery 100 is obtained.

[0079] The power generation element 40 can also be manufactured, for example, using a powder molding method. A guide with holes is placed on the positive electrode 20, and a solid electrolyte is filled into the guide. The surface of the solid electrolyte is smoothed, and the negative electrode 30 is placed on top of the solid electrolyte. In this way, the solid electrolyte layer 10 is sandwiched between the positive electrode 20 and the negative electrode 30. Then, pressure is applied to the positive electrode 20 and the negative electrode 30 to pressure mold the solid electrolyte. By pressure molding, a laminate is obtained in which the positive electrode 20, the solid electrolyte layer 10, and the negative electrode 30 are stacked in this order.

[0080] The intermediate layer 70 can be formed by applying a pressure of 3.0 tons to the laminate for more than one hour in an atmosphere of 85°C or higher. The thickness of the intermediate layer 70 can be changed by changing the heating temperature and pressurizing time.

[0081] Next, external terminals are welded to the positive electrode current collector 22 of the positive electrode 20 and the negative electrode current collector 32 of the negative electrode 30, respectively, using a known method, thereby electrically connecting the positive electrode current collector 22 or the negative electrode current collector 32 to the external terminals. After that, the laminate connected to the external terminals is housed in the outer casing 50, and the opening of the outer casing 50 is sealed by heat sealing. Through these steps, the solid-state battery 100 according to this embodiment is obtained.

[0082] The solid battery 100 according to this embodiment contains SO2 in the solid electrolyte layer 10 ３ This suppresses the reduction of Zr and inhibits the decomposition of the solid electrolyte. As a result, the solid battery 100 according to this embodiment exhibits excellent cycle characteristics even in high-temperature environments.

[0083] While embodiments of this disclosure have been described in detail above with reference to the drawings, the configurations and combinations thereof in each embodiment are merely examples, and additions, omissions, substitutions, and other modifications to the configurations are possible without departing from the spirit of this disclosure.

[0084] "Example 1" In a glove box with a dew point of approximately -75°C, ZrCl ４ and Li ２ SO ３ and ZrCl ４ : Li ２ SO ３ The powder was weighed in a 1:1 molar ratio. The raw material powder was placed into a sealed zirconia container for a planetary ball mill, which already contained 5 mmΦ zirconia balls. The container was sealed with a lid, which was then screwed onto the container body. The gap between the lid and the container was further sealed with polyimide tape. Polyimide tape has the effect of blocking moisture.

[0085] A sealed zirconia container was placed in a planetary ball mill. The raw materials were mixed using the planetary ball mill, and the mechanochemical reaction was carried out for 24 hours. The planetary ball mill's rotation speed was set to 300 rpm and its revolution speed to 300 rpm, with the rotation and revolution directions being opposite. A solid electrolyte material was prepared using this procedure.

[0086] A solid electrolyte layer was prepared by pressing 50 mg of solid electrolyte at a pressure of 0.6 tons for 1 minute. Next, 4 mg of negative electrode material was added to one surface of the solid electrolyte layer 10 and pressed at a pressure of 0.6 tons for 1 minute. The negative electrode material was Li.

[0087] Next, the positive electrode mixture was added to the surface opposite to the surface where the pressed solid electrolyte negative electrode mixture was laminated. The positive electrode mixture contains positive electrode active material, solid electrolyte, and conductive additive in a ratio of 60 parts by mass: 35 parts by mass: 5 parts by mass. The positive electrode active material is lithium cobalt oxide (LiCoO2). ２The solid electrolyte was the same as that used in the solid electrolyte layer. Carbon black was used as the conductive additive.

[0088] Next, the laminate was pressed with a pressure of 3.0 tons for 1 minute. Then, the laminate was pressed with a pressure of 3.0 tons for 1 hour in an 85°C atmosphere. Finally, the molded body was restrained with a force of 3 Nm using a restraining jig and sealed in an aluminum pouch with terminals. A full cell for charge-discharge evaluation was fabricated using this procedure.

[0089] Furthermore, the compositional analysis of the solid electrolyte layer, fabricated under the same conditions as the full cell used for charge-discharge evaluation, was performed using SEM-EDX. The compositional analysis was conducted using a solid-state battery in a discharged state. By performing the compositional analysis, the compositional ratio of each element in the solid electrolyte layer was identified. The compositional ratio of Li to other elements was determined by EELS measurement using TEM. In addition, the interface between the solid electrolyte layer and the negative electrode was measured using TEM to identify the intermediate layer.

[0090] [Cycle Characteristics] Cycle characteristics were determined using a secondary battery charge / discharge test device (manufactured by Hokuto Denko Co., Ltd.) in the following manner.

[0091] The battery was charged at a constant current charging rate of 0.2C (1C is the current value at which charging is completed in 1 hour when constant current charging is performed at 25°C) until the battery voltage reached 4.2V, and then discharged at a constant current discharge rate of 0.2C until the battery voltage reached 2.5V. The cycle characteristics were measured in a temperature environment of 70°C. The discharge capacity after the completion of charging and discharging was detected, and the battery capacity Q before the cycle test was determined. １ They sought it.

[0092] The above battery capacity Q １ The battery whose capacity was determined was then again charged using a secondary battery charge / discharge test device with a constant current charge rate of 0.2C until the battery voltage reached 4.2V, and then discharged with a constant current discharge rate of 0.2C until the battery voltage reached 2.5V. The above charge / discharge was counted as one cycle, and 100 charge / discharge cycles were performed. After that, the discharge capacity after 100 charge / discharge cycles was detected, and the battery capacity Q after 100 cycles was determined. ２ They sought it.

[0093] The battery capacity Q calculated above １ Q２ From this, the capacity retention rate after 100 cycles was calculated. The capacity retention rate E is given by E = Q ２ / Q １ It can be calculated by multiplying by 100.

[0094] Examples 2-6: Examples 2-6 show the process of forming a solid electrolyte layer with ZrCl ４ and Li ２ SO ３ The difference from Example 1 is that the mixing ratio was changed. Other conditions were the same as in Example 1, and the evaluation was carried out accordingly. In Examples 4 to 6, lithium sulfite was confirmed in the solid electrolyte layer. In addition, in Examples 4 to 6, multiple compositions were confirmed in the intermediate layer.

[0095] Examples 7 and 8: Examples 7 and 8 show the process of forming a solid electrolyte layer with ZrCl ４ Part of ZrX ４ The difference from Example 1 is that (X = F or Br) was changed. The evaluation was carried out under the same conditions as in Example 1.

[0096] Examples 9-14: In Examples 9-14, when forming the solid electrolyte layer, ZrCl ４ and Li ２ SO ３ The difference from Example 1 is the addition of a third ingredient. Other conditions were the same as in Example 1, and the evaluation was carried out accordingly. The mixing ratios of each ingredient and the specific type of the third ingredient are shown in Tables 1 and 2.

[0097] Examples 15-34: In Examples 15-34, when forming the solid electrolyte layer, ZrCl ４ and Li ２ SO ３ The difference from Example 1 is the addition of a third ingredient. Other conditions were the same as in Example 1, and the evaluation was carried out accordingly. The mixing ratios of each ingredient and the specific type of the third ingredient are shown in Tables 1 and 2.

[0098] "Examples 35-38" Examples 35-38 differ from Example 1 in that the negative electrode composite material was changed from Li to a Li-M (M = Si, Mg, Zn, or Ag) alloy. Other conditions were the same as in Example 1, and the evaluation was carried out accordingly.

[0099] "Examples 39-43" Examples 39-43 differ from Example 1 in that they use two types of negative electrode active materials to constitute the negative electrode composite. Example 39 used a mixture of Li:Si = 50 parts by mass:50 parts by mass as the negative electrode composite. Examples 40 and 43 used a mixture of Li:graphite = 50 parts by mass:50 parts by mass as the negative electrode composite. Example 43 differs from Example 40 in that instead of pressing the laminate at a pressure of 3.0 tons for 1 hour at an 85°C atmosphere, the laminate was pressed at a pressure of 3.0 tons for 1 hour at a 100°C atmosphere. Example 41 used a mixture of Li:Zn = 50 parts by mass:50 parts by mass as the negative electrode composite. Example 42 used a mixture of Li:Ag = 50 parts by mass:50 parts by mass as the negative electrode composite. Other conditions were the same as in Example 1, and evaluation was performed.

[0100] "Example 44" Example 44 differs from Example 1 in that a solid electrolyte was added to the negative electrode mixture. The mixing ratio of the negative electrode active material (Li) and the solid electrolyte (SE) in the negative electrode mixture was 60 parts by mass: 40 parts by mass. Other conditions were the same as in Example 1, and the evaluation was carried out.

[0101] "Example 45" Example 45 differs from Example 1 in that the laminate was not subjected to a 3.0-ton press in an 85°C atmosphere. In Example 45, even when the interface between the solid electrolyte layer and the negative electrode was measured using TEM, no intermediate layer could be identified. The evaluation was carried out under the same conditions as in Example 1.

[0102] "Comparative Example 1" Comparative Example 1 differs from Example 1 in that the negative electrode composite material was changed from Li to a mixture of graphite and a solid electrolyte. The mixing ratio of graphite and solid electrolyte (SE) in the negative electrode composite material was 70 parts by mass: 30 parts by mass. Other conditions were the same as in Example 1, and the evaluation was carried out.

[0103] "Comparative Examples 2-5" Comparative Examples 2-5 use Li as the second raw material when preparing a solid electrolyte. ２ SO ３ The only difference from Example 1 is that the raw material was changed. Other conditions were the same as in Example 1, and the evaluation was carried out.

[0104] "Comparative Example 6" Comparative Example 6 differs from Example 1 in that the negative electrode composite material is changed from Li to a Li-In alloy. The evaluation was carried out under the same conditions as in Example 1.

[0105] The results of Examples 1 to 43 and Comparative Examples 1 to 6 are summarized in Tables 1 and 2.

[0106]

[0107]

[0108] Examples 1 to 45 exhibited superior cycle characteristics in high-temperature environments compared to Comparative Examples 1 to 6. In Comparative Example 1, a graphite negative electrode was used, resulting in the negative electrode potential being 1.0V or higher relative to the Li potential during charging and discharging. The reason is unclear, but at this potential, SO ３ It is thought that sufficient cycling characteristics could not be obtained because the high-temperature reduction resistance of the solid electrolyte containing was reduced. Comparative Examples 2 to 5 use solid electrolytes containing SO ３ It is thought that because it did not contain ions, the reduction of Zr could not be sufficiently suppressed, and therefore sufficient cycle characteristics could not be obtained. In Comparative Example 6, because a Li-In negative electrode was used, it is thought that sufficient cycle characteristics could not be obtained because the In from the Li-In alloy continued to diffuse into the solid electrolyte layer during charging and discharging.

[0109] Furthermore, in Examples 15 to 34, the thickness of the intermediate layer was greater compared to Example 1. Although this is within the range of variation in the thickness of the intermediate layer, it is thought that the substitution of a portion of the Zr in the solid electrolyte caused a portion of the Cl, which was strongly bound to Zr, to react with Li, making it easier for the intermediate layer to form.

[0110] According to the present invention, it is possible to provide a solid-state battery that exhibits excellent cycle characteristics even in high-temperature environments.

[0111] 10 Solid electrolyte layer 20 Positive electrode 22 Positive electrode current collector 24 Positive electrode active material layer 30 Negative electrode 32 Negative electrode current collector 34 Negative electrode active material layer 40 Power generation element 50 Outer casing 52 Metal foil 54 Resin layer 60, 62 Terminals 70 Intermediate layer

Claims

Positive electrode and, The negative electrode and, The system comprises a solid electrolyte layer sandwiched between the positive electrode and the negative electrode, The negative electrode comprises Li or a Li-M alloy. M is one or more elements selected from the group consisting of Si, Sn, Zn, Mg, Ag, and Al. The solid electrolyte layer consists of Li, Zr, and SO ３ A solid electrolyte containing X A solid-state battery in which X is one or more elements selected from the group consisting of F, Cl, Br, and I. 　 With an additional middle class, The aforementioned intermediate layer is located between the negative electrode and the solid electrolyte layer. The solid battery according to claim 1, wherein the intermediate layer includes Li and X. 　 With an additional middle class, The aforementioned intermediate layer is located between the negative electrode and the solid electrolyte layer. The solid-state battery according to claim 1, wherein the thickness of the intermediate layer is 1 nm or more and 200 nm or less. 　 The solid electrolyte layer is The molar ratio of S to Zr is between 0.20 and 3.

0. The solid battery according to claim 1, wherein the molar ratio of X to Zr is 2.0 or more and 10.0 or less. 　 The solid electrolyte is Li ａ Zr ｂ E ｃ (SO ３ ) ｄ G ｅ X ｆ ... (1) is expressed as, In equation (1), E is at least one element selected from the group consisting of Na, K, Ba, Ca, Mg, Al, Y, Sr, La, Sc, In, Yb, Hf, Ce, Gd, Dy, Ta, Nb, W, Fe, Gは、OH、BO ２ 、BO ３ 、BO ４ 、B ３ O ６ 、B ４ O ７ 、CO ３ 、NO ３ 、AlO ２ 、SiO ３ 、SiO ４ 、Si ２ O ７ 、Si ３ O ９ 、Si ４ O １１ 、Si ６ O １８ 、PO ３ 、PO ４ 、P ２ O ７ 、P ３ O １０ 、SO ４ 、SO ５ 、S ２ O ３ 、S ２ O ４ 、S ２ O ５ 、S ２ O ６ 、S ２ O ７ 、S ２ O ８ 、SO ３ F、SO ２ F ２ 、BF ４ 、PF ６ 、BOB、(COO) ２ 、N、AlCl ４ 、CF ３ SO ３ 、CH ３ COO、CF ３ COO、OOC-(CH ２ ) ２ -COO、OOC-CH ２ -COO、OOC-CH(OH)-CH(OH)-COO、OOC-CH(OH)-CH ２ -COO、C ６ H ５ SO ３ OOC-CH=CH-COO (maleate), OOC-CH=CH-COO (fumarate), C(OH)(CH ２ COOH) ２ COO, AsO ４ Bio ４ ,CrO ４ MnO ４ , PtF ６ , PtCl ６ , PtBr ６ , PtI ６ SbO ４ SeO ４ TeO ４ It is at least one group selected from the group consisting of HClO and O, The solid-state battery according to claim 1, wherein a satisfies 0.5 ≤ a < 6.0, b satisfies 0.2 < b < 1.0, c satisfies 0 ≤ c < 1.0, d satisfies 0.1 < d < 5.0, e satisfies 0 ≤ e ≤ 1.0, and f satisfies 3.0 < f ≤ 6.

1. The solid battery according to claim 1, wherein the solid electrolyte further comprises lithium sulfite particles. 　 The solid-state battery according to claim 1, wherein the negative electrode further comprises graphite, silicon, zinc, or silver. 　 The solid battery according to claim 1, wherein the negative electrode further comprises the solid electrolyte. 　 The solid battery according to claim 1, wherein the positive electrode further comprises the solid electrolyte.

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