Method for manufacturing an all-solid bromide ion battery

Abstract

To provide an all-solid bromide ion battery capable of being charged / discharged, by which a dense solid electrolyte can be obtained, and a manufacturing method thereof.SOLUTION: An all-solid bromide ion battery 10 of the present invention comprises: a positive electrode layer 13; a negative electrode layer 11; and a solid electrolyte layer 12 disposed between the positive and negative electrode layers. The solid electrolyte layer 12 contains a compound represented by Pb1-XKXBr2-X (where X is a number that satisfies 0<X<1). The compound can be obtained by performing a mechanical milling process on a mixture containing PbBr2 and KBr. A method for manufacturing a solid bromide ion battery comprises the step of pressing with the compound disposed as a solid electrolyte between the positive and negative electrode materials.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to an all-solid-state bromide ion battery and a method for manufacturing the same.

Background Art

[0002] A lithium-ion battery is a battery that uses Li + as a carrier and is characterized by a high voltage. On the other hand, a halide ion battery that uses a halide ion such as F - as a carrier is theoretically said to have an energy density 1.5 to 3 times that of the current lithium-ion battery and is expected as a promising candidate for post-lithium-ion batteries.

[0003] For example, Patent Document 1 describes a positive electrode active material used in a fluoride ion battery, which has a composition represented by Pb 2-x Cu 1+x F 6 (0 ≦ x < 2). It is described that this positive electrode active material obtained a high discharge capacity in the first cycle and also had little decrease in the discharge capacity in the second cycle.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] As halide ion batteries using fluorides and chlorides, although many documents such as Patent Document 1 have reported them, there is no report so far of successful charge and discharge for bromide ion batteries. Since bromide has a tendency to have higher plasticity than fluoride and chloride, it is considered advantageous for the production of solid-state batteries.

[0006] Therefore, an object of the present invention is to provide an all-solid-state bromide ion battery that can obtain a dense solid electrolyte and can be charged and discharged, and a method for manufacturing the same.

Means for Solving the Problems

[0007] To achieve the above object, in one aspect of the present invention, there is provided an all-solid-state bromide ion battery including a positive electrode layer, a negative electrode layer, and a solid electrolyte layer disposed between the positive electrode layer and the negative electrode layer, wherein the solid electrolyte layer contains a compound represented by Pb 1-X K X Br 2-X (wherein X is a number satisfying 0 < X < 1).

[0008] Further, in another aspect of the present invention, there is provided a method for manufacturing an all-solid-state bromide ion battery, including a step of subjecting a mixture containing PbBr 2 and KBr to mechanical milling treatment to obtain a solid electrolyte, and a step of pressing with the solid electrolyte disposed between a positive electrode material and a negative electrode material, thereby obtaining an all-solid-state bromide ion battery including a positive electrode layer, a negative electrode layer, and a solid electrolyte layer disposed between the positive electrode layer and the negative electrode layer.

Effects of the Invention

[0009] According to the present invention as described above, by adopting a compound represented by Pb 2 in which a part of the Pb sites in the crystal structure of PbBr 1-X K X Br 2-X is doped with K as a solid electrolyte and configuring it as an all-solid-state bromide ion battery, a dense solid electrolyte can be obtained, and an all-solid-state bromide ion battery that can be charged and discharged and a method for manufacturing the same can be provided.

Brief Description of the Drawings

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Embodiments for Carrying Out the Invention

[0011] Hereinafter, with reference to the accompanying drawings, an embodiment of an all-solid-state bromide ion battery and a method for manufacturing the same according to the present invention will be described in detail.

[0012] As shown in FIG. 1, the all-solid-state bromide ion battery 10 of the present embodiment includes a positive electrode layer 13, a negative electrode layer 11, and a solid electrolyte layer 12 disposed between the positive electrode layer and the negative electrode layer. The solid electrolyte layer 12 contains Pb 1-X K X Br 2-XIt contains a compound represented by (where X is a number satisfying 0 < X < 1). Optionally, a protective layer 14 may be further provided outside the positive electrode layer, that is, on the side opposite to the solid electrolyte layer. Each layer will be described in detail.

[0013] The solid electrolyte layer 12 contains, as a solid electrolyte, Pb 1-X K X Br 2-X a compound represented by, which is K-doped in a part of the Pb sites of the crystal structure of PbBr 2 . As a result, vacancies are formed at the Br 2 sites in the crystal structure of PbBr - , and the ionic conductivity of Br - can be improved.

[0014] In the above formula representing the doping amount of K, X is preferably a number satisfying 0 < X ≤ 0.1, more preferably a number satisfying 0 < X ≤ 0.05, and still more preferably a number satisfying 0.01 ≤ X ≤ 0.05.

[0015] The solid electrolyte layer 12 is preferably a compact obtained by pressure-molding solid electrolyte particles. Since the solid electrolyte particles are not sintered and are bromides, they are soft materials with excellent plasticity. By pressure-molding, the particles can adhere to each other and also adhere to the adjacent positive electrode layer 13 and negative electrode layer 11.

[0016] The thickness of the solid electrolyte layer 12 is preferably 1 μm or more, more preferably 100 μm or more. On the other hand, the thickness of the solid electrolyte layer 12 is preferably 1000 μm or less, more preferably 500 μm or less.

[0017] The positive electrode layer 13 includes an electrode mixture containing at least a positive electrode active material. As the positive electrode active material, metal bromides are preferred, for example, bismuth bromide (BiBr 3 ), copper bromide (CuBr, CuBr 2 ), silver bromide (AgCl), iron bromide (FeBr 2 ), etc.

[0018] The electrode mixture of the positive electrode layer 13 may contain a solid electrolyte in order to reduce the interfacial resistance. As the solid electrolyte used in the electrode mixture of the positive electrode layer 13, similar to the solid electrolyte layer 12, Pb 1-X K X Br 2-X (wherein X is a number satisfying 0 < X < 1) is preferably used. Other examples of the solid electrolyte include, for example, SnBr 2 and PbBr 2 , SrBr 2 etc. may also be used.

[0019] The proportion of the solid electrolyte in the electrode mixture of the positive electrode layer 13 is preferably 50 parts by mass or more, more preferably 100 parts by mass or more, based on 100 parts by mass of the positive electrode active material. On the other hand, the proportion of the solid electrolyte in the electrode mixture is preferably 200 parts by mass or less, more preferably 150 parts by mass or less.

[0020] The electrode mixture of the positive electrode layer 13 is an insulator and may contain a conductive agent in order to impart electronic conductivity. As the conductive agent, for example, a carbon material, a metal compound, etc. may be used. Examples of the carbon material include, for example, carbon black (such as acetylene black, ketjen black, furnace black, etc.), graphite powder, fibrous carbon materials, etc. Examples of the metal compound include, for example, a metal having electrical conductivity, a metal alloy, a metal oxide.

[0021] In the case of a carbon material, the proportion of the conductive agent in the electrode mixture of the positive electrode layer 13 is preferably 10 parts by mass or more, more preferably 30 parts by mass or more, based on 100 parts by mass of the positive electrode active material. On the other hand, the proportion of the conductive agent in the electrode mixture is preferably 100 parts by mass or less, more preferably 50 parts by mass or less.

[0022] The positive electrode layer 13 is preferably a compact obtained by pressure-molding electrode mixture particles. The electrode mixture particles are not sintered and are soft materials excellent in plasticity because they contain bromide. By pressure-molding, the particles can adhere to each other and also adhere to the adjacent solid electrolyte layer 12.

[0023] The thickness of the positive electrode layer 13 is preferably 1 μm or more, more preferably 100 μm or more. On the other hand, the thickness of the positive electrode layer 13 is preferably 1000 μm or less, more preferably 500 μm or less.

[0024] The negative electrode layer 11 contains at least a negative electrode active material. As the negative electrode active material, an active material having a potential lower than that of the positive electrode active material is used. Examples of such active materials include simple metals such as lead (Pb) and tin (Sn), alloys, their oxides, and their bromides, and others such as lanthanum bromide (LaBr 3 ) and magnesium bromide (MgBr 2 ).

[0025] The negative electrode layer 11 may be a compacted powder obtained by pressure-molding negative electrode active material particles, or may be a foil or plate of the negative electrode active material. The thickness of the negative electrode layer 11 is preferably 1 μm or more, more preferably 100 μm or more. On the other hand, the thickness of the negative electrode layer 11 is preferably 1000 μm or less, more preferably 500 μm or less.

[0026] The protective layer 14 is an optionally provided layer. By the protective layer 14, contact between the current collector and the electrode binder is prevented, and the reaction between the two is suppressed, so that the cycle characteristics can be further improved. The protective layer 14 preferably includes a protective material containing a solid electrolyte and a conductive agent. As the solid electrolyte used in the protective material, similar to the solid electrolyte layer 12, Pb 1-X K X Br 2-X (wherein X is a number satisfying 0 < X < 1) is preferably used. Other examples of the solid electrolyte include SnBr 2 and PbBr 2 , SrBr 2 , etc. may also be used. Also, as the conductive agent used in the protective material, the same carbon materials and metal compounds as those in the electrode binder of the positive electrode layer 13 may be used.

[0027] The protective layer 14 is preferably a compacted powder obtained by pressure-molding protective material particles. Since the protective layer 14 is not involved in the charge and discharge capacity of the battery, its thickness is preferably small, preferably 500 μm or less, and more preferably 100 μm or less. The lower limit of the thickness is not particularly limited, but for example, 1 μm or more is preferable.

[0028] According to the all-solid-state bromide ion battery 10 having such a configuration, since a compound represented by Pb 1-X K X Br 2-X is used for the solid electrolyte of the solid electrolyte layer 12, the Br - ion conductivity of the solid electrolyte layer 12 can be improved, and the all-solid-state chloride ion battery 10 capable of charge and discharge can be provided.

[0029] Next, a method for manufacturing the all-solid-state bromide ion battery according to the present embodiment will be described. As shown in FIG. 2, this method includes, as three raw materials 21a and 21b of the solid electrolyte, mixing PbBr 2 and KBr, and subjecting this mixture to a mechanical milling process to obtain a solid electrolyte 23, and a pressing process (not shown) of obtaining an all-solid-state bromide ion battery by pressing with the solid electrolyte 23 disposed between the positive electrode material and the negative electrode material.

[0030] This method may optionally further include a second mechanical milling step 25 of mixing the solid electrolyte 23 and the conductive agent 24, and subjecting this mixture to a mechanical milling process to obtain a conductive coating material 26 in which the solid electrolyte is coated with the conductive agent. The conductive coating material 26 can be used as a protective material for forming a protective layer, and an all-solid-state bromide ion battery can be obtained by pressing in a state where the protective material, the positive electrode material, the solid electrolyte, and the negative electrode material are arranged in this order in the pressing step.

[0031] Further, this method may optionally further include a third mechanical milling step 28 of mixing the conductive coating material 26 and the positive electrode active material 27 and subjecting this mixture to a mechanical milling treatment to obtain an electrode mixture 29. The electrode mixture 29 is used as a positive electrode material in the pressing step. Each of the above steps will be described in detail.

[0032] In the first mechanical milling step 22, first, Pb represented as a solid electrolyte 1-X K X Br 2-X To obtain a compound represented by, PbBr as its raw material 2 And KBr are mixed so as to have a desired composition. That is, in terms of molar ratio, PbBr 2 :KBr is mixed so as to be 1-X:X. Then, by subjecting the mixture of each powder of PbBr 2 And KBr to a mechanical milling treatment, Pb 1-X K X Br 2-X A powder of the compound represented by can be obtained. X is a number satisfying 0 < X < 1. For example, as shown in FIG. 2, when X = 0.01, PbBr 2 And KBr are mixed at a molar ratio of 0.99:0.01 to obtain a solid electrolyte 23 of Pb 0.99 K 0.01 Br 1.99 Can be obtained.

[0033] As the mechanical milling treatment, for example, a ball mill, a vibration mill, a turbo mill, mechanofusion, a disk mill, etc. can be used. The rotation speed and treatment time of the mechanical milling treatment are such that each powder of the raw materials PbBr 2 And KBr becomes Pb 1-X K X Br 2-X It may be carried out until it becomes a powder of the compound represented by, for example, the rotation speed is 400 to 600 rpm and the treatment time is 3 to 12 hours. The mechanical milling treatment may be carried out dry or wet.

[0034] In the second mechanical milling step 25, first, the solid electrolyte 23 and the conductive agent 24 are mixed. As shown in FIG. 2, the solid electrolyte 23 is preferably the solid electrolyte 23 obtained in the first mechanical milling step 22, but the present invention is not limited thereto. Additionally, as the solid electrolyte, SnBr 2 or PbBr 2 , SrBr 2 etc. may be used. Since the specific examples of the conductive agent 24 and the blending ratio of the solid electrolyte 23 and the conductive agent 24 are described in the above description of the positive electrode layer, the description here is omitted.

[0035] Then, a mechanical milling treatment is performed on the mixture containing the solid electrolyte 23 and the conductive agent 24 to obtain a conductive coating material 26. The conductive coating material 26 is an aggregate of particles in which the surface of the solid electrolyte particles is coated with the conductive agent. For example, as shown in FIG. 2, when Pb 0.99 K 0.01 Br 1.99 is used as the solid electrolyte 23 and carbon black (C) is used as the conductive agent 24, as the conductive coating material 26, an aggregate of particles in which the surface of Pb 0.99 K 0.01 Br 1.99 particles is carbon-coated can be obtained, and in this specification, it is represented as Pb 0.99 K 0.01 Br 1.99 / C.

[0036] The apparatus used for the mechanical milling treatment is the same as that in the first mechanical milling step. The rotation speed and treatment time of the mechanical milling treatment may be performed until the surface of the solid electrolyte particles is covered with the conductive agent. For example, the rotation speed is 400 - 600 rpm and the treatment time is 3 - 12 hours. The mechanical milling treatment may be performed dry or wet.

[0037] In the third mechanical milling step 28, first, the conductive coating material 26 and the positive electrode active material 27 are mixed. As shown in FIG. 2, the conductive coating material 26 is preferably the conductive coating material 26 obtained in the second mechanical milling step 25. However, the present invention is not limited thereto, and a collection of particles in which other conductive agents are coated on other solid electrolyte particles may also be used. The blending ratio of the conductive coating material 26 and the positive electrode active material 27 is determined by the ratio of the mass of the solid electrolyte in the conductive coating material 26 to the mass of the positive electrode active material. Since the ratio of the solid electrolyte to the positive electrode active material and specific examples of the positive electrode active material are described in the above description of the positive electrode layer, the description here is omitted.

[0038] Then, the mixture containing the conductive coating material 26 and the positive electrode active material 27 is subjected to a mechanical milling treatment to obtain an electrode mixture 29. The electrode mixture 29 is an amorphous body of the conductive coating material and the positive electrode active material. For example, as shown in FIG. 2, when Pb 0.99 K 0.01 Br 1.993 / C is used as the conductive coating material 26 and bismuth bromide (BiBr 3 ) is used as the positive electrode active material 27, the obtained electrode mixture 29 is represented as BiBr 3 / Pb 0.99 K 0.01 Br 1.99 / C in this specification.

[0039] The apparatus used for the mechanical milling treatment is the same as that in the first mechanical milling step. The rotation speed and treatment time of the mechanical milling treatment may be performed until an amorphous body of the conductive coating material and the positive electrode active material is obtained. For example, the rotation speed is 100 to 400 rpm and the treatment time is 3 to 12 hours. The mechanical milling treatment may be performed dry or wet.

[0040] In the pressing step (not shown), by pressing in the order of the positive electrode composite material 29, the solid electrolyte 23, and the negative electrode material obtained as described above, an all-solid-state bromide ion battery including a positive electrode layer, a solid electrolyte layer, and a negative electrode layer in this order can be formed. As the negative electrode material, a negative electrode active material can be used. Since the negative electrode active material is described in the above description of the negative electrode layer, the description here is omitted. Further, in order to form an all-solid-state bromide ion battery further including a protective layer, it may be pressed in the order of the conductive coating material 26, the positive electrode composite material 29, the solid electrolyte 23, and the negative electrode material obtained as described above.

[0041] The pressure during pressing may be any pressure as long as the particles of the solid electrolyte 23 obtained as described above can undergo plastic deformation to form a dense solid electrolyte layer. For example, 255 to 510 MPa is preferable. The temperature during pressing may be normal temperature. Heat treatment such as firing is not necessary.

[0042] According to the manufacturing method of the all-solid-state bromide ion battery of such a process, the solid electrolyte 23, the electrode composite material 29, and the conductive coating material, which are the materials of the solid electrolyte layer, the positive electrode layer, and an optional protective layer constituting the battery, can be efficiently obtained, and an all-solid-state bromide ion battery capable of reversible charge and discharge can be obtained by an easy manufacturing process of pressure-molding the battery constituent materials. Further, since firing is not required, an increase in resistance due to side reactions can also be avoided.

Example

[0043] [1. Solid Electrolyte] PbBr in a pot in a glove box under an Ar atmosphere 2Pb and KBr were encapsulated and mixed at three molar ratios of 0.99:0.01, 0.97:0.03, and 0.95:0.05, respectively, and these mixtures were subjected to mechanical milling treatment at 600 rpm for 12 hours using a planetary ball mill (manufactured by Fritch, Premium line P-7). Among the three obtained samples, for the sample mixed at a molar ratio of 0.99:0.01, an XRD pattern was obtained using an X-ray diffraction (XRD) measurement device (manufactured by Rigaku, product number: Miniflex600). The results are shown in Figure 3.

[0044] As shown in Figure 3, by the Rietveld method, which is an analytical method optimized to minimize the difference between the experimental (observed) and calculated XRD patterns, a single phase in which part of the Pb sites in the crystal structure of PbBr 2 is doped with K, that is, Pb 0.99 K 0.01 Br 1.99 was obtained (in Figure 3, the experiment and calculation almost overlap). Note that the Bragg Positions indicate the peaks of the spectrum.

[0045] Also, for the Pb 0.99 K 0.01 Br 1.99 sample obtained above, as well as PbF 2 and PbBr 2 as comparative examples, powders pulverized by a planetary ball mill at 600 rpm for 12 hours were observed with a scanning electron microscope (SEM) for the compacted bodies molded at 510 MPa. Those images are shown in Figure 4.

[0046] The compacted body of PbF 2 was observed to have many gaps as shown in Figure 4(a), and the relative density was 85.6%. Also, the compacted body of PbBr 2 was very dense as shown in Figure 4(b), and the relative density was 88.5%. The compacted body of Pb 0.99 K 0.01 Br 1.99 was, as shown in Figure 4(c), similar to that of PbBr 2Although some gaps were observed, the relative density was 86.3%. It was found that compared with fluoride, it has high plasticity and excellent moldability when used in all-solid-state batteries.

[0047] Also, for the three samples obtained as described above, an AC impedance test was conducted using the HS cell (manufactured by Takashima Shoten) shown in Fig. 5. As shown in Fig. 5, the HS cell 50 is formed by stacking a cell container 51 with a flange, a sample cell 60, a cylindrical guide 52, a cell lid 53 with a flange, and a pressing member 54 in order, and fixing the cell container 51 with a flange and the cell lid 53 with a flange with four sets of bolts 56 and nuts 57 to form a cell for battery evaluation tests. As shown in Fig. 6, the sample cell 60 was first prepared by uniaxially pressing the above sample at 510 MPa into a pellet 62 with a diameter of 10 mm, and the obtained pellet 62 with Pt sputtering on both sides to form Pt layers 61a and 61b was used. Then, an AC impedance test was conducted in the temperature range of 25 to 160 °C. Also, for comparison, a sample cell was prepared and tested in the same manner for PbBr 2 The results are shown in Fig. 7.

[0048] From the Arrhenius plot shown in Fig. 7, compared with the room-temperature conductivity of PbBr 2 , for all concentrations, the samples doped with KBr 2 showed a conductivity improvement of more than one order of magnitude at room temperature, showing about 4×10 -7 S / cm. This is presumably because the doping of KBr 2 formed vacancies at the Br 2 sites in the crystal structure of PbBr - , improving the ionic conductivity of Br - .

[0049] [2. All-solid-state bromide ion battery] Using the samples obtained as described above as a solid electrolyte, an all-solid-state bromide ion battery was fabricated and a charge-discharge test was conducted.

[0050] First, Pb 0.99 K 0.01 Br1.99 Acetylene black was mixed with the sample in a mass ratio of 5:1. Then, this mixture was subjected to mechanical milling treatment at 600 rpm for 12 hours using a ball mill to obtain a carbon-coated material (Pb 0.99 K 0.01 Br 1.99 / C). Furthermore, BiBr 3 was mixed with this in a mass ratio of 2:1. Then, this mixture was subjected to mechanical milling treatment at 150 rpm for 12 hours using a planetary ball mill to prepare an electrode composite material (BiBr 3 / Pb 0.99 K 0.01 Br 1.99 / C).

[0051] For the solid electrolyte, 330 mg of the above Pb 0.99 K 0.01 Br 1.99 sample was used, for the protective material, 180 mg of the above carbon-coated material was used, for the positive electrode material, 60 mg of the above electrode composite material was used, and a Pb plate was used for the negative electrode material. Note that the Pb of the negative electrode was charged in an excessive amount with respect to the mass of the electrode composite material which is the positive electrode. Then, the protective material, positive electrode material, solid electrolyte, and negative electrode material were arranged in this order and pressed at room temperature under a pressure of 510 MPa to obtain a coin-shaped all-solid cell with a diameter of 10 mm in which a protective layer, positive electrode layer, solid electrolyte layer, and negative electrode layer were laminated in this order.

[0052] The all-solid cell thus obtained was subjected to a charge-discharge test using the PEEK cell (manufactured by MTI Japan) shown in FIG. 8. As shown in FIG. 8, the PEEK cell 80 is a cell for battery evaluation test obtained by stacking a negative electrode side plate 81 made of polyether ether ketone (PEEK), an all-solid cell 10’, a cylindrical guide 82, and a positive electrode side plate 83 made of PEEK in this order. The all-solid cell 10’ is, as shown in FIG. 1, one in which a protective layer 14, a positive electrode layer 13, a solid electrolyte layer 12, and a negative electrode layer 11 are laminated in this order. Then, in a glove box, at 160 °C, 50 μA / cm 2The charge-discharge test was conducted under the following conditions. In addition, in order to confirm the oxidation-reduction mechanism of charge and discharge, the surface of the positive electrode was measured by X-ray photoelectron spectroscopy (XPS). The results are shown in FIGS. 9 to 11. For comparison, BiF 3 was used for the positive electrode, Ce for the negative electrode, and La 0.9 Ba 0.1 F 2.9 was used for the fluoride ion battery, and the charge-discharge profile is shown in FIG. 12.

[0053] From the charge-discharge profile shown in FIG. 9 and the cycle characteristics shown in FIG. 10, the all-solid-state cell exhibited an initial discharge capacity corresponding to a 2.6 electron reaction, and reversible charge and discharge proceeded. This can be said to be very high compared to the initial discharge capacity corresponding to a 1.8 electron reaction of the fluoride ion battery shown in FIG. 12. Also, a reversible capacity of 119 mAh / g was observed even at the 10th cycle, and it was confirmed that the cycle characteristics did not deteriorate significantly. Compared with the fluoride ion battery shown in FIG. 12, the charge capacity retention rate at the 10th cycle was 80% for the all-solid-state bromide ion battery of the present invention, while it was 66% for the fluoride ion battery. Furthermore, as shown in FIG. 11, in the all-solid-state bromide ion battery of the present invention, the redox of Bi 3+ →Bi metal→Bi 3+ was confirmed during charge and discharge, and it became clear that the redox of Bi proceeded reversibly.

Explanation of symbols

[0054] 10 All-solid-state bromide ion battery 11 Negative electrode layer 12 Solid electrolyte layer 13 Positive electrode layer 14 Protective layer 22 First mechanical milling process 25 Second mechanical milling process 28 Third mechanical milling process 50 HS cell 60 Sample cell 80 PEEK cell

Claims

1. PbBr ２ A step of subjecting a mixture containing PbBr and KBr to a first mechanical milling treatment to obtain a solid electrolyte, wherein the solid electrolyte contains a compound represented by Pb 1-X K X Br 2-X (wherein X is a number satisfying 0 < X ≦ 0.1), A step of subjecting a mixture containing a part of the solid electrolyte and a conductive agent to a second mechanical milling treatment to obtain a protective material; A step of subjecting a mixture containing a part of the protective material and a positive electrode active material containing a metal bromide to a third mechanical milling treatment to obtain an electrode mixture as a positive electrode material; A step of pressing in a state where the protective material, the positive electrode material, the solid electrolyte, and the negative electrode material are arranged in this order, to obtain an all-solid-state bromide ion battery in which a protective layer, a positive electrode layer, a solid electrolyte layer, and a negative electrode layer are arranged in this order. A method for manufacturing an all-solid-state bromide ion battery including the above steps.

2. The method for manufacturing an all-solid-state bromide ion battery according to Claim 1, wherein X in the formula satisfies 0 < X ≤ 0.

05.

3. The method for manufacturing an all-solid-state bromide ion battery according to Claim 1 or 2, wherein the solid electrolyte layer has a cubic perovskite-type crystal at room temperature (25°C).

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