JP6766376B2 - Electrode, battery and electrode manufacturing method - Google Patents

Description

The present invention relates to an electrode, a battery and a method for manufacturing an electrode, and more particularly to a method for manufacturing an electrode used for an all-solid-state battery, an all-solid-state battery and an electrode used for an all-solid-state battery.

Conventionally, as a battery of this type, an all-solid secondary battery including a positive electrode having a positive electrode active material, a negative electrode having a negative electrode active material, and a solid electrolyte that is interposed between the positive electrode and the negative electrode and conducts lithium ions. Has been proposed (see, for example, Patent Document 1). In this battery, the energy density can be further increased by solidifying the active material using Li ₃ BO ₃ or Li _2.358 Al _0.214 BO ₃ or the like, regardless of the vapor phase method.

International Publication No. 2012/176805 Pamphlet

However, in the method for manufacturing a battery of Patent Document 1 described above, the active material layer is solidified by heating, but the temperature is still high. From the viewpoint of energy consumption and the manufacturing process of the all-solid-state battery, it has been required to lower the heating temperature.

The present invention has been made in view of such a problem, and an object of the present invention is to provide an electrode, a battery, and a method for manufacturing an electrode, which have ionic conductivity and can be solidified at a lower temperature.

As a result of diligent research to achieve the above-mentioned object, the present inventors have found that if a plurality of kinds of fluxes containing lithium are used, they can be solidified at a lower temperature while having ionic conductivity. It was found and the present invention was completed.

That is, the electrode of the present invention is
An electrode used in all-solid-state batteries
Active material particles that occlude and release lithium,
The above includes 1 or more of lithium fluoride and lithium chloride, and a lithium boron-containing oxide containing lithium, boron and the element A (1 or more of C, Al, Si, Ga, Ge, In and Sn). With the eutectic mixture that exists around the active material particles,
It is provided with an active material layer in which

The battery of the present invention includes the above-mentioned electrode and a solid electrolyte layer adjacent to the electrode.

The method for manufacturing an electrode of the present invention
Active material particles that absorb and release lithium, one or more of lithium fluoride and lithium chloride that are eutectic mixtures, and one of lithium, boron, and element A (C, Al, Si, Ga, Ge, In, and Sn). It includes a lithium boron-containing oxide which is a eutectic mixture containing the above) and a step of preparing an active material layer in which the mixture containing the above is fired at a temperature of 400 ° C. or higher and 650 ° C. or lower to prepare an active material layer.

In the method for producing an electrode, a battery and an electrode of the present invention, an active material layer can be produced by solidifying at a lower temperature while having ionic conductivity. The reason for obtaining such an effect is that, for example, since the eutectic mixture has a lower melting point than the original substance constituting the eutectic mixture, ionic conduction is obtained by using a flux of the eutectic mixture having a low melting point in a specific combination. It is presumed that the active material can be solidified at a lower temperature while having the property.

The explanatory view which shows an example of the structure of the all-solid-state lithium secondary battery 10. The relationship between the amount of LiX (X is a halogen) added to Li _2.2 B _0.2 C _0.8 O ₃ and the melting point. DTA measurement result of Li _2.2 B _0.2 C _0.8 O ₃ . DTA measurement results of eutectic mixture of Li _2.2 B _0.2 C _0.8 O ₃ , LiF and LiCl. DTA measurement results of eutectic mixture of Li _2.2 B _0.2 C _0.8 O ₃ , LiF and LiCl. Nyquist plot of a eutectic mixture of Li _2.2 B _0.2 C _0.8 O ₃ , LiF and LiCl. Cyclic voltamogram of all-solid-state lithium secondary battery containing eutectic mixture.

(electrode)
The electrode of the present invention includes an active material layer in which active material particles and a eutectic mixture existing around the active material particles are mixed. This electrode is suitable for an electrode of an all-solid-state battery, and may be made on a base material of a solid electrolyte layer constituting the all-solid-state battery. Further, the electrode may be a positive electrode using a positive electrode active material as the active material particles, or a negative electrode using a negative electrode active material as the active material particles. Further, the electrode may be provided with a current collector adjacent to the active material layer. The electrode may have active material particles dispersed in a eutectic mixture. In this electrode, the presence of a eutectic mixture having lithium ion conductivity between the active material particles makes it easier to secure a lithium ion conduction path between the active material particles.

The active material occludes and releases lithium, and may be used as a positive electrode active material. Examples of the positive electrode active material include compounds containing lithium and a transition metal element, and examples thereof include oxides containing lithium and a transition metal element, and phosphoric acid compounds containing lithium and a transition metal element. Specifically, a lithium manganese composite oxide having a basic composition formula of Li _(1-x) MnO ₂ (0 <x <1, etc., the same applies hereinafter) or Li _(1-x) Mn ₂ O _4, etc., basic composition Lithium cobalt composite oxide whose formula is Li _(1-x) CoO _2, etc., Lithium nickel composite oxide whose basic composition formula is Li _(1-x) NiO _2, etc., Basic composition formula is Li _(1-x) Lithium nickel cobalt manganese composite oxides such as Ni _1/3 Co _1/3 Mn _1/3 O ₂ and lithium vanadium composite oxides with a basic composition formula of LiV ₂ O ₃ and transition metals such as V ₂ O ₅ Oxides and the like can be mentioned. In addition, a phosphoric acid compound such as LiFePO ₄ as a basic composition formula can also be mentioned. Of these, lithium transition metal composite oxides, such as LiCoO ₂ , LiNiO ₂ , and LiMnO ₂ , are more preferred. It should be noted that the illustrated chemical formula is not intended to be limited to a stoichiometric composition, and some elements may be deleted or excessive, and some elements may be replaced with other elements. It may be (the same applies hereinafter).

Alternatively, the active material may be a negative electrode active material. Examples of the negative electrode active material include oxides containing lithium and a transition metal element. Specific examples thereof include lithium titanate having a basic composition formula of Li ₄ Ti ₅ O ₁₂ .

The eutectic mixture is a lithium boron-containing oxide containing one or more of lithium fluoride and lithium chloride, lithium, boron, and element A (one or more of C, Al, Si, Ga, Ge, In, and Sn). And, including. This eutectic mixture is a compact body that is filled in the gaps between the active material particles, conducts lithium ions, and fixes the active material particles. Lithium fluoride and lithium chloride contained in the eutectic mixture are fluxes having low lithium ion conductivity but high effect of lowering the firing temperature. It is preferable that the eutectic mixture contains both lithium fluoride and lithium chloride because the firing temperature can be further lowered. The lithium boron-containing oxide is a flux having a lower melting temperature than the active material particles and has lithium ion conductivity. The element A may be substituted with a part of lithium of Li ₃ BO ₃ , a part of boron may be substituted, or both may be substituted. When both are replaced, they may be replaced with the same kind of element or different kinds of elements. The lithium-boron-containing oxide, for ^{_{example, Li + s (B 1-}} t, A t) may be represented by the u ⁺ O ^2- _w. Wherein, t satisfies 0 ≦ t <1, u is _{(B 1-t, A t} ) is the average valence of, s, u, v satisfies the relation s + u = v / 2. The lithium boron-containing oxide may be represented by, for example, Li _{2 + x} B _x C _1-x O ₃ (in the formula, x satisfies 0 <x ≦ 1). Such a material in which boron is replaced with carbon is suitable because the ionic conductivity increases. x preferably satisfies 0.1 ≦ x ≦ 0.6, and more preferably 0.2 ≦ x ≦ 0.4. This is because the ionic conductivity becomes higher.

The eutectic mixture preferably contains a lithium boron-containing oxide in the range of 15 mol% or more and 70 mol% or less with respect to the entire eutectic mixture. The lithium boron-containing oxide is preferably contained in a larger amount in the eutectic mixture in consideration of the conductivity of lithium ions, more preferably 30 mol% or more, still more preferably 40 mol% or more. Further, the lithium boron-containing oxide is preferably contained in the eutectic mixture in a smaller amount in consideration of a decrease in the calcination temperature, more preferably 60 mol% or less, still more preferably 50 mol% or less. Further, the eutectic mixture preferably contains lithium fluoride in a range of 15 mol% or more and 70 mol% or less with respect to the entire eutectic mixture. Lithium fluoride is preferably contained in a larger amount in the eutectic mixture in consideration of a decrease in the firing temperature, more preferably 30 mol% or more, still more preferably 40 mol% or more. Further, lithium fluoride is preferably contained in the eutectic mixture in a smaller amount in consideration of the conductivity of lithium ions, more preferably 60 mol% or less, still more preferably 50 mol% or less. Further, the eutectic mixture preferably contains lithium chloride in a range of 15 mol% or more and 70 mol% or less with respect to the entire eutectic mixture. Lithium chloride is preferably contained in a larger amount in the eutectic mixture in consideration of a decrease in the calcination temperature, more preferably 30 mol% or more, still more preferably 40 mol% or more. Further, lithium chloride is preferably contained in the eutectic mixture in a smaller amount in consideration of the conductivity of lithium ions, more preferably 60 mol% or less, still more preferably 50 mol% or less. The eutectic mixture always contains a lithium boron-containing oxide, but may further contain both lithium fluoride and lithium chloride. By doing so, the firing temperature of the active material layer can be further lowered, which is preferable. At this time, the lithium boron-containing oxide is in the range of 20 mol% or more and 40 mol% or less, the lithium fluoride is in the range of 20 mol% or more and 40 mol% or less, and the lithium chloride is in the range of 20 mol% or more and 40 mol% or less with respect to the whole eutectic mixture. It is preferable to include it in a range.

The active material layer may contain active material particles in the range of 50% by volume or more and 85% by volume or less, and may contain a eutectic mixture in the range of 15% by volume or more and 50% by volume or less. From the viewpoint of battery capacity, more active material particles are preferably contained in the active material layer, more preferably 60% by volume or more, still more preferably 75% by volume or more. At this time, the eutectic mixture is 40% by volume or less and 25% by volume or less, respectively. Further, from the viewpoint of the adhesiveness of the active material particles, the eutectic mixture is preferably contained in a larger amount in the active material layer, more preferably 30% by volume or more, still more preferably 40% by volume or more. At this time, the active material particles are 70% by volume or less and 60% by volume or less, respectively.

Collectors include aluminum, titanium, stainless steel, nickel, iron, calcined carbon, conductive polymers, conductive glass, etc., as well as aluminum, copper, etc. for the purpose of improving adhesiveness, conductivity, and oxidation resistance. The surface of the material treated with carbon, nickel, titanium, silver, or the like can be used. For these, it is also possible to oxidize the surface. Further, the current collector may be formed on the active material layer by printing, vapor deposition, or the like. Examples of the shape of the current collector include foil, film, sheet, net, punched or expanded, lath, porous body, foam, and fiber group forming body.

(battery)
The battery of the present invention includes the above-mentioned electrode and a solid electrolyte layer adjacent to the electrode. This battery may be an all-solid-state lithium secondary battery. This battery may be provided with an electrode having an active material layer containing active material particles and a eutectic mixture as a positive electrode, a negative electrode, or a positive electrode and a negative electrode. When the above-mentioned electrodes are used as a positive electrode and a negative electrode, the firing temperature can be further lowered during the integral firing of the positive electrode and the negative electrode, which is preferable. The positive electrode may be the above-mentioned electrode, and the negative electrode may be a Li metal or a Li alloy.

The solid electrolyte layer is composed of a solid electrolyte and has higher lithium ion conductivity than, for example, a lithium boron-containing oxide. The solid electrolyte is preferably an oxide-based inorganic solid electrolyte, and examples thereof include a garnet-type lithium ion conductive oxide. The garnet-type lithium ion conductive oxide has, for example, a basic composition Li _{5 + x} La ₃ Zr _x M _2-x O ₁₂ (in the formula, M is Sc, Ti, V, Y, Nb, Hf, Ta, Al. , Si, Ga, and one or more elements selected from the group consisting of Ge, x may be represented by 1.4 ≦ x <2). In such a case, the lithium ion conductivity is high, and the lithium ion conductivity of the electrode can be further increased. Further, when x satisfies 1.6 ≦ x ≦ 1.95, the conductivity is higher, which is preferable. Further, if x satisfies 1.65 ≦ x ≦ 1.9, the conductivity becomes almost maximum, which is more preferable. Specific examples thereof include Li _6.75 La ₃ Zr _1.75 Nb _0.25 O ₁₂ . Details of the garnet-type lithium ion conductive oxide represented by the basic composition Li _{5 + x} La ₃ Zr _x M _2-x O ₁₂ are described in, for example, Japanese Patent Application Laid-Open No. 2010-202499. Examples of the solid electrolyte include glass ceramics, Li nitrides, halides, and oxidates. Specifically, Li _1.5 Al _0.5 Ge _1.5 (PO ₄ ) ₃ , Li _{1 + X} Ti ₂ Si _X P _3-X O ₁₂ · AlPO ₄ , Li _3.25 Ge _0.25 P _0.25 S ₄ , Li ₄ SiO ₄ , Li _{4 SiO 4 -LiI-LiOH, xLi} 3 PO 4 - (1-x) Li 4 SiO 4, Li 2 SiS 3, Li 3 PO 4 -Li 2 S-SiS 2, and the like phosphorus sulfide compound.

In the electrode or the solid electrolyte on which the electrode is formed, it is preferable that the active material particles and the solid electrolyte do not deteriorate or generate a reaction product. For example, when the electrode and the solid electrolyte are XRD-measured using CuKα rays, it is preferable that the peak of the reaction product between the lithium boron-containing oxide and the active material and the solid electrolyte is not confirmed. Such a case is preferable because the formation of an altered layer or a third phase that reduces the conductivity of lithium ions is suppressed.

The shape of the battery is not particularly limited, and examples thereof include a coin type, a button type, a sheet type, a laminated type, a cylindrical type, a flat type, and a square type. Further, a plurality of such batteries may be connected in series and applied to a large-sized battery used for an electric vehicle or the like.

The structure of this battery is not particularly limited, and examples thereof include the structure shown in FIG. FIG. 1 is an explanatory diagram showing an example of the structure of the all-solid-state lithium secondary battery 10. This all-solid-state lithium secondary battery has a solid electrolyte layer 11, a positive electrode active material layer 13 formed on one side of the solid electrolyte layer 11, and a negative electrode active material layer formed on the other side of the solid electrolyte layer 11. It has 16. A current collector 14 is formed on the surface of the positive electrode active material layer 13, and a current collector 17 is formed on the surface of the negative electrode active material layer 16. The positive electrode active material layer 13 and the current collector 14 are the positive electrode 12, and the negative electrode active material layer 16 and the current collector 17 are the negative electrode 15. The positive electrode active material layer 13 contains the active material particles 21 of the composite oxide and the eutectic mixture 22 existing around the active material particles 21.

(Method of manufacturing electrodes)
The method for producing an electrode of the present invention includes a step of preparing an active material layer for producing an active material layer. In this step, active material particles that absorb and release lithium, one or more of lithium fluoride and lithium chloride as a eutectic mixture, lithium, boron, and elements A (C, Al, Si, Ga, Ge, In, and A mixture containing a lithium boron-containing oxide containing 1 or more of Sn) and forming a eutectic mixture is fired at a temperature of 400 ° C. or higher and 650 ° C. or lower. In this step, since one or more of lithium fluoride and lithium chloride and a lithium boron-containing oxide are contained, the firing temperature can be lowered. As the active material particles, lithium boron-containing oxide, and the like, those described above can be used. Further, in this step, a solvent or a binder may be added to the raw material of the active material layer to form a paste or clay, which may be formed on a base material of a solid electrolyte or a current collector.

In this step, in addition to the lithium boron-containing oxide, lithium fluoride and lithium chloride may be used and calcined at a temperature of 540 ° C. or lower. The lithium boron-containing oxide, lithium fluoride, and lithium chloride may be blended in the above-mentioned blending ratio of the electrodes. For example, it is preferable to add lithium boron-containing oxide, lithium fluoride and lithium chloride in the range of 20 mol% or more and 40 mol% or less, and in the range of 25 mol% or more and 36 mol% or less, respectively, with respect to the entire eutectic mixture. It is more preferable to blend. In such a range, the firing temperature can be 500 ° C. or lower, more preferably 450 ° C. or lower, which is preferable. Further, the active material particles and the raw material of the eutectic mixture may be blended in the blending ratio of the electrodes described above. The firing temperature may be, for example, a temperature higher than the melting point of the raw material of the eutectic mixture obtained by DTA measurement. The DTA measurement may be performed, for example, by using alumina as a reference, setting the sample amount to 10 mg, and performing the DTA measurement in the atmosphere at a heating rate of 10 ° C./min.

According to the electrode, the battery, and the method for manufacturing the electrode described above, the active material layer can be produced by solidifying at a lower temperature while having ionic conductivity. The reason for obtaining such an effect is that, for example, since the eutectic mixture has a lower melting point than the original substance constituting the eutectic mixture, ionic conduction is obtained by using a flux of the eutectic mixture having a low melting point in a specific combination. It is presumed that the active material can be solidified at a lower temperature while having the property.

It goes without saying that the present invention is not limited to the above-described embodiment, and can be implemented in various aspects as long as it belongs to the technical scope of the present invention.

For example, in the above-described embodiment, the battery is mainly described as an all-solid-state lithium secondary battery, but the battery is not particularly limited thereto. For example, the battery may contain a liquid or may be a primary battery.

Hereinafter, an example in which the electrode and the battery of the present invention are specifically manufactured will be described. It goes without saying that the present invention is not limited to the following examples, and can be carried out in various embodiments as long as it belongs to the technical scope of the present invention.

[Examination of flux]
Lithium _2.2 B _0.2 C _0.8 O ₃ particles (hereinafter also referred to as LBCO particles) having lithium conductivity are used as a filler (also serving as a flux) for fixing the active material, and lithium halide is used as a flux for further lowering the melting point. Using (LiX), the relationship between the amount added (mol%) and the melting point was examined. Any one of LiF, LiCl, LiBr and LiI was added to LBCO at a predetermined molar ratio, mixed in a mortar, and the melting point was measured with a DTA measuring device (Thermo plus EVO2 manufactured by Rigaku Co., Ltd.). The DTA measurement was carried out in the air at a heating rate of 10 ° C./min using alumina as a reference and setting the sample amount to 10 mg. FIG. 2 is a diagram showing the relationship between the amount of LiX (X is a halogen) added to Li _2.2 B _0.2 C _0.8 O ₃ and the melting point. Table 1 summarizes the types, amounts and melting points of lithium halide. When LBCO and LiF were mixed, the melting point dropped to about 640 ° C. when LiF was contained in an amount of 50 to 70 mol%. Further, when LBCO and LiCl were mixed, the melting point decreased to about 520 ° C. when LiCl was contained in an amount of 60 to 70 mol%. On the other hand, when LBCO and LiBr were mixed, the melting point did not decrease much as compared with the simple substance, and the temperature was 500 ° C. or higher. When LBCO and LiI were mixed, the melting point decreased to 420 ° C. when 60 to 90 mol% of LiI was contained. However, the Li I system was unsuitable because solid phase Li ₅ IO ₆ was produced. Therefore, it was found that LiF and LiCl are effective as a flux that lowers the melting point.

[Comparative Example 1]
The DTA measurement was performed only on the LBCO particles, and the melting point thereof was determined. FIG. 3 shows the DTA measurement results of Li _2.2 B _0.2 C _0.8 O ₃ . As shown in FIG. 3, the point indicated by the arrow in the figure was the melting point, which was 696 ° C.

[Example 1]
LBCO particles, LiF particles and LiCl particles were mixed in a mortar. The molar ratio was LBCO: LiF: LiCl = 32: 32: 36. The DTA measurement of this eutectic mixture was performed. FIG. 4 shows the DTA measurement results of a eutectic mixture of Li _2.2 B _0.2 C _0.8 O ₃ , Li F and Li Cl. In this Example 1, it was clarified that the melting point was 445 ° C., and an extremely large decrease in melting point was obtained as compared with the LBCO particles alone.

[Example 2]
LBCO particles, LiF particles and LiCl particles were mixed in a mortar. The molar ratio was LBCO: LiF: LiCl = 41: 41: 18. The DTA measurement of this eutectic mixture was performed. FIG. 5 shows the DTA measurement results of a eutectic mixture of Li _2.2 B _0.2 C _0.8 O ₃ , Li F and Li Cl. In this Example 2, it was clarified that the melting point was 522 ° C., and a large decrease in melting point was obtained as compared with the LBCO particles alone.

(Electrical conductivity)
LBCO, LiF and LiCl were blended in the blending ratio of Example 1, and the electric conductivity of the eutectic mixture that was heat-solidified was measured. The eutectic mixture having the compounding ratio of Example 1 was prepared by uniaxial pressing to prepare pellets. The pellet was calcined at 500 ° C. to melt it, and then the temperature was lowered to room temperature to solidify it. Li was pressure-bonded to the front and back surfaces of the pellet to measure the bipolar impedance as an electrode. Using an AC impedance analyzer (FRA1255B manufactured by Solartron) in a constant temperature bath, obtain the resistance value from the arc of Nyquist plot under the conditions of frequency 0.01Hz to 1MHz and amplitude voltage 100mV, and calculate the electrical conductivity from this resistance value. did. FIG. 6 is a Nyquist plot of a eutectic mixture of Li _2.2 B _0.2 C _0.8 O ₃ , LiF and LiCl from Example 1. The bulk resistance calculated from the measurement result of FIG. 6 was 2.6 MΩ. Further, when the ionic conductivity was calculated from the electrode area of 0.53 cm ² and the pellet thickness of 0.22 cm, it was 1.7 × 10 ^-7 (S / cm).

(Manufacturing of all-solid-state lithium secondary battery)
LiCoO ₂ powder (hereinafter referred to as LCO, having an average particle size of 1.7 μm) as a positive electrode active material, LBCO powder, LiF powder, and LiCl powder were mixed in a mortar. The raw materials (LBCO, LiF, LiCl) of the positive electrode active material and the eutectic mixture were set to 73:27 in volume ratio. The composition of the eutectic mixture was LBCO: LiF: LiCl = 32: 32: 36 (same as in Example 1) in terms of molar ratio. A binder (EC vehicle manufactured by Nissin Kasei) was added to this powder and kneaded to prepare a paste containing LCO, LBCO, LiF and LiCl. This paste was printed on a solid electrolyte substrate by a screen printing machine and baked under heat treatment conditions of 500 ° C. and 1 h to form a positive electrode. As the solid electrolyte substrate, a plate-like body of Li _6.75 La ₃ Zr _1.75 Nb _0.25 O ₁₂ , which is a garnet-type oxide having lithium ion conductivity, was used. By depositing Li on the back surface of the solid electrolyte substrate on which the positive electrode was formed to form a negative electrode, an all-solid-state battery having the eutectic mixture of Example 1 on the positive electrode was produced.

(Battery evaluation)
As a battery evaluation, a cyclic voltammogram (CV) was measured. The CV measurement was performed using an electrochemical measurement system (148505B manufactured by Solartron) under the condition of a potential scanning speed of 0.1 mV / s. FIG. 7 is a cyclic voltammogram (CV) of an all-solid-state lithium secondary battery containing the eutectic mixture of Example 1 in the positive electrode active material layer. As shown in FIG. 7, a redox current is flowing in the CV, and the produced all-solid-state lithium secondary battery was produced by firing at a low temperature of 500 ° C., but it was found that the battery was charged and discharged. In the conventional all-solid-state lithium secondary battery in which the positive electrode active material layer was formed using only LBCO, the redox current did not flow at all because the LBCO did not melt when fired at 500 ° C.

The present invention is available in the field of the battery industry.

10 all-solid lithium secondary battery, 11 solid electrolyte layer, 12 positive electrode, 13 positive electrode active material layer, 14 current collector, 15 negative electrode, 16 negative electrode active material layer, 17 current collector, 21 positive electrode active material particles, 22 Crystal mixture.

Claims (8)

An electrode used in all-solid-state batteries
Active material particles that occlude and release lithium,
The above includes 1 or more of lithium fluoride and lithium chloride, and a lithium boron-containing oxide containing lithium, boron and the element A (1 or more of C, Al, Si, Ga, Ge, In and Sn). With the eutectic mixture that exists around the active material particles,
With a mixed active material layer ,
The eutectic mixture contains the lithium boron-containing oxide in the range of 15 mol% or more and 70 mol% or less, the lithium fluoride in the range of 15 mol% or more and 70 mol% or less, and the lithium chloride in the range of 15 mol% or more. It is contained in the range of 70 mol% or less,
The active material layer contains the active material particles in the range of 50% by volume or more and 85% by volume or less, and the eutectic mixture in the range of 15% by volume or more and 50% by volume or less.
electrode. The electrode according to claim 1, wherein the lithium boron-containing oxide is Li _{2 + x} B _x C _1-x O ₃ (in the formula, x satisfies 0 <x ≦ 1). The electrode according to claim 1 or 2 , wherein the active material particles are lithium composite oxide particles. The electrode according to any one of claims 1 to 3 and
A battery comprising a solid electrolyte layer adjacent to the electrode. Active material particles that absorb and release lithium, one or more of lithium fluoride and lithium chloride that are eutectic mixtures, and one of lithium, boron, and element A (C, Al, Si, Ga, Ge, In, and Sn). look including the active material layer forming step is attained for forming the active material layer and the lithium-boron-containing oxide having a eutectic mixture, a mixture comprising by firing at a temperature of 650 ° C. 400 ° C. or higher include higher) and,
In the active material layer preparation step, the lithium boron-containing oxide is in the range of 15 mol% or more and 70 mol% or less, the lithium fluoride is in the range of 15 mol% or more and 70 mol% or less, and the chloride is added to the whole eutectic mixture. Lithium is blended in the range of 15 mol% or more and 70 mol% or less, the active material particles are blended in the range of 50% by volume or more and 85% by volume or less, and the raw material to be the eutectic mixture is blended in the range of 15% by volume or more and 50% by volume or less. To do,
Electrode manufacturing method. The method for producing an electrode according to claim 5 , wherein in the active material layer manufacturing step, lithium fluoride and lithium chloride are used and fired at a temperature of 540 ° C. or lower. According to claim 5 or 6 , in the step of preparing the active material layer, Li _{2 + x} B _x C _1-x O ₃ (where x satisfies 0 <x ≦ 1) is used as the lithium boron-containing oxide. The method for manufacturing an electrode according to the description. In the active material layer manufacturing step, lithium composite oxide particles are used as the active material particles.
The method for manufacturing an electrode according to any one of claims 5 to 7 .

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