JP2017157359A - Electrode, battery and method of manufacturing electrode - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare an active material layer having ion conductivity by lower-temperature solidification.SOLUTION: An all-solid type lithium secondary battery 10 comprises a positive electrode 12 having a positive electrode active material layer 13 in which positive electrode active material particles 21 capable of occluding and releasing lithium, and a eutectic mixture 22 around the active material particles 21 are mixed. The eutectic mixture includes: one or more of lithium fluoride and lithium chloride; and a lithium-and-boron-containing oxide including lithium, boron and an element A (one or more of C, Al, Si, Ga, Ge, In and Sn). The all-solid type lithium secondary battery may be arranged so that a negative electrode active material layer 16 of a negative electrode 15 has the eutectic mixture.SELECTED DRAWING: Figure 1

Description

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

Conventionally, this type of battery includes an all-solid-state secondary battery that includes 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, by solidifying the active material using Li ₃ BO ₃ or Li _2.358 Al _0.214 BO ₃ , the energy density can be further increased without using the gas phase method.

International Publication No. 2012/176805 Pamphlet

  However, in the battery manufacturing method 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 from the viewpoint of the manufacturing process of an all solid state battery, it has been demanded to lower the heating temperature.

  This invention is made | formed in view of such a subject, and it aims at providing the manufacturing method of the electrode, battery, and electrode which can be solidified at low temperature, having ion conductivity.

  As a result of diligent research to achieve the above-described object, the present inventors have found that, when a plurality of types of fluxes including lithium are used, it is possible to solidify at a lower temperature while having ionic conductivity. As a result, the present invention has been completed.

That is, the electrode of the present invention is
An electrode used in an all solid state battery,
Active material particles that occlude and release lithium;
One or more of lithium fluoride and lithium chloride, and a lithium boron-containing oxide containing lithium, boron, and element A (one or more of C, Al, Si, Ga, Ge, In, and Sn). A eutectic mixture present around the active material particles;
Active material layer in which is mixed.

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

The method for producing the electrode of the present invention comprises:
Active material particles that occlude and release lithium; one or more of lithium fluoride and lithium chloride that form a eutectic mixture; lithium, boron, and element A (1 of C, Al, Si, Ga, Ge, In, and Sn) And a lithium boron-containing oxide that is a eutectic mixture and is fired at a temperature of 400 ° C. to 650 ° C. to produce an active material layer.

  The electrode, battery, and electrode manufacturing method of the present invention can produce an active material layer by solidifying at a lower temperature while having ion conductivity. The reason why such an effect can be obtained is that, for example, the eutectic mixture has a melting point lower than that of the original material constituting the eutectic mixture. It is presumed that the active material can be solidified at a lower temperature while having properties.

FIG. 3 is an explanatory diagram showing an example of the structure of an all solid-state lithium secondary battery 10. Graph showing the relationship between the added amount and the melting point of LiX (X is halogen) to _{Li 2.2 B 0.2 C 0.8 O 3} . Li _2.2 B _0.2 C _0.8 O ₃ of DTA measurements. _{Li 2.2 B 0.2 C 0.8 O 3} , DTA measurement results of the eutectic mixture of LiF and LiCl. _{Li 2.2 B 0.2 C 0.8 O 3} , DTA measurement results of the eutectic mixture of LiF and LiCl. Nyquist plot of eutectic mixture of Li _2.2 B _0.2 C _0.8 O ₃ , LiF and LiCl. Cyclic voltammogram of an all-solid lithium secondary battery containing a 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 produced on a base material of a solid electrolyte layer constituting the all solid state battery. Further, this electrode may be a positive electrode using a positive electrode active material as active material particles, or a negative electrode using a negative electrode active material as active material particles. The electrode may include a current collector adjacent to the active material layer. This 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 absorbs and releases lithium, and may be a positive electrode active material. Examples of the positive electrode active material include a compound containing lithium and a transition metal element. Examples thereof include an oxide containing lithium and a transition metal element, and a phosphate compound containing lithium and a transition metal element. Specifically, a lithium manganese composite oxide whose basic composition formula is Li _(1-x) MnO ₂ (0 <x <1, etc., the same shall apply hereinafter), Li _(1-x) Mn ₂ O _4, etc., basic composition Lithium cobalt composite oxide having a formula of Li _(1-x) CoO ₂ or the like, lithium nickel composite oxide having a basic composition formula of Li _(1-x) NiO ₂ or the like, and a basic composition formula of Li _(1-x) Lithium nickel cobalt manganese composite oxide such as Ni _1/3 Co _1/3 Mn _1/3 O _2, lithium vanadium composite oxide whose basic composition formula is LiV ₂ O ₃ , transition metal such as V ₂ O ₅ An oxide etc. are mentioned. Also the like phosphoric acid compounds such as LiFePO ₄ basic formula. Of these, lithium transition metal composite oxides such as LiCoO ₂ , LiNiO ₂ , and LiMnO ₂ are more preferable. Note that the chemical formulas illustrated are not intended to be limited to those of the stoichiometric composition, and some elements may be deficient or excessive, and some elements may be substituted with other elements. (The same shall apply hereinafter).

Alternatively, the active material may be a negative electrode active material. Examples of the negative electrode active material include an oxide containing lithium and a transition metal element. Specific examples 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 at least one of lithium fluoride and lithium chloride, and lithium, boron, and element A (one or more of C, Al, Si, Ga, Ge, In, and Sn). And including. This eutectic mixture is a dense body that fills 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 that have a low lithium ion conductivity but a high effect of reducing 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 melting temperature lower than that of the active material particles, and has lithium ion conductivity. The element A may substitute a part of lithium in Li ₃ BO ₃ , may substitute a part of boron, or may substitute both. When both are substituted, they may be substituted with the same kind of elements or with 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. In the formula, t satisfies 0 ≦ t <1, u is the average valence of (B _1−t , A _t ), and s, u, v satisfy the relational expression of 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 (where x satisfies 0 <x ≦ 1). Thus, what substituted boron with carbon is suitable, since an ionic conductivity increases. x preferably satisfies 0.1 ≦ x ≦ 0.6, and more preferably satisfies 0.2 ≦ x ≦ 0.4. This is because the ionic conductivity becomes larger.

  The eutectic mixture preferably contains the lithium boron-containing oxide in a 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 included in the eutectic mixture more in consideration of the lithium ion conductivity, more preferably 30 mol% or more, and 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 firing temperature, more preferably 60 mol% or less, and even more preferably 50 mol% or less. Moreover, it is preferable that lithium fluoride is contained in the eutectic mixture in the range of 15 mol% or more and 70 mol% or less with respect to the whole eutectic mixture. Lithium fluoride is preferably contained in the eutectic mixture in consideration of a decrease in the firing temperature, more preferably 30 mol% or more, and still more preferably 40 mol% or more. Further, in consideration of lithium ion conductivity, lithium fluoride is preferably contained in the eutectic mixture in a smaller amount, more preferably 60 mol% or less, and still more preferably 50 mol% or less. Moreover, it is preferable that lithium chloride is contained in the eutectic mixture in the range of 15 mol% or more and 70 mol% or less with respect to the entire eutectic mixture. Lithium chloride is preferably included in the eutectic mixture in consideration of a decrease in the firing temperature, more preferably 30 mol% or more, and even more preferably 40 mol% or more. Further, in consideration of lithium ion conductivity, lithium chloride is preferably contained in the eutectic mixture in a smaller amount, more preferably 60 mol% or less, and still more preferably 50 mol% or less. The eutectic mixture necessarily includes a lithium boron-containing oxide, but may further include both lithium fluoride and lithium chloride. This is preferable because the firing temperature of the active material layer can be further lowered. At this time, the lithium boron-containing oxide is in the range of 20 mol% to 40 mol%, the lithium fluoride is in the range of 20 mol% to 40 mol%, and the lithium chloride is in the range of 20 mol% to 40 mol% with respect to the entire eutectic mixture. It is preferable to include in a range.

  The active material layer may contain active material particles in the range of 50% by volume to 85% by volume and the eutectic mixture in the range of 15% by volume to 50% by volume. 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, and even more preferably 75% by volume or more. At this time, a eutectic mixture is 40 volume% or less and 25 volume% or less, respectively. Moreover, it is preferable that more eutectic mixture is contained in an active material layer from a viewpoint of the sticking property of active material particle, 30 volume% or more is more preferable, and 40 volume% or more is still more preferable. At this time, the active material particles are 70% by volume or less and 60% by volume or less, respectively.

  Current collectors include aluminum, titanium, stainless steel, nickel, iron, calcined carbon, conductive polymer, conductive glass, and aluminum, copper, etc. for the purpose of improving adhesion, conductivity, and oxidation resistance. A surface treated with carbon, nickel, titanium, silver or the like can be used. For these, the surface can be oxidized. The current collector may be formed on the active material layer by printing or vapor deposition. Examples of the shape of the current collector include foil, film, sheet, net, punched or expanded, lath, porous, foam, and formed fiber group.

(battery)
The battery of the present invention includes the electrode described above and a solid electrolyte layer adjacent to the electrode. This battery may be an all-solid lithium secondary battery. In this battery, an electrode including an active material layer containing active material particles and a eutectic mixture may be provided as a positive electrode, a negative electrode, or a positive electrode and a negative electrode. When the above-mentioned electrode is 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 electrode described above, and the negative electrode may be Li metal or Li alloy.

The solid electrolyte layer is made of a solid electrolyte and, for example, has a higher lithium ion conductivity than 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 is, for example, a basic composition Li _{5 + x} La ₃ Zr _x M _2−x O ₁₂ (wherein M is Sc, Ti, V, Y, Nb, Hf, Ta, Al). One or more elements selected from the group consisting of Si, Ga and Ge, x may be represented by 1.4 ≦ x <2). In such a thing, lithium ion conductivity is high and the lithium ion conductivity of an electrode can be raised more. Moreover, if x satisfies 1.6 ≦ x ≦ 1.95, the conductivity is higher, which is preferable. Furthermore, if x satisfies 1.65 ≦ x ≦ 1.9, the conductivity is almost maximized, which is more preferable. Specific examples include Li _6.75 La ₃ Zr _1.75 Nb _0.25 O ₁₂ . The 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 solid electrolytes include glass ceramics, Li nitrides, halides, and oxyacid salts. 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 change in quality or produce a reaction product. For example, when an electrode or a solid electrolyte is subjected to XRD measurement using CuKα rays, it is preferable that a peak of a reaction product between the lithium boron-containing oxide, the active material, and the solid electrolyte is not confirmed. If it is such, generation | occurrence | production of the deteriorated layer and 3rd phase which reduce the electrical conductivity of lithium ion is suppressed, and it is preferable.

  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 connected in series may be applied to a large-sized battery used for an electric vehicle or the like.

  Although the structure of this battery is not particularly limited, for example, the structure shown in FIG. FIG. 1 is an explanatory diagram showing an example of the structure of an all solid-state lithium secondary battery 10. This all solid-state lithium secondary battery includes 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. 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 includes composite oxide active material particles 21 and a eutectic mixture 22 present around the active material particles 21.

(Method for manufacturing electrode)
The manufacturing method of the electrode of this invention includes the active material layer preparation process which produces an active material layer. In this step, active material particles that occlude and release lithium, one or more of lithium fluoride and lithium chloride that form a eutectic mixture, lithium, boron, and element A (C, Al, Si, Ga, Ge, In, and And a lithium boron-containing oxide that is a eutectic mixture containing at least one of Sn) and 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 the lithium boron-containing oxide are included, the firing temperature can be further lowered. As the active material particles and the lithium boron-containing oxide, those described above can be used. In this step, a solvent or a binder may be added to the raw material of the active material layer so as to form a paste or clay, and may be formed on a solid electrolyte substrate or current collector.

  In this step, in addition to the lithium boron-containing oxide, lithium fluoride and lithium chloride may be used and fired at a temperature of 540 ° C. or lower. What is necessary is just to mix | blend lithium boron containing oxide, lithium fluoride, and lithium chloride with the compounding ratio in the electrode mentioned above. For example, it is preferable to mix each of lithium boron-containing oxide, lithium fluoride, and lithium chloride in the range of 20 mol% to 40 mol%, and in the range of 25 mol% to 36 mol% with respect to the entire eutectic mixture. It is more preferable to mix. In such a range, the firing temperature can be 500 ° C. or lower, and more preferably 450 ° C. or lower. Moreover, what is necessary is just to mix | blend the active material particle and the raw material of a eutectic mixture with the compounding ratio in the electrode mentioned above. The firing temperature may be, for example, a temperature higher than the melting point by measuring the melting point of the eutectic mixture by DTA measurement. The DTA measurement may be performed, for example, using alumina as a reference, a sample amount of 10 mg, and a temperature rising rate of 10 ° C./min in the atmosphere.

  According to the electrode, battery, and electrode manufacturing method described above, the active material layer can be produced by solidifying at a lower temperature while having ionic conductivity. The reason why such an effect can be obtained is that, for example, the eutectic mixture has a melting point lower than that of the original material constituting the eutectic mixture. It is presumed that the active material can be solidified at a lower temperature while having properties.

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

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

  Below, the example which produced the electrode and battery of this invention concretely is demonstrated. In addition, this invention is not limited to the following Examples at all, and it cannot be overemphasized that various aspects may be implemented as long as it belongs to the technical scope of this invention.

[Examination of flux]
Li _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 lowering the melting point. Using (LiX), the relationship between the addition amount (mol%) and the melting point was examined. Any one of LiF, LiCl, LiBr and LiI was added to LBCO at a predetermined molar ratio and mixed in a mortar, and the melting point was measured with a DTA measuring device (Thermo plus Thermo plus EVO2). The DTA measurement was performed using alumina as a reference, a sample amount of 10 mg, and a temperature increase rate of 10 ° C./min in the air. FIG. 2 is a graph showing the relationship between the amount of LiX (X is halogen) added to Li _2.2 B _0.2 C _0.8 O ₃ and the melting point. Table 1 summarizes the types, addition amounts and melting points of lithium halides. When LBCO and LiF were mixed, the melting point dropped to about 640 ° C. when 50 to 70 mol% of LiF was included. Further, when LBCO and LiCl were mixed, the melting point dropped 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 was not lowered so much as that of the single substance, and the temperature was 500 ° C. or higher. When LBCO and LiI were mixed, the melting point decreased to 420 ° C. when LiI was contained in an amount of 60 to 90 mol%. However, the LiI system was not suitable because Li ₅ IO _{6 in the} solid phase was produced. Therefore, it was found that LiF and LiCl are effective as fluxes that lower the melting point.

[Comparative Example 1]
DTA measurement was performed using only LBCO particles, and the melting point was determined. FIG. 3 shows the DTA measurement result 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 is 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. DTA measurement of this eutectic mixture was performed. FIG. 4 is a DTA measurement result of a eutectic mixture of Li _2.2 B _0.2 C _0.8 O ₃ , LiF and LiCl. In Example 1, the melting point was 445 ° C., and it became clear that an extremely large melting point drop 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. DTA measurement of this eutectic mixture was performed. FIG. 5 shows a DTA measurement result of a eutectic mixture of Li _2.2 B _0.2 C _0.8 O ₃ , LiF and LiCl. In Example 2, the melting point was 522 ° C., and it became clear that a large drop in melting point was obtained as compared with LBCO particles alone.

(Electrical conductivity)
The electrical conductivity of the eutectic mixture obtained by blending LBCO, LiF and LiCl at the blending ratio of Example 1 and solidifying by heating was measured. Pellets were produced from the eutectic mixture having the blending ratio of Example 1 by uniaxial pressing. The pellet was fired at 500 ° C. and melted, and then the temperature was lowered to room temperature to solidify. Li-electrode was pressure-bonded to the front and back surfaces of the pellet, and bipolar impedance measurement was performed as an electrode. Using a AC impedance analyzer (Solartron FRA1255B) in a thermostatic chamber, the resistance value is calculated from the arc of the Nyquist plot under the conditions of frequency 0.01 Hz to 1 MHz and amplitude voltage 100 mV, and the electrical conductivity is calculated from this resistance value. did. 6 is a Nyquist plot of the eutectic mixture of Li _2.2 B _0.2 C _0.8 O ₃ , LiF and LiCl of Example 1. FIG. The bulk resistance calculated from the measurement result of FIG. 6 was 2.6 MΩ. Further, when the ionic conductivity was determined 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).

(Preparation of all-solid lithium secondary battery)
LiCoO ₂ powder (hereinafter referred to as LCO; average particle size is 1.7 μm) as a positive electrode active material, LBCO powder, LiF powder and LiCl powder were mixed in a mortar. The material for the positive electrode active material and the eutectic mixture (LBCO, LiF, LiCl) was 73:27 by volume ratio. The composition of the eutectic mixture was LBCO: LiF: LiCl = 32: 32: 36 (same as in Example 1) in molar ratio. A binder (LCO, LBCO, LiF and LiCl) was prepared by adding a binder (EC vehicle manufactured by Nisshin Kasei) to this powder and kneading. This paste was printed on a solid electrolyte substrate by a screen printer and baked under heat treatment conditions of 500 ° C. for 1 hour to form a positive electrode. As the solid electrolyte substrate, a plate 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 this positive electrode was formed to form a negative electrode, an all-solid battery comprising the eutectic mixture of Example 1 as the positive electrode was produced.

(Battery evaluation)
As a battery evaluation, a cyclic voltammogram (CV) was measured. CV measurement was performed using an electrochemical measurement system (148055B 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 lithium secondary battery including the eutectic mixture of Example 1 in the positive electrode active material layer. As shown in FIG. 7, an oxidation-reduction current flows in CV, and the produced all-solid lithium secondary battery was produced by low-temperature firing at 500 ° C., but was found to be charged and discharged. In the conventional all-solid lithium secondary battery in which the positive electrode active material layer was formed using only LBCO, no oxidation-reduction current flowed because LBCO did not melt by firing at 500 ° C.

  The present invention can be used in the field of the battery industry.

  DESCRIPTION OF SYMBOLS 10 All-solid-state 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 particle, 22 Crystal mixture.

Claims (12)

An electrode used in an all solid state battery,
Active material particles that occlude and release lithium;
One or more of lithium fluoride and lithium chloride, and a lithium boron-containing oxide containing lithium, boron, and element A (one or more of C, Al, Si, Ga, Ge, In, and Sn). A eutectic mixture present around the active material particles;
An electrode comprising an active material layer in which is mixed.   The eutectic mixture includes the lithium boron-containing oxide in a range of 15 mol% to 70 mol%, the lithium fluoride is included in a range of 15 mol% to 70 mol%, and the lithium chloride is 15 mol% or more. The electrode according to claim 1, which is contained in a range of 70 mol% or less.   The active material layer includes the active material particles in a range of 50% by volume to 85% by volume and the eutectic mixture in a range of 15% by volume to 50% by volume. Electrode. The lithium boron-containing oxide according to any one of claims 1 to 3, wherein Li _{2 + x} B _x C _1-x O ₃ (wherein x satisfies 0 <x ≦ 1). electrode.   The electrode according to claim 1, wherein the active material particles are lithium composite oxide particles. The electrode according to any one of claims 1 to 5,
A battery comprising: a solid electrolyte layer adjacent to the electrode.   Active material particles that occlude and release lithium; one or more of lithium fluoride and lithium chloride that form a eutectic mixture; lithium, boron, and element A (1 of C, Al, Si, Ga, Ge, In, and Sn) An active material layer forming step of baking an active material layer at a temperature of 400 ° C. or higher and 650 ° C. or lower to form an active material layer. Production method.   The method for manufacturing an electrode according to claim 7, wherein in the active material layer manufacturing step, firing is performed at a temperature of 540 ° C. or lower using lithium fluoride and lithium chloride.   In the active material layer preparation step, the lithium boron-containing oxide is in the range of 15 mol% to 70 mol%, the lithium fluoride is in the range of 15 mol% to 70 mol%, and the chloride is based on the entire eutectic mixture. The manufacturing method of the electrode of Claim 8 which mix | blends lithium in 15 mol% or more and 70 mol% or less.   The said active material layer preparation process mix | blends the said active material particle in the range of 50 volume% or more and 85 volume% or less, and the raw material used as the said eutectic mixture in the range of 15 volume% or more and 50 volume% or less. 10. The method for producing an electrode according to any one of 9 above. The active material layer manufacturing step uses Li _{2 + x} B _x C _1-x O ₃ (wherein x satisfies 0 <x ≦ 1) as the lithium boron-containing oxide. The manufacturing method of the electrode of any one.   The method for producing an electrode according to claim 7, wherein in the active material layer manufacturing step, lithium composite oxide particles are used as the active material particles.

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