KR20120015418A - Solid lithium ion secondary battery and electrode usable with same - Google Patents

Abstract

PURPOSE: A solid lithium ion secondary battery is provided to reduce the amount of a solid electrolyte in electrode, and to increase the density of active material in electrode, thereby increasing the capacity per unit volume, conducting an electrode reaction more uniformly. CONSTITUTION: A solid lithium ion secondary battery(30) comprises: a negative electrode containing negative electrode material which is able to do intercalation and de-intercalation of lithium; a positive electrode containing positive electrode material which is able to do intercalation and de-intercalation of lithium; and a solid electrolyte layer installed between the positive electrode and the negative electrode. Among the positive electrode and the negative electrode, at least one electrode comprises the lithium salt of a cyclic imide. The content of the cyclic imide is 1-40 weight%.

Description

Solid lithium ion secondary battery and electrode usable with same

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a solid lithium ion secondary battery suitable for use as a vehicle battery or a large storage battery such as an electric vehicle, a hybrid electric vehicle, and an electrode that can be used therein.

Lithium ion secondary batteries have increased demand in various fields such as electric vehicles, hybrid electric vehicles, and large storage batteries because of their high electrochemical capacity, high operating potential, and excellent charge / discharge cycle characteristics. As such applications are expanded, there has been a demand for improved safety and high performance of lithium ion secondary batteries. However, conventional lithium ion secondary batteries, in which a nonaqueous electrolyte containing lithium salt dissolved in an organic solvent as an electrolyte, are highly likely to ignite at about 150 ° C., which raises the question of safety. For this reason, recently, solid lithium ion secondary batteries using a solid electrolyte having lithium ion conductivity for the purpose of improving safety have been attracting attention.

In such a solid lithium ion secondary battery, a solid electrolyte is added to an electrode in addition to an active material in order to secure a migration path of lithium ion in an electrode (see Japanese Patent Application Laid-Open No. 2010-146936).

However, since the solid electrolyte composed of Li ₂ S-P ₂ S ₅ and the like which is widely used is, for example, in the form of particles having a particle size of about 0.1 to 20 µm and a large volume, the amount of the active material added to the electrode is increased by the amount thereof. This decreases, causing the problem of a decrease in volume per volume.

In addition, in order for the battery reaction to proceed smoothly, it is necessary for the electrodes to be in a uniform state.However, when a solid electrolyte consisting of sulfides and oxides is added to the electrode, it is difficult to uniformly disperse the solid electrolyte in the solvent or binder. It is difficult to uniformly spread the electrode mixture on the whole. Also, depending on the type of solvent or binder used to disperse the solid electrolyte, the conductivity may be reduced.

Accordingly, one object of the present invention is to provide a solid lithium ion secondary battery having high safety and high capacity in view of the above phenomenon.

Another object of the present invention is to provide an electrode for a solid lithium secondary battery, which is useful for producing a high-solid-state lithium lithium ion secondary battery having high safety and high capacity.

One aspect of the present invention to achieve the above object,

Lithium lithium ion secondary with a negative electrode containing a negative electrode active material capable of inserting and deinserting lithium, a positive electrode containing a positive electrode active material capable of inserting and deinserting lithium, and a solid electrolyte layer disposed between the positive electrode and the negative electrode As a battery,

Provided is a solid lithium lithium ion secondary battery in which at least one of the anode and the cathode contains a lithium salt of a cyclic imide.

The content of lithium salt of the cyclic cyclic imide may be 1 to 40% by weight in at least one of the anode and the cathode.

Lithium salts of the cyclic imides include cyclo-tetrafluoroethane-1,2-bis (sulfonyl) imide lithium ((CF ₂ SO ₂ ) ₂ NLi) and cyclo-hexafluoropropane-1,3-bis (Sulfonyl) imide lithium (CF ₂ (CF ₂ SO ₂ ) ₂ NLi)) may be at least one selected from.

The solid electrolyte layer may contain a solid electrolyte having a lithium ion conductivity of 10 ⁻⁴ S / cm or more.

In at least one of the anode and the cathode, the lithium salt of the 'cyclic' imide may be present in a state of coating the surface of the active material of the electrode.

The solid electrolyte is _{Li 3 N, LISICON (Lithium Super} Ionic Conductor), LIPON (Li 3 + y PO 4-x N x), Thio-LISICON (Li 3 .25 Ge 0 .25 P 0 .75 S 4), Li ₂ S, Li ₂ SP ₂ S ₅ , Li ₂ S-SiS ₂ , Li ₂ S-GeS ₂ , Li ₂ SB ₂ S ₅ , Li ₂ S-Al ₂ S ₅ , and Li ₂ O-Al ₂ O ₃ At least one selected from the group consisting of -TiO ₂ -P ₂ O ₅ (LATP), polyethylene oxide, and boric acid ester polymer.

The positive electrode active material may be an oxide or sulfide of a transition metal selected from Mn, Co, Ni, Fe, and Al.

The negative electrode active material is lithium, indium, tin, aluminum, silicon or alloys thereof; Transition metal oxides; Or carbonaceous material.

Another aspect of the present invention to achieve the above object,

An electrode for a solid lithium secondary battery containing an electrode active material capable of inserting and deinserting lithium,

The said electrode provides the electrode for solid lithium secondary batteries containing the lithium salt of a cyclic imide.

The content of lithium salts of the 'cyclic' imide in the 'electrode' may be 1 to 40% by weight.

Lithium salts of the cyclic imides are cyclo-tetrafluoroethane-1,2-bis (sulfonyl) imide lithium ((CF ₂ SO ₂ ) ₂ NLi) and cyclo-hexafluoropropane-1,3-bis (Sulfonyl) imide lithium (CF ₂ (CF ₂ SO ₂ ) ₂ NLi)) may be at least one selected from.

The lithium salt of the 'cyclic' imide in the 'electrode' may be present in a 'coated' surface of the active material of the electrode.

In other words, the solid lithium ion secondary battery according to the present invention comprises a positive electrode, a negative electrode, and a solid electrolyte layer disposed between the positive electrode and the negative electrode, and the positive electrode and / or the negative electrode contain a lithium salt of a cyclic imide. . In the present invention, both the anode and the cathode may both contain lithium salts of cyclic imides, but only one electrode may contain lithium salts of cyclic imides.

According to the present invention, by adding a lithium salt of a cyclic imide having lithium ion conductivity to the electrode, the amount of addition of the solid electrolyte to the electrode can be reduced by that amount. Since the lithium salt of the cyclic imide is not as large as the solid electrolyte in the form of particulates, when the lithium salt of the cyclic imide is added to the slurry for the electrode mixture instead of the solid electrolyte, the lithium of the cyclic imide is added to the surface of the active material. The salt can be coated thinly, so that a small amount of lithium ion conductivity can be obtained in comparison with the solid electrolyte, and the lithium ion conductor can be more uniformly dispersed in the electrode. For this reason, according to the present invention, the density of the active material in the electrode can be increased, so that the capacity per volume of the solid lithium ion secondary battery can be increased.

In addition, the lithium salt of the cyclic imide also exhibits excellent contactability with the active material and excellent coating properties when added to the electrode mixture, so that the slurry-like electrode mixture, which contains the lithium salt of the cyclic imide, can be applied to the current collector in a thin manner to form a sheet. have.

The amount of lithium salt of the cyclic cyclic imide in the positive electrode and / or the negative electrode may be 1 to 40% by weight.

The lithium salt of the cyclic imide is, for example, cyclo-tetrafluoroethane-1,2-bis (sulfonyl) imide lithium ((CF ₂ SO ₂ ) ₂ NLi), cyclo-hexafluoropropane- 1,3-bis (sulfonyl) imide lithium (CF ₂ (CF ₂ SO ₂ ) ₂ NLi)) and the like.

As the solid electrolyte contained in the solid electrolyte layer, one having a lithium ion conductivity of 10 ⁻⁴ S / cm or more can be suitably used.

According to the present invention, the amount of solid electrolyte in the electrode can be reduced, the density of active materials in the electrode can be increased, the capacity per volume of the solid lithium ion secondary battery can be increased, and the electrode reaction can be carried out more uniformly. For this reason, according to the present invention, it is possible to obtain a solid lithium lithium secondary battery having high safety and high capacity.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows the electrode of a prior art example (a) and this invention (b).
FIG. 2 is a schematic diagram showing the configuration of a solid lithium ion secondary battery prepared in Examples. FIG.

The following describes the embodiments of the solid lithium ion secondary battery according to the present invention.

The solid lithium lithium ion secondary battery according to the present embodiment is composed of a positive electrode, a negative electrode, and a solid electrolyte layer sandwiched between these electrodes.

At least one of the anodes and the cathode contains a lithium salt of the cyclic imide.

The lithium salt of the cyclic imide may be, for example, a compound represented by the following formulas (1) to (4). The lithium salt of such cyclic cyclic imide may be used alone or two or more kinds thereof may be used in combination.

Among the lithium salts of such cyclic cyclic imides, 6 represented by cyclo-tetrafluoroethane-1,2-bis (sulfonyl) imide lithium and (2) having a 5-membered ring structure represented by formula (1). A cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide lithium having a toroidal structure can be suitably used. Such a lithium salt of the cyclic imide can exhibit stable lithium ion conductivity even under a high voltage environment near 4V.

In addition, polyimide may be used as a binder in a conventional lithium ion secondary battery in which a nonaqueous electrolyte is used, but a lithium salt of a cyclic imide is used as a binder of a conventional lithium ion secondary battery in which a nonaqueous electrolyte is used. The lithium salt of such cyclic cyclic imide is dissolved in an organic solvent. Therefore, the lithium salt of the cyclic imide used in the present invention cannot be used as a binder of a conventional lithium ion secondary battery in which a nonaqueous electrolyte is used.

Fig. 1A shows a conventional electrode 10 in which only a solid electrolyte is added as a lithium ion conductor. In this electrode 10, since a particulate and large volume of solid electrolyte is added, the density of the active material in the electrode decreases, and thus the solid lithium ion secondary battery obtained has a low capacity per volume.

On the other hand, in the electrode of the present invention, which uses a lithium salt of a cyclic imide as a lithium ion conductor, the lithium salt of a cyclic imide exists in a thinly coated surface of the active material, as shown in Fig. 1 (b). By adding a lithium salt of a cyclic imide to the electrode, the amount of solid electrolyte in the electrode, which is about 40% by weight, can be reduced to about 5 to 10% by weight. You can also set the amount of addition to zero. For this reason, according to this embodiment, the density of the active material in an electrode can be improved, and the solid lithium ion secondary battery with a large capacity per volume can be obtained. In addition, the coating layer based on the lithium salt of a cyclic imide may have a nonuniform thickness, and may be dotted.

In addition, in the embodiment shown in Fig. 1, as the active material, one consisting of secondary particles (particle size: about 0.1 to 1 μm), which is agglomerated, is used, and as a solid electrolyte, particle size is about 0.1 to about 20 μm is used.

The lithium content of the lithium salt of the cyclic imide in the positive electrode or negative electrode may be 1 to 40% by weight, for example, 5 to 20% by weight or 5 to 10% by weight. If the content of lithium salt of the cyclic imide is less than 1% by weight, the amount of solid electrolyte added cannot be sufficiently reduced, and the capacity per volume may be insufficient. On the other hand, if the content of lithium salt of the cyclic imide exceeds 40% by weight, the rate characteristic may deteriorate.

The positive electrode and the negative electrode each contain active substances in addition to the lithium salt of the cyclic imide.

The positive electrode active material is not particularly limited as long as lithium can be inserted and removed, and may be, for example, an oxide or a sulfide including a transition metal such as Mn, Co, Ni, Fe, and Al. A specific example of such a positive electrode active material is _{LiMn 2 O 4, LiCoO 2,} LiNiO 2, LiFeO 2, LiNi 1/3 Co 1/3 Mn 1/3 O 2, LiNi 0 .8 Co 0 .2 O 2, LiNi 0. _8, and the like _{Co 0 .15 Al 0 .05 O 2} . These cathode active materials may be used alone or in combination of two or more thereof.

The negative electrode active material is not particularly limited as long as the alloy can be alloyed with lithium or the lithium can be inserted and removed, and examples thereof include metals such as lithium, indium, tin, aluminum, silicon, and alloys thereof; Transition metal oxides such as _{Li 4/3 Ti 5/3} O 4, SnO; Artificial Graphite, Graphite Carbon Fiber, Resin Calcined Carbon, Pyrolysis Vapor Growth Carbon, Coke, Mesocarbon Microbeads (MCMB), Furfuryl Alcohol Resin Calcined Carbon, Polyacene, Pitch Carbon Fiber, Vapor Growth Carbon Fiber, Natural Graphite, Egg Carbon materials such as graphitizable carbon; and the like. These negative electrode active materials may be used alone, or two or more thereof may be used in combination.

The positive electrode and the negative electrode may be appropriately selected and blended into a powder made of the above-described active material, for example, an additive such as a conductive agent, a binder, a filler, a dispersant, and an ion conductive agent.

The conductive agent may be, for example, graphite, carbon black, acetylene black, Ketjen black, carbon fiber, metal powder, or the like. The binder may be, for example, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, or the like. In addition, the positive electrode and the negative electrode may be blended with a solid electrolyte, which will be described later, as necessary.

In order to manufacture a positive electrode or a negative electrode, for example, the above-described active material, a lithium salt of a cyclic imide, and a mixture of various additives are prepared and consolidated into pellets by a hydraulic press into a positive electrode or a negative electrode, or The above-described active material, the above-described lithium salt of the cyclic imides, and various additives are added to a solvent such as water or an organic solvent to form a slurry or paste, and the resulting slurry or 스트 paste is used in a current collector phase using a doctor 상 blade method or the like. Epoxy coating, drying, rolling and consolidation with a roll or the like to form an anode or a cathode can be used.

The current collector may be, for example, a plate or sheet made of indium, copper, magnesium, stainless steel, titanium, iron, cobalt, nickel, zinc, aluminum, germanium, lithium, an alloy thereof, or the like.

In addition, when using a metal or a group alloy as a cathode active material, a metal sheet may be used as a cathode as it is.

The solid electrolyte layer contains a lithium ion conductor composed of an inorganic compound, an organic compound, or a complex thereof as a solid electrolyte.

Without specific limitation inorganic hwahapmulneun, for _{example, Li 3 N, LISICON, LIPON} (Li 3 + y PO 4-x N x), Thio-LISICON (Li 3 .25 Ge 0 .25 P 0 .75 S 4) , Li ₂ S alone, Li ₂ SP ₂ S ₅ , Li ₂ S-SiS ₂ , Li ₂ S-GeS ₂ , Li ₂ SB ₂ S ₅ , Li ₂ S-Al ₂ S ₅ , Li ₂ O-Al ₂ S ₅ , Li ₂ O—Al ₂ O ₃ —TiO ₂ —P ₂ O ₅ (LATP), and the like. Such inorganic compounds may have structures such as crystals, amorphous, glass, glass ceramics, and the like.

The organic compound is not particularly limited, and may be, for example, polyethylene oxide (PEO), boric acid ester polymer, or the like.

The inorganic / organic composite is not particularly limited, and may be, for example, a composite of Li ₂ SP ₂ S ₅ , which is an inorganic solid electrolyte, and polyethylene oxide, which is an organic solid electrolyte.

In the present embodiment, among such solid electrolytes, the lithium ion conductivity is preferably 10 ⁻⁴ S / cm or more, and the solid electrolyte having such lithium ion conductivity is, for example, amorphous Li ₂ SP ₂ S _5. And the like.

The solid lithium ion secondary battery according to the present embodiment can be produced by laminating and pressing such anodes, solid electrolyte layers, and cathodes, or laminating and pressing these materials (mixtures).

Example

Although the present invention will be described in more detail with reference to the following examples, the present invention is not limited to these examples.

(Example 1)

The positive electrode active material of _{LiNi 0 .8 Co 0 .15 Al 0} .05 O 2, a sulfide solid electrolyte of _{Li 2 SP 2 S 5 (80-20mol} %), CF 2 of 6-membered ring imide compounds (CF ₂ SO _{2) 2} NLi and VGCF (phase-grown carbon fiber) serving as a conductive agent were mixed at a weight ratio of 80: 5: 10: 5, dispersed in toluene to prepare a slurry. After apply | coating this slurry on the SUS sheet using a doctor blade, it dried at 110 degreeC and used as a positive electrode. Similarly, using a graphite as a negative electrode active material, a slurry was prepared in the same manner as the positive electrode, and coated on a SUS sheet to form a negative electrode.

Each of the above electrodes was punched to Φ 13 mm, sandwiched Li ₂ SP ₂ S ₅ (80-20 mol%) as a sulfide solid electrolyte between the positive electrode and the negative electrode, and pressed at 4 t / cm ² , followed by a 3N · m torque wrench. Was applied to the cell, and a solid lithium ion secondary battery 30 having the configuration shown in FIG. 2 was produced. In addition, the lithium ion conductivity of Li ₂ SP ₂ S ₅ (80-20 mol%) used as the solid electrolyte in the present example is 3 × 10 ⁻⁴ S / cm.

(Example 2)

A solid lithium ion secondary battery was produced in the same manner as in Example 1 except that the composition of the positive electrode and the negative electrode was set to a weight ratio of 60: 25: 10: 5.

(Example 3)

A solid lithium ion secondary battery was produced in the same manner as in Example 1 except that the composition of the anode electrode was set at a weight ratio of 70: 10: 15: 5 and the composition of the cathode electrode was set at a weight ratio of 60: 25: 10: 5.

(Example 4)

A solid lithium ion secondary battery was produced in the same manner as in Example 1 except that the composition of the positive electrode and the negative electrode was set to a weight ratio of 60: 0: 35: 5 and no solid electrolyte was added to the electrode.

(Example 5)

A solid lithium ion secondary battery was produced in the same manner as in Example 1 except that LiCoO ₂ was used as the positive electrode active material and the composition of the positive electrode and the negative electrode was changed to a weight ratio of 60: 25: 10: 5.

(Example 6)

A solid lithium ion secondary battery was produced in the same manner as in Example 1 except that LiMn ₂ O ₄ was used as the positive electrode active material and the composition of the positive electrode and the negative electrode was set to a weight ratio of 60: 25: 10: 5.

(Example 7)

A solid lithium ion secondary battery was produced in the same manner as in Example 1 except that (CF ₂ SO ₂ ) ₂ NLi having a 5-membered ring structure was used as the lithium salt of the cyclic imide.

(Comparative Example 1)

A solid lithium ion secondary battery was prepared in the same manner as in Example 1 except that the electrode was prepared without adding lithium salts of solid electrolyte and cyclic imide with the composition of the anode and cathode electrodes at a weight ratio of 80: 0: 0: 20. Made.

(Comparative Example 2)

A high lithium lithium ion secondary battery was produced in the same manner as in Example 1 except that the lithium salt of the cyclic imide was not added to the electrode with the composition of the positive electrode and the negative electrode as the weight ratio 80: 15: 0: 5.

(Comparative Example 3)

Solid lithium was used in the same manner as in Example 1, except that LiCoO ₂ was used as the positive electrode active material, and the composition of the positive electrode and the negative electrode was weight ratio 60: 35: 0: 5, and the lithium salt of the cyclic imide was not added to the electrode. An ion secondary battery was produced.

(Comparative Example 4)

Solid lithium was used in the same manner as in Example 1 except that LiCoO ₂ was used as the positive electrode active material, and the composition of the positive electrode and the negative electrode was weight ratio 80: 15: 0: 5, and the lithium salt of the cyclic imide was not added to the electrode. An ion secondary battery was produced.

(Comparative Example 5)

LiMn ₂ O ₄ was used as the positive electrode active material, and the composition of the positive electrode and the negative electrode was 60: 35: 0: 5, and the lithium salt of the cyclic imide was not added to the electrode in the same manner as in Example 1 A solid lithium ion secondary battery was produced.

(Performance evaluation)

The capacity | capacitance was measured by carrying out charge / discharge at 4.2-2.5V with a current density of 20 microamperes / cm <^2> (initial capacity) about the solid lithium ion secondary battery produced by each Example and the comparative example. The capacity at the time of 1C discharge was made into the value when the current value of 1.1 mA / cm <^2> flowed. The rate characteristic of each Example and the comparative example was computed as the relative value (%) which made the 1C capacity of Example 1 100%. These results are shown in Table 1.

[Table 1]

As can be seen from the results shown in Table 1, in Examples 1 to 7 in which a lithium salt of a cyclic imide was added to an electrode, a solid lithium ion battery having excellent capacity and volumetric properties per volume was obtained. In addition, even in Example 4, in which no solid electrolyte was added to the electrode, a battery having a capacity and a rate characteristic that could be sufficiently provided in practical use was obtained. In contrast, the solid lithium lithium ion batteries obtained in Comparative Examples 1 to 5 in which no lithium salt of cyclic imide was added to the electrode were compared with the examples using the same activating material, and in particular, the capacity per volume was lowered.

10: electrode of conventional solid lithium ion secondary battery
20: Electrode of solid lithium ion secondary battery according to one embodiment of the present invention
30: solid lithium ion secondary battery according to one embodiment of the present invention

Claims (14)

Solid lithium ion secondary with a negative electrode containing a negative electrode active material capable of inserting and deinserting lithium, a positive electrode containing a positive electrode active material capable of inserting and deinserting lithium, and a solid electrolyte layer provided between the positive electrode and the negative electrode As a battery,
A solid lithium ion secondary battery in which at least one of the positive electrode and the negative electrode contains a lithium salt of a cyclic imide. The solid lithium lithium ion secondary battery according to claim 1, wherein the lithium content of the lithium salt of the cyclocyclic imide is from 1 to 40% by weight in at least one of the positive electrode and the negative electrode. 3. The lithium salt of claim 1, wherein the lithium salt of the cyclic imide is cyclo-tetrafluoroethane-1,2-bis (sulfonyl) imide lithium ((CF ₂ SO ₂ ) ₂ NLi) and cyclo-. At least one kind of solid lithium ion secondary battery selected from hexafluoropropane-1,3-bis (sulfonyl) imide lithium (CF ₂ (CF ₂ SO ₂ ) ₂ NLi)). The solid lithium ion secondary battery according to claim 1 or 2, wherein the solid electrolyte layer contains a solid electrolyte having a lithium ion conductivity of 10 ⁻⁴ S / cm or more. The solid lithium lithium ion secondary battery according to claim 1 or 2, wherein, in at least one of the anode and the cathode, the lithium salt of the ring-shaped imide is present in a state of covering the surface of the active material of the electrode. The method of claim 1 or claim 2, wherein the solid electrolyte is _{Li 3 N, LISICON (Lithium Super} Ionic Conductor), LIPON (Li 3 + y PO 4 - x N x), Thio-LISICON (Li 3 .25 Ge 0 _{.25 P 0 .75 S 4),} Li 2 S, Li 2 SP 2 S 5, Li 2 S-SiS 2, Li 2 S-GeS 2, Li 2 SB 2 S 5, Li 2 S-Al 2 S 5 And at least one solid lithium ion secondary battery selected from the group consisting of Li ₂ O—Al ₂ O ₃ —TiO ₂ —P ₂ O ₅ (LATP), polyethylene oxide, and boric acid ester polymer. The solid lithium lithium ion secondary battery according to claim 1 or 2, wherein the cathode active material is an oxide or sulfide of a transition metal selected from Mn, Co, Ni, Fe, and Al. The method of claim 1 or 2, wherein the anode active material is lithium, indium, tin, aluminum, silicon or alloys thereof; Transition metal oxides; Solid lithium lithium ion secondary battery as a carbon material. An electrode for a solid lithium secondary battery containing an electrode active material capable of inserting and deinserting lithium,
The electrode for solid lithium secondary batteries in which the said electrode contains the lithium salt of cyclic imide 10. The electrode for a solid lithium lithium ion secondary battery according to claim 9, wherein the lithium content of the lithium salt of the cyclic imide is 1 to 40% by weight in the electrode. The lithium salt of the cyclic imide according to claim 9 or 10, wherein the lithium salt is cyclo-tetrafluoroethane-1,2-bis (sulfonyl) imide lithium ((CF ₂ SO ₂ ) ₂ NLi) and cyclo- An electrode for a solid lithium ion secondary battery, which is at least one selected from hexafluoropropane-1,3-bis (sulfonyl) imide lithium (CF ₂ (CF ₂ SO ₂ ) ₂ NLi)). The electrode for a solid lithium ion secondary battery according to claim 9 or 10, wherein the lithium salt of said ring-shaped imide exists in the state which coat | covered the surface of the active material of the said electrode. The electrode of claim 9 or 10, wherein the electrode active material is an oxide or sulfide of a transition metal selected from Mn, Co, Ni, Fe, and Al. The method according to claim 9 or 10, wherein the electrode active material is lithium, indium, tin, aluminum, silicon or alloy thereof; Transition metal oxides; Or an electrode for a solid lithium lithium ion secondary battery that is a carbonaceous material.

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