JP2001015102A - Nonaqueous electrolyte secondary battery and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the capacity and the cycle characteristic by forming a negative electrode with a compound of Li, two or more kinds out of 36, kinds of elements including Ce and other, and one or more kinds out of 9 kinds of elements including Al. SOLUTION: A negative electrode comprises a compound having a composition expressed by formula Li αM1βM2γ. In the formula, M1 is two or more kinds of elements out of Ce, Ti, Zr, B, P, Mg, Ca, Sr, Ba, T, La, Cr, Mo, W, Mn, Co, Ir, Ni, Fe, Pd, Cu, Ag, Zn, Na, K, V, Nb, Al, Ga, In, Is, Ge, Sn, Pb, Sb, and Bi. M2 is one or more kinds of elements out of Al, Ga, In, Is, Ge, Sn, Pb, Sb, and Bi, wherein, elements M1 and M2 shall be prevented from mutually overlapped. The α, β, and γ are set to 0<=α<100, 0.1<=β<11, and γ=1 respectively. FeCuSn, etc., are illustrated as suitable compounds.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a non-aqueous electrolyte secondary battery and a method for producing the same. More specifically, the present invention relates to a non-aqueous electrolyte secondary battery including a highly reliable negative electrode having high electric capacity and suppressed generation of dendrite, having a high energy density and free from short-circuit due to dendrite growth, and a method for manufacturing the same.

[0002]

2. Description of the Related Art Many studies have been made on non-aqueous electrolyte secondary batteries using lithium or a lithium compound as a negative electrode since high voltage and high energy density can be expected.
Until now, as positive electrode active materials for non-aqueous electrolyte secondary batteries,
LiMn ₂ O ₄ , LiCoO ₂ , LiNiO ₂ , V ₂ O ₅ , C
Oxides of transition metals such as r ₂ O ₅ , MnO ₂ , TiS ₂ and MoS ₂ and chalcogen compounds are known. These have a layered or tunnel structure, and have a crystal structure through which lithium ions can enter and exit. On the other hand, as a negative electrode active material, metallic lithium is often studied. However, when metallic lithium is used, there is a problem in that dendritic lithium precipitates on the surface during charging, which lowers the charge / discharge efficiency and causes an internal short circuit due to contact with the positive electrode.

In order to solve the above problem, studies have been made on the use of a lithium-based alloy such as lithium-aluminum for the negative electrode, which can occlude and release lithium while suppressing the growth of dendritic lithium. However, in the case of using a lithium-based alloy, there is a problem in cycle characteristics, such as repetition of deep charge / discharge, resulting in miniaturization of electrodes.

In recent years, a lithium ion battery using a carbon material for a negative electrode, which has a smaller capacity than metallic lithium and a lithium-based alloy but can reversibly store and release lithium, and has excellent cycle characteristics and safety, has been commercialized. Have been. Under such circumstances, studies have been made to use an oxide for the negative electrode in order to further increase the capacity. For example, crystalline SnO or SnO
It has been proposed that No. ₂ is a negative electrode material having a higher capacity than conventional WO ₂ or the like (JP-A-7-122274 and JP-A-7-235293). In addition, SnSi
A proposal has been made to improve the cycle characteristics by using an amorphous oxide such as O ₃ or SnSi _1-x P _x O ₃ for the negative electrode (Japanese Patent Application Laid-Open No. 7-288123). However, no satisfactory properties have yet been obtained.

[0005]

SUMMARY OF THE INVENTION In view of the above-mentioned circumstances, the present invention provides a non-aqueous electrolyte secondary battery having a high capacity and excellent cycle characteristics which does not generate dendrite by occluding lithium during charging and a method of manufacturing the same. The purpose is to provide.

[0006]

The present invention comprises a chargeable / dischargeable positive electrode, a non-aqueous electrolyte, and a chargeable / dischargeable negative electrode,
Negative formula ^(1): LiαM 1 βM made of a compound having a composition represented by ² gamma (1), wherein (1),
M ¹ is Ce, Ti, Zr, B, P, Mg, Ca, Sr,
Ba, Y, La, Cr, Mo, W, Mn, Co, Ir,
Ni, Fe, Pd, Cu, Ag, Zn, Na, K, V,
Nb, Al, Ga, In, Si, Ge, Sn, Pb, S
b and Bi are at least two kinds of elements selected from the (M ¹ ) group, and M ² is Al, Ga, In, S
at least one element selected from the group (M ² ) consisting of i, Ge, Sn, Pb, Sb and Bi, wherein the element selected from M ¹ and the element selected from M ² overlap with each other 0 ≦ α <100, 0.1 ≦ β <11
And γ = 1.

The compound having the composition represented by the formula (1) preferably has a single phase or an alloy phase of an element selected from the group (M ² ).

[0008] The average crystallite diameter of the single phase of the element selected from the group (M ² ) is preferably 0.01 to 10 µm.

The average particle size of the compound having the composition represented by the formula (1) is preferably 0.05 to 60 μm.

The negative electrode preferably comprises 100 parts by weight of a compound having the composition represented by the formula (1) and 5 to 50 parts by weight of a carbon-based material.

Further, according to the present invention, the compound having the composition represented by the formula (1) is prepared by using a mechanical alloy method, a liquid quenching method,
The present invention relates to a method for manufacturing a nonaqueous electrolyte secondary battery, which is synthesized by any one of an ion beam sputtering method, a vacuum evaporation method, a plating method, and a CVD method.

[0012]

The non-aqueous electrolyte secondary battery of the embodiment of the present invention, the formula ^(1): LiαM 1 βM negative electrode made of a compound having a composition represented by ² gamma (1) is used. In the formula (1), M ¹ is Ce, Ti, Zr, B, P, M
g, Ca, Sr, Ba, Y, La, Cr, Mo, W, M
n, Co, Ir, Ni, Fe, Pd, Cu, Ag, Z
n, Na, K, V, Nb, Al, Ga, In, Si, G
(M ¹ ) group consisting of e, Sn, Pb, Sb and Bi;
Preferably Ce, Ti, Zr, B, P, Mg, Ca, S
r, Ba, Y, La, Cr, Mo, W, Mn, Co, I
r, Ni, Fe, Pd, Cu, Ag, Zn, Na, K,
V and Nb, more preferably Fe, Nb
At least two elements, preferably two to four elements, selected from the group consisting of i, Co, Mn, Cu and Ti. Since two or more elements are used as M ¹ , an effect such as amorphization due to distortion of the compound or stabilization of the structure when Li is inserted can be obtained.

In the formula (1), M ² is Al, Ga, In, S
It is a (M ² ) group consisting of i, Ge, Sn, Pb, Sb and Bi, preferably at least one element selected from Sn and Si. However, the element selected from M ¹ and the element selected from M ² do not overlap each other, and M ¹ ≠ M ² .

In the equation (1), α changes within the range of 0 ≦ α <100, preferably 0 ≦ α <30, as the battery is charged and discharged. When α becomes 100 or more, dendrite starts to grow. Also, 0.1 ≦ β <11, preferably 0.5 ≦
Satisfies β ≦ 5 and γ = 1. When β is less than 0.1, the structure becomes unstable when Li is inserted, and when β is 11 or more, the effect of amorphizing the compound or stabilizing the structure when Li is inserted cannot be obtained, resulting in low capacity.

Preferred specific examples of the compound having the composition represented by the formula (1) include, for example, FeCuSn, FeT
iSn, FeNiSi ₃ , CoNiSi ₂ , MnTiAl
₃ , Mg _1.8 Sr _0.2 Ge, TiZrPb and the like.

The compound having the composition represented by the formula (1) preferably has a simple phase or an alloy phase of an element selected from the group (M ² ) from the viewpoint of increasing the capacity of the battery.
The preferred content of these phases in the compound is 10 to 8
0% by weight, more preferably 15 to 50% by weight. If the content of these phases is too small, the effect due to the presence of these phases cannot be sufficiently obtained.
The structure tends to be unstable when i is inserted. The presence of these phases can be determined from an X-ray diffraction diagram or the like.

The average crystallite diameter of the elementary phase of the element selected from the group (M ² ) is 0.01 to 10 μm, more preferably 0.01 to 10 μm, from the viewpoint of suppressing the expansion of the active material and maintaining the reactivity.
To 1 μm, and the average crystallite diameter of the alloy phase is preferably 0.01 to 1 μm. The average particle size of the compound having the composition represented by the formula (1) is
From the viewpoint of stabilizing characteristics and controlling the structure, 0.05 to 6
It is preferably 0 μm, more preferably 0.1 to 30 μm.

The negative electrode according to the non-aqueous electrolyte secondary battery of the present invention may be, for example, a compound 10 having a composition represented by the formula (1):
It is obtained by mixing and mixing 5 to 50 parts by weight of a carbon-based material, an appropriate amount of a binder and an appropriate amount of a solvent with respect to 0 parts by weight, and then molding the mixture into a predetermined shape. As the carbon-based material, graphite, acetylene black, a low-crystalline carbon material, or the like is preferably used, and as the binder, polytetrafluoroethylene or the like is preferably used, but not limited thereto.

The compound having the composition represented by the formula (1) according to the non-aqueous electrolyte secondary battery of the present invention may be produced by any method, including a mechanical alloy method, a liquid quenching method, and an ion beam sputtering method. It can be more easily manufactured by any one of the methods, the vacuum deposition method, the plating method, and the CVD (gas phase chemical reaction) method, particularly, the liquid quenching method and the mechanical alloy method. For example, in the liquid quenching method, a low-crystalline compound or an amorphous compound having fine crystallites can be obtained by quenching with a single roll at a rate of 10 ⁵ to 10 ⁶ K / sec. In addition, the mechanical alloy method can obtain fine crystallites on the order of nanometers (nm) and can obtain a phase state such as a solid solution phase that cannot be obtained by a conventional thermal method.

The non-aqueous electrolyte secondary battery of the present invention can be obtained in the same manner as a conventional battery, except that a negative electrode comprising the above compound is used. Therefore, the conventional chargeable / dischargeable positive electrode and nonaqueous electrolyte can be used without any particular limitation.

[0021]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

First, the test cell shown in FIG. 1 and the cylindrical battery shown in FIG. 2 used in the following Examples and Comparative Examples will be described. The test cell was used to evaluate the electrode characteristics of the negative electrode, and the cylindrical battery was used to evaluate the cycle characteristics of the battery using the negative electrode.

(Test Cell) A mixture was prepared by mixing 7 g of the negative electrode active material powder, 2 g of graphite powder as a conductive agent, and 1 g of polyethylene powder as a binder. 0.1 g of this mixture was pressure-molded into a disk having a diameter of 17.5 mm to obtain a test electrode 1. The test electrode 1 was placed in the case 2 as shown in FIG. 1, and the microporous polypropylene separator 3 was placed thereon. A mixed solution of ethylene carbonate and dimethoxyethane in which lithium perchlorate (LiClO ₄ ) was dissolved at a volume ratio of 1 mol / l as a non-aqueous electrolyte was poured onto the separator 3. On top of this, inside diameter 17.
A 5 mm disk-shaped metallic lithium 4 was stuck, and a sealing plate 6 with a polypropylene gasket 5 attached to the outer periphery was placed and sealed to form a test cell.

(Cylindrical battery) LiMn as a positive electrode active material
_1.8 Co _0.2 O ₄ is composed of Li ₂ CO ₃ , Mn ₃ O ₄ and CoC
O ₃ was mixed at a predetermined molar ratio and synthesized by heating at 900 ° C. This was classified to 100 mesh or less to obtain a positive electrode active material. 8 g of an aqueous dispersion of polytetrafluoroethylene as a resin component was mixed with 100 g of the positive electrode active material, 10 g of graphite powder as a conductive agent and a binder, and pure water was added to form a paste. This was applied to a titanium core material, dried and rolled to obtain a positive electrode plate.

A negative electrode active material, graphite powder as a conductive agent, and polytetrafluoroethylene as a binder were included in a weight ratio of 60: 3.
The mixture was mixed at a ratio of 0:10, and a petroleum solvent was further added to form a paste. This was applied to a copper core material and dried at 100 ° C. to obtain a negative electrode plate.

Using the obtained positive electrode plate and negative electrode plate, a cylindrical battery was assembled as follows. As shown in FIG.
Between a positive electrode plate 8 having a positive electrode lead 7 of the same material as the core material attached by spot welding and a negative electrode plate 10 having a negative electrode lead 9 of the same material as the core material attached by spot welding, A separator 11 made of a wide band-shaped porous polypropylene was disposed, and the whole was spirally wound to form an electrode body. Insulating plates 12 and 13 made of polypropylene were arranged on the upper and lower sides of the electrode body, respectively, and inserted into the battery case 14. After forming a step in the upper part of the battery case 14, a mixed solution of ethylene carbonate and dimethoxyethane in which lithium perchlorate is dissolved so as to have a concentration of 1 mol / l as a non-aqueous electrolyte is poured. The solution was sealed and sealed with a sealing plate 15.

When the X-ray diffraction diagrams of the compounds according to Examples 1 to 15 below were analyzed, all the compounds were found to have (M
² ) Set the elementary phase or alloy phase of the element selected from the group to 10
In the range of 70% by weight. In addition, the average crystallite diameter of each of the single phases is in the range of 0.01 to 1 μm, and the average particle diameter of each compound is 1 to 30 μm.
m.

Example 1 Raw materials were blended so as to have the compositions (molar ratios) shown in Tables 1 to 9, and this was mixed with 20 stainless steel balls (1/2 inch in diameter) with an inner volume of 0.5. Liter in a stainless steel pot mill,
It closed under argon atmosphere. This mill is rotated at a rotation speed of 15
The mixture was operated at rpm for one week to obtain a powdery compound having the composition represented by the formula (1).

A test cell was assembled by using each of the above compounds as an active material of a test electrode. Cathode polarization was performed at a constant current of 2 mA until the potential of the test electrode became 0 V with respect to the lithium metal counter electrode (the test electrode was connected to the negative electrode). Assuming that this corresponds to charging.) Then, the anode was anodically polarized until the potential of the test electrode became 1.5 V with respect to the lithium metal counter electrode (this corresponds to discharging when the test electrode was assumed to be a negative electrode). Thereafter, cathodic polarization and anodic polarization were repeated. Active material for test electrode 1
Tables 1 to 9 show the initial discharge capacity per g.

Next, a cylindrical battery was assembled using each of the above compounds as a negative electrode active material. The obtained battery was tested at a test temperature of 30.
° C, charge / discharge current 1 mA / cm ² , charge / discharge voltage 4.3 ~
The charge / discharge cycle under the condition of 2.6 V was repeated, and the capacity retention ratio at the 100th cycle relative to the first cycle was determined. The results are shown in Tables 1 to 9.

[0031]

[Table 1]

[0032]

[Table 2]

[0033]

[Table 3]

[0034]

[Table 4]

[0035]

[Table 5]

[0036]

[Table 6]

[0037]

[Table 7]

[0038]

[Table 8]

[0039]

[Table 9]

Example 2 The same operation as in Example 1 was performed, except that the raw materials were blended to have the compositions (molar ratios) shown in Tables 10 to 18, and the same evaluation was performed. The results are shown in Tables 10 to 18.

[0041]

[Table 10]

[0042]

[Table 11]

[0043]

[Table 12]

[0044]

[Table 13]

[0045]

[Table 14]

[0046]

[Table 15]

[0047]

[Table 16]

[0048]

[Table 17]

[0049]

[Table 18]

Example 3 The same operation as in Example 1 was performed, except that the raw materials were mixed so as to have the compositions (molar ratios) shown in Tables 19 to 27, and the same evaluation was performed. The results are shown in Tables 19 to 27.

[0051]

[Table 19]

[0052]

[Table 20]

[0053]

[Table 21]

[0054]

[Table 22]

[0055]

[Table 23]

[0056]

[Table 24]

[0057]

[Table 25]

[0058]

[Table 26]

[0059]

[Table 27]

Example 4 The same operation as in Example 1 was carried out, except that the raw materials were blended so as to have the compositions (molar ratios) shown in Tables 28 to 36, and the same evaluation was performed. The results are shown in Tables 28 to 36.

[0061]

[Table 28]

[0062]

[Table 29]

[0063]

[Table 30]

[0064]

[Table 31]

[0065]

[Table 32]

[0066]

[Table 33]

[0067]

[Table 34]

[0068]

[Table 35]

[0069]

[Table 36]

Example 5 The same operation as in Example 1 was performed, except that the raw materials were blended so as to have the compositions (molar ratios) shown in Tables 37 to 45, and the same evaluation was performed. The results are shown in Tables 37 to 45.

[0071]

[Table 37]

[0072]

[Table 38]

[0073]

[Table 39]

[0074]

[Table 40]

[0075]

[Table 41]

[0076]

[Table 42]

[0077]

[Table 43]

[0078]

[Table 44]

[0079]

[Table 45]

Example 6 The same operation as in Example 1 was performed, except that the raw materials were blended so as to have the compositions (molar ratios) shown in Tables 46 to 54, and the same evaluation was performed. The results are shown in Tables 46 to 54.

[0081]

[Table 46]

[0082]

[Table 47]

[0083]

[Table 48]

[0084]

[Table 49]

[0085]

[Table 50]

[0086]

[Table 51]

[0087]

[Table 52]

[0088]

[Table 53]

[0089]

[Table 54]

Example 7 The same operation as in Example 1 was performed, except that the raw materials were blended so as to have the compositions (molar ratios) shown in Tables 55 to 63, and the same evaluation was performed. The results are shown in Tables 55 to 63.

[0091]

[Table 55]

[0092]

[Table 56]

[0093]

[Table 57]

[0094]

[Table 58]

[0095]

[Table 59]

[0096]

[Table 60]

[0097]

[Table 61]

[0098]

[Table 62]

[0099]

[Table 63] Example 8 The same operation as in Example 1 was performed, except that the raw materials were blended to have the compositions (molar ratios) shown in Tables 64 to 72, and the same evaluation was performed. The results are shown in Tables 64-72.

[0100]

[Table 64]

[0101]

[Table 65]

[0102]

[Table 66]

[0103]

[Table 67]

[0104]

[Table 68]

[0105]

[Table 69]

[0106]

[Table 70]

[0107]

[Table 71]

[0108]

[Table 72]

Comparative Example 1 An operation was performed in the same manner as in Example 1 except that a conventionally reported metal or intermetallic compound shown in Table 73 was used as an active material, and the same evaluation was performed. The results are shown in Table 73.

[0110]

[Table 73]

From the results shown in Tables 1 to 73, the batteries of the examples had a high capacity, a high capacity retention rate and excellent cycle characteristics, whereas the batteries of the comparative examples had a remarkably low capacity retention rate. I understand.

[0112] "Comparative Example 2" (1) the β in fixed to 0.9, except that the combination of elements shown in Tables 74 and 75 using an element of only one as M ¹ is performed The same operation as in Example 1 was performed, and the same evaluation was performed. Table 74 shows the results.
And 75.

[0113]

[Table 74]

[0114]

[Table 75]

Example 9 The same operation as in Example 1 was carried out, except that the composition was changed as shown in Tables 76 to 77 in which the content of ^one of the two types of M ¹ was changed. The capacity retention was evaluated. The results are shown in Tables 76 to 77.

[0116]

[Table 76]

[0117]

[Table 77]

Example 10 The same operation as in Example 1 was carried out, except that the composition was changed as shown in Tables 78 to 79 in which the content of ^one of the two types of M ¹ was changed. The capacity retention was evaluated. The results are shown in Tables 78 to 79.

[0119]

[Table 78]

[0120]

[Table 79]

Example 11 The same operation as in Example 1 was carried out, except that the composition shown in Tables 80 to 81 was changed, except that the content of ^one of the two types of M ¹ was changed. The capacity retention was evaluated. The results are shown in Tables 80 to 81.

[0122]

[Table 80]

[0123]

[Table 81] Example 12 The same operation as in Example 1 was carried out, except that the compositions shown in Tables 82 to 83 were changed, except that the content of ^one of the two types of M1 was changed, and the capacity retention ratio was similarly changed. Was evaluated. The results are shown in Tables 82 to 83.

[0124]

[Table 82]

[0125]

[Table 83]

Example 13 The same operation as in Example 1 was carried out except that the compositions shown in Tables 84 to 85 were changed, except that the content of ^one of the two types of M ¹ was changed. The capacity retention was evaluated. The results are shown in Tables 84 to 85.

[0127]

[Table 84]

[0128]

[Table 85] Example 14 The same operation as in Example 1 was performed, except that the composition shown in Tables 86 to 87 was changed, except that the content of ^one of the two types of M ¹ was changed. Was evaluated. The results are shown in Tables 86 to 87.

[0129]

[Table 86]

[0130]

[Table 87] Example 15 The same operation as in Example 1 was performed, except that the composition shown in Tables 88 to 89 was changed, except that the content of ^one of the two types of M ¹ was changed, and the capacity retention ratio was similarly changed. Was evaluated. The results are shown in Tables 88 to 89.

[0131]

[Table 88]

[0132]

[Table 89]

After the cathodic polarization and the cathodic and anodic polarization were repeated 10 cycles, the test cells according to all the examples were disassembled, and the test electrodes were taken out and observed. Was not seen. This indicates that dendrite does not easily grow on the surface of the compound (active material) in each of the above Examples. In addition, the test electrode after cathode polarization was
As a result of the analysis, the amounts of lithium contained in the active material were all within the range satisfying the formula (1).

[0134]

According to the present invention, a highly reliable non-aqueous electrolyte secondary battery having high capacity, extremely excellent cycle characteristics, high energy density and no short circuit due to dendrite can be obtained.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view of a test cell for evaluating the electrode characteristics of a negative electrode used in a nonaqueous electrolyte secondary battery of the present invention.

FIG. 2 is a cross-sectional view of a cylindrical battery showing an example of the non-aqueous electrolyte secondary battery of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Test electrode 2 Case 3 and 11 Separator 4 Metal lithium 5 Gasket 6 Sealing plate 7 Positive electrode lead 8 Positive electrode plate 9 Negative electrode lead 10 Negative electrode plate 12 Upper insulating plate 13 Lower insulating plate 14 Battery case 15 Sealing plate

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hideharu Takezawa 1006 Kazuma Kadoma, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (72) Hiromu Matsuda 1006 Kadoma Kadoma Kadoma City, Osaka Matsushita Electric Industrial Co., Ltd. F-term (reference) 5H003 AA02 AA04 BA00 BB02 BC05 BC06 BD00 BD02 BD04 5H014 AA02 EE05 EE07 HH01 5H029 AJ03 AJ05 AK03 AL02 AL06 AL12 AM03 AM04 AM05 AM07 BJ02 BJ03 BJ12 BJ14 CJ00 CJ24 H17J18 HJ

Claims (6)

[Claims] 1. A chargeable / dischargeable positive electrode, a non-aqueous electrolyte, and a chargeable / dischargeable negative electrode, wherein the negative electrode has a composition represented by the formula (1): LiαM ¹ βM ² γ (1) And in equation (1)
M ¹ is Ce, Ti, Zr, B, P, Mg, Ca, Sr,
Ba, Y, La, Cr, Mo, W, Mn, Co, Ir,
Ni, Fe, Pd, Cu, Ag, Zn, Na, K, V,
Nb, Al, Ga, In, Si, Ge, Sn, Pb, S
b and Bi are at least two kinds of elements selected from the (M ¹ ) group, and M ² is Al, Ga, In, S
at least one element selected from the group (M ² ) consisting of i, Ge, Sn, Pb, Sb and Bi, wherein the element selected from M ¹ and the element selected from M ² overlap with each other 0 ≦ α <100, 0.1 ≦ β <11
And non-aqueous electrolyte secondary battery characterized by γ = 1. 2. The non-aqueous electrolyte secondary battery according to claim 1, wherein the compound having the composition represented by the formula (1) has a simple phase or an alloy phase of an element selected from the group (M ² ). 3. The average crystallite diameter of a single phase of an element selected from the group (M ² ) is 0.01 to 10 μm.
The non-aqueous electrolyte secondary battery according to the above. 4. The compound having the composition represented by the formula (1) has an average particle size of 0.05 to 60 μm.
3. The non-aqueous electrolyte secondary battery according to any one of 3. 5. The non-aqueous electrolyte secondary battery according to claim 1, wherein the negative electrode comprises 100 parts by weight of a compound having a composition represented by the formula (1) and 5 to 50 parts by weight of a carbon-based material. . 6. A compound having a composition represented by the formula (1) is synthesized by any of a mechanical alloy method, a liquid quenching method, an ion beam sputtering method, a vacuum evaporation method, a plating method, and a CVD method. Claim 1
The method for producing a nonaqueous electrolyte secondary battery according to any one of claims 1 to 5.