JP3426901B2 - Non-aqueous electrolyte secondary battery - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous electrolyte secondary battery, and more particularly to an improvement in a negative electrode thereof.

[0002]

2. Description of the Related Art A non-aqueous electrolyte secondary battery using lithium or a lithium compound as a negative electrode is expected to have a high voltage and a high energy density, and much research has been conducted. Until now, LiMn ₂ O ₄ , Li
CoO ₂ , LiNiO _2, V ₂ O ₅ , Cr ₂ O ₅ , MnO ₂ , T
Oxides of transition metals such as iS 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, lithium metal has been widely studied as a negative electrode active material. However, there is a problem in that lithium is deposited in a dendritic manner on the lithium surface during charging, and the charging / discharging efficiency is reduced, or an internal short circuit occurs upon contact with the positive electrode.

As means for solving such a problem, studies have been made on the use of a negative electrode made of a lithium alloy such as lithium-aluminum which can suppress the dendritic growth of lithium and occlude / release lithium. However,
In the case of using a lithium alloy, if the charge and discharge are repeated deeply, the electrode becomes finer, and there is a problem in the cycle characteristics. Therefore, there is a proposal to suppress the miniaturization of the electrode by using an alloy of aluminum or the like to which another element is added as an electrode (Japanese Patent Application Laid-Open Nos. 62-119856 and 4-109562). . However, the characteristics have not been sufficiently improved, and at present the capacity is smaller than those of these negative electrode active materials, but a carbon material that can store and release lithium reversibly and has excellent cycleability and safety is used for the negative electrode. Lithium-ion batteries have been put to practical use.

Under these circumstances, with the aim of further increasing the capacity,
Proposal of using an oxide such as crystalline SnO or SnO ₂ for the negative electrode (JP-A-7-122274, JP-A-7-124274)
-235293), and furthermore, SnSiO ₃ and SnS.
A proposal has been made to improve the cycle characteristics by using an amorphous oxide such as i _1-x P _x O ₃ for the negative electrode (Japanese Unexamined Patent Publication No.
-288123). However, the characteristics have not yet been sufficiently improved.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a negative electrode for a non-aqueous electrolyte secondary battery having excellent charge / discharge cycle characteristics in view of the above prior art. An object of the present invention is to provide a negative electrode which occludes lithium upon charging, does not generate dendrites, has a large electric capacity, and has an excellent cycle life.

[0006]

SUMMARY OF THE INVENTION The non-aqueous electrolyte secondary of the present invention
The battery has a chargeable / dischargeable positive electrode, a non-aqueous electrolyte, and a charge / discharge
A possible negative electrode, and the active material of the negative electrode has at least
PredeterminedTungstic acidsalt, Molybdic acidsalt, Titanic acid
salt, Chromic acidsalt, Zirconic acidsalt, Niobatesalt,tantalum
acidsalt,andManganic acidsaltSelected from the group consisting of
At least oneofUse metal salts or metalloid salts.The gold
The metal or metalloid MI of the genus salt or metalloid salt is Al,
Si, Pb, Cd, Bi, Sb, In, Zn, Mg, G
at least one selected from the group consisting of e and Ga
Wherein the tungstate is MIWO _Four and
MIWO ₆ At least one selected from the group consisting of
And the molybdate is MIMoO _Four And MI
Mo _Four O ₆ At least one selected from the group consisting of
And the titanate is MITiO _Four , MITiO _Five And
And MITi _Three O ₇ At least one selected from the group consisting of
The zirconate salt is MIZrO. _Four And
The chromate is MICrO. _Four , MICr _Two O _Four and
MICrO ₆ At least one selected from the group consisting of
Wherein the niobate is MINbO _Four , MINb _Two O
₆ And MINb _Two O ₇ Less selected from the group consisting of
And the tantalum salt is MITaO _Four You
And MITa _Two O ₇ At least selected from the group consisting of
One kind, wherein the manganate is MIMnO _Four and
MIMnO ₆ At least one selected from the group consisting of
It is. The present invention also provides a chargeable / dischargeable positive electrode,
Comprising a negative electrode capable of charging and discharging, and an active material of the negative electrode.
Quality is Al _Three (WO _Four ) _Three , AlWO _Four , Si (WO _Four ) _Two ,
PbWO _Four , CdWO _Four , Bi _Two WO ₆ , Bi _Two (W
O _Four ) _Three , In _Two (WO _Four ) _Three , In (WO _Three ) _Three , Sb _Two (W
O _Four ) _Three , ZnWO _Four , Ga _Two (WO _Four ) _Three , Ga _Two (WO _Three )
_Three , Ge (WO _Four ) _Two , Ge (WO _Three ) _Two , MgWO _Four , Al
_Two (MoO _Four ) _Three , SiMo _Two O ₈ , PbMoO _Four , CdMo
O _Four , Bi _Two (MoO _Four ) _Three , In _Two (MoO _Four ) _Three , InM
o _Four O ₆ , Sb _Two (MoO _Four ) _Three , ZnMoO _Four , Ga _Two (M
oO _Four ) _Three , GeMoO _Four , MgMoO _Four , AlTiO _Five ,
SiTiO ₈ , PbTi _Three O ₇ , Bi _Two TiO _Five , Bi _Two Ti
_Two O ₇ , In _Two TiO _Five , Sb _Three Ti _Two O _Ten , GaTiO _Five ,
MgTiO _Four , Al _Two (ZrO _Three ) _Three , SiZrO _Four , Bi _Two
(ZrO _Three ) _Three , In _Two (ZrO _Three ) _Three , Sb _Two (Zr
O _Three ) _Three , Ga _Two (ZrO _Three ) _Three , Si (CrO _Four ) _Two , Pb _Three
CrO ₆ , PbCrO _Four , CdCr _Two O _Four , Bi _Two CrO ₆ ,
In _Two CrO ₆ , Sb _Two (CrO _Four ) _Three , ZnCrO _Four , Ga
_Two (CrO _Four ) _Three , GeCrO _Four , MgCr _Two O ₇ , AlNb
O _Four , SiNbO _Four , PbNb _Two O ₆ , Pb _Two Nb _Two O ₇ , C
d _Two Nb _Two O ₇ , BiNbO _Four , InNbO _Four , SbNb
O _Four , ZnNb _Two O ₆ , GaNbO _Four , GeNb _Two O ₆ , Mg
Nb _Two O ₆ , AlTaO _Four , SiTa _Two O ₇ , Pb _Two Ta
_Two O ₇ , Cd _Two Ta _Two O ₇ , BiTaO _Four , InTaO _Four , S
bTaO _Four , Zn _Two Ta _Two O ₇ , GaTaO _Four , Ge _Two Ta _Two
O ₇ , Mg _Two Ta _Two O ₇ , Al _Two MnO ₆ , Bi _Two MnO _Four , B
i _Two MnO ₆ , In _Two MnO _Four , In _Two MnO ₆ , Sb _Two Mn
O _Four , Sb _Two MnO ₆ And Ga _Two MnO _Four From the group consisting of
Non-aqueous water characterized by at least one selected from
The present invention relates to an electrolyte secondary battery.The negative electrode comprises an active material, carbon
It is preferred to be composed of a mixture of a material and a binder.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, as a result of studying various metal salts as a negative electrode active material, the metal or metalloid is composed of tungstic acid composed of oxygen and tungsten, molybdic acid composed of oxygen and molybdenum, and oxygen and titanium. titanate, oxygen and chromic acid of chromium, zirconate consisting of oxygen and zirconium, niobium acid consisting of oxygen and niobium tantalate consisting of oxygen and tantalum, which a manganate consisting of oxygen and manganese, a transition metal salt It is based on the finding that a compound having an enclosed crystal structure has high capacity and excellent cycle characteristics. At present, details of the storage site for Li of these metal salts are unknown, but the tungstic acid, molybdic acid, titanic acid, chromic acid, zirconic acid, niobic acid, tantalic acid,
The crystal structure of the metal salt or metalloid salt include any transition metal manganese acid, believed to act effectively against expansion and contraction of the negative electrode active material with the entry and exit of large amounts of Li.

The metal or metalloid of the metal salt or metalloid salt which is the negative electrode active material of the present invention is Al , Si,
Pb, Cd, Bi, In, Zn, Mg, Ge, and G
It is preferably at least one selected from the group consisting of a. P b in the middle, an In, Bi is particularly preferred.
Examples of the metal tungstate or metalloid tungstate include MIWO ₄ and MIWO ₆ . Here, MI represents the above-mentioned metal or metalloid. As metal molybdate or metalloid molybdate,
MIMoO ₄ , MIMo ₄ O _{6 and the} like.

[0009] As the metal titanate or a semi-metal _{titanates, M ITiO 4, MITiO 5,} MITi 3 like O ₇ and the like. Examples of the metal zirconate or metalloid zirconate include M IZrO ₄ . Metal chromic acid or as the metalloid chromate, M IC
rO ₄ , MICr ₂ O ₄ , MICrO _{6 and the} like.
As metal niobate and metalloid niobate, MINb
O ₄ , MINb ₂ O ₆ , MINb ₂ O _{7 and the} like.

Examples of the metal tantalate or the metalloid tantalate include MITaO ₄ and MITa ₂ O ₇ . Metal manganate or metalloid manganese salt, and the like M IMnO _4, MIMnO _6. Among them, metal chromates or metalloid chromates,
Metal tungstates or metalloid tungstates, metal molybdates or metalloid molybdates, metals manganese salt or a metalloid manganate, metal tantalate or metalloid tantalate salts. Metal chromates, metalloid chromates, metal tungstates, metalloid tungstates, metal molybdates, metalloid molybdates are particularly preferred for improving cycle characteristics.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, specific embodiments of the present invention will be described. Example 1 First, a test cell shown in FIG. 1 was prepared in order to examine the electrode characteristics of various metal tungstic acids or metalloid tungstates shown in Table 1 as a negative electrode active material. 6 g of active material powder, 3 g of graphite powder as a conductive agent,
And 1 g of polyethylene powder as a binder was mixed to prepare a mixture. 0.1 g of this mixture was pressed into a disk having a diameter of 17.5 mm to obtain an electrode 1. This electrode 1 is in case 2
And a separator 3 made of a microporous polypropylene film was placed thereon. A non-aqueous electrolyte composed of a mixed solution of ethylene carbonate and dimethoxyethane at a volume ratio of 1: 1 in which 1 mol / l of lithium perchlorate (LiClO ₄ ) was dissolved was injected onto the separator. A metal lithium 4 having a diameter of 17.5 mm was adhered on the inner side, and a sealing plate 6 having a gasket 5 made of polypropylene on the outer periphery was combined and sealed to form a test cell.

[0013] Cathode polarization of this test cell at a constant current of 2 mA until the electrode becomes 0 V with respect to the Li counter electrode (corresponding to charging when the active material electrode is viewed as a negative electrode).
Then, anodic polarization (corresponding to discharge) was performed until the voltage of the electrode reached 1.5 V. The electrode characteristics were evaluated by repeating this cathodic polarization and anodic polarization. Table 2 shows a comparative example.
Crystalline WO ₂ , Fe ₂
Oxide or sulfide of O ₃ , SnO, PbO, SnS, and amorphous SnSiO ₃ , SnSi _0.8 P _0.2
Regarding the _O3.1 metal oxide, a test cell was prepared in the same manner as in the example, and the electrode characteristics were evaluated in the same manner. Table 1
The discharge capacity per 1 g of the active material at the cycle is shown. It was found that all the cells of this example were charged and discharged. After the cathode polarization in the 10th cycle of this test cell was completed, the test cell was disassembled, and no deposition of metallic Li was observed in any case. From the above, it was found that in the electrode using the active material of the present invention, Li was occluded in the electrode by the cathodic polarization, and the occluded Li was released by the anodic polarization, and no metal Li was deposited.

Next, in order to evaluate the cycle characteristics of the batteries using various metal tungstic acids or metalloid tungstates shown in Table 1 for the negative electrode, cylindrical batteries shown in FIG. 2 were prepared. The manufacturing procedure is as follows. LiMn _1.8 Co _0.2 O ₄ , which is a positive electrode active material, is composed of Li ₂ CO ₃ and Mn ₃ O
₄ and CoCO ₃ were mixed at a predetermined molar ratio and heated at 900 ° C. to synthesize. Furthermore, what classified this into 100 mesh or less was used as the positive electrode active material. To 100 g of the positive electrode active material, 10 g of carbon powder as a conductive agent, 8 g of an aqueous dispersion of polytetrafluoroethylene as a binder in solid content, and pure water were added to form a paste. This paste was applied to a titanium core material, dried, and then rolled to obtain a positive electrode. On the other hand, various metal tungstic acids or metalloid tungstates, which are negative electrode active materials, graphite powder as a conductive agent, and Teflon binder as a binder are mixed at a weight ratio of 60:30:10. A paste was formed using a system solvent. After this paste was applied to a copper core material, it was dried at 100 ° C. to obtain a negative electrode plate. A microporous polypropylene film was used as a separator.

A positive electrode plate 11 having a positive electrode lead 14 made of the same material as the core material attached by spot welding;
5 and a strip of porous polypropylene separator 13 having a width wider than the electrode plate interposed between the two electrode plates was spirally wound to form an electrode plate group. This electrode plate group is placed on the upper and lower sides of a polypropylene insulating plate 16,
17 and inserted into a battery case 18 to form a step on the upper portion of the battery case 18, and then a non-aqueous electrolytic solution of ethylene carbonate and dimethoxyethane in which 1 mol / l lithium perchlorate is dissolved. An isobaric mixed solution is injected, and the positive electrode terminal 20
And sealed with a sealing plate 19 having These batteries were subjected to a charge / discharge cycle test at a test temperature of 30 ° C., a charge / discharge current of 1 mA / cm ² , and a charge / discharge voltage range of 4.3 V to 2.6 V.
Table 1 shows the discharge capacity retention ratio at the 100th cycle with respect to the discharge capacity at the cycle.

[0015]

[Table 1]

Further, as comparative examples, crystalline WO ₂ , Fe ₂ O ₃ , SnO, and
PbO, SnS oxide or sulfide, amorphous Sn
With respect to the metal oxides of SiO ₃ and SnSi _0.8 P _0.2 O _3.1 , a test battery was prepared in the same manner as described above, and the cycle characteristics were similarly evaluated. Table 2 shows the results. The battery using the metal tungstate or metalloid tungstate of the present example as the negative electrode active material has improved cycle characteristics as compared with the conventional metal oxide.

[0017]

[Table 2]

Example 2 In this example, a test cell similar to that of Example 1 was prepared in order to examine the electrode characteristics of various metal molybdates or metalloid molybdates shown in Table 3 as a negative electrode active material. And evaluated under the same conditions. Table 3
Shows the results. It was found that all the cells of this example were charged and discharged. After the cathode polarization in the 10th cycle of this test cell was completed, the test cell was disassembled, and no deposition of metallic Li was observed in any case. From the above, it was found that in the electrode using the active material of the present invention, Li was occluded in the electrode by cathodic polarization, and the occluded Li was released by anodic polarization, and no metal Li was deposited. Next, in order to evaluate the cycle characteristics of a battery using various types of metal molybdic acid or metalloid molybdate for the negative electrode, a cylindrical battery similar to that of Example 1 was manufactured and evaluated under the same conditions. Table 3 shows the results. The battery using the metal molybdate or metalloid molybdate of the present example as the negative electrode active material has improved cycle characteristics as compared with the conventional metal oxide.

[0019]

[Table 3]

Example 3 In this example, a test cell similar to that of Example 1 was used to examine the electrode characteristics of various metal titanates or metalloid titanates shown in Table 4 as a negative electrode active material. It was fabricated and evaluated under the same conditions. It was found that all the cells of this example were charged and discharged. After the cathode polarization in the 10th cycle of this test cell was completed, the test cell was disassembled, and no deposition of metallic Li was observed in any case. From the above, it was found that, in the electrode using the active material of the present example, Li was occluded in the electrode by cathodic polarization, the occluded Li was released by anodic polarization, and no metal Li was deposited. Next, in order to evaluate the cycle characteristics of a battery using various metal titanates or metalloid titanates for the negative electrode, a cylindrical battery similar to that of Example 1 was manufactured and evaluated under the same conditions. Table 4 shows the results. The battery using the metal borate of this example as the negative electrode active material had improved cycle characteristics as compared with the conventional metal oxide. Above all, the hydrogen-containing metal borate salt containing hydrogen had further improved cycle characteristics.

[0021]

[Table 4]

Example 4 In this example, a test cell similar to that of Example 1 was used to study the electrode characteristics of various metal zirconates or metalloid zirconates shown in Table 5 as a negative electrode active material. It was fabricated and evaluated under the same conditions. It was found that all the cells of this example were charged and discharged. After the cathode polarization in the 10th cycle of this test cell was completed, the test cell was disassembled, and no deposition of metallic Li was observed in any case. As described above, in the electrode using the active material of this example, Li was occluded in the electrode by cathodic polarization,
It was found that the occluded Li was released by the anodic polarization, and no metal Li was deposited. Next, in order to evaluate the cycle characteristics of a battery using various metal zirconates or metalloid zirconates for the negative electrode, a cylindrical battery similar to that of Example 1 was manufactured and evaluated under the same conditions. Shows the results.
The battery using the metal zirconate or the metalloid zirconate of this example as the negative electrode active material has improved cycle characteristics as compared with the conventional metal oxide.

[0023]

[Table 5]

Reference Example 1 In this reference example, a test cell similar to that of Example 1 was used to examine the electrode characteristics of various metal vanadates or metalloid vanadates shown in Table 6 as a negative electrode active material. It was fabricated and evaluated under the same conditions. It was found that all of the cells of this reference example were charged and discharged. After the cathode polarization in the 10th cycle of this test cell was completed, the test cell was disassembled, and no deposition of metallic Li was observed in any case. As described above, in the electrode using the active material of the present reference example, Li was occluded in the electrode by cathodic polarization, and L was occluded by anodic polarization.
It was found that i was released and no metal Li was deposited.
Next, in order to evaluate the cycle characteristics of batteries using various metal vanadates or metalloid vanadates for the negative electrode,
A cylindrical battery similar to that of Example 1 was manufactured, and evaluated under the same conditions. The battery using the metal vanadate or the metalloid vanadate of this reference example as the negative electrode active material has improved cycle characteristics as compared with the conventional metal oxide.

[0025]

[Table 6]

Example 5 In this example, a test cell similar to that of Example 1 was used to examine the electrode characteristics of various metal chromates or metalloid chromates shown in Table 7 as a negative electrode active material. It was fabricated and evaluated under the same conditions. It was found that all the cells of this example were charged and discharged. After the cathode polarization in the 10th cycle of this test cell was completed, the test cell was disassembled.
No precipitation of metallic Li was observed in any case. From the above, the electrode using the active material of the present example was Li-cathode-polarized.
Was occluded in the electrode, the occluded Li was released by anodic polarization, and no metal Li was deposited. Next, in order to evaluate the cycle characteristics of a battery using various metal chromates or metalloid chromates for the negative electrode, a cylindrical battery similar to that of Example 1 was manufactured and evaluated under the same conditions. Table 7 shows the results. The battery using the metal chromate or the metalloid chromate of this example as the negative electrode active material has improved cycle characteristics as compared with the conventional metal oxide.

[0027]

[Table 7]

Example 6 In this example, a test cell similar to that of Example 1 was used to study the electrode characteristics of various metal niobates or metalloid niobates shown in Table 8 as a negative electrode active material. It was fabricated and evaluated under the same conditions. It was found that all the cells of this example were charged and discharged. After the cathode polarization in the 10th cycle of this test cell was completed, the test cell was disassembled.
No precipitation of metallic Li was observed in any case. From the above, the electrode using the active material of the present example was Li-cathode-polarized.
Was occluded in the electrode, the occluded Li was released by anodic polarization, and no metal Li was deposited. Next, in order to evaluate the cycle characteristics of a battery using various metal niobates or metalloid niobates for the negative electrode, a cylindrical battery similar to that of Example 1 was manufactured and evaluated under the same conditions.
Was . Table 8 shows the results. The battery using the metal niobate or the metalloid niobate of this example as the negative electrode active material has improved cycle characteristics as compared with the conventional metal oxide.

[0029]

[Table 8]

Example 7 In this example, a test cell similar to that in Example 1 was used in order to examine the electrode characteristics of various metal tantalate or metalloid tantalate shown in Table 9 as a negative electrode active material. It was fabricated and evaluated under the same conditions. It was found that all the cells of this example were charged and discharged. After the cathode polarization in the 10th cycle of this test cell was completed, the test cell was disassembled, and no deposition of metallic Li was observed in any case. As described above, in the electrode using the active material of the present example, Li was occluded in the electrode by the cathodic polarization, and L was occluded by the anodic polarization.
It was found that i was released and no metal Li was deposited.
Next, in order to evaluate the cycle characteristics of batteries using various metal tantalate or metalloid tantalate for the negative electrode,
A cylindrical battery similar to that of Example 1 was manufactured and evaluated under the same conditions. Table 9 shows the results. The battery using the metal tantalate or the metalloid tantalate of the present example as the negative electrode active material has improved cycle characteristics as compared with the conventional metal oxide.

[0031]

[Table 9]

Example 8 In this example, a test cell similar to that of Example 1 was used to examine the electrode characteristics of various metal manganates or semimetal manganates shown in Table 10 as a negative electrode active material. Made,
Evaluation was performed under the same conditions. It was found that all the cells of this example were charged and discharged. After the cathode polarization in the 10th cycle of this test cell was completed, the test cell was disassembled, and no deposition of metallic Li was observed in any case. From the above, it was found that, in the electrode using the active material of the present example, Li was occluded in the electrode by cathodic polarization, the occluded Li was released by anodic polarization, and no metal Li was deposited. Next, in order to evaluate the cycle characteristics of a battery using various metal manganates or semimetal manganates for the negative electrode, a cylindrical battery similar to that of Example 1 was manufactured and evaluated under the same conditions. Table 10 shows the results. The battery using the metal tantalate or the metalloid tantalate of the present example as the negative electrode active material has improved cycle characteristics as compared with the conventional metal oxide.

[0033]

[Table 10]

In the examples, LiMn _1.8
An example using Co _0.2 O ₄ has been described, but LiMn ₂ O _4, L
Needless to say, the same effect can be obtained also when the positive electrode having reversibility with respect to charge / discharge such as iCoO ₂ and LiNiO ₂ is used.

[0035]

According to the present invention, it is possible to provide a negative electrode which provides a highly reliable non-aqueous electrolyte secondary battery having a high capacity and an extremely excellent cycle life.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view of a test cell for evaluating electrode characteristics of an active material of the present invention.

FIG. 2 is a longitudinal sectional view of a cylindrical battery using the negative electrode of the present invention.

[Explanation of symbols]

1 Test electrode 2 cases 3 separator 4 Metal Li 5 Gasket 6 sealing plate 11 Positive electrode 12. Negative electrode of the present invention 13 Separator 14 Positive lead plate 15 Negative electrode lead plate 16 Upper insulating plate 17 Lower insulating plate 18 Battery case 19 Sealing plate 20 Positive terminal

   ────────────────────────────────────────────────── ─── Continuation of front page    (72) Inventor Toyoguchi ▲ Yoshi ▼ Toku               1006 Kadoma Kadoma, Kadoma City, Osaka Matsushita Electric               Kiki Sangyo Co., Ltd.                (56) References JP-A-6-338325 (JP, A)                 JP-A-6-275269 (JP, A)                 JP-A-7-29607 (JP, A)                 JP-A-6-60867 (JP, A)                 JP-A-8-241707 (JP, A)                 JP-A-6-302320 (JP, A)                 JP-A-6-215770 (JP, A)                 JP-A-4-264370 (JP, A)                 JP-A-7-85878 (JP, A)                 JP-A-6-275263 (JP, A)                 JP-A-7-302587 (JP, A)                 JP-A-10-69922 (JP, A)                 JP-A-10-27627 (JP, A)                 JP-A-10-27586 (JP, A)                 JP-A-9-320587 (JP, A)                 JP-A-9-309728 (JP, A)                 JP-A-9-309727 (JP, A)                 JP-A-9-306491 (JP, A)                 JP-A-9-199179 (JP, A)                 Special table 2000-503622 (JP, A)

Claims (3)

(57) [Claims] 1. A rechargeable positive electrode, a nonaqueous electrolyte, and includes a chargeable and dischargeable negative electrode, the active material of the negative electrode, tungstic acid salts, molybdate salts, titanates, chromic acid
Least one salt, zirconate salts, niobate, is selected from the group consisting of tantalum salts and <br/> manganate,
By weight of metal salt or metalloid salt, metal or metalloid MI of the metal salt or metalloid salt,
Al, Si, Pb, Cd, Bi, Sb, In, Zn, M
g selected from the group consisting of g, Ge, and Ga
And tungstate is the same as MIWO ₄ and MIWO ₆ .
At least one member selected from the group consisting of MIMoO ₄ and MIMo ₄ O
₆ , wherein said titanate is MITiO ₄ , MITiO ₅ and M
At least one selected from the group consisting of ITi ₃ O ₇
The zirconate salt is MIZrO ₄ and the chromate salt is MICrO ₄ , MICr ₂ O ₄ and
At least one selected from the group consisting of MICrO ₆
, And the said niobate salt, MINbO _4, MINb ₂ O ₆ and
At least one selected from the group consisting of MINb ₂ O ₇
, And the said tantalate salt, MITaO ₄ and mita ₂ O ₇
It is at least one selected from the group consisting of, wherein the manganese salt is, MIMnO ₄ and MIMnO ₆
A non-aqueous electrolyte secondary battery, which is at least one selected from the group consisting of : (2)A chargeable and dischargeable positive electrode, a non-aqueous electrolyte, and
A negative electrode capable of charging and discharging, wherein the active material of the negative electrode is Al
_Three (WO _Four ) _Three , AlWO _Four , Si (WO _Four ) _Two , PbW
O _Four , CdWO _Four , Bi _Two WO ₆ , Bi _Two (WO _Four ) _Three , In _Two
(WO _Four ) _Three , In (WO _Three ) _Three , Sb _Two (WO _Four ) _Three , Zn
WO _Four , Ga _Two (WO _Four ) _Three , Ga _Two (WO _Three ) _Three , Ge (W
O _Four ) _Two , Ge (WO _Three ) _Two , MgWO _Four , Al _Two (Mo
O _Four ) _Three , SiMo _Two O ₈ , PbMoO _Four , CdMoO _Four , B
i _Two (MoO _Four ) _Three , In _Two (MoO _Four ) _Three , I nMo _Four O ₆ ,
Sb _Two (MoO _Four ) _Three , ZnMoO _Four , Ga _Two (Mo
O _Four ) _Three , GeMoO _Four , MgMoO _Four , AlTiO _Five , S
iTiO ₈ , PbTi _Three O ₇ , Bi _Two TiO _Five , Bi _Two Ti _Two
O ₇ , In _Two TiO _Five , Sb _Three Ti _Two O _Ten , GaTiO _Five , M
gTiO _Four , Al _Two (ZrO _Three ) _Three , SiZrO _Four , Bi
_Two (ZrO _Three ) _Three , In _Two (ZrO _Three ) _Three , Sb _Two (ZrO _Three )
_Three , Ga _Two (ZrO _Three ) _Three , Si (CrO _Four ) _Two , Pb _Three Cr
O ₆ , PbCrO _Four , CdCr _Two O _Four , Bi _Two CrO ₆ , In
_Two CrO ₆ , Sb _Two (CrO _Four ) _Three , ZnCrO _Four , Ga
_Two (CrO _Four ) _Three , GeCrO _Four , MgCr _Two O ₇ , AlNb
O _Four , SiNbO _Four , PbNb _Two O ₆ , Pb _Two Nb _Two O ₇ , C
d _Two Nb _Two O ₇ , BiNbO _Four , InNbO _Four , SbNb
O _Four , ZnNb _Two O ₆ , GaNbO _Four , GeNb _Two O ₆ , Mg
Nb _Two O ₆ , AlTaO _Four , SiTa _Two O ₇ , Pb _Two Ta
_Two O ₇ , Cd _Two Ta _Two O ₇ , BiTaO _Four , InTaO _Four , S
bTaO _Four , Zn _Two Ta _Two O ₇ , GaTaO _Four , Ge _Two Ta _Two
O ₇ , Mg _Two Ta _Two O ₇ , Al _Two MnO ₆ , Bi _Two MnO _Four , B
i _Two MnO ₆ , In _Two MnO _Four , In _Two MnO ₆ , Sb _Two Mn
O _Four , Sb _Two MnO ₆ And Ga _Two MnO _Four From the group consisting of
Non-aqueous water characterized by at least one selected from
Electrolyte secondary battery. 3. The negative electrode further comprises a carbon material and a binder.
The non-aqueous electrolyte secondary battery according to claim 1, comprising: