JPH05135760A - Nonaqueous electrolyte secondary battery and manufacture thereof - Google Patents

Abstract

PURPOSE:To provide a nonaqueous electrolyte secondary battery having no discharge capacity reduction caused by the charge/discharge capacity difference of a negative electrode and easy to manufacture and its manufacture. CONSTITUTION:An electrode plate incorporating a positive electrode active material is manufactured, it is dipped in a liquid incorporating a lithium agent such as butyl lithium, phenyl lithium, naphthyl lithium, or lithium iodide to form a positive electrode plate, and a battery is constituted. An electrode body faced with a positive electrode 1 and a negative electrode 2 via a separator 3 is dipped in a liquid incorporating the lithium agent to constitute the battery. The electrode body is inserted into a battery jar 9, the liquid incorporating the lithium agent is filled in the battery jar 9, an electrolyte is added, and it is sealed to manufacture the battery.

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 using a lithium salt as a positive electrode active material and a material which absorbs and releases lithium for a negative electrode, and a method for producing the same.

[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 be a high voltage, high energy density battery, and many studies have been conducted for practical use.

Conventionally, as a positive electrode active material for a non-aqueous electrolyte secondary battery,
Then V₂O_Five, Cr₂O_Five, MnO₂, TiS₂Is known
Has been. Also, recently, by Thackray et al.
Mn₂O_FourCan be a positive electrode active material for the above battery system.
Reported (Material Research Bulletin 1983 1
8: 461-472). This positive electrode active material Li _xM
n₂O_FourThe relationship between the X value and the open circuit potential is shown in FIG. Potential curve
Has flat parts around 4.0V and 2.8V and has two stages.
Become. Therefore, the charging / discharging voltage range is 4.5V to 3V.
Charge up to V and discharge using a potential flat part around 4.0V.
By carrying out an electric cycle, it becomes a 4V class secondary battery.
Can be used. In addition, the positive electrode active material Li_xCo
O₂The relationship between the X value and the open circuit voltage is shown in FIG. Potential curve
Has a potential flat part near 4.0V and 1.2V.
In the case of, as in FIG. 2, a potential flat portion around 4.0 V is used.
Charging and discharging cycle by
Can be used as a pond.

On the other hand, a large amount of metallic lithium has been studied for the negative electrode. However, there is a problem in that resin-like lithium is deposited on the surface of lithium during charging, and if charge / discharge cycles are repeated, charge / discharge efficiency decreases or an internal short circuit occurs due to contact with the positive electrode. Therefore, various carbon materials, metals such as aluminum, alloys, or oxides have been studied as materials capable of suppressing the resinous growth of lithium and absorbing and releasing lithium.

[0005]

However, in the conventional battery as described above, a negative electrode active material such as a carbon material or aluminum metal and LiMn ₂ O ₄ , LiM as a positive electrode active material are used.
When a battery is formed using nO ₂ , LiCoO ₂ , LiNiO ₂ , LiFeO ₂ or γ-LiV ₂ O ₅ , lithium released from the positive electrode active material by the first charge is occluded in the negative electrode active material, This reverse reaction occurs in the subsequent discharge,
Lithium ions are released from the negative electrode active material and occluded in the positive electrode active material. Therefore, the only lithium ions involved in this battery reaction are the lithium ions initially present in the positive electrode, and the amount of this lithium ion determines the battery capacity. However, when the above-mentioned negative electrode active material is used, all the lithium ions occluded in the negative electrode active material by the first charge cannot be released by the subsequent discharge (in the negative electrode active material by the first charge, When the amount of stored lithium ions and the amount of lithium ions released from the negative electrode active material by the first discharge are compared, the former method becomes larger: charge / discharge capacity difference). As described above, since lithium ions that are taken into the negative electrode active material by the first charge and are not involved in the subsequent battery reaction are present, the number of reversibly transferable lithium ions in the battery is decreased, and the battery capacity is decreased. To do.

Therefore, Li _x Mn ₂ O ₄ , L is added to the positive electrode active material.
_{i sx MnO 2, Li x CoO} 2, Li x NiO 2, Li x Fe
Using O ₂ or γ-Li _x V ₂ O ₅ (X> 1), it has been considered to supplement lithium ions that are occluded in the negative electrode active material and are not released with excess lithium ions present in the positive electrode active material. It was

As a method of synthesizing such a positive electrode active material containing excess Li, a method of adding an excessive lithium salt at the time of raw material charging or a positive electrode active material as disclosed in JP-A-2-265167 is disclosed. It has been proposed to lithiate the powder with butyllithium. Taracon et al. Have proposed a method of obtaining Li _x Mo ₂ O ₄ having an excess of lithium by an ion exchange reaction of NaMo ₂ O ₄ with lithium iodide. (U.S. Pat. No. 4,710,439).

However, for example, Li _x Mn ₂ O ₄ and Li _x Mn obtained by charging excess lithium during the synthesis of the raw materials and heating
_{O 2, Li x CoO 2,} Li x NiO 2, Li x FeO 2 , or _{γ-Li x V 2 O 5} (X> 1) is reacted with moisture in air or the _{like, LiMn 2 O 4, LiMnO 2} , LiCoO ₂ , LiN
iO ₂ , LiFeO ₂ or γ-LiV ₂ O ₅ and LiOH
Will be decomposed into. Therefore, Li _x Mn ₂ O ₄ , L
i _x MnO ₂ , Li _x CoO ₂ , Li _x NiO ₂ , Li _x Fe
Water cannot be used as a solvent in the pulverizing and classifying steps carried out after synthesizing O ₂ or γ-Li _x V ₂ O ₅ (X> 1). It was necessary to carry out in an active gas atmosphere or in dry air. Also, in the method of immersing the positive electrode active material powder in a lithiating agent such as butyllithium after synthesizing the positive electrode active material to dope lithium into the positive electrode active material, the positive electrode active material containing excess lithium does not react with water. Since it is unstable and reacts with moisture in the air, it is necessary to use a non-aqueous solvent in a dry atmosphere when producing an electrode plate composed of a positive electrode active material, a conductive agent and a binder.

The present invention solves such a problem, and provides a non-aqueous electrolyte secondary battery which is easy to manufacture and does not have a decrease in discharge capacity due to a difference in charge / discharge capacity of a negative electrode, and a method for manufacturing the same. The purpose is.

[0010]

In order to solve this problem, the present invention prepares an electrode plate containing a positive electrode active material, which is treated with a lithiating agent such as butyl lithium, phenyl lithium, naphthyl lithium or lithium iodide. A battery is constructed by using a positive electrode plate prepared by immersing in a liquid containing the positive electrode.

Further, the battery is constructed by immersing an electrode body having positive and negative electrodes opposed to each other through a separator in a liquid containing the above-mentioned lithiating agent.

Further, the battery is manufactured by inserting the electrode body into a battery case, injecting a liquid containing a lithiating agent into the battery case, adding an electrolytic solution and sealing the battery.

[0013]

According to the non-aqueous electrolyte secondary battery of the present invention and the manufacturing method thereof, LiMn ₂ O ₄ , LiMnO ₂ , LiCoO ₂ , L
iNiO _2, LiFeO ₂ or γ-LiV ₂ O ₅ butyllithium, the step of immersing in a liquid containing a lithiating agent, such as phenyllithium or lithium iodide, the solvent and the positive electrode active material and the conductive agent and a binder Kneading using, coating,
By performing after the positive electrode plate is dried, it is not necessary to use a non-aqueous solvent in all steps up to the positive electrode plate, and the working atmosphere also needs to be performed in an inert gas from which moisture has been removed or in dry air. There is no. Furthermore, by inserting the above electrode body into a battery case and then injecting the above lithiating agent into the battery case, there is no loosening of the electrode due to swelling of the electrode when the electrode is immersed, and workability during battery assembly is improved. Can be made

[0014]

EXAMPLES A non-aqueous electrolyte secondary battery and a method of manufacturing the same according to one example of the present invention will be described below with reference to the drawings.

[0015] a (Example 1) LiMn ₂ O ₄ is Li ₂ CO ₃ and Mn ₃ O ₄ 3: were mixed in a molar ratio of 4 was synthesized by heating at 900 ° C.. LiCoO ₂ is Li ₂ C
It was synthesized by mixing O ₃ and CoCo ₃ in a molar ratio of 1: 2 and heating at 900 ° C. LiMnO ₂ is Li ₂ C
It was obtained by mixing O ₃ and MnCO ₃ in a molar ratio of 1: 2 and heating at 800 ° C. LiNiO ₂ is LiOH and N
It was obtained by mixing i (NO ₃ ) ₂ in a molar ratio of 1: 1 and heating at 800 ° C. LiFeO ₂ is Li ₂ CO ₃ Fe
Obtained by mixing (OH) ₃ in a molar ratio of 1: 2 and heating to 650 ° C. γ-LiV ₂ O ₅ is Li ₂ CO ₃ and V
Obtained by mixing ₂ O ₅ 1: 2 and heating to 700 ° C. Further, these were crushed and classified to 100 mesh or less, and used as the positive electrode active material.

Next, for the negative electrode plate, 100 g of graphite which is an active material, and 10 parts of polyfluorinated ethylene as a binder were used.
g was added, a paste was formed using water, and this was applied to a nickel core material and dried.

The positive electrode plate was prepared by adding 10 g of carbon powder as a conductive agent and 5 g of polytetrafluoroethylene as a binder to 100 g of the positive electrode active material, adding water and kneading to form a paste. It was prepared by coating on a core material and drying. This electrode plate was immersed in a 1.65 mol / liter n-butyllithium hexane solution and used as a positive electrode plate. At this time, Li _x Mn ₂ O ₄ , Li _x MnO ₂ , and Li _x Co such that the lithium in the positive electrode active material is in excess of 15%.
O ₂ , Li _x NiO ₂ , Li _x FeO ₂ or γ-Li _x V
Six types of positive electrode active materials having an X value of ₂ O ₅ of 1.15 were obtained. Using such a positive electrode plate, batteries (A), (B), (C), (D), (E) and (F) were produced by the following method.

The structure of the battery of this embodiment is shown in FIG. The electrode body is a strip-shaped porous polypropylene separator having a width wider than both electrode plates, between a positive electrode plate 1 having a positive electrode lead 4 made of the same material as the core material attached by spot welding and a negative electrode plate 2 having a negative electrode lead 5. 3 is interposed and the whole is spirally wound. Further, polypropylene insulating plates 6 and 7 are arranged on the upper and lower sides of the electrode body, respectively, and inserted into the battery case 8 to form a step 8a on the upper part of the battery case 8. A propylene carbonate solution in which mol / liter of lithium perchlorate is dissolved is injected, and the sealing plate 9
Seal with and make a battery.

Further, as Comparative Example 1, LiM was used as the positive electrode active material.
n ₂ O ₄ , LiMnO ₂ , LiCoO ₂ , LiNiO ₂ , L
iFeO ₂ and r-LiV ₂ O ₅ were used, and 10 g of carbon powder as a conductive agent was added to 100 g of the positive electrode active material.
A positive electrode plate prepared by adding 5 g of polytetrafluoroethylene as a binder, adding water and kneading to form a paste, applying it to a titanium core material, and drying it, and a negative electrode plate prepared in the same manner as in Example 1. Using the same method as in Example 1, batteries (a1), (b1), (c1), (d1), (e
1) and (f1). As Comparative Example 2, the positive electrode active material powder was dipped in a liquid containing n-butyllithium,
(A2), (b2), (c2), (d2), (e2), batteries using the positive electrode plate manufactured by the same method as in Comparative Example 1
(F2). The batteries thus produced are summarized in (Table 1).

[0020]

[Table 1]

In the voltage range shown in (Table 1) of the above battery,
Charging / discharging was performed at a charging / discharging current of 0.5 mAh / cm ² . The results are summarized in (Table 2).

[0022]

[Table 2]

As shown in FIG. 2, the positive electrode active material Li _x Mn ₂ O ₄ changes its potential by releasing lithium by charging and occluding the lithium released by discharging. Then, by performing charging / discharging from 3.0 V to 4.5 V, the x value changes from 1.0 to 0.3,
The amount of lithium that can be used for charging and discharging from V to 4.5 V is about 0.7 electron. Therefore, when this positive electrode active material is used, a high-capacity battery can be constructed by using all lithium (0.7 electrons) that can be used in charge / discharge from 3.0 V to 4.5 V for the reaction. it can.

However, the battery (a1) of the comparative example using graphite for the negative electrode had a charge capacity of 410 mAh at the first cycle, whereas the discharge capacity was 328 mAh, and the difference in capacity between charge and discharge was 82 mAh. It was The lithium having a charge / discharge capacity difference of 82 mAh generated in the first cycle is occluded in graphite, which is the negative electrode active material, and does not participate in the subsequent charge / discharge reaction. Therefore, the battery capacity in the second cycle is 32
It became 7 mAh. In this case, since the first cycle of charging does not participate in the subsequent battery reaction while the lithium of 0.15 electrons is occluded in the graphite, charging / discharging of the positive electrode active material Li _x Mn ₂ O ₄ The X value varies from 0.85 to 0.3, and the amount of lithium used for charging and discharging is 0.55 electrons. Therefore, when graphite is used for the negative electrode, the battery capacity is reduced by about 20%. LiMnO ₂ , LiCoO ₂ , LiNiO ₂ , Li as the positive electrode active material
Batteries (b1), (c1), (d1), (e1), (f1) of Comparative Example 1 using FeO ₂ or r-LiV ₂ O ₅
For the same reason, the battery capacity of the second cycle is 32
It becomes about 0 mAh to 390 mAh.

On the other hand, in the battery (A), which is one of the present embodiments, the positive electrode active material was prepared by previously absorbing excessively the lithium of the charge / discharge capacity difference generated in the battery (a1).
i _x Mn ₂ O ₄ (X = 1.15) is used. When charging and discharging are actually performed, the charge capacity in the first cycle of the battery (A) is 493 mAh and the discharge capacity is 411 mAh.
In this case as well, a charge / discharge capacity difference of 82 mAh occurs in the first cycle, and this 82 mAh of lithium is used in the battery (a1).
Similarly to the above, it is occluded in graphite, which is the negative electrode active material, and does not participate in the subsequent charge / discharge reaction. However, the lithium stored in graphite of the negative electrode active material and not involved in charging / discharging is supplemented by 0.15 electron worth of lithium stored excessively in the positive electrode active material, and in the second cycle charging / discharging, the positive electrode active material is not charged. Material Li _x Mn ₂
The amount of lithium X in O ₄ changes in the range of 1.0 to 0.3, and the amount of lithium used for charge and discharge is 0.7 electrons. Therefore, it is possible to eliminate the decrease in battery capacity due to the negative electrode active material. In addition, batteries (B), (C),
The same applies to (D), (E), and (F). The charge and discharge capacities in the second cycle are the batteries (b1), (c1), and
It can be seen that the battery capacities are large as compared with (d1), (e1), and (f1).

The batteries (a2) to (f2) of Comparative Example 2 were also used.
Is a non-lithiated positive electrode active material.
Even more capacity than the batteries of ponds (a1) to (f1)
Has dropped. Positive electrode plate used for battery (a2) of Comparative Example 2
The results of X-ray diffraction measurement of are shown in FIG. Also, at the same time
The results of X-ray diffraction of the positive electrode plate used in the battery (a1) are also shown in
did. As shown in FIG. 4, the electrode plate used in (a1) is
Spinel type LiMn ₂O_FourCan show the diffractogram of
Recognize. However, the electrode plate used for (a2) also has the same spin rate.
Nell type LiMn₂O_FourShows the diffraction peak of
A diffraction peak which seems to be LiOH was shown. These things
The electrode used in the battery (a2) contains an excess of lithium.
Li_1.15Mn₂O_FourReacts with the water used to make the electrode plate
And LiMn₂O_FourAnd it has been divided into LiOH
Conceivable. Thus, LiO is contained in the electrode of the battery (a2).
The battery capacity was greatly reduced due to the residual H.
Seem. The same applies to batteries (b2) to (f2).
It was found that the battery capacity had decreased due to the reason.

Example 2 In Example 1, the case where a graphite material was used as the negative electrode active material was explained, but in this Example, the case where aluminum powder having a larger charge / discharge capacity difference was used as the negative electrode active material. explain.

An electrode plate using LiMn ₂ O ₄ as the positive electrode active material was added to 100 g of the positive electrode active material in the same manner as in Example 1 by adding 10 g of carbon powder as a conductive agent and 5 g of polytetrafluoroethylene as a binder. It was made into a paste using water, applied to a titanium core material, and dried. This electrode plate was immersed in a hexane solution of n-butyllithium to prepare a positive electrode plate having a Li _x Mn ₂ O ₄ value of 1.35 in the electrode.

As the negative electrode, 100 g of aluminum powder as an active material and 1 part of polyfluorinated ethylene as a binder were used.
0 g was added, water was used to form a paste, which was applied to a nickel core material and dried. A battery was assembled in the same manner as in Example 1 using the positive electrode plate and the negative electrode plate thus produced. This battery is referred to as (G).
As a comparative example, a battery composed of a positive electrode plate using LiMn ₂ O ₄ as a positive electrode active material and not subjected to lithiation treatment and a negative electrode plate using aluminum powder as a negative electrode active material (g
1). In addition, the positive electrode active material powder LiMn ₂ O ₄ was added to n-
An active material Li _1.35 Mn ₂ O ₄ prepared by immersing in a hexane solution containing butyllithium was used, and the positive electrode plate and the negative electrode plate were prepared by kneading the active material Li _1.35 Mn ₂ O ₄ with water and a binder. The prepared battery is referred to as (g2). These batteries (G), (g1) and (g2) have a battery range of 4.2V-
Charging and discharging were performed under the conditions of 3.0 V and current of 0.5 mAh / cm ² . The results are shown in (Table 3).

[0030]

[Table 3]

The charge capacity in the first cycle of the battery (g1) of the comparative example using LiMn ₂ O ₄ as the positive electrode active material was 412 mA.
Therefore, the discharge capacity is 206 mAht, which is very small. This is because the difference in charge and discharge capacities of the aluminum powder used as the negative electrode active material is large.
Due to the presence of 6 mAh. On the other hand, in the battery (G) of this example, Li _x Mn ₂ O ₄ (X =, in which the lithium was excessively occluded in the positive electrode active material in consideration of the charge / discharge capacity difference of the negative electrode).
1.35) is used, the charge capacity in the first cycle is 614 mAh, and the discharge capacity is 411 mAh.
It became h. Comparing the charge and discharge capacities in the second cycle between the battery (G) of this example and the battery (g1) of comparative example 1, it can be seen that the capacity of the battery (G) of this example is about twice as large. Further, the battery (g2) was 3% for the same reason as in Example 1.
It has the smallest capacity of the two batteries.

In this embodiment, an example in which LiMn ₂ O ₄ is used as the positive electrode active material has been described, but the positive electrode active materials LiMnO ₂ , LiCoO ₂ , LiNiO ₂ , LiFe shown in the first embodiment are used.
Similar results were obtained when at least one selected from the group consisting of O _{2 and} γ-LiV ₂ O ₅ was used as the positive electrode active material.

Example 3 As in Example 1, 100 g of positive electrode active material LiMn ₂ O ₄ and 10 g of carbon powder as a conductive agent were used.
Then, 10 g of polyfluoroethylene as a binder was added, and water was added to form a paste, which was applied to a titanium core material and dried to form an electrode. The negative electrode was also manufactured by the same method as in Example 1. Further, an electrode body is constructed by spirally winding the whole between a positive electrode and a negative electrode with a strip-shaped separator wider than both electrode plates, and polypropylene insulating plates are provided above and below the electrode body. Distribute and insert into battery case, n
-Inject a hexane solution of butyllithium and leave it for a predetermined time, then remove the hexane solution and use it as a non-aqueous electrolyte.
A propylene carbonate solution in which 1 mol / liter of lithium perchlorate was dissolved was injected and sealed with a sealing plate to form a battery. This battery is designated as (H). The battery (H) charge / discharge test was conducted in a voltage range of 4.3 to 3.0 V and a radio wave of 0.5
Charging / discharging was performed under the condition of mAh / cm ² . The charging / discharging capacities of the batteries (H) of the present Example at the 1st and 2nd cycles are shown in (Table 4).

[0034]

[Table 4]

The charge capacity in the first cycle is 494 mAh.
Then, the discharge capacity was 413 mAh. Comparing the charge and discharge capacities in the second cycle with the batteries (a1) and (a2) of the comparative example, the method of the battery (H) of the present example was 85 mA each.
h, 104 mAh large. A battery produced by a method in which such a positive electrode and a negative electrode were spirally inserted through a separator and was inserted into a battery case, and a liquid of butyllithium was injected therein also obtained the same results as in Examples 1 and 2. ..

A battery prepared by winding an electrode plate and a separator wound in a spiral shape, immersing the solution in butyllithium or phenyllithium, drying it, inserting it into a battery case, and injecting an electrolytic solution. Had the same effect. The battery of this embodiment has advantages that the electrode is not loosened due to the swelling of the electrode when immersed in the electrode, and the workability during battery assembly can be improved.

In this example, LiMn was used as the positive electrode active material.
An example in which graphite is used as the negative electrode active material of ₂ O ₄ has been described, but as the positive electrode active material, LiMnO ₂ , LiCoO ₂ , L
iNiO _2, LiFeO ₂ or γ-LiV ₂ O _5, there are also the effects on all of the combinations using negative example graphite material or aluminum having a capacitance difference in first eye of charge and discharge as the negative electrode active material.

In the above examples, a calibration curve was prepared using the concentration of n-butyllithium used for the treatment, the treatment time, and the amount of lithium in the positive electrode active material that was chemically quantified. Of lithium was determined.

Not only n-butyllithium but also s
Similar effects can be obtained with a lithiating agent such as ec-, tert-butyllithium, phenyllithium, naphthyllithium, or lithium iodide. The reactivity with the positive electrode active material was in the order of tert-butyllithium>sec-butyllithium>n-butyllithium>phenyllithium>naphthyllithium> lithium iodide. However, n-butyllithium was the easiest to handle in work.

Further, in the embodiment, the amount of the electrolyte is 1 mol / mol.
The case of using a propylene carbonate solution in which liter of lithium perchlorate is dissolved has been described. Similar effects were obtained with electrolytes containing carbonates such as ethylene carbonate and gamma-butyl lactone and esters such as methyl acetate.

Not limited to graphite and aluminum powder,
It goes without saying that the present invention is also effective for substances that store and release lithium having different charge and discharge capacities, such as aluminum alloys, WO ₂ and Fe ₂ O ₃ .

[0042]

As is apparent from the above description of the embodiments, according to the present invention, the positive electrode active materials LiMn ₂ O ₄ and LiMn
By dipping O ₂ , LiCoO ₂ , LiNiO ₂ , LiFeO ₂ or γ-LiV ₂ O ₅ in a liquid containing a lithiating agent such as butyllithium or phenyllithium, water can be used in the subsequent manufacturing steps. That is, the step of lithiation is performed after the electrode plate is manufactured or after the electrode body in which the positive electrode and the negative electrode are opposed to each other with the separator interposed therebetween, and further after the electrode body is inserted into the battery case, the active material is pulverized and classified. In addition, water can be used as a coolant during the production of the electrode. In addition, it is not necessary to perform these steps in an inert gas atmosphere from which moisture is removed or in a dry air poisoning,
Work efficiency is improved. Furthermore, it is possible to provide a battery that does not cause a decrease in capacity due to the difference in charge / discharge capacity of the negative electrode, which is of great industrial significance.

[Brief description of drawings]

FIG. 1 is a vertical cross-sectional view showing the structure of a battery used in an example of the present invention.

FIG. 2 shows the Li in the active material of the same positive electrode active material Li _x Mn ₂ O _4.
The figure which shows the relationship between quantity X and open circuit potential.

FIG. 3 is a diagram showing the relationship between the Li amount X in the active material of the positive electrode active material Li _x CoO ₂ and the open circuit potential.

FIG. 4 is an X-ray diffraction diagram of a positive electrode plate used for a battery (a1) and a battery (a2).

[Explanation of symbols]

 1 Positive electrode 2 Negative electrode 3 Separator 4 Positive electrode lead plate 5 Negative electrode lead plate 6 Upper insulating plate 7 Lower insulating plate 8 Battery case 9 Sealing plate

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masaki Hasegawa 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd.

Claims (3)

[Claims] 1. LiMn ₂ O ₄ , Li as a positive electrode active material
An electrode composed of at least one selected from the group of MnO ₂ , LiCoO ₂ , LiNiO ₂ , LiFeO ₂ or γ-LiV ₂ O ₅ , and a conductive agent and a binder is provided as n-butyllithium, sec-butyllithium, tert. A positive electrode prepared by immersing in a liquid containing at least one selected from the group consisting of butyllithium, phenyllithium, naphthyllithium, or lithium iodide; and a negative electrode that occludes lithium by charging and releases lithium by discharging. Non-aqueous electrolyte secondary battery. 2. LiMn ₂ O ₄ , Li as a positive electrode active material
A positive electrode using at least one selected from the group of MnO ₂ , LiCoO ₂ , LiNiO ₂ , LiFeO ₂ or γ-LiV ₂ O ₅ , and a negative electrode which occludes lithium by charging and releases lithium by discharging via a separator. After facing each other,
n-butyllithium, sec-butyllithium, ter
It is immersed in a liquid containing at least one selected from the group consisting of t-butyllithium, phenyllithium, naphthyllithium, or lithium iodide, and then the positive electrode and the negative electrode are placed in a battery case, and a nonaqueous electrolytic solution is further added. Manufacturing method of non-aqueous electrolyte secondary battery. 3. LiMn ₂ O ₄ , Li as a positive electrode active material
A positive electrode using at least one selected from the group of MnO ₂ , LiCoO ₂ , LiNiO ₂ , LiFeO ₂ or γ-LiV ₂ O ₅ , and a negative electrode which occludes lithium by charging and releases lithium by discharging via a separator. Facing each other and placed in a battery case, and a liquid containing at least one selected from the group of n-butyllithium, sec-butyllithium, tert-butyllithium, phenyllithium, naphthyllithium, or lithium iodide is injected, and A method for manufacturing a non-aqueous electrolyte secondary battery in which a non-aqueous electrolyte is injected.