JPH103907A - Lithium secondary battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a lithium secondary battery, capable of high capacity and high speed charging/discharging (high current charging/discharging), and excellent in a charge/discharging cycle characteristics. SOLUTION: A copper foil applied with carbon particles carrying fine particles of a metal forming an alloy with lithium, and of another metal forming no alloy with lithium, or carbon powder carrying fine particles of an intermetallic compound of both types of metallic fine particles is adopted as a negative electrode 17. An aluminum foil applied with a mixture of LiCoO2 active material and artificial graphite is adopted as a positive electrode 15. Polyethylene-made porous film separators 19 are arranged between the positive and negative electrodes, the positive and negative electrodes 15 and 17 and the separators 19 are wound to be housed in a battery can, and 1MLiPF6 /EC- DMC is fitted in as an electrolyte. The can realize high capacity and high speed charging/discharging (high current charging/discharging), and also improve the cycle life.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithium secondary battery, and more particularly, to a negative electrode for a lithium secondary battery having a large discharge capacity, a high power density and a high charge / discharge rate and excellent cycle characteristics. Lithium secondary batteries are used as power sources for electric vehicles, memory backup, and portable equipment. For example, when installed in electronic devices, notebook computers, word processors, mobile phones, cordless phone handsets, portable faxes, portable printers, headphone stereos, video movies, LCD TVs, handy cleaners, portable CDs, electric shavers, electronic translators, Used for car phones, transceivers, power tools, memory cards, etc. In addition, it can be used in combination with medical equipment (pacemaker, hearing aid, shoulder massager, etc.) for consumer use, or for space use or solar cells.

[0002]

2. Description of the Related Art Conventionally, lithium (Li) metal and alloys such as Li-Al and Li-Pb have been used as a negative electrode of a lithium secondary battery. The short circuit and cycle life of the negative electrode are short,
There was a disadvantage that the energy density was low. Recently, research on using a carbon material for a negative electrode has been actively conducted to solve these problems. This type of negative electrode is disclosed, for example, in Japanese Patent Laid-Open No. 5-299073.
And Japanese Patent Application Laid-Open Nos. Hei 2-121258, Hei 6-349482, and Hei 7-335623.
The configuration in Japanese Patent Application Laid-Open No. 5-299073 discloses that the surface of highly crystalline carbon particles forming a core is coated with a film containing a metal element of Group VIII,
Further, the electrode material is a carbon composite having carbon coated thereon, whereby the carbon material having a turbostratic structure on the surface assists the intercalation of lithium, and at the same time, is filled because the surface area of the electrode is large. It is said that the discharge capacity and the charge / discharge rate have been significantly improved. JP-A-2-
In the publication of 121258, H / C <0.15, interplanar spacing> 3.
By using a mixture of a carbon material having a crystallite size Lc <150 ° in the 37 ° direction and the C-axis direction and a metal alloyable with Li, the charge / discharge cycle life is long and the charge / discharge characteristics at a large current are good. And In JP-A-6-349482, a carbon composite having copper oxide adhered on the surface of all or a part of graphite particles capable of intercalating / deintercalating lithium is used as an electrode material. Since a composite oxide of lithium and copper that progresses reversibly is formed in the electrochemically reduced copper, the capacity can be increased. On the other hand, JP-A-7-33
In Japanese Patent No. 5263, it is possible to reduce the contact resistance between active materials or to reduce the contact resistance between a current collector and an active material by adding a metal as a conductive auxiliary to carbon used for a negative electrode or a positive electrode active material. It is possible to suppress a decrease in capacity as much as possible even at high rate discharge (large current discharge). If it is limited to the negative electrode, the orientation of graphite on the current collector can be prevented by adding alloys such as stainless steel and permalloy to graphite other than metal carriers such as nickel, copper, silver, and aluminum. It is said that the proportion facing the electrolytic solution side is increased, the diffusion of ions is facilitated, and a large current discharge is possible. The present inventors have disclosed in Japanese Patent Application No. 7-15676 a high capacity and a high power density by using carbon particles carrying particles of 1000 mm or less of a metal forming an alloy with lithium on the surface of carbon particles as a negative electrode material. An application has been filed to provide a lithium secondary battery having an excellent increase in cycle and excellent cycle characteristics.
However, in each case, the difficulty in preparing the negative electrode carbon material and the theoretical capacity of carbon were not drawn out, and the output density was not yet sufficient. In particular, there has been a problem that it has to be greatly improved in terms of high-speed charging and discharging (high-current charging and discharging). Therefore, the energy density and the power density were insufficient for mounting on electric vehicles and motorcycles.

As described above, when a carbon material and a composite material are used as a negative electrode, the theoretical capacity of carbon cannot be drawn out, the preparation of the negative electrode carbon material is difficult, and high-speed charging and discharging (high-current charging and discharging) can be performed. There was no problem.

[0004]

DISCLOSURE OF THE INVENTION The present inventors have made intensive studies to solve the above-mentioned problems, and by using a negative electrode having a specific structure, high-capacity, high-speed charge / discharge is possible and charge / discharge is possible. It is an object of the present invention to complete a lithium secondary battery having excellent cycle characteristics, and to provide the same.

[0005]

Means for Solving the Problems The present inventors have obtained the following findings and completed the present invention based on the following findings. First, the cycle characteristics of the conventional negative electrode and the improved negative electrode were examined, and the measurement results are shown in FIG. Here, the carbon used as the negative electrode is natural graphite that has been subjected to a high-purification treatment, and has a particle size of about 11 μm. A paste obtained by dissolving ethylene propylene terpolymer (hereinafter abbreviated as EPDM) in diethylbenzene as a binder in carbon and using carbon and EPDM in a weight ratio of 94: 6 is used as a current collector. The paste is applied to a copper foil with a thickness of 20 μm. Separately, the paste is used as a current collector, with a thickness of 0.9 mm and a porosity of 93%.
Into a copper foam metal having a three-dimensional network structure. Here, the former is called a conventional negative electrode, and the latter is called an improved negative electrode. After air-drying, both were vacuum-dried at 80 ° C. for 3 hours, molded at a pressure of 0.5 ton / cm ² , and further vacuum-dried at 150 ° C. for 2 hours.
Each was used as a negative electrode. One of these negative electrodes is combined with a lithium metal counter electrode with a polypropylene microporous membrane serving as a separator therebetween, and 1 MLiPF ₆ / ethylene carbonate-dimethoxyethane (hereinafter referred to as EC-D) is used as an electrolyte.
A test cell using lithium metal as a reference electrode was assembled. Using this test cell, each of the conventional negative electrode and the improved negative electrode was subjected to a cycle test at a charge / discharge rate of 120 mA / g of carbon and a potential width of charge / discharge: 0.01 to 1.0 V.

As is clear from FIG. 1, when the conventional negative electrode 1 is used, the discharge capacity decreases every cycle, and after about 500 cycles, the discharge capacity decreases to about 60 times the initial capacity.
%. On the other hand, 50 using the improved negative electrode 2
Even after 0 cycles, the drop rate is as small as 4.5%,
The effect of improving the current collector was recognized. This experimental fact shows that the improved electrode with a three-dimensional network structure was able to suppress the reduction of the current collection effect between carbon particles due to electrode swelling due to volume changes due to repeated charging and discharging. Conceivable. Then, the following experiment was conducted to verify the above. That is, it was examined whether the same effect can be obtained by adding metal fibers to the negative electrode mixture.

FIG. 2 shows the result. The experiment of FIG. 2 is almost the same as that of FIG. 1, but the outline of the measurement conditions is shown below. The carbon used was artificial graphite having a particle size of about 3 μm, and copper fibers having a wire diameter of 10 μm were mixed at a weight ratio of 90:10. Polyvinylidene fluoride (hereinafter, referred to as a binder)
PVDF) (abbreviated as PVDF), a paste obtained by mixing the above mixture and PVDF in a weight ratio of 90:10 was applied to a 20 μm-thick copper foil as a current collector, air-dried, and then dried. After vacuum drying at a temperature of 0.5 ° C. for 3 hours and molding at a pressure of 0.5 t / cm ² , the product was further vacuum dried at 120 ° C. for 2 hours to obtain a negative electrode. This negative electrode was combined with a lithium metal counter electrode with a polypropylene microporous membrane interposed, and a test using 1 MLiPF ₆ / ethylene carbonate + dimethoxycarbonate (hereinafter abbreviated as EC + DMC) as an electrolyte and lithium metal as a reference electrode The cell was assembled. The charge / discharge rate was 120 mA per g of carbon, and the upper and lower limit potentials of the charge / discharge were 1.0 V and 0.01 V, respectively. The results obtained are shown in FIG. FIG. 2 also shows the characteristics of the negative electrode to which no copper fiber was added. As is clear from the results of FIG.
It was found that the discharge capacity was large and the decrease in each cycle was extremely small. Similar results were obtained for a negative electrode using copper powder instead of copper fiber. From the above results, increasing the current collection performance of the negative electrode mixture layer is an important factor for improving the discharge capacity and cycle characteristics.Rather than simply mixing carbon and conductive fibers or conductive powder, carbon is used. By supporting fine particles of a metal that forms an alloy with lithium on top, the same effect can be obtained even if the amount of addition (support) is smaller than that of a mixed system of carbon and conductive materials, It has been found that an alloying capacity can be used, and that a new function can be expected in which electric conductivity and thermal conductivity can be improved by interposing a metal between carbon particles. In the cycle test of the negative electrode of this application, stable performance was shown up to about 300 cycles.

Then, as a result of further detailed examination, it was found that carbon particles carrying fine particles of a metal which forms an alloy with lithium and a metal not forming an alloy on carbon as a negative electrode or carbon particles carrying fine particles of an alloy of both. The use of particles makes it possible to surprisingly add high-speed charge / discharge (high current) in addition to the above-mentioned functions as compared with the case where carbon particles carrying fine particles of a metal that does not form an alloy with lithium on carbon are used as a negative electrode. Charge / discharge), that is, the energy density per kg of battery weight
It has been found that it is possible to discharge an output of 350 w or more for 20 minutes or more.

That is, according to the present invention, a negative electrode of a unit cell constituting a lithium secondary battery is characterized in that carbon particles carrying both a metal forming an alloy with lithium and a metal not forming an alloy, or a carbon particle carrying both metals. Is a lithium secondary battery characterized in that a carbon particle supported by forming an alloy is held on a current collector. As the lithium secondary battery, one having a capacity of 0.5 wh to 50 kwh is used.
The lithium secondary battery equipped with the above-described negative electrode enables an output having an energy density of 350 W or more per 1 kg of battery weight to be discharged for 20 minutes or more. Further, the metal is preferably used in the form of fine particles having a particle size of 1000 ° or less, and the amount of the metal carried is 30% based on the total weight of carbon and the metal.
% Or less, preferably 1 to 10% by weight or less, and the addition ratio of a metal that forms an alloy with Li and a metal that does not form an alloy is:
The weight ratio is 1: 9 to 9: 1, preferably 1: 3 to 3: 1.

Further, the present invention is an electric vehicle or a motorcycle equipped with a motor powered by the lithium secondary battery. This lithium secondary battery has a charge / discharge rate of 1 C or more and 350 watts per liter of battery capacity.
Those having an energy density of h or more are used. As carbon used in the present invention, those capable of intercalating and deintercalating lithium, for example, natural graphite,
Graphitizable material obtained from petroleum coke or coal pitch coke, etc. heat-treated at a high temperature of 2500 ° C or higher,
Mesophase carbon or amorphous carbon and mixtures thereof are used. The average particle size is 50 μm or less, preferably 1 to 20 μm. The shape may be spherical, massive, scale-like, fibrous, or a crushed product thereof.

The supported metals forming an alloy with lithium include Al, Sb, B, Ba, Bi, Cd, Ca, Ga,
In, Ir, Pb, Hg, Si, Ag, Sr, Te, T
At least one of i and Sn is selected, but preferably (1) an alloy composition having a high lithium content, (2)
Relatively low atomic weight, relatively high density, (3) easy reduction, (4) low oxidation-reduction potential of lithium alloy,
It is preferable to satisfy various conditions such as (5) there is little problem in disposal, and (6) it is relatively inexpensive.

Next, at least one of Fe, Ni, Cu, Pt and Au is selected as a metal which does not form an alloy with lithium. Preferably, (1) the oxidation potential is high, and (2) reduction is It is preferable to satisfy various conditions such as easy, (3) little problem in disposal, and (4) relatively low cost. Metal loading methods include vapor deposition, sputtering, wet reduction, electrochemical reduction, plating, and gas-phase reduction gas treatment, but the most suitable loading method is selected according to the type of metal used. Should be applied. The amount of metal carried is preferably 30 wt% or less, preferably 1 to 10 wt%, as the total amount of both. The addition ratio of the metal that forms an alloy with lithium and the metal that does not form an alloy with lithium is 1: 9 to 9: 1, preferably 1: 3 to 3: 1. If the addition ratio of the two metals is not in the above range, the effect of high-speed charge / discharge (high-current charge / discharge) cannot be obtained.

In order to form an alloy with a metal which forms an alloy with lithium and a metal which does not form an alloy, for example, Cu and Sn are supported on carbon particles by wet reduction, and dried carbon powder is placed in a reducing gas stream. The heat treatment is performed at a predetermined temperature. Furthermore, the particle size of the supported metal is determined by considering the precipitation and dissolution rate of the lithium alloy during charge and discharge in the case of a metal formed of an alloy. 1000 mm or less is desirable to increase points. Furthermore, the particle size of the supported metal is determined by considering the precipitation and dissolution rate of lithium metal during charge and discharge in the case of a metal that forms an alloy, and in the case of a metal that does not form an alloy, between carbons that affect electron conductivity. 1000 mm or less is desirable to increase the contact point.

A negative electrode is prepared using the metal-supported carbon particles obtained as described above. In this case, a binder is used. The binder is not particularly limited as long as it does not react with an electrolytic solution such as EPDM, PVDF, and polytetrafluoroethylene. The amount of the binder is 1 to carbon.
30 wt%, preferably 5 to 15 wt% is suitable. The shape of the negative electrode using the above-mentioned mixture can be adapted to the shape of a battery by, for example, filling a film or foam metal on a sheet, film, or metal foil (see FIG. 4). The thickness of the mixture layer is preferably in the range of 10 to 200 μm.

By combining the negative electrode thus obtained with a commonly used positive electrode, a separator and an electrolytic solution, an optimal lithium secondary battery can be obtained. The active materials used for the positive electrode include LiCoO ₂ , LiNiO ₂ and LiMn ₂ O ₄
A composite oxide containing lithium such as may be used,
A mixture of a conductive agent such as carbon black or carbon and an adhesive is applied to a current collector such as an Al foil to form a positive electrode.

As the separator, a porous film of polypropylene, polyethylene or polyolefin is used. As the electrolytic solution, two types such as propylene carbonate (PC), ethylene carbonate (EC), 1,2-dimethoxyethane (DME), dimethoxycarbonate (DMC), diethyl carbonate (DEC), and methyl ethyl carbonate (MEC) are used. The above mixed solvents are used. LiPF ₆ , LiB
There are F ₄ , LiClO _{4 and the} like, and those dissolved in the above-mentioned solvents are used.

An improved carbon negative electrode for a lithium secondary battery uses carbon particles carrying fine particles of a metal that forms an alloy with lithium and a metal that does not form an alloy or carbon particles carrying fine particles of an alloy of both. Thereby, (1) the discharge capacity is increased, (2) the output density is improved, (3) the electric conductivity is improved, and the speed of the charge / discharge reaction is improved.
(4) Since the charge / discharge capacity of an alloy formed with lithium as an additional metal can be used, a value exceeding the theoretical capacity of graphite of 372 mAh / g can be obtained. (5) The metal supporting the reaction site on the carbon particle surface causing the irreversible capacity (6) Naturally, the output density of the battery is also increased because the discharge capacity is increased. (7) The cycle characteristics are improved accompanying the above (2), and the heat dissipation in the assembled battery is improved. A remarkable effect is obtained such that the property can be improved.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below with reference to examples. However, the technical scope of the present invention is not limited to these examples.

[0019]

【Example】

[Example 1] Artificial graphite subjected to high purification treatment (interplanar spacing d ₀₀₂₎
= 3.359 °, crystallite size Lc = 540 °, specific surface area = 10m ² /
g) Suspend 9.5 g in 450 ml of water containing 25 ml of ethanol. This was heated to about 55 ° C., and 0.39 g of silver nitrate (AgNO ₃ ) and 0.95 g of copper nitrate (Cu (NO ₃ ) ₂ .3H ₂ O) were added and dissolved with vigorous stirring. To this, 100 ml of water containing 8 ml of hydrazine (N ₂ H ₄ ) is dropped by a microtube pump, and the simultaneous reduction reaction is completed in about 3 hours. Thereafter, the mixture was filtered and washed with water, and vacuum dried at 350 ° C. for 6 hours. According to chemical analysis, the amount of metal in the obtained powder A was 2.
Ag is 2.45% by weight and Cu is 2.32% by weight with respect to 5% by weight.
Met. Further, when the existence states of Ag and Cu were examined by X-ray diffraction, a very small amount of diffraction lines based on cuprous oxide: Cu ₂ O were recognized in addition to the diffraction lines of Ag and Cu in a metal state. Next, when the dispersion state of Ag and Cu was observed by an energy dispersive electron probe microanalysis, the Ag and Cu particles were distributed over the entire surface of the graphite particles, and were slightly concentrated on the end surfaces of the graphite particles. Further, when the size of the metal particles was observed with a transmission electron microscope, several hundreds of particles were almost uniformly dispersed.

Example 2 Highly purified natural graphite (d ₀₀₂ = 3.362 °, Lc = 330 °, specific surface area = 20 m ² /
The same operation as in Example 1 was performed using g) to obtain Powder B. [Example 3] 9.5 g of artificial graphite subjected to a high-purification treatment was applied to 25 m
Suspend in 450 ml of water containing l ethanol. About 55
The mixture was heated to ℃ and 0.39 g, AgNO ₃ and 1.24 g of nickel nitrate (Ni (NO ₃ ) ₂ .6H ₂ O) were added and dissolved with vigorous stirring.
0.5% by weight of sodium tetraborohydride (N
aBH ₄ ) Drop the aqueous solution with a micro tube pump,
Complete the simultaneous reduction reaction over time. After that,
It was washed with water and vacuum dried at 350 ° C. for 6 hours. Powder C obtained
According to chemical analysis, the amount of metal in each
Ag was 2.44% by weight and Ni was 2.30% by weight with respect to 2.5% by weight. In addition, when the existence state of Ag and Ni was examined by X-ray diffraction, a very small amount of diffraction line based on NiO was recognized in addition to the diffraction lines of Ag and Ni in a metal state. Next, when the dispersion state of Ag and Ni was observed by an energy dispersive electron probe microanalysis, Ag and Ni were distributed over the entire surface of the graphite particles, and were slightly concentrated on the end surfaces of the graphite particles. Further, when the size of the metal particles was observed with a filtration electron microscope, several hundreds of particles were almost uniformly dispersed.

Example 4 The same operation as in Example 3 was performed using natural graphite that had been subjected to a high-purification treatment to obtain powder D. Example 5 A mixture of 25 ml of ethanol and 450 ml of water was mixed at 55 ° C.
Warm up. After adding and dissolving 0.5 g of potassium hydrogen phthalate thereto, 0.39 g of AgNO ₃ and Cu (NO ₃ ) were stirred with vigorous stirring.
It was added ₂ · 3H ₂ O 0.95g dissolved. Next, 9.5 g of highly purified artificial graphite is added and suspended. A 0.5% by weight aqueous solution of NaBH ₄ is dropped with a microtube pump while vigorously stirring this suspension, and the simultaneous reduction reaction is completed over about 3 hours. Thereafter, the mixture was filtered, washed with water, and vacuum dried at 350 ° C. for 6 hours. The powder E obtained was the powder A of Example 1.
However, the particle size of the metal particles on carbon was smaller than that of the powder A, and the dispersion state was improved.

Example 6 2 ml acetic acid-25 ml ethanol
In a mixed solution of _{25mlH 2 O 0.475gSnCl 2 · 2H 2} O and 0.95gCu (NO
₃₎ was dissolved ₂ · 3H ₂ O, distilled water was added to 400 ml. 9.5 g of highly purified artificial graphite is suspended in this solution and heated to about 50 ° C. The suspension is then stirred vigorously with water.
A reducing agent solution containing 1.7 g of NaBH ₄ is dropped into 100 ml to carry out a reduction reaction. Thereafter, the resultant was washed with filtered water and vacuum-dried at 150 ° C. for 20 hours to obtain a powder F. In the X-ray diffraction of the powder, in addition to a diffraction line based on graphite, a diffraction line of Cu and Sn in a metal state and a diffraction line of a trace amount of cuprous oxide were recognized.

[Comparative Example 1]
Only 98 g of AgNO ₃ was added and 5 wt% A
g / artificial graphite powder G was obtained. Comparative Example 2 In the operation of Example 5, 0.95 g of Cu (N
O _{3) 2} · 3H ₂ O alone were added, 2.5 weight% C under the same conditions
u / artificial graphite powder H was obtained.

Example 7 The above Examples 1 to 6 and Comparative Example 1
The powders A to H obtained in the above steps 2 and 3 were mixed with a N-methylpyrrolidone solution of PVDF as a binder.
A paste having a weight ratio of 90:10 was applied to a copper foil having a thickness of 20 μm as a current collector, air-dried, vacuum-dried at 80 ° C. for 3 hours, and molded at a pressure of 0.5 ton / cm ^2. And 120 more
It vacuum-dried at 2 degreeC for 2 hours, and obtained the negative electrodes AH. Further, the negative electrode I was obtained by the above-mentioned operation using only the artificial graphite subjected to the high-purification treatment. These negative electrodes were combined with a lithium metal counter electrode through a polyester porous membrane, and 1 M Li
A test cell using PF ₆ / EC + DMC and lithium metal for the reference electrode was assembled. Charge / discharge speed is 120m / g carbon
A, the upper and lower limit potentials of charge and discharge were set to 1.0 V and 0.01 V, respectively. The obtained results are summarized in Table 1 as discharge capacity [mAh / g · (carbon + metal)].

[0025]

[Table 1]

The discharge capacities of the negative electrodes I, G, F and E were measured when the charge / discharge rate was changed, and the results are shown in FIG. As is apparent from the figure, the negative electrode E according to the present invention has a large discharge capacity even when the charge / discharge rate is high. Incidentally, in order to maintain a discharge capacity of 250 mAh / g, when the negative electrode made of artificial graphite alone is assumed to be 1.0, the artificial graphite negative electrode carrying 5 wt% Ag is about 1.7, and the artificial graphite negative electrode carrying 2.5 wt% Cu is about 1.6, 2.5 wt% Ag. The artificial graphite loaded with -2.5% by weight of Cu was about 3.2 times, and was found to be a negative electrode material that could withstand high-speed charge / discharge (high-current charge / discharge). The negative electrodes A, B,
The same test was performed for C, D, and F.
Almost the same result was obtained.

Example 8 The powder F obtained in Example 6 was heat-treated at 550 ° C. for 3 hours in a 4% H ₂ / He gas stream. X-ray analysis of this powder showed diffraction lines based on alloying in addition to diffraction lines based on Cu and Sn metals. The negative electrode was evaluated in the same manner as in Example 7 using this powder. The discharge capacity was almost the same value as the negative electrode using powder F.

Embodiment 9 In the operation of Embodiment 1, C
The powders were charged so that the weight ratio of u: Ag was 3: 1 and the powder was obtained by the same operation. The negative electrode was evaluated in the same manner as in Example 7 using this powder. The discharge capacity showed a value almost equivalent to that of the negative electrode using powder A. Example 10 The procedure of Example 1 was repeated except that the weight ratio of Cu: Ag was 1: 3, and a powder was obtained by the same operation. The negative electrode was evaluated in the same manner as in Example 7 using this powder. The discharge capacity showed a value almost equivalent to that of the negative electrode using powder A.

[Embodiment 11] In the operation of Embodiment 1,
Cu: Ag was added so as to have a weight ratio of 9: 1, and a powder was obtained by the same operation. Using this powder, as in Example 7,
The negative electrode was evaluated. The discharge capacity was 350 mAh / g with respect to the value of 370 mAh / g of the negative electrode using powder A.

Example 12 In the operation of Example 1,
The powders were charged so that the weight ratio of Cu: Ag was 1: 9, and a powder was obtained by the same operation. Using this powder, as in Example 7,
The negative electrode was evaluated. The discharge capacity showed a value of 360 mAh / g. [Example 13] In the operation of Example 1, 20% of artificial graphite was used.
3.85 ° spacing between parts by weight obtained from the dooz surface of X-ray analysis
Powder was obtained which was replaced by amorphous. The negative electrode was evaluated in the same manner as in Example 7 using this powder. The discharge capacity was almost the same as that of the negative electrode using powder A.

Example 14 On an aluminum foil having a thickness of 20 μm,
LiCoO ₂ active material, artificial graphite and PVDF in a weight ratio of 87:
9: 4 mixture was applied on both sides, dried and rolled, and 90μ on one side
The powder E obtained in Example 5 was applied to a positive electrode 15 having a thickness of 20 m and a copper foil having a thickness of 20 μm by weight ratio of PVDF to PVDF of 9: 1.
Is applied to both sides, dried and rolled to make one side
A negative electrode 17 having a thickness of 58 μm and a porous membrane separator 19 made of polyethylene having a thickness of 25 μm were wound as shown in FIG. 4 and housed in a battery can having an outer dimension of 14φ−47 mm, and 1 MLiPF ₆ / The characteristics were evaluated using EC-DMC.

The test conditions were as follows: charge / discharge rate: 1 C, charge end voltage 4.2 V, discharge end voltage 2.5 V. As a result, an energy density of 350 wh / l was obtained, and stable performance was shown up to 300 cycles.

[0033]

As described above, by using a novel negative electrode in a lithium secondary battery, it is possible to provide a lithium secondary battery having particularly high discharge capacity, output density and charge / discharge rate and excellent cycle characteristics. This lithium secondary battery is used as a power source for driving electric vehicles, memory backups, and portable devices.

[Brief description of the drawings]

FIG. 1 is a cycle characteristic diagram of a conventional negative electrode and an improved negative electrode.

FIG. 2 is a cycle characteristic diagram of a copper fiber-added negative electrode and a non-added negative electrode.

FIG. 3 is a diagram showing the relationship between the charge / discharge rate and discharge capacity of a negative electrode according to the present invention and a conventional / improved negative electrode.

FIG. 4 is a configuration diagram of a cylindrical battery of the present invention.

[Explanation of symbols]

1: Cycle characteristics of conventional negative electrode, 2: Cycle characteristics of improved negative electrode, 3: Cycle characteristics of copper fiber-added negative electrode, 4: Cycle characteristics of non-added negative electrode, 5: Charge-discharge rate and discharge capacity of negative electrode of the present invention Relationship 6: Relationship between charge / discharge speed and discharge capacity of negative electrode using Ag-supported artificial graphite powder, 7 Relationship between charge / discharge speed and discharge capacity of negative electrode using Cu-supported artificial graphite powder,
8 Relationship between charge / discharge rate and discharge capacity of negative electrode using artificial graphite powder, 15 positive electrode, 16 positive electrode terminal, 17 negative electrode, 18 negative electrode terminal, 19 separator

Claims (8)

[Claims] 1. A negative electrode of a unit cell constituting a lithium secondary battery is characterized in that carbon particles carrying both a metal forming an alloy with lithium and a metal not forming an alloy or a metal forming an alloy with both metals A lithium secondary battery characterized in that the carbon particles supported as described above are held by a current collector. 2. The lithium secondary battery used is 0.5 wh.
2. The lithium secondary battery according to claim 1, wherein the lithium secondary battery has a capacity of about 50 kwh. 3. The lithium secondary battery according to claim 1, wherein the metal is fine particles having a particle size of 1000 ° or less. 4. The lithium secondary battery according to claim 1, wherein the ratio of the metal that forms an alloy with lithium and the metal that does not form an alloy with lithium is 1: 9 to 9: 1. 5. An electric vehicle equipped with a motor using the lithium secondary battery according to claim 1 as a power source. 6. The charge / discharge rate of a lithium secondary battery is 1 C
The electric vehicle according to claim 5, wherein the energy density is 350 wh / l (battery capacity) or more. 7. A motorcycle equipped with a motor using the lithium secondary battery according to claim 1 as a power source. 8. The charge and discharge rate of the lithium secondary battery is as follows:
The motorcycle according to claim 7, wherein the energy density is not less than 1C and not less than 350 wh / l (battery capacity).