JP2003187803A - Lithium secondary cell - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a lithium secondary cell which has a high output and a high capacity by reducing the resistance of a positive electrode active substance by controlling the structure thereof. <P>SOLUTION: The lithium secondary cell has the positive electrode active substance, having the cubic spinel structure with Li and Mn as main components and constituted of secondary particles aggregated from primary particles, wherein the primary particle has a predetermined shape close to an octahedron having flat crystal surfaces, an average diameter of which particle is not less than 1 μm nor more than 20 μm. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to reducing the resistance of a positive electrode active material by controlling the particle morphology of the positive electrode active material,
As a result, the present invention relates to a lithium secondary battery that realizes reduction of internal resistance and enables large current discharge.

[0002]

2. Description of the Related Art In recent years, portable electronic devices such as mobile phones, VTRs, and notebook computers have been rapidly reduced in size and weight. As batteries for power supplies thereof, lithium transition metal composite oxide is used as a positive electrode active material. Secondary batteries using a carbonaceous material as a negative electrode active material and an organic electrolytic solution in which a Li ion electrolyte is dissolved in an organic solvent as an electrolytic solution have been used.

Such a battery is generally called a lithium secondary battery or a lithium ion battery,
Since the energy density is large and the cell voltage is as high as about 4V, not only the portable electronic device but also the low-pollution vehicle is actively spread to the general public due to recent environmental problems. It is also attracting attention as a motor drive power source for electric vehicles (EVs) or hybrid electric vehicles (HEVs) being designed.

Here, in order to drive a motor such as an EV, a voltage of 100 V or higher, preferably 200 V or higher is indispensable, but the unit cell voltage of the lithium secondary battery is determined by the material constituting the battery. The open circuit voltage is 4.2V at most, and the actual operating voltage is 3V ~
Since it is about 4V, it is necessary to connect and use a plurality of unit cells in series.

Further, a predetermined acceleration performance in EV etc.,
In order to obtain climbing performance and the like, lithium secondary batteries are required to have characteristics such as large capacity and high output. For example, HEV
However, since the motor is in a mode that assists the output during acceleration, a high output is required for the lithium secondary battery that drives the motor. Here, a large output means that a large current flows, a current of 100 A or more can frequently flow, and a current of 500 A may flow even for a short time. At this time, as described above, since the unit cells are connected in series, the same amount of current flows in each unit cell.

Further, in the case where the EV and the like have the same battery capacity, in order to increase the continuous traveling distance, it is necessary to reduce loss due to Joule heat and the like during discharging. In addition, it is important to suppress a decrease in battery capacity due to repeated charging and discharging and maintain good long-term reliability, that is, cycle characteristics.

[0007]

In order to stably discharge such a large current or to reduce the loss during charging / discharging, it is necessary to reduce the internal resistance of the unit cell. Therefore, when the resistance of each constituent member to the internal resistance was analyzed, it was found that the resistance of the positive electrode active material was large. Therefore, it has been conventionally attempted to add conductive fine particles such as acetylene black to the positive electrode active material to improve the conductivity and reduce the internal resistance of the battery. this is,
Lithium cobalt oxide (LiCoO ₂ ) and lithium manganate (LiMn) used as the positive electrode active material.
_{This is because 2} O ₄ ), lithium nickel oxide (LiNiO ₂ ) and the like are mixed conductors having both lithium ion conductivity and electronic conductivity, and their electron conductivity is not necessarily large.

Here, when acetylene black is not added, the contact between the powders of the positive electrode active material deteriorates, the internal resistance of the battery increases, and the utilization rate of the positive electrode active material decreases, resulting in generally poor battery characteristics. Is reduced. From this, it is clear that the addition of acetylene black contributes to the reduction of the internal resistance of the battery and the improvement of the cycle characteristics, but the addition of acetylene black reduces the filling amount of the positive electrode active material, and This will reduce the capacity. Therefore, the addition amount of acetylene black is set to an appropriate amount by comparing the positive effect of reducing the internal resistance with the negative effect of decreasing the battery capacity.

However, in order to improve the conductivity of the positive electrode active material, the electric resistance of the positive electrode active material itself is reduced, and addition of acetylene black is expected only to expect an effect of auxiliary conductivity improvement. It is considered preferable.

Generally, when the crystallinity of the positive electrode active material is high,
It is considered that the mobility of lithium ions and electrons in the charged particles is improved. That is, it is considered that the conductivity of the positive electrode active material can be increased by increasing the crystallinity of the positive electrode active material. However, it is difficult to clearly discuss the difference in crystallinity from the peak position and the width by the X-ray diffraction method which is a usual means for investigating the crystallinity.
On the other hand, in morphology (morphology) observation of the positive electrode active material by SEM (scanning electron microscope), the difference in crystallinity can be clearly determined, unlike the X-ray diffraction method.

[0011]

Means for Solving the Problems The present invention has been made in view of the problems of the above-mentioned conventional techniques, and an object of the present invention is to control the morphology of the positive electrode active material to obtain the positive electrode active material. It is intended to provide a high-output, high-capacity lithium secondary battery by lowering its resistance. That is,
According to the present invention, there is provided a lithium secondary battery comprising Li and Mn as main components, having a cubic spinel structure, and using a positive electrode active material composed of secondary particles in which primary particles are aggregated. Provided is a lithium secondary battery characterized in that primary particles have a substantially octahedral shape defined below, which is composed of flat crystal faces, and the average particle size is 1 μm or more and 20 μm or less. It Substantial octahedron shape: Shapes close to octahedron, which is the automorphism of cubic spinel structure, with smooth crystal planes intersecting each other to form clear ridges, and the apex formed by intersecting four octahedron surfaces is perfect Shape not formed on the surface but formed in the shape of a face or a ridge, a shape in which another crystal face appears at the ridge portion formed by intersecting two faces of an octahedron, and a part of these shapes Any of the shapes lacking (however, if the primary particles of the shape share a crystal plane or other primary particle crystals are grown from a part of the surface of the primary particles, and the primary particles are (Including the case of forming a polyhedron with an octahedron as a structural unit by sharing a crystal face intricately)

Here, in the lithium secondary battery of the present invention, the positive electrode active material contains primary particles having at least one side of a flat crystal plane of 0.2 μm or more, and more preferably 1 μm or more. Preferably. The average particle diameter of the primary particles of the positive electrode active material is 1 μm or more and 20 μm or less. Further, the Li / Mn ratio in the positive electrode active material is 0.
It is preferably larger than 5. The maximum particle size of the secondary particles composed of the primary particles having such characteristics is preferably 50 μm or less. In addition, it is preferable to add acetylene black as a conductive auxiliary material to such a positive electrode active material as in the conventional case. The battery capacity of the lithium secondary battery using the positive electrode active material according to the present invention is preferably 2 Ah or more, and a suitable application of the lithium secondary battery is a power source for driving a motor of an electric vehicle or a hybrid electric vehicle. To be

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION First, the positive electrode active material used in the lithium secondary battery of the present invention will be described below. The positive electrode active material contains lithium and manganese as main components and has a cubic spinel structure lithium manganate (stoichiometric composition: L
iMn ₂ O ₄ ) is used. However, LiMn ₂ O ₄ used in the lithium secondary battery of the present invention is not limited to those having such a stoichiometric composition, and cations are deficient as long as the crystal structure is maintained. Alternatively, it may be present in excess, while oxygen ions may be deficient or present in excess. LiMn ₂ O ₄ has excellent characteristics such that it is preferable as a material for general-purpose batteries because it is inexpensive, and that it is particularly suitable as a power source for driving a motor for electric vehicles and the like because it has a high output density.

It should be noted that having Li and Mn as main components means that
A part of Mn may be replaced with other elements such as Li, Fe, Mn, and N.
i, Mg, Zn, B, Al, Co, Cr, Si, Ti,
It may be partially substituted with one or more kinds of cations selected from substitutional elements M such as Sn, P, V, Sb, Nb, Ta, Mo and W, and as a substitutional element, It means that the additive may contain B, Mo, or W as an additive.

Here, among the LiMn ₂ O ₄ described above, in particular, when Li / Mn ratio is larger than 0.5, internal resistance is higher than that in the case of using stoichiometric composition. Furthermore, it is possible to obtain a high output battery, which is further reduced, which is preferable. As an example of a Li / Mn ratio of more than 0.5, Li (Li _x
Examples thereof include Mn _2-X ) O ₄ (X is a substitution amount), LiM _X Mn _2-X O _{4 in} which a part of Mn is substituted with the substitution element M other than Li, and the like. The former Li / Mn ratio is (1 + X) /
The Li / Mn ratios of (2-X) and the latter are given by 1 / (2-X), respectively, so that when X> 0, both Li / Mn ratios are
The Mn ratio is always greater than 0.5.

Further, the positive electrode active material having such a composition and crystal structure further has a particle structure (particle morphology) as shown in the SEM observation photograph of FIG. 1 (hereinafter referred to as “SEM photograph”). The primary particles are mainly composed of flat crystal faces, and most of the primary particles have a substantially octahedral shape. That is, on the surface of the primary particle, smooth crystal planes intersect with each other to form a clear ridge, and the shape thereof is close to that of an octahedron which is the automorphism of the cubic spinel structure.

Here, in the primary particles observed in FIG. 1, the vertices formed by intersecting the four faces of the octahedron are not completely formed, but are formed in the shape of faces or edges. Or, another crystal plane appears at the edge formed by intersecting two faces of the octahedron, and further, some primary particles share a crystal plane, or a part of the surface of the primary particle From this, it is also observed that other primary particle crystals are growing.
However, although the shape of such primary particles is not a perfect octahedron, it can be generally regarded as an octahedron shape. That is, it goes without saying that the "substantially octahedral shape" in the present invention includes such various shapes, and some of these shapes are missing, or the primary particles have complicated crystal planes. Those that share a polyhedron are also included.

The positive electrode active material of the lithium secondary battery of the present invention is mainly composed of primary particles having the above-mentioned form, and all the primary particles have a substantially octahedral shape. It does not have to be (but does not include anything other than the shape that occurs within the normal error distribution range during manufacturing). This is also understood from the fact that, in general, the growth of crystal planes may not occur uniformly under the influence of the grain size of raw materials, impurities in the raw materials, temperature distribution in the furnace during synthesis, etc. Should be.

The positive electrode active material described above preferably contains primary particles in which at least one side of a flat crystal plane has a length of 0.2 μm or more, more preferably 1 μm or more. The average particle diameter of the primary particles of the positive electrode active material is 1 μm or more and 20 μm or less. Further, the maximum particle size of the secondary particles composed of the primary particles is preferably 50 μm or less. The minimum particle size of primary particles is 0.05.
It is preferable that the average particle size of the secondary particles is 1 μm or more, and the minimum particle size of the secondary particles is 1 μm or more. Note that the particle size of the primary particles here is represented by the particle size obtained by performing image analysis on the SEM image because the primary particles cannot be isolated and measured, while the secondary particle size is the laser particle size. It is a value obtained by a diffraction method or the like.

The reason for limiting the particle size is as follows. That is, when a lithium secondary battery is manufactured using a positive electrode active material, generally, the positive electrode active material is molded into a plate shape by a press molding method, or a positive electrode active material and a conductive auxiliary agent are dissolved in a solvent in which a binder is dissolved. Is added to the surface of the metal foil to form a layer, and when the average primary particle size is 0.1 μm or less, the amount of binder added to the positive electrode active material is increased. In addition, when preparing a slurry, it is necessary to add another peptizer or a dispersant in order to suppress aggregation of the positive electrode active material and maintain good dispersibility. As a result, the energy density of the produced battery is lowered, which is not preferable. There is also a problem that the current efficiency in the battery is lowered when the particle size is small.

On the other hand, if the particle size of the positive electrode active material is large, sufficient filling density and mechanical strength cannot be obtained by press molding,
In addition, when a slurry is prepared, particles are likely to settle in the slurry and uniform coating cannot be performed, and the thickness of the positive electrode active material layer to be formed is at most about 100 μm. When a positive electrode active material having an average particle size of more than 50 μm is used, the thickness of the positive electrode active material layer is formed by two particles, resulting in a problem that flatness and homogeneity are deteriorated and the filling rate is not increased. .

It should be noted that not all particles have to satisfy the range of the particle size of such a suitable positive electrode active material, and the particle size is out of the specified range such as crushed fragments or agglomerated powder. It should be understood that the primary particles and the secondary particles are allowed to be mixed in a range that does not adversely affect the above-mentioned reason, and to the extent that they are not usually measured by the above-mentioned particle size measuring method. is there.

Now, in manufacturing such a positive electrode active material of the present invention, each element (L
i, Mn and, if necessary, a mixture of salts and / or oxides (including a substitution element and an additional element) in an oxidizing atmosphere in a range of 700 ° C. to 900 ° C. for 5 hours to 50 hours. Done.

Here, when the firing temperature (synthesis temperature) is low, grain growth does not easily occur, and it becomes difficult to obtain a positive electrode active material composed of primary particles having a desired particle size and shape. On the other hand, when the synthesis temperature is high, individual primary particles grow by grain growth, and at the same time, neck growth starts between the primary particles, the neck portion becomes rounded, and the desired particle size and shape are You won't get it. actually,
If the primary particle diameter is set to 20 μm or more, it is impossible to obtain substantially octahedral primary particles due to the neck growth. Further, the positive electrode active material needs to be used as a powder, but when such neck growth, that is, sintering starts, there is a demerit that a pulverization process is required after the synthesis. It is not preferable because it may change to a crystalline phase.

From these facts, conversely, it is possible to adjust the average particle diameter of the primary particles and further change the morphology of the primary particles by appropriately setting the raw material composition and the firing conditions. Is. For example, B of Comparative Example 2 described later
_In the positive electrode active material to which ₂ O ₃ was added, grain growth was remarkably observed, and the entire primary particles were rounded.
It is also possible to suppress the grain growth by lowering the synthesis temperature and / or shortening the synthesis time to obtain a positive electrode active material having substantially octahedral primary particles.

By the way, materials other than the positive electrode active material used for producing the lithium secondary battery of the present invention are not particularly limited, and various conventionally known materials can be used. For example, as the negative electrode active material, an amorphous carbonaceous material such as soft carbon or hard carbon, or a highly graphitized carbonaceous material such as artificial graphite or natural graphite is used, and the separator is a lithium ion permeable material having micropores. A polyethylene film having a three-layer structure sandwiched between porous polypropylene films permeable to lithium ions is preferably used.

Further, as the organic electrolytic solution, ethylene carbonate (EC), diethyl carbonate (DE
C), carbonate-based compounds such as dimethyl carbonate (DMC), propylene carbonate (PC) and γ
-Dissolve one or more kinds of lithium complex fluorine compounds such as LiPF ₆ and LiBF ₄ as electrolytes or lithium halides such as LiClO _{4 in} a single solvent or a mixed solvent of organic solvents such as butyrolactone, tetrahydrofuran and acetonitrile. What was done can be used.

When such a positive electrode active material is used, the resistance of the positive electrode active material layer can be reduced as shown in Examples described later, and in this case, it is necessary to increase the addition amount of the conductive additive. Has the advantage that the filling amount of the positive electrode active material itself can be increased, and such an effect is remarkable in a battery having a battery capacity of 2 Ah or more, that is, a battery in which a large amount of positive electrode active material is filled. can get. Also,
When the positive electrode active material of the present invention is used, good cycle characteristics are obtained, and in consideration of such characteristics, the lithium secondary battery of the present invention is suitable as a motor driving power source for EV or HEV. Used.

[0029]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but it goes without saying that the present invention is not limited to the following Examples.

(Preparation of Positive Electrode Active Material) First, in the positive electrode active materials according to the examples, commercially available Li ₂ CO ₃ , MnO ₂ , and Ti were used as starting materials so as to have the compositions shown in the examples of Table 1.
It was produced by weighing and mixing powders of O ₂ and NiO, and firing at 800 ° C. for 24 hours in an oxidizing atmosphere. The obtained positive electrode active material had primary particles having a substantially octahedral shape as shown in FIG. Further, as Comparative Example 1, commercially available LiMn ₂ O ₄ was used. As shown in the SEM photograph of FIG. 2, the particle structure (microstructure) was such that primary particles of about 0.2 μm were aggregated to form amorphous secondary particles. Further, as the comparative example 2, using a commercially available Li ₂ CO _3, powder of MnO _2, B ₂ O ₃ as starting material L
i: Mn: B = 1: 2: 0.03 were weighed and mixed to have a molar ratio composition, and the mixture was mixed in an oxidizing atmosphere at 800 ° C. for 2
The positive electrode active material obtained by firing for 4 hours was used. The particle structure (microstructure) of the positive electrode active material of Comparative Example 2 is the SEM of FIG.
As shown in the photograph, while leaving a substantially octahedral-shaped flat crystal face in a part, the ridges and vertices were formed into curved surfaces, and the shape was generally rounded.

[0031]

[Table 1]

(Production of Battery (Coin Cell)) First, for each of the various positive electrode active materials shown in Table 1, acetylene black as a conductive material and polyvinylidene fluoride (PVDF) as a binder were used as positive electrode active materials. Weight ratio 50:
The mixture was mixed at a ratio of 2: 3 to prepare a positive electrode material. 0.02 g of the positive electrode material has a diameter of 20 m at a pressure of 300 kg / cm ^2.
A positive electrode was formed by press molding into a disk shape of mφ. Next, the prepared positive electrode, an electrolytic solution prepared by dissolving LiPF ₆ as an electrolyte in an organic solvent in which EC and DEC are mixed at an equal volume ratio to a concentration of 1 mol / L, and a negative electrode made of carbon. , And a separator separating the positive electrode and the negative electrode were used to produce a coin cell.

(Measurement and Results of Internal Resistance of Battery) The prepared coin cell was 1 C depending on the capacity of the positive electrode active material.
Rate constant current-constant voltage charge up to 4.1V and discharge at 1C rate constant current up to 2.5V. Only one cycle of charge / discharge test is performed. The internal resistance of the battery was obtained by dividing the difference with the voltage immediately after that (voltage difference) by the discharge current. Then, a value obtained by dividing the internal resistance of each battery by the internal resistance of the battery manufactured using the positive electrode active material of Comparative Example 1 was defined as the internal resistivity. Therefore, in Comparative Example 1, the internal resistivity is 100%. The results are shown in Table 1. The internal resistance is greatly reduced in both the example and the comparative example 2, and in particular, the positive electrode active material of the comparative example 2 shows a great effect of reducing the resistance, but in the comparative example 2, the cycle characteristic described later is poor. There's a problem.

(Cycle Operation Test) Next, in order to examine cycle characteristics, each battery was charged at a constant current of 1 C rate-4.1 V at a constant voltage and a 1 C rate according to the capacity of the positive electrode active material. A cycle operation test was performed in which discharge up to 2.5 V was repeated at a constant current. Where 1
A value obtained by dividing the discharge capacity of the battery after the completion of the 00th cycle by the discharge capacity of the first battery was defined as a capacity retention rate, and the values are shown in Table 1. The larger this ratio, the smaller the decrease in the discharge capacity of the battery, but in the examples,
A high capacity retention rate of 86% was obtained. Although Comparative Example 2 had a small internal resistivity, it had a low capacity retention rate and had a problem in use as a secondary battery in which charging and discharging are repeated.

From the comparison between the above-mentioned Examples and Comparative Examples 1 and 2, it can be said that the morphology of the primary particles of the positive electrode active material has a great influence on the internal resistance and cycle characteristics of the battery. Furthermore, from the comparison between Example and Comparative Example 2, even if the synthesis conditions are the same, the morphology of the primary particles can be changed by changing the composition. Therefore, the morphology of the primary particles of the positive electrode active material is an important factor for obtaining effects such as reduction of internal resistance and improvement of cycle characteristics,
Needless to say, the compositions and firing conditions of the above examples are merely examples having a desired primary particle morphology, and the present invention is not limited to the compositions and firing conditions of the examples.

(Production and Evaluation of Battery Using Wound Internal Electrode Body) Next, using the positive electrode active material having the composition of Example and Comparative Example 1, a battery having a wound internal electrode body was prepared by the following procedure. It was produced by. First, a positive electrode active material to which a predetermined amount of acetylene black was added was dispersed in a solution of PVDF dissolved in normal methylpyrrolidone (NMP) to obtain a slurry. Next, this slurry was applied on both sides of an aluminum foil having a thickness of 20 μm, a length of 3600 mm and a width of 200 mm by using a roll coater method, and a positive electrode plate having a one-side coating thickness adjusted to 100 μm by a roll press was produced.

On the other hand, for the negative electrode plate, a highly graphitized carbon fiber was used as a negative electrode active material, and a predetermined amount of this was added to an NMP solution in which PVDF was dissolved to prepare a slurry, and the prepared slurry had a thickness of 10 μm, length 4000
It was prepared by double-sided coating on a copper foil having a width of 200 mm and a width of 200 mm and adjusting the coating thickness on one side to 80 μm.

A microporous separator (thickness: 25 μm, length: 4500 m) having a three-layer structure in which a polyethylene film is sandwiched between polypropylene films so that the positive electrode plate and the negative electrode plate thus produced do not contact each other
m, width: 220 mm), the current collecting tab was attached to each electrode plate by ultrasonic welding to produce a wound type internal electrode body, which was inserted into a battery case, and then EC and DEC The mixed solvent of was filled with an electrolytic solution in which LiPF ₆ as an electrolyte was dissolved, and finally the battery case was sealed to produce a battery having an outer diameter of 50 mmφ and a length of 240 mm.

The battery thus prepared was charged at a constant current of 10 A
It was fully charged by 4.1V constant voltage charging. The battery capacity when fully charged was 22 A for the batteries of Example and Comparative Example 1, respectively.
h, 25 Ah. Then, as in the case of the coin cell test described above, except that the rate during charge / discharge was 0.2 C, the internal resistivity and the capacity retention rate were obtained, and as a result, the same result as that of the coin cell was obtained.

[0040]

As described above, in the lithium secondary battery of the present invention using the positive electrode active material having the predetermined shape in which the primary particles have a substantially octahedral shape, the internal resistance is significantly reduced, and A remarkable effect that good cycle characteristics are obtained can be obtained. As a result, there is no need to increase the amount of the conductive additive added, and there is an effect that the amount of the positive electrode active material filled can be increased to increase the battery capacity and energy density.

[Brief description of drawings]

FIG. 1 is an SEM photograph showing one form of a particle structure of a positive electrode active material which is preferably used in the lithium secondary battery of the present invention.

FIG. 2 SE showing another form of the particle structure of the positive electrode active material.
It is an M photograph.

FIG. 3 is an SEM photograph showing yet another form of the particle structure of the positive electrode active material.

Continued front page    F term (reference) 5H029 AJ03 AJ05 AJ06 AK03 AL06                       AL07 AL08 AM02 AM03 AM04                       AM05 AM07 BJ14 DJ17 EJ04                       EJ12 HJ02 HJ04 HJ05 HJ19                 5H050 AA07 AA08 AA12 BA17 CA09                       CB07 CB08 CB09 EA10 EA24                       FA05 FA19 HA02 HA04 HA05                       HA19

Claims (7)

[Claims] 1. A lithium secondary battery comprising Li and Mn as main components, having a cubic spinel structure, and using a positive electrode active material composed of secondary particles in which primary particles are aggregated. A lithium secondary battery characterized in that the particles have a substantially octahedral shape defined below, which is composed of flat crystal faces, and the average particle size is 1 μm or more and 20 μm or less. Substantial octahedron shape: Shapes close to octahedron, which is the automorphism of cubic spinel structure, with smooth crystal planes intersecting each other to form clear ridges, and the apex formed by intersecting four octahedron surfaces is perfect Shape not formed on the surface but formed in the shape of a face or a ridge, a shape in which another crystal face appears at the ridge portion formed by intersecting two faces of an octahedron, and a part of these shapes Any of the shapes lacking (however, if the primary particles of the shape share a crystal plane or other primary particle crystals are grown from a part of the surface of the primary particles, and the primary particles are (Including the case of forming a polyhedron with an octahedron as a structural unit by sharing a crystal face intricately) 2. The lithium secondary battery according to claim 1, wherein the positive electrode active material contains the primary particles having a length of at least one side of the flat crystal plane of 0.2 μm or more. . 3. The lithium secondary battery according to claim 2, wherein the positive electrode active material contains the primary particles in which at least one side of the flat crystal surface has a length of 1 μm or more. 4. The lithium secondary battery according to claim 1, wherein the Li / Mn ratio in the positive electrode active material is larger than 0.5. 5. The lithium secondary battery according to claim 1, wherein the maximum particle size of the secondary particles is 50 μm or less. 6. The lithium secondary battery according to claim 1, which has a battery capacity of 2 Ah or more. 7. The lithium secondary battery according to claim 1, which is used in an electric vehicle or a hybrid electric vehicle.