JP2014203566A - Nonaqueous electrolyte secondary battery, and method for manufacturing positive electrode thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a nonaqueous electrolyte secondary battery which is arranged so that the reduction of an amount of gas generation at overcharge can be suppressed.SOLUTION: A nonaqueous electrolyte secondary battery comprises: a positive electrode; a negative electrode; a nonaqueous electrolyte including a gas-generating additive agent which generates gas by performing a decomposition reaction on the positive electrode at overcharge; and a current cut-off part for cutting off electric current according to the generated gas. The positive electrode includes: a positive electrode current collector; and a positive electrode mixture layer provided on the surface of the positive electrode current collector. The positive electrode mixture layer includes composite particles including a positive electrode active material, a conductive material, and a binder. The positive electrode mixture layer has a density of 2.5-2.9 g/cm. Particle diameters (median diameter D50) of the composite particles are substantially the same as a thickness of the positive electrode mixture layer.

Description

  The present invention relates to a non-aqueous electrolyte secondary battery and a method for producing the positive electrode.

  One of the techniques for improving the safety of a nonaqueous electrolyte secondary battery (for example, a lithium ion secondary battery) is a CID (Current Interrupt Device) mechanism. Generally, when a lithium ion secondary battery is overcharged, the electrolyte is electrolyzed to generate gas and heat. The CID mechanism is a mechanism that stops the charging of the lithium ion secondary battery by detecting gas and heat generated during overcharging.

  Patent Document 1 discloses a technique related to a non-aqueous electrolyte secondary battery that can improve cycle characteristics under high voltage and large current charging conditions. The positive electrode with which the nonaqueous electrolyte secondary battery concerning patent document 1 is provided has a positive electrode layer and the electrical power collector which carries the said positive electrode layer. The positive electrode layer includes composite particles and active material particles containing active material particles, a conductive material, and a resin. When the average particle diameter of the active material particles is A and the average particle diameter of the composite particles is B, the value of B / A is 3-30.

JP 2002-083585 A

  As described in the background art, the CID mechanism is a mechanism that stops the charging of the lithium ion secondary battery by detecting gas and heat generated during overcharge. For example, in a CID mechanism that stops charging by detecting gas generated during overcharging, it is necessary to increase the amount of gas generated during overcharging in order to operate the CID mechanism appropriately.

  However, when composite particles such as those used in Patent Document 1 are used for the positive electrode mixture layer of the non-aqueous electrolyte secondary battery, the strength of the composite particles is so low that the positive electrode manufacturing process (particularly, the positive electrode mixture) In the layer pressing step), the composite particles are crushed and voids in the positive electrode mixture layer are reduced. For this reason, the decomposition reaction of the gas generating additive in the positive electrode is suppressed, and there is a problem that the amount of gas generated during overcharging is reduced.

  In view of the above problems, an object of the present invention is to provide a nonaqueous electrolyte secondary battery capable of suppressing a decrease in the amount of gas generated during overcharge and a method for producing the positive electrode.

A nonaqueous electrolyte secondary battery according to an aspect of the present invention includes a positive electrode and a negative electrode, a nonaqueous electrolyte containing a gas generating additive that generates a gas by decomposing at the positive electrode during overcharge, and the generated gas. And a current interrupting unit that interrupts the current according to the above. The positive electrode includes a positive electrode current collector and a positive electrode mixture layer provided on a surface of the positive electrode current collector, and the positive electrode mixture layer includes composite particles including a positive electrode active material, a conductive material, and a binder. In addition, the density of the positive electrode mixture layer is 2.5 to 2.9 g / cm ³ , and the particle size (median diameter D50) of the composite particles and the film thickness of the positive electrode mixture layer are substantially the same.

  In the non-aqueous electrolyte secondary battery, a difference between a particle size (median diameter D50) of the composite particles and a film thickness of the positive electrode mixture layer may be within ± 2.25 μm.

  In the non-aqueous electrolyte secondary battery, a particle size (median diameter D50) of the composite particles and a film thickness of the positive electrode mixture layer may be 30 to 50 μm.

  In the non-aqueous electrolyte secondary battery, the positive electrode mixture layer may include 91 to 95% by weight of the positive electrode active material, 3 to 6% by weight of the conductive material, and 2 to 3% by weight of the binder. .

  In the non-aqueous electrolyte secondary battery, the positive electrode active material may include nickel cobalt lithium manganate.

  In the non-aqueous electrolyte secondary battery, the gas generating additive may include at least one of cyclohexylbenzene and biphenyl.

A method for producing a positive electrode of a non-aqueous electrolyte secondary battery according to one embodiment of the present invention includes preparing a positive electrode active material, a conductive material, and a binder, and combining the positive electrode active material, the conductive material, and the binder. A positive electrode mixture containing the composite particles is applied to a positive electrode current collector to form a positive electrode mixture layer, and the density of the positive electrode mixture layer is 2.5 to 2.9 g / cm ^3. In this way, the positive electrode mixture layer is pressed so that the film thickness of the positive electrode mixture layer is substantially the same as the particle size (median diameter D50) of the composite particles.

  In the positive electrode manufacturing method, the difference between the particle size (median diameter D50) of the composite particles and the film thickness of the positive electrode mixture layer may be within ± 2.25 μm.

  In the method for producing the positive electrode, the composite particles may have a particle size (median diameter D50) and a film thickness of the positive electrode mixture layer of 30 to 50 μm.

  When preparing the positive electrode active material, the conductive material and the binder, the positive electrode active material may be 91 to 95% by weight, the conductive material 3 to 6% by weight, and the binder 2 to 3% by weight.

  In the method for producing the positive electrode, lithium cobalt cobalt manganate may be used as the positive electrode active material.

  According to the present invention, it is possible to provide a non-aqueous electrolyte secondary battery capable of suppressing a decrease in gas generation during overcharge and a method for producing the positive electrode.

It is a figure for demonstrating the mechanism in which gas generate | occur | produces at the time of overcharge. It is a flowchart for demonstrating the manufacturing method of the positive electrode of the lithium ion secondary battery concerning embodiment. It is a table | surface which shows the material and composition of the positive electrode of the lithium ion secondary battery concerning an Example. It is sectional drawing which shows the structure of the positive electrode of the lithium ion secondary battery concerning an Example. It is a figure for demonstrating the method to measure the quantity of the generated gas. It is a graph which shows the relationship between the particle size of composite particle | grains, and the gas generation amount (when the film thickness of a positive mix layer is 50 micrometers). It is a graph which shows the relationship between the particle size of a composite particle, and the gas generation amount (when the film thickness of a positive mix layer is 40 micrometers). It is a graph which shows the relationship between the particle size of a composite particle, and the gas generation amount (when the film thickness of a positive mix layer is 30 micrometers). It is the result of having measured the pore distribution of the positive mix layer using the mercury intrusion method. It is a graph which shows the relationship between the particle size of composite particle | grains, and IV resistance (when the film thickness of a positive mix layer is 50 micrometers). It is a graph which shows the relationship between the particle size of composite particle | grains, and IV resistance (when the film thickness of a positive mix layer is 40 micrometers). It is a graph which shows the relationship between the particle size of composite particle | grains, and IV resistance (when the film thickness of a positive mix layer is 30 micrometers). It is a graph which shows the relationship between the particle size of a composite particle, and the gas generation amount when a composite particle is formed using a fluidized bed coating technique (when the film thickness of the positive electrode mixture layer is 50 μm).

  Hereinafter, a nonaqueous electrolyte secondary battery (hereinafter referred to as a lithium ion secondary battery) according to an embodiment of the present invention will be described. The lithium ion secondary battery according to the present embodiment includes at least a positive electrode, a negative electrode, a nonaqueous electrolyte, and a current interrupting unit.

  First, the mechanism by which gas is generated during overcharge will be described with reference to FIG. As shown in FIG. 1, the positive electrode 10 includes a positive electrode current collector 11 and a positive electrode mixture layer including a positive electrode active material 12 and a conductive material 13 formed on the surface of the positive electrode current collector 11. The negative electrode 20 includes a negative electrode current collector 21 and a negative electrode mixture layer including a negative electrode active material 22 formed on the surface of the negative electrode current collector 21. An electrolyte containing a gas generating additive is filled between the positive electrode 10 and the negative electrode 20. As the gas generating additive, for example, cyclohexylbenzene (CHB) or biphenyl (BP) can be used.

  At the time of overcharge, the gas generating additive (CHB, BP) is oxidized in the positive electrode 10 to generate radical cations. At this time, the gas generating additives (CHB, BP) donate electrons to the positive electrode. The electrons move from the positive electrode 10 to the negative electrode 20 via the wiring 15. Thereafter, a polymerization product is generated by a polymerization reaction of a plurality of radical cations. At this time, protons are released into the electrolyte. The protons receive electrons from the negative electrode 20 to generate hydrogen gas.

  Next, the configuration of the lithium ion secondary battery according to the present embodiment will be described in detail.

<Positive electrode>
The positive electrode includes a positive electrode current collector and a positive electrode mixture layer provided on the surface of the positive electrode current collector. The positive electrode mixture layer includes composite particles including a positive electrode active material, a conductive material, and a binder.

The positive electrode active material is a material capable of inserting and extracting lithium ions, and for example, lithium cobaltate (LiCoO ₂ ), lithium manganate (LiMn ₂ O ₄ ), lithium nickelate (LiNiO ₂ ), and the like can be used. _{It may} also be a material obtained by mixing LiCoO 2, LiMn ₂ O _4, the LiNiO ₂ at an arbitrary ratio. For example, nickel cobalt lithium manganate (LiNi _1/3 Co _1/3 Mn _1/3 O ₂ ) in which these materials are mixed at an equal ratio can be used. The particle diameter of the positive electrode active material is, for example, 4.0 to 8.0 μm (median diameter D50). Note that the positive electrode active material is not limited to these materials, and may be any material as long as it is a material capable of inserting and extracting lithium ions.

  As the conductive material, for example, acetylene black (AB) or a graphite-based material can be used. For example, the primary particle size of acetylene black is 30 to 50 nm, and the secondary particle size is 1.0 to 2.0 μm.

  As the binder, for example, polyvinylidene fluoride (PVdF), styrene butadiene rubber (SBR), polytetrafluoroethylene (PTFE), carboxymethyl cellulose (CMC), or the like can be used. As the positive electrode current collector, aluminum or an alloy containing aluminum as a main component can be used.

In the present embodiment, the density of the positive electrode mixture layer is 2.5 to 2.9 g / cm ³ . The particle diameter of the composite particles (median diameter D50, hereinafter the same) is substantially the same as the film thickness of the positive electrode mixture layer (the film thickness on one side after the pressing step). Here, the particle size of the composite particles is substantially the same as the film thickness of the positive electrode mixture layer. For example, the difference between the particle size of the composite particles and the film thickness of the positive electrode mixture layer is within ± 2.25 μm. Say a case. Moreover, for example, the particle diameter of the composite particles and the film thickness of the positive electrode mixture layer can be set to 30 to 50 μm.

  As an example of the composition of the positive electrode mixture layer, the positive electrode mixture layer contains 91 to 95% by weight of the positive electrode active material, 3 to 6% by weight of the conductive material, and 2 to 3% by weight of the binder. be able to.

  In addition, the particle size described in the present specification was measured by a laser diffraction / scattering method using Microtrack MT3000II manufactured by Nikkiso Co., Ltd.

  Next, the manufacturing method of the positive electrode of the lithium ion secondary battery concerning this Embodiment is demonstrated using FIG. When manufacturing a positive electrode, first, a positive electrode active material, a conductive material, and a binder are prepared (step S1). As the positive electrode active material, the conductive material, and the binder, the materials described above can be used.

  Next, the positive electrode active material, the conductive material, and the binder are combined to form composite particles (step S2). The composite particles can be formed using a mechanical coating technique, a fluidized bed coating technique, a spray drying technique, or the like. When forming composite particles using a mechanical coating technique, for example, Nobilta (registered trademark), which is a mechanical coating device manufactured by Hosokawa Micron Corporation, can be used. Moreover, when forming composite particles using a fluidized bed coating technique, for example, a rolling fluidized coating apparatus MP-01 manufactured by Paulec Co., Ltd. can be used. Moreover, when forming composite particles using a spray drying technique, for example, a spray dryer manufactured by Okawara Chemical Industries Co., Ltd. can be used. The composite particles are particles formed by agglomeration of a positive electrode active material (particle size: 4.0 to 8.0 μm), a conductive material, and a binder, and have a particle size of, for example, 30 to 50 μm.

  Note that the method for forming the composite particles described above is an example, and any technique can be used as long as the composite particles can be formed by combining the positive electrode active material, the conductive material, and the binder. Good.

Thereafter, the composite particles are put in a solvent such as water or NMP (N-methyl-2-pyrrolidone) and kneaded to form a positive electrode mixture (step S3). And this positive electrode compound material is apply | coated to 12-15 micrometers thick aluminum foil, and a positive electrode compound material layer is formed (step S4). Thereafter, the positive electrode mixture layer is pressed so that the density of the positive electrode mixture layer is 2.5 to 2.9 g / cm ³ (step S5). At this time, the thickness of the positive electrode mixture layer is set to be substantially the same as the particle size of the composite particles.

<Negative electrode>
The negative electrode can be produced by kneading a negative electrode active material, a dispersant, and a binder, applying the kneaded negative electrode mixture onto a negative electrode current collector, and drying. The negative electrode active material is a material capable of inserting and extracting lithium ions, and for example, a powdery carbon material made of graphite or the like can be used. As the negative electrode current collector, for example, copper, nickel, or an alloy thereof can be used.

<Nonaqueous electrolyte>
The nonaqueous electrolyte is a composition in which a supporting salt is contained in a nonaqueous solvent. Here, as the non-aqueous solvent, one or two selected from the group consisting of propylene carbonate (PC), ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), and the like. More than one type of material can be used. In addition, as support salts, LiPF ₆ , LiBF ₄ , LiClO ₄ , LiAsF ₆ , LiCF ₃ SO ₃ , LiC ₄ F ₉ SO ₃ , LiN (CF ₃ SO ₂ ) ₂ , LiC (CF ₃ SO ₂ ) ₃ , LiI 1 type, or 2 or more types of lithium compounds (lithium salt) selected from these etc. can be used.

  Moreover, the non-aqueous electrolyte of the lithium ion secondary battery according to the present embodiment includes a gas generating additive that generates gas by decomposing at the positive electrode during overcharge. Here, as the gas generating additive, for example, cyclohexylbenzene (CHB), biphenyl (BP), or a mixture thereof can be used. In other words, at least one of cyclohexylbenzene (CHB) and biphenyl (BP) can be used as the gas generating additive. The gas generating additive is not limited to these materials, and any material may be used as long as it is a material that generates gas by a decomposition reaction at the positive electrode during overcharge.

<Separator>
The lithium ion secondary battery according to the present embodiment may include a separator. As the separator, a porous polymer film such as a porous polyethylene film, a porous polyolefin film, and a porous polyvinyl chloride film, or a lithium ion or ion conductive polymer electrolyte film may be used alone or in combination. it can.

<Lithium ion secondary battery>
After laminating with the separator interposed between the positive electrode and the negative electrode produced as described above, the laminated body is formed into a flatly wound form (rolled electrode body). And a wound electrode body is accommodated in the container of the shape which can accommodate the said wound electrode body. The container includes a flat rectangular parallelepiped container body having an open upper end and a lid that closes the opening. As a material constituting the container, a metal material such as aluminum or steel can be used. Further, for example, a container formed by molding a resin material such as polyphenylene sulfide resin (PPS) or polyimide resin may be used. On the upper surface (that is, the lid) of the container, a positive electrode terminal electrically connected to the positive electrode of the wound electrode body and a negative electrode terminal electrically connected to the negative electrode of the wound electrode body are provided. In addition, a non-aqueous electrolyte is accommodated inside the container.

<Current interrupter>
The current interrupting unit interrupts the current according to the gas generated by the decomposition reaction of the gas generating additive at the positive electrode during overcharge. That is, the current interrupting unit stops charging the lithium ion secondary battery when the pressure inside the lithium ion secondary battery becomes equal to or higher than a predetermined value due to the gas generated during overcharging. As the current interrupting unit, for example, a mechanism that interrupts the current supplied to the lithium ion secondary battery by deforming the container of the lithium ion secondary battery when the internal pressure of the lithium ion secondary battery increases is used. be able to.

  As such a mechanism, for example, a mechanism in which charging is stopped by disconnecting a wiring that supplies current to at least one of a positive electrode and a negative electrode of the lithium ion secondary battery by deforming a container of the lithium ion secondary battery. Can be used. In addition, a sensor that detects deformation of the container of the lithium ion secondary battery and a circuit that stops charging according to the measurement result of the sensor are provided, and when the deformation of the container is detected by the sensor, the lithium ion secondary battery You may comprise so that charge may be stopped. In addition, when a pressure sensor that detects the internal pressure of the container of the lithium ion secondary battery and a circuit that stops charging according to the measurement result of the pressure sensor are provided, and the internal pressure of the container exceeds a predetermined pressure Alternatively, the charging of the lithium ion secondary battery may be stopped.

  With the lithium ion secondary battery according to the present embodiment described above, it is possible to suppress a decrease in the amount of gas generated during overcharge.

  As described in the background art, in the CID mechanism that stops the charging of the lithium ion secondary battery by detecting the gas generated at the time of overcharging, the amount of gas generated at the time of overcharging in order to properly operate the CID mechanism. Need to be increased. For this reason, it was necessary to add a predetermined amount of gas generating additive to the electrolyte.

  However, since the gas generating additive deteriorates battery characteristics such as an increase in battery resistance and a deterioration in durability, it is necessary to reduce the amount of the gas generating additive as much as possible. On the other hand, if the amount of gas generating additive added is reduced, the amount of gas generated during overcharging decreases, and there is a problem that the CID mechanism does not operate properly.

  Further, when composite particles such as those used in Patent Document 1 are used for the positive electrode mixture layer of the non-aqueous electrolyte secondary battery, the strength of the composite particles is so low that the positive electrode manufacturing process (particularly, the positive electrode mixture) In the layer pressing step), the composite particles are crushed, and voids (porosity) in the positive electrode mixture layer are reduced. For this reason, there has been a problem that the decomposition reaction of the gas generating additive in the positive electrode is suppressed and the amount of gas generated during overcharge is reduced.

  That is, a gas generating additive (for example, cyclohexylbenzene (CHB) or biphenyl (BP)) generates gas by oxidative decomposition at the positive electrode. However, when the composite particles are crushed in the pressing process of the positive electrode mixture layer and the voids in the positive electrode mixture layer are reduced, the area where the gas generating additive and the positive electrode mixture layer are in contact with each other is reduced. Decomposition reaction is inhibited. For this reason, there has been a problem that the amount of gas generated during overcharge is reduced.

  In order to solve such a problem, in the lithium ion secondary battery according to the present embodiment, the particle size (median diameter D50) of the composite particles constituting the positive electrode mixture layer and the film thickness of the positive electrode mixture layer are It is made to be substantially the same. Thus, by making the particle size of the composite particles and the film thickness of the positive electrode mixture layer substantially the same, the composite particles are prevented from being collapsed in the positive electrode manufacturing process (particularly, the positive electrode mixture layer pressing step). And reduction of voids in the positive electrode mixture layer can be suppressed.

  That is, since the composite particles are weaker than the positive electrode active material alone, the composite particles are easily crushed in the positive electrode manufacturing process (particularly, the positive electrode mixture layer pressing process). When the composite particles are crushed in this way, the composite particles are compressed with high density, and voids in the positive electrode mixture layer are reduced. However, if the particle diameter of the composite particles and the film thickness of the positive electrode mixture layer are substantially the same, the composite particles can be prevented from being broken in the positive electrode manufacturing process (particularly, the positive electrode mixture layer pressing process). For this reason, the reduction | decrease of the space | gap in a positive mix layer can be suppressed. Therefore, the amount of the electrolyte that permeates into the positive electrode mixture layer can be increased, and the chance of the decomposition reaction of the gas generating additive can be increased. As a result, the amount of gas generated during overcharging can be increased.

  Furthermore, in the lithium ion secondary battery according to the present embodiment, the amount of gas generated during overcharge can be increased, so the amount of gas generating additive added to the electrolyte can be reduced. Therefore, it is possible to suppress an increase in battery resistance and deterioration in durability due to the addition of the gas generating additive.

  Since the strength of the positive electrode active material alone is higher than that of the composite particles, the positive electrode active material alone is less likely to be crushed than the composite particles. For this reason, even if the particle diameter (4.0-8.0 micrometers) of a positive electrode active material and the film thickness of a positive electrode compound material layer are made substantially the same, it is assumed that the effect of this invention is not acquired so much. That is, the effect of the present invention is particularly prominent when the positive electrode mixture layer is formed using composite particles having a strength lower than that of the positive electrode active material alone.

Next, examples of the present invention will be described.
<Production of lithium ion secondary battery>
First, a method for manufacturing a positive electrode will be described. FIG. 3 shows materials and compositions used for manufacturing the positive electrode. 91% by weight of LiNi _1/3 Co _1/3 Mn _1/3 O ₂ as a positive electrode active material, 6% by weight of acetylene black (AB) and a graphite-based material as a conductive material, and 3% by weight of polyfluoride as a binder Vinylidene (PVdF) was prepared for each.

Then, a positive electrode active material (LiNi _1/3 Co _1/3 Mn _1/3 O ₂ ), a conductive material (acetylene black (AB), graphite-based material), and a binder (polyvinylidene fluoride (PVdF)) are mixed. These composite particles were formed using spray drying techniques. For the formation of the composite particles by the spray drying technique, a spray dryer manufactured by Okawara Chemical Industries Co., Ltd. was used.

Thereafter, the composite particles and an NMP (N-methyl-2-pyrrolidone) solution were mixed and kneaded using a planetary despa (manufactured by Iwata Tekko Co., Ltd.) to form a positive electrode mixture. And as shown in FIG. 4, the positive mix was apply | coated on the aluminum foil (12-15 micrometers) which is a positive electrode collector, and the positive mix layer was formed. After applying the positive electrode mixture, pressing was performed such that the density of the positive electrode mixture layer was 2.5 to 2.9 g / cm ³ . At this time, the basis weight (single side) of the positive electrode mixture layer was 12.5 to 14.5 mg / cm ² .

  In this example, samples each having a composite particle size (median diameter D50) of 25 to 60 μm and a positive electrode mixture layer thickness of 30 to 50 μm were prepared. At this time, the error of the particle size of the composite particles was within ± 2.25 μm.

  Next, a method for manufacturing a negative electrode will be described. First, natural graphite powder, SBR (styrene butadiene rubber), and CMC (carboxymethyl cellulose) are dispersed in water so that the mass ratio of these materials is 98.6: 0.7: 0.7. A negative electrode mixture was produced. Thereafter, the negative electrode mixture was applied to a copper foil (negative electrode current collector) having a thickness of 10 μm and dried to prepare a negative electrode.

The positive electrode and negative electrode produced by the above method were laminated via a separator (made of porous polyethylene), and this laminate was housed in a battery container together with a nonaqueous electrolyte, and the opening of the battery container was sealed airtight. As the non-aqueous electrolyte, a mixed solvent containing EC, EMC, and DMC at a volume ratio of 3: 3: 4 and containing LiPF ₆ as a supporting salt at a concentration of about 1 mol / liter was used. Also, 2 wt% cyclohexylbenzene (CHB) and 2 wt% biphenyl (BP) were added as gas generating additives. Thus, a test lithium ion secondary battery was produced.

<Measurement of generated gas>
The amount of gas generated was measured using the following method (Archimedes method). First, the laminated body of the positive electrode, the negative electrode, and the separator produced by the above method and the non-aqueous electrolyte are accommodated in a lamellar cell as a battery container, and the volume (initial value: Va) of the lamellar after accommodation is measured. did. The volume of the ramice was measured by the following method. As shown in FIG. 5, a predetermined amount of a fluorine-based liquid 31 (3M Fluorinert (registered trademark)) was poured into a beaker 30. Then, the lamellar 35 containing the laminate and the non-aqueous electrolyte was submerged in a beaker containing the fluorinated liquid 31, and the weight of the fluorinated liquid 32 increased when the lamicelle 35 was added was measured. Using the measured weight of the fluorinated liquid 32 and the density of the fluorinated liquid, the volume of the lamicelle 35 was calculated.

  Then, the lithium ion secondary battery produced by the above method was overcharged and held for a predetermined time to generate gas. Thereafter, the volume (Vb) of the ramicelle is measured using the above method, and the initial value (Va) of the volume of the ramicelle is subtracted from the volume (Vb) of the ramicelle after the gas is generated. Asked.

  FIG. 6A is a graph showing the relationship between the particle size of the composite particles and the amount of gas generated (when the film thickness of the positive electrode mixture layer is 50 μm). As shown in FIG. 6A, when the particle size of the composite particles is 50 μm, that is, when the particle size of the composite particles constituting the positive electrode mixture layer and the film thickness of the positive electrode mixture layer are substantially the same, the amount of gas generated is Increased. Specifically, when the particle size of the composite particles is 25 μm, 30 μm, 40 μm, and 60 μm, the gas generation amount is about 92 cc / Ah, whereas when the particle size of the composite particles is 50 μm, the gas generation amount is Increased by about 20% to about 114 cc / Ah.

  FIG. 6B is a graph showing the relationship between the particle size of the composite particles and the amount of gas generated (when the film thickness of the positive electrode mixture layer is 40 μm). As shown in FIG. 6B, when the particle diameter of the composite particles is 40 μm, that is, when the particle diameter of the composite particles constituting the positive electrode mixture layer and the film thickness of the positive electrode mixture layer are substantially the same, the amount of gas generated is Increased. Specifically, when the particle size of the composite particles is 25 μm, 30 μm, 50 μm, and 60 μm, the gas generation amount is about 74 cc / Ah, whereas when the particle size of the composite particles is 40 μm, the gas generation amount is Increased by about 20% to about 91 cc / Ah.

  FIG. 6C is a graph showing the relationship between the particle size of the composite particles and the amount of gas generated (when the film thickness of the positive electrode mixture layer is 30 μm). As shown in FIG. 6C, when the particle diameter of the composite particles is 30 μm, that is, when the particle diameter of the composite particles constituting the positive electrode mixture layer and the film thickness of the positive electrode mixture layer are substantially the same, the amount of gas generated is Increased. Specifically, when the composite particle size is 25 μm, 40 μm, 50 μm, and 60 μm, the gas generation amount is about 56 cc / Ah, whereas when the composite particle size is 30 μm, the gas generation amount is Increased by about 20% to 69 cc / Ah.

  For example, when the film thickness of the positive electrode mixture layer shown in FIG. 6A is 50 μm, in the region where the particle diameter of the composite particles is smaller than 50 μm, 2 to 3 composite particles overlap in the film thickness direction of the positive electrode mixture layer. These composite particles are considered to have been crushed by the pressing process. In the region where the particle diameter of the composite particles is larger than 50 μm, the number of composite particles in the film thickness direction of the positive electrode mixture layer is one. For example, in the case of 60 μm, the film thickness of the positive electrode mixture layer is 50 μm. It is considered that the composite particles were crushed during the process. On the other hand, when the particle diameter of the composite particles is about 50 μm, the number of composite particles in the film thickness direction of the positive electrode mixture layer is one, and further when the film thickness of the positive electrode mixture layer is 50 μm. It is considered that the decrease in voids in the positive electrode mixture layer could be suppressed because the composite particles were not crushed. Such a phenomenon is considered to occur similarly when the film thickness of the positive electrode mixture layer shown in FIG. 6B is 40 μm or when the film thickness of the positive electrode mixture layer shown in FIG. 6C is 30 μm.

<Measurement of pore distribution>
FIG. 7 shows the result of measuring the pore distribution of the positive electrode mixture layer produced as described above using a mercury intrusion method. In FIG. 7, the solid line indicates the case where the particle diameter of the composite particles constituting the positive electrode mixture layer and the film thickness of the positive electrode mixture layer are substantially the same (Example), and the broken line indicates the composite constituting the positive electrode mixture layer. The case where the particle diameter of the particles and the film thickness of the positive electrode mixture layer are different (comparative example) is shown.

  As shown in FIG. 7, when the particle diameter of the composite particles and the film thickness of the positive electrode mixture layer are substantially the same (Example), the particle diameter of the composite particles and the film thickness of the positive electrode mixture layer are different. The pore volume contained in the positive electrode mixture layer was larger than that of (Comparative Example). Therefore, when the particle size of the composite particles and the film thickness of the positive electrode mixture layer are substantially the same, the amount of electrolyte that penetrates into the positive electrode mixture layer increases, and as a result, the amount of gas generated during overcharge. Is considered to have increased.

<Measurement of IV resistance>
IV resistance was measured about each lithium ion secondary battery produced as mentioned above. The measurement of IV resistance was performed as follows. First, each lithium ion secondary battery was adjusted to SOC 20% by constant current constant voltage (CCCV) charging under a temperature condition of −6.7 ° C. Thereafter, the lithium ion secondary battery was discharged at a predetermined discharge rate under the same temperature condition, and a voltage value 10 seconds after the start of discharge was plotted to create an IV characteristic graph. From the slope of this IV characteristic graph, the internal resistance (IV resistance) of each lithium ion secondary battery was calculated.

  FIG. 8A is a graph showing the relationship between the particle size of the composite particles and the IV resistance when the film thickness of the positive electrode mixture layer is 50 μm. FIG. 8B is a graph showing the relationship between the particle diameter of the composite particles and the IV resistance when the film thickness of the positive electrode mixture layer is 40 μm. FIG. 8C is a graph showing the relationship between the particle diameter of the composite particles and the IV resistance when the thickness of the positive electrode mixture layer is 30 μm.

  As shown in FIG. 8A, when the film thickness of the positive electrode mixture layer was 50 μm, the IV resistance value became substantially constant without depending on the particle size of the composite particles. Further, as shown in FIG. 8B, when the film thickness of the positive electrode mixture layer was 40 μm, the IV resistance value became substantially constant without depending on the particle size of the composite particles. Further, as shown in FIG. 8C, even when the film thickness of the positive electrode mixture layer was 30 μm, the IV resistance value became substantially constant without depending on the particle size of the composite particles. Therefore, it was confirmed that even when the particle diameter of the composite particles constituting the positive electrode mixture layer and the film thickness of the positive electrode mixture layer were made substantially the same, the IV resistance value was not affected. That is, the amount of gas generated could be increased without increasing the IV resistance value.

<When other composite technologies are used>
In order to verify whether the effect of the present invention can be obtained even when the composite particle manufacturing method is different, the composite particle was manufactured using a fluidized bed coating technique instead of the spray drying technique. That is, when producing the positive electrode, the positive electrode active material (LiNi _1/3 Co _1/3 Mn _1/3 O ₂ ), conductive material (acetylene black (AB), graphite-based material), and binder shown in FIG. (Polyvinylidene fluoride (PVdF)) was mixed, and composite particles were formed using a fluidized bed coating technique. For the formation of the composite particles, a rolling fluidized coating apparatus MP-01 manufactured by Paulec Co., Ltd. was used. Since the other method of manufacturing the lithium ion secondary battery is the same as that in the case of using the spray drying technique, a duplicate description is omitted.

  FIG. 9 is a graph showing the relationship between the particle size of the composite particles and the amount of gas generated when the composite particles are formed using the fluidized bed coating technique (when the film thickness of the positive electrode mixture layer is 50 μm). As shown in FIG. 9, when the particle diameter of the composite particles is 50 μm, that is, when the particle diameter of the composite particles constituting the positive electrode mixture layer and the film thickness of the positive electrode mixture layer are substantially the same, the amount of gas generated is Increased. Specifically, when the composite particle size is 25 μm, 30 μm, 40 μm, and 60 μm, the gas generation amount is about 104 cc / Ah, whereas when the composite particle size is 50 μm, the gas generation amount is However, it increased by about 20% to about 126 cc / Ah. Therefore, it was confirmed that the effect of the present invention was obtained without depending on the method for producing composite particles.

  The present invention has been described with reference to the above-described embodiment and examples. However, the present invention is not limited only to the configurations of the above-described embodiment and examples. It goes without saying that various modifications, corrections, and combinations that can be made by those skilled in the art within the scope of the invention are included.

DESCRIPTION OF SYMBOLS 10 Positive electrode 11 Positive electrode collector 12 Positive electrode active material 13 Conductive material 15 Wiring 20 Negative electrode 21 Negative electrode collector 22 Negative electrode active material

Claims (11)

A positive electrode and a negative electrode;
A non-aqueous electrolyte containing a gas generating additive that generates gas by decomposing at the positive electrode during overcharge;
A non-aqueous electrolyte secondary battery comprising a current interrupting unit that interrupts current according to the generated gas,
The positive electrode includes a positive electrode current collector and a positive electrode mixture layer provided on a surface of the positive electrode current collector,
The positive electrode mixture layer includes composite particles including a positive electrode active material, a conductive material, and a binder,
The positive electrode mixture layer has a density of 2.5 to 2.9 g / cm ³ ,
The particle size (median diameter D50) of the composite particles and the film thickness of the positive electrode mixture layer are substantially the same.
Non-aqueous electrolyte secondary battery.   2. The nonaqueous electrolyte secondary battery according to claim 1, wherein a difference between a particle diameter (median diameter D50) of the composite particles and a film thickness of the positive electrode mixture layer is within ± 2.25 μm.   The nonaqueous electrolyte secondary battery according to claim 1 or 2, wherein a particle diameter (median diameter D50) of the composite particles and a film thickness of the positive electrode mixture layer are 30 to 50 µm. The positive electrode mixture layer is
4. The non-aqueous electrolyte secondary battery according to claim 1, comprising 91 to 95 wt% of the positive electrode active material, 3 to 6 wt% of the conductive material, and 2 to 3 wt% of the binder. .   The non-aqueous electrolyte secondary battery according to any one of claims 1 to 4, wherein the positive electrode active material includes nickel cobalt lithium manganate.   The non-aqueous electrolyte secondary battery according to any one of claims 1 to 5, wherein the gas generating additive includes at least one of cyclohexylbenzene and biphenyl. Prepare a positive electrode active material, a conductive material and a binder,
Compounding the positive electrode active material, the conductive material and the binder to form composite particles,
A positive electrode mixture containing the composite particles is applied to a positive electrode current collector to form a positive electrode mixture layer,
The positive electrode mixture layer is pressed so that the density of the positive electrode mixture layer is 2.5 to 2.9 g / cm ³ ,
The film thickness of the positive electrode mixture layer is made substantially the same as the particle size (median diameter D50) of the composite particles.
A method for producing a positive electrode.   The method for producing a positive electrode according to claim 7, wherein a difference between a particle size (median diameter D50) of the composite particles and a film thickness of the positive electrode mixture layer is within ± 2.25 μm.   The method for producing a positive electrode according to claim 7 or 8, wherein a particle size (median diameter D50) of the composite particles and a film thickness of the positive electrode mixture layer are 30 to 50 µm.   When preparing the positive electrode active material, the conductive material and the binder, 91 to 95% by weight of the positive electrode active material, 3 to 6% by weight of the conductive material, and 2 to 3% by weight of the binder are prepared. The manufacturing method of the positive electrode as described in any one of Claims 7 thru | or 9.   The manufacturing method of the positive electrode as described in any one of Claims 7 thru | or 10 which uses nickel cobalt lithium manganate as the said positive electrode active material.

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