JPWO2013145752A1 - Non-aqueous electrolyte secondary battery electrode and non-aqueous electrolyte secondary battery using the same - Google Patents

Abstract

An electrode for a non-aqueous electrolyte secondary battery in which the conductivity is not easily lowered even after a press treatment, and a non-aqueous electrolyte secondary battery using the same are provided. An electrode for a nonaqueous electrolyte secondary battery containing an electrode mixture containing an active material capable of occluding and releasing lithium, wherein porous aluminum having a porosity of 80 to 95% is used as a current collector. The electrode mixture material is filled in the hole, and the particle diameter da of the active material and the hole diameter dp of the porous aluminum satisfy da / dp ≦ 0.10. [Selection] Figure 2

Description

  The present invention relates to an electrode for a nonaqueous electrolyte secondary battery in which the conductivity is not easily lowered even when a press treatment is performed, and a nonaqueous electrolyte secondary battery using the same.

  In recent years, non-aqueous electrolyte secondary batteries have become widespread for reasons such as having a high energy density. Such a nonaqueous electrolyte secondary battery utilizes the principle of charging and discharging by moving lithium ions between the positive electrode and the negative electrode. In non-aqueous electrolyte secondary batteries, lithium metal oxides such as lithium cobalt oxide, lithium manganate, lithium nickelate, and lithium iron phosphate are being put into practical use or commercialized as positive electrode active materials. As the negative electrode active material, a carbon material such as graphite is used. An electrode mixture obtained by adding a conductive agent or a binder to the positive electrode active material and the negative electrode active material is supported on a current collector of a metal foil such as an aluminum foil or a copper foil to form a positive electrode or a negative electrode. .

  Since the battery capacity depends on the amount of the active material, the capacity of the battery can be increased by supporting as much active material as possible on the current collector. When a metal foil such as an aluminum foil or a copper foil is used as the current collector, the metal foil is inferior to the porous body in that it has a two-dimensional structure and has a small amount of active material to be supported. Therefore, it is conceivable to use a three-dimensional porous body such as a foam or a nonwoven fabric as the current collector in order to increase the amount of the active material carried on the electrode. For example, Patent Document 1 discloses a resin-made nonwoven fabric, a conductive layer formed on the surface of the nonwoven fabric, and an aluminum electrolytic plating formed on the surface of the conductive layer using a bath in which an aluminum salt is dissolved in a non-aqueous solvent. A current collector made of a three-dimensional porous body composed of layers is described. Patent Document 2 describes a non-woven nickel-chrome porous current collector in which non-woven nickel is chromized to have a chromium content of 25% by mass or more.

  However, these current collectors have oxidation resistance and electrolytic solution resistance, and are improved in porosity, which is suitable for industrial production, and further, a positive electrode that does not cause a short circuit even if the electrode group is wound. In order to provide a battery, a fibrous structure represented as such a three-dimensional network is insufficient to firmly hold an active material that repeatedly expands and contracts during repeated charge and discharge. Met.

  In addition, as a method for producing a porous metal, a molten metal foaming method (Patent Document 3) in which a foaming agent such as titanium hydride is mixed in a molten metal and solidified in a state containing the generated gas, or metal powder and A spacer method (Patent Document 4) is known in which a spacer material such as sodium chloride is mixed and compression-molded, and then the metal powder is heated by energization to remove the spacer material.

  However, the porous aluminum that can be produced in Patent Document 3 is a closed cell type in which the pores are independent, and cannot be used as an electrode because it cannot be filled with an active material or infiltrated with an electrolyte. Moreover, since the hole formed in the porous aluminum which can be produced by the spacer method described in Patent Document 4 is surrounded by a sintered metal powder, a structure suitable for holding the active material firmly However, in the method using spark plasma sintering (SPS), a large current is required, so that the size is limited and it is difficult to produce a practical porous metal. In addition, in porous aluminum having pores with such a structure, the pore walls are damaged by the filler when pressed with a filler such as an active material in the pores, and the conductivity of the porous aluminum is reduced. There has been a problem of lowering. Further, in Patent Document 5, an aluminum alloy layer is formed on the surface of a resin body having communication holes by a vapor phase method or the like, and the resin body is thermally decomposed to obtain a hollow fiber-like aluminum porous body from which the resin body has been removed. A non-aqueous electrolyte battery current collector filled with an active material is described. However, in such a current collector, there is a problem that the filled active material is merely held in a form in which the hollow fiber pillars are the core, and the active material is easily dropped from the aluminum porous body. In addition, as illustrated in FIG. 4, such an aluminum porous body forms a communication hole in which a space portion other than a hollow fiber shape is integrally expanded three-dimensionally without a wall.

JP 2010-9905 A JP 2009-176517 A JP-A-11-302765 JP 2004-156092 A JP 2011-249260 A

  The present invention has been made in view of the above circumstances, and an electrode for a non-aqueous electrolyte secondary battery in which there is no decrease in the conductivity of the electrode due to the active material damaging the porous aluminum wall during the press treatment, and the use thereof The purpose is to provide a non-aqueous electrolyte secondary battery.

  As a result of intensive studies to solve the problems of the prior art, the present inventors have determined that the structure of the electrode for a non-aqueous electrolyte secondary battery is a porous aluminum current collector having a structure different from that of a conventional porous metal and the pores in the porous aluminum current collector. It has been found that by filling the electrode mixture containing the active material into the pores of the porous aluminum current collector, the active material can be supported in the holes and falling off can be prevented. Furthermore, since the active material particle diameter da and the porous aluminum pore diameter dp satisfy da / dp ≦ 0.10, the active material does not damage the porous aluminum wall during the press treatment, so that the electrode conductivity decreases. As a result, it has been found that the battery characteristics can be improved by increasing the electrode capacity.

  That is, the present invention is the electrode for a non-aqueous electrolyte secondary battery containing an electrode mixture containing an active material capable of occluding and releasing lithium according to claim 1, wherein porous aluminum having a porosity of 80 to 95% is used. The electrode mixture is filled in the pores as a current collector, and the particle diameter da of the active material and the pore diameter dp of porous aluminum satisfy da / dp ≦ 0.10. A secondary battery electrode was obtained.

  According to a second aspect of the present invention, in the first aspect, the electrode mixture includes a conductive additive and a binder in addition to the active material, and the ratio of the active material to the total electrode mixture is 85 to 95% by mass. It was supposed to be.

  According to a third aspect of the present invention, the nonaqueous electrolyte secondary battery electrode according to the first or second aspect of the present invention includes at least one of a positive electrode and a negative electrode, and a separator disposed between the positive and negative electrodes, and a nonaqueous electrolyte. Thus, a non-aqueous electrolyte secondary battery was obtained.

  The electrode for a nonaqueous electrolyte secondary battery according to the present invention is composed of porous aluminum filled with an electrode mixture containing an active material in the pores, and the active material particle diameter da and the porous aluminum pore diameter dp are da. By satisfying /dp≦0.10, the active material does not damage the porous aluminum wall during the press treatment, and the decrease in the conductivity of the electrode can be prevented. As a result, a non-aqueous electrolyte secondary battery with low internal resistance and high capacity can be obtained.

It is an electron micrograph which shows the inside of the porous aluminum electrical power collector used by this invention. It is a schematic diagram showing the active material accommodated in the hole of a porous aluminum electrical power collector in case the particle diameter da of an active material and the hole diameter dp of a porous aluminum electrical power collector satisfy da / dp <= 0.10. . It is a schematic diagram showing the active material accommodated in the hole of a porous aluminum electrical power collector in case the particle diameter da of an active material and the hole diameter dp of a porous aluminum electrical power collector satisfy da / dp> 0.10. . It is a microscope picture which shows the inside of the conventional aluminum porous body.

  The porous aluminum current collector used for the electrode for a nonaqueous electrolyte secondary battery according to the present invention will be described in detail below. Such porous aluminum can be applied to one of the positive electrode and negative electrode current collectors or to both current collectors.

(A) Porous aluminum current collector The porous aluminum current collector used in the present invention is formed by press-molding a mixed powder of an aluminum powder and a support powder mixed at a predetermined volume ratio, and then forming the compact in an inert atmosphere. It is obtained by heat treatment in a sintered body and finally removing the supporting powder. Further, the mixed powder may be combined with a metal plate. As shown in FIG. 1, the porous aluminum current collector is composed of holes from which the supporting powder has been removed, and bonded metal powder walls of sintered aluminum powder that form the periphery of the holes. Many fine holes are formed in the bonded metal powder wall, and the structure is an open cell type in which the holes are connected by these fine holes.

  The porosity of the porous aluminum current collector, that is, the porosity before the press treatment described later is defined as 80 to 95%. If the porosity is less than 80%, there are few holes connecting the holes, and a predetermined amount of active material cannot be filled in the holes, which makes it difficult to increase the capacity of the battery. In addition, the fact that the active material is not sufficiently filled means that the electrolytic solution is also difficult to permeate, and the space is compressed by the press treatment, which makes it difficult for the electrolytic solution to enter, contributing to the battery reaction. The amount of active material that can be produced is reduced and the utilization rate of the active material is reduced. On the other hand, if the porosity exceeds 95%, the strength of the current collector itself is insufficient, and it is impossible to produce an electrode by filling the holes with a mixture. A more preferable porosity of the porous aluminum current collector is 85 to 90%.

Here, the porosity p (%) of the porous aluminum current collector before the press treatment is calculated by the following formula (1).
p = [{hv− (hw / 2.7)} / hv] × 100 (1)
here,
hv: the total volume of the porous aluminum current collector before the press treatment (cm ³ )
hw: Mass (g) of porous aluminum current collector before press treatment
2.7: Density of aluminum material (g / cm ³ ).

(B) Aluminum powder Pure aluminum powder, aluminum alloy powder, or a mixture thereof is used for the aluminum powder used in the present invention. In the case where the alloy components cause corrosion resistance deterioration under the usage environment, it is preferable to use pure aluminum powder. Pure aluminum is aluminum having a purity of 99.0 mass% or more.

  On the other hand, when it is desired to obtain higher strength, it is preferable to use aluminum alloy powder or a mixture of this and pure aluminum powder. As the aluminum alloy, 1000 series, 2000 series, 3000 series, 4000 series, 5000 series, 6000 series, and 7000 series aluminum alloys are used.

  The particle size of the aluminum powder is preferably 1 to 50 μm. In order to uniformly cover the surface of the support powder with the aluminum powder in the production of the porous aluminum current collector, the particle size of the aluminum powder is preferably smaller and more preferably 1 to 10 μm. The particle size of the aluminum powder is defined by the median diameter measured by the laser diffraction scattering method (microtrack method).

(C) Additive element powder You may use the mixture which added the additive element powder to the pure aluminum powder. As such an additive element, a plurality of elements consisting of a single element selected from magnesium, silicon, titanium, iron, nickel, copper, zinc and the like or any combination of two or more are preferably used. Such a mixture forms an alloy of aluminum and an additive element by heat treatment. Depending on the type of additive element, an intermetallic compound of aluminum and the additive element is further formed. Various effects can be obtained by including such an aluminum alloy or an intermetallic compound. For example, in an aluminum alloy of aluminum and an additive element such as silicon or copper, the melting point of the aluminum powder is lowered and the temperature required for the heat treatment can be lowered, so that the energy required for production can be reduced and the strength by alloying can be reduced. Will improve. Further, when an intermetallic compound of aluminum and an additive element such as nickel is formed, heat is generated and sintering is promoted, and a structure in which the intermetallic compound is dispersed is formed, so that high strength can be achieved.

  The additive element powder may be added to the aluminum alloy powder, or the additive element powder may be added to a mixture of the aluminum alloy powder and the pure aluminum powder. In these cases, new alloy systems and intermetallic compounds are formed. Furthermore, an additive element alloy powder obtained by alloying a plurality of additive element powders may be used as the additive element powder.

The addition amount of the additive element powder or additive element alloy powder to the aluminum alloy powder or pure aluminum powder is appropriately determined based on the chemical formula amount of the alloy or intermetallic compound to be formed.
The particle size of the additive element powder is preferably 1 to 50 μm. In order to achieve sufficient mixing with the pure aluminum powder, the aluminum alloy powder, and the support powder, it is preferably finer, and at least finer than the support powder is used. The particle diameter of the additive element powder is defined by the median diameter measured by the laser diffraction scattering method (microtrack method) in the same manner as the aluminum powder.

(D) Support powder In this invention, what has melting | fusing point higher than melting | fusing point of aluminum powder is used as support powder. When the mixed powder is combined with a metal plate, a powder having a melting point higher than the lower melting point of the aluminum powder and the metal plate is used. As such a supporting powder, a water-soluble salt is preferable, and sodium chloride and potassium chloride are preferably used from the viewpoint of availability. Since the space formed by removing the support powder becomes pores of porous aluminum, the particle size of the support powder is reflected in the pore diameter. Therefore, the particle size of the support powder used in the present invention is preferably 100 to 1000 μm. The particle size of the support powder is defined by the opening of the sieve. Accordingly, porous aluminum having a uniform pore diameter can be obtained by making the particle diameter of the support powder uniform by classification.

(E) Metal plate In this invention, you may use in the state which mixed powder and the metal plate were compounded. The metal plate is a non-porous plate or foil, and a net-like body such as a perforated wire mesh, expanded metal, or punching metal. The metal plate serves as a support, and the strength of the porous aluminum current collector is improved and the conductivity is further improved. As the metal plate, a material that does not evaporate or decompose during heat treatment, specifically, a metal such as aluminum, titanium, iron, nickel, copper, or an alloy thereof can be suitably used.

The composite of the mixed powder and the metal plate refers to an integrated state in which, for example, when a metal mesh is used for the metal plate, the entire net is covered with the mixed powder while filling the mixed powder in the mesh. When, for example, a catalyst or an active material is filled in porous aluminum provided with bonded metal powder walls on both sides of the metal plate, if the metal plate is a perforated network, the filling is from one side of the region divided by the metal plate. However, since the other region can be filled, the metal plate is preferably a net-like body. Here, the perforated means a mesh part of a metal mesh, a punch part of a punching metal, a mesh part of an expanded metal, and a gap part between fibers of metal fibers.
The pore diameter of the pores of the network may be larger or smaller than the diameter of the holes obtained by removing the support powder from the joined mixed powder.
It is preferable that the aperture ratio of the perforated hole in the network is large so as not to impair the porosity of the porous aluminum current collector.

(F) Mixing method The mixing ratio of the aluminum powder and the support powder is preferably such that Val / (Val + Vs), which is the volume ratio of the aluminum powder, is 5 to 20%, more preferably 10 where the respective volumes are Val and Vs. ~ 15%. Here, the volumes Val and Vs are values obtained from the respective mass and specific gravity. When the volume ratio of the aluminum powder exceeds 20%, the support powder content is too small and the support powders exist independently without contacting each other, and the support powder cannot be removed sufficiently. . Support powder that cannot be removed causes corrosion of porous aluminum. On the other hand, when the volume ratio of the aluminum powder is less than 5%, the wall constituting the porous aluminum becomes too thin, so that the strength of the porous aluminum becomes insufficient, and handling and shape maintenance become difficult.
In order to achieve a state where the support powder is sufficiently covered with the aluminum powder, the particle size (dal) of the aluminum powder is sufficiently smaller than the particle size (ds) of the support powder, for example, dal / ds. Is preferably 0.10 or less.

  The mixing means for mixing aluminum with the support powder may be a vibration stirrer or a container rotating mixer, but is not particularly limited as long as a sufficient mixing state can be obtained.

(G) Compounding method When the mixed powder is filled in a molding die, the mixed powder and the metal plate may be combined. As a composite form, a metal plate may be sandwiched between mixed powders, or a mixed powder may be sandwiched between metal plates. Further, the composite of the mixed powder and the metal plate can be repeated to make multiple stages. In the case of compounding, mixed powders having different particle sizes and mixing ratios of aluminum powder and support powder, and a plurality of different types of metal plates can be combined.

(H) Pressure molding method The pressure during pressure molding is preferably 200 MPa or more. By forming by applying sufficient pressure, the aluminum powders rub against each other, and the strong oxide film on the surface of the aluminum powder that inhibits the sintering of the aluminum powders is destroyed. This oxide film confines molten aluminum and prevents it from coming into contact with each other, and is inferior in wettability with molten aluminum and has the effect of rejecting liquid aluminum. Therefore, when the pressure of pressure molding is less than 200 MPa, the destruction of the oxide film on the surface of the aluminum powder is insufficient, and the aluminum melted during heating oozes out of the molded body to form a ball-shaped aluminum lump. There is a case. The porosity of porous aluminum becomes higher than the target by forming the aluminum lump. Therefore, the formation of such an aluminum lump is detrimental in that the porosity of the porous aluminum cannot be controlled. In addition, there is a problem in that the shape collapses due to the formation of an aluminum lump and must be removed. The porous aluminum wall on which the molding pressure is as large as the apparatus and mold used allow is strong, which is preferable. However, if it exceeds 400 MPa, the effect tends to be saturated. For the purpose of enhancing the releasability of the pressure-molded body, it is preferable to use a lubricant such as a fatty acid such as stearic acid, a metal soap such as zinc stearate, various waxes, synthetic resins, and olefinic synthetic hydrocarbons.

(I) Heat treatment method The heat treatment is carried out at a temperature not lower than the melting point of the aluminum powder to be used and lower than the melting point of the supporting powder. The melting point of the aluminum powder is a temperature at which a liquid phase of pure aluminum or an aluminum alloy is generated. By heating to a temperature at which a liquid phase is generated, the liquid phase oozes out from the aluminum powder, and the aluminum powders are bonded metallically by contacting the liquid phases.

  When the heat treatment temperature is lower than the melting point, aluminum is not melted, so that bonding between the aluminum powders and between the aluminum powder and the metal plate becomes insufficient. Moreover, when heated above the melting point, the aluminum covering the surface of the support powder located on the outermost surface of the sintered body is removed, and a sintered body having a surface with a large aperture ratio is formed. A large aperture ratio of the sintered body is advantageous for filling the active material when applied to the current collector.

  When the heating temperature is equal to or higher than the melting point of the support powder, the support powder is melted. When a water-soluble salt such as sodium chloride or potassium chloride is used as the support powder, the heat treatment is preferably performed at a temperature lower than 700 ° C., more preferably lower than 680 ° C. When heated at a temperature equal to or higher than the melting point of the support powder, the shape of the porous body cannot be maintained as the support powder melts. In addition, the higher the temperature, the lower the viscosity of the molten aluminum, and the molten aluminum oozes out to the outside of the pressure-molded body, forming a convex aluminum lump. By forming an aluminum lump, the porosity of porous aluminum becomes higher than intended. The formation of such an aluminum lump is detrimental in that the porosity of porous aluminum cannot be controlled. In addition, there is a problem in that the shape collapses due to the formation of an aluminum lump and must be removed. The heat holding time in the heat treatment is preferably about 1 to 60 minutes. Further, a load may be applied to the pressure-formed body during the heat treatment to compress the pressure-formed body, or heating and cooling may be repeated a plurality of times.

The inert atmosphere for performing the heat treatment is an atmosphere for suppressing oxidation of aluminum, and an atmosphere of vacuum; nitrogen, argon, hydrogen, decomposed ammonia and a mixed gas thereof is preferably used, and a vacuum atmosphere is preferable. The vacuum atmosphere is preferably 2 × 10 ⁻² Pa or less, more preferably 1 × 10 ⁻² Pa or less. When it exceeds 2 × 10 ⁻² Pa, removal of moisture adsorbed on the surface of the aluminum powder becomes insufficient, and oxidation of the aluminum surface proceeds during heat treatment. As described above, the oxide film on the aluminum surface is inferior in wettability with liquid aluminum, and as a result, molten aluminum oozes out to form a ball-like lump. In the case of an inert gas atmosphere such as nitrogen, it is preferable that the oxygen concentration is 1000 ppm or less and the dew point is −30 ° C. or less.

(J) Support powder removal method The support powder in the sintered body is preferably removed by eluting the support powder into water. The supporting powder can be easily eluted by a method such as immersing the sintered body in a sufficient amount of water bath or flowing water bath. The support powder eluted in water is removed from the sintered body through the fine holes formed in the metal powder wall. When a water-soluble salt is used as the support powder, the water for eluting it is preferably free from impurities such as ion exchange water or distilled water, but tap water is not particularly problematic. The immersion time is usually appropriately selected within the range of several hours to 24 hours. Elution can be promoted by applying vibration by ultrasonic waves or the like during the immersion.

(K) Electrode As a nonaqueous electrolyte secondary battery electrode according to the present invention, either a positive electrode or a negative electrode can be applied. Such an electrode contains an electrode mixture containing an active material capable of occluding and releasing lithium. The electrode mixture is supported in a state of being filled in the pores of the porous aluminum current collector described above. The electrode mixture may contain a conductive additive and a binder in addition to the active material.

  When the electrode is a positive electrode, the positive electrode active material used is not particularly limited as long as it can be used for a non-aqueous electrolyte secondary battery. For example, lithium cobaltate, lithium manganate, lithium nickelate, phosphoric acid Lithium metal oxides such as iron lithium are used. When an electrode is a negative electrode, the negative electrode active material used will not be restrict | limited especially if it can be used for a nonaqueous electrolyte secondary battery.

  By adding a conductive additive to the electrode mixture in both the positive electrode and the negative electrode, the conductivity of the entire electrode is improved. It does not specifically limit as a conductive support agent, A well-known or commercially available thing can be used. Examples thereof include carbon black such as acetylene black and ketjen black, activated carbon, graphite and the like.

  By adding a binder to the electrode mixture in both the positive electrode and the negative electrode, the binding of the components via the binder, that is, the bonding between the active materials, between the conductive assistants, and between the active material and the conductive auxiliary agent is strengthened. Thus, the active material is less likely to fall off the current collector. It does not specifically limit as a binder to be used, A well-known or commercially available thing can be used. For example, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinylpyrrolidone (PVP), polyvinyl chloride (PVC), polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer, styrene butadiene rubber (SBR), polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC) and the like.

  Usually, a conductive additive and a binder are added to the electrode mixture. In this case, the active material with respect to the total electrode mixture (active material + conductive additive + binder) is added to both the positive electrode and the negative electrode. The proportion is preferably 85 to 95% by weight. If this ratio is less than 85% by weight, the active material is insufficient, and a high battery capacity cannot be achieved. On the other hand, if this ratio exceeds 95% by weight, the conductivity of the entire electrode is lowered, and sufficient bonding between the components and between the components cannot be obtained, so that a high battery capacity cannot be achieved.

In such a non-aqueous electrolyte secondary battery electrode, the particle diameter da of the active material and the pore diameter dp of the porous aluminum before the press treatment must satisfy da / dp ≦ 0.10. However, when the active material particles are aggregated to form secondary particles, da is treated as the diameter of the secondary particles. FIG. 2 schematically shows a case where this ratio is satisfied. In this case, since da is sufficiently smaller than dp, the active material 1 is accommodated in the holes 3 without damaging the porous aluminum wall 2 during the pressing process. On the other hand, as schematically shown in FIG. 3, when da / dp> 0.1, da is not sufficiently smaller than dp, so that the active material 1 in the hole 3 is porous during the pressing process. The aluminum wall 2 is strongly pressed and damaged (4 in the figure is a damaged portion). As a result, the conductivity of the electrode is reduced. The lower limit value of da / dp is not particularly specified, but 1 × 10 ⁻⁵ is set as the lower limit value. In the active material inferior in conductivity and ion conductivity, the smaller the particle size da, the higher the efficiency of the electrode reaction. Therefore, the smaller da is preferable from the viewpoint of battery performance. However, as the particle size da becomes smaller, the surface area of the active material increases, and there is a need to increase the proportion of the conductive auxiliary agent for ensuring the conductivity between the active materials. As a result, there is a concern that the ratio of the active material in the composite material decreases, leading to a decrease in the energy density of the battery. Therefore, it is not preferable to use an active material whose particle size is less than several tens of nm. From the relationship with the particle size of the support powder used for producing the porous aluminum current collector, da / dp is preferably 1 × 10 ⁻⁵ .

  The particle diameter da of the active material refers to the equivalent circle diameter of the active material. That is, the diameter of a circle having the same area as the cross-sectional area of the active material. The cross-sectional area of the active material is numerically calculated by microscopic observation, and the equivalent circle diameter is calculated therefrom to determine the particle diameter da. Ten or more active material samples are observed with a microscope, and the particle diameter da is determined by an arithmetic average value.

  When the porous aluminum hole has a shape having a major axis and a minor axis, the pore diameter dp means the major axis of the hole. When the hole is circular, the hole diameter dp refers to the diameter. By observing the cross section of the porous aluminum current collector before the press treatment with a microscope, the hole diameter dp is measured for 10 or more holes, and the hole diameter dp is determined based on the arithmetic average value thereof.

  Next, the manufacturing method of the electrode for nonaqueous electrolyte secondary batteries is demonstrated. Usually, the porous aluminum current collector is filled in a slurry state in which an active material, a conductive additive and a binder are dispersed in a solvent. The concentrations of the active material, the conductive additive and the binder in the slurry are not limited, and may be appropriately selected from the viewpoint of slurry viscosity. Further, a thickener may be added to adjust the viscosity, and a dispersant may be added to obtain a good dispersion state. The solvent for the slurry is not particularly limited, and for example, N-methyl-2-pyrrolidone, water and the like are preferably used. When using polyvinylidene fluoride as a binder, it is preferable to use N-methyl-2-pyrrolidone as a solvent. When using polytetrafluoroethylene, polyvinyl alcohol, carboxymethylcellulose, or the like as a binder, water is used. It is preferable to use it as a solvent.

A slurry in which components of an active material, a conductive additive and a binder (thickener and / or dispersant as required) are dispersed in a solvent is obtained by, for example, porous aluminum current collection by a known method such as a press-fitting method. Filled in the body. In the press-fitting method, a slurry is disposed on one side using a porous aluminum current collector as a diaphragm, and the other side is a slurry permeation side. The pores of the porous aluminum current collector are filled with the above components by reducing the pressure on the other permeate side and allowing the slurry to permeate. Instead, the above-mentioned components may be filled in the pores of the porous aluminum current collector by pressurizing the slurry disposed on one side.
Further, in place of the press-fitting method, the porous aluminum current collector is immersed in a slurry in which each of the above components is dispersed in a solvent, and each of the above components is diffused into the pores of the porous aluminum current collector (hereinafter referred to as “immersion”). May be adopted).
In the press-fitting method and the dipping method, the electrode mixture in the slurry is filled into the pores of the porous aluminum through the fine holes formed in the bonded metal powder wall.
The electrode filled with the above components as described above is dried by scattering the solvent at 50 to 200 ° C.

  Thus, the electrode density is adjusted by the press process which pressurizes using the roll press machine, a flat plate press machine, etc. for the electrode obtained. The thickness of the electrode after the press treatment is preferably 0.2 to 0.9 times the thickness before the press treatment. In particular, it is desirable to perform a press treatment with a flat plate press. This is because, in the press treatment using a roll press, the porous aluminum current collector may be distorted and the electrode may collapse.

(L) Non-aqueous electrolyte secondary battery The non-aqueous electrolyte secondary battery according to the present invention is a non-aqueous electrolyte using an electrode manufactured as described above, a separator disposed between electric wires, and a non-aqueous electrolyte. It is assembled into an electrolyte secondary battery. In addition, although it is preferable that both a positive electrode and a negative electrode, or only a positive electrode is comprised with the said electrode, you may comprise only a negative electrode with the said electrode.

As the separator, generally used polymer films such as polyethylene (PE) and polypropylene (PP) are used. As the non-aqueous electrolyte, lithium hexafluorophosphate (LiPF ₆ ) or lithium perchlorate (LiClO ₄ ) dissolved in an organic solvent such as ethylene carbonate (EC) or diethyl carbonate (DEC) can be used.

  The present invention will be specifically described below with reference to invention examples and comparative examples. The present invention is not limited to the following invention examples and comparative examples.

(Invention Examples 1 to 5 and Comparative Examples 6 to 8)
First, a porous aluminum current collector used for the electrode for a nonaqueous electrolyte secondary battery according to the present invention was produced as follows.
As the aluminum powder, the following pure aluminum powders (A1, A3) having different particle diameters were used. As the supporting powder, sodium chloride powders (B1 to B4) having different particle diameters and potassium chloride (C1) having a particle diameter of 605 μm were used. As shown in Table 1, each powder was mixed at a predetermined volume ratio to prepare a mixed powder.

This mixed powder was filled in a mold having a 10 mm × 30 mm hole and pressure-molded at the pressure shown in Table 1. The filling amount of the mixture was set to a weight at which the thickness of the pressure-molded body was 1 mm. A sintered body was produced by heat-treating the pressure-formed body at a temperature and time shown in Table 1 in an atmosphere having a maximum ultimate pressure of 1 × 10 ⁻² Pa or less, and the obtained sintered body was heated to 20 ° C. The support powder was eluted by immersing in running water (tap water) for 6 hours to prepare porous aluminum samples 1 to 8 (width 12 mm × length 30 mm × thickness 1 mm). Samples 1 to 8 were before press treatment without filling the electrode mixture, and the thickness was measured with a micrometer.

<Pure aluminum powder, (Aluminum purity 99.7 mass% or more)>
A1: Median diameter 3 μm (melting point: 660 ° C.)
A3: Median diameter 17 μm (melting point: 660 ° C.)

<Sodium chloride powder>
B1: Particle size 925 μm (medium value of sieve opening) (melting point: 800 ° C.)
B2: Particle size 605 μm (medium value of sieve opening) (melting point: 800 ° C.)
B3: Particle size 400 μm (median sieve opening) (melting point: 800 ° C.)
B4: Particle size 120 μm (median sieve opening) (melting point: 800 ° C.)
<Potassium chloride powder>
C1: Particle size 605 μm (medium value of sieve opening) (melting point: 776 ° C.)

  Next, by changing the mold to one having a hole of φ13 mm and using the porous aluminum current collector sample produced by the same method as described above, the non-aqueous electrolyte secondary battery according to the present invention is used as follows. A positive electrode was produced.

(Preparation of positive electrode)
Carbon-coated lithium iron phosphate as a positive electrode active material; acetylene black as a conductive additive; PVDF as a binder was used in parts by weight shown in Table 2. Then, 100 parts by weight of the above total was dispersed in 200 parts by weight of NMP as a solvent to prepare a slurry.

  Using the immersion method, the porous aluminum current collector samples 1 to 7 prepared above were immersed in a slurry (1 liter) in which a positive electrode active material, a conductive additive and a binder were dispersed in a solvent, and the pressure was reduced. (−0.1 MPa). After the immersion, excess slurry adhered to the front and back surfaces of the porous aluminum current collector was scraped off with a spatula. The porous aluminum current collector sample 8 was not used for slurry immersion and subsequent tests because the porosity was too high to maintain the shape.

  Next, the porous aluminum current collector sample filled with the slurry was placed in a drying apparatus and dried at 80 ° C. for 2 hours to prepare positive electrode samples of invention examples and comparative examples shown in Table 2. Furthermore, these were pressed to a thickness of 0.7 mm using a flat plate press.

  Table 2 shows the porosity of the porous aluminum current collector before the press treatment, da / dp, the electrode mixture filling amount after the press treatment, and the electrical resistance ratio before and after the press treatment, measured as follows. .

(Porosity)
The porosity of the porous aluminum current collector before the press treatment was determined according to the above formula (1).

(Da / dp)
da / dp was determined as follows. First, for da, a cross-sectional image of the active material obtained by SEM observation was numerically calculated, and this was calculated as a circle-equivalent diameter to obtain the particle size da. The same observation was performed on 10 active material samples, and the particle diameter da was determined from the arithmetic average value. As for dp, the cross section of the porous aluminum sample not filled with the electrode mixture was observed by SEM, the major axis or the diameter was measured for 10 or more holes, and the pore diameter dp was determined from the arithmetic average value. Da / dp was determined from da and dp determined as described above.

(Electrode mixture filling amount)
The filling amount of the electrode mixture before the press treatment was determined as follows. First, the volume of the porous aluminum is divided by the density of the material (aluminum material) constituting the porous aluminum to obtain the volume of the material constituting the porous aluminum current collector, and this volume is subtracted from the electrode volume to obtain the spatial volume. (Cm ³ ) was determined. Next, the mass (g) of the electrode mixture was determined by subtracting the mass of the porous aluminum current collector sample before filling the electrode mixture from the mass of the positive electrode after the press treatment. Then, the mass (g) of the electrode mixture was divided by the space volume (cm ³ ) to determine the mass of the electrode mixture per unit volume of the space, and this was used as the electrode mixture filling amount. The electrode material filling amount was 0.7 g / cm ³ or more as acceptable, and less than that was unacceptable.

(Electric resistance ratio)
The electrical resistance ratio before and after the press treatment was determined as follows. A porous aluminum sample after being filled with the electrode mixture of the positive electrode and before the press treatment, and a positive electrode sample subjected to the press treatment are used, and each sample is divided into four at intervals of 10 mm along the length direction. Two electrode terminals were provided. And the electrical resistance of each sample was measured by the four probe method. When the ratio (Ra / Rb) of the electric resistance Ra of the sample after the press treatment to the electric resistance Rb of the sample before the press treatment was 1.5 or less, it was judged as acceptable, and when it exceeded that, it was judged as unacceptable.

(Production of evaluation cell)
A bipolar evaluation cell using the positive electrode sample subjected to the press treatment as a working electrode was produced. Lithium metal was used for the counter electrode. As the electrolytic solution, a non-aqueous electrolytic solution in which 1.3 mol / L of LiPF ₆ was dissolved in a mixed solvent of ethylene carbonate and ethyl methyl carbonate (3: 7 by volume) was used, and a microporous polyethylene membrane was used as the separator. It was. For the exterior body, a resin container in which a polypropylene block was processed was used, and the electrode group was housed and sealed so that the open ends of the terminals provided on the working electrode and the counter electrode were exposed to the outside.

(Battery test)
A performance test was performed using the evaluation cell produced as described above, and the electrode capacity per unit mass of the positive electrode active material was determined as follows.
The fabricated evaluation cell was charged to 4 V at 0.2 C, then discharged at 0.2 C, and the product of the current that flowed until the voltage dropped below 2 V during discharge and the time required for discharge was defined as the electrode capacity. A value obtained by dividing the electrode capacity by the mass of the active material filled in the positive electrode sample was defined as the electrode capacity per unit mass of the positive electrode active material. Here, the mass of the active material filled in the positive electrode sample is the mass (g) of the electrode mixture obtained by subtracting the mass of the porous aluminum current collector sample before filling the electrode mixture from the positive electrode mass after the press treatment. Was obtained by multiplying this by the mass ratio of the positive electrode active material in the positive electrode mixture.
Table 2 shows the electrode capacity per unit mass (1 g) of the positive electrode active material. 100 mAh / g or more was accepted and less than that was rejected.

  In Invention Examples 1 to 5, the porosity and da / dp are within the ranges specified in the present invention, and the electrode mixture filling amount, the electric resistance ratio, and the electrode capacity per unit mass of the positive electrode active material were acceptable. It was.

  On the other hand, in Comparative Example 6, since da / dp was too large, the electrical resistance ratio was unacceptable.

  In Comparative Example 7, since the porosity of the porous aluminum current collector was too low, the electrode mixture filling amount was unacceptable. Moreover, it was difficult for the electrolytic solution to enter the active material, and the electrode capacity per unit mass of the positive electrode active material was unacceptable.

  In Comparative Example 8, since the porosity of the porous aluminum current collector was too high, the porous aluminum could not keep its shape, and a positive electrode in which the electrode mixture was filled in the pores of the porous aluminum current collector was produced. could not. Therefore, the electrode mixture filling amount and the electric resistance ratio could not be measured, and the battery performance could not be evaluated.

  In the electrode for a nonaqueous electrolyte secondary battery according to the present invention, the active material does not damage the porous aluminum wall at the time of press treatment, and can prevent a decrease in conductivity in the electrode. As a result, the battery characteristics of the nonaqueous electrolyte secondary battery can be improved by increasing the electrode capacity.

DESCRIPTION OF SYMBOLS 1 ... Active material 2 ... Porous aluminum wall 3 ... Porous hole of porous aluminum 4 ... Damaged part of porous aluminum wall da ... Active material particle size dp ... Porous aluminum Pore diameter

Claims (3)

  An electrode for a non-aqueous electrolyte secondary battery containing an electrode mixture containing an active material capable of occluding and releasing lithium, wherein porous aluminum having a porosity of 80 to 95% is used as a current collector in the hole. An electrode for a nonaqueous electrolyte secondary battery, which is filled with an electrode mixture, and wherein the particle diameter da of the active material and the pore diameter dp of porous aluminum satisfy da / dp ≦ 0.10.   The non-aqueous electrolyte 2 according to claim 1, wherein the electrode mixture includes a conductive additive and a binder in addition to the active material, and the ratio of the active material to the total electrode mixture is 85 to 95 mass%. Secondary battery electrode.   A nonaqueous electrolyte comprising: the nonaqueous electrolyte secondary battery electrode according to claim 1 or 2 as at least one of a positive electrode and a negative electrode; and a separator disposed between the positive and negative electrodes, and a nonaqueous electrolyte. Secondary battery.

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