JP2015225761A - Electrode active material mixture, electrode manufactured by use thereof, and nonaqueous electrolyte secondary battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrode active material mixture for manufacturing an electrode for a nonaqueous electrolyte secondary battery, in which an electrode active material, etc. are dispersed uniformly.SOLUTION: An electrode active material mixture comprises: an electrode active material; a conductive assistant; a binding material; polyether; and water for dispersing the electrode active material, the conductive assistant, and the binding material. The electrode active material consists of a substance, such as LiAlMnO, LiNiMnO, LiTiO, or TiO(B), which lithium ions can reversibly go out of/into.

Description

  The present invention relates to an electrode composition for a non-aqueous electrolyte secondary battery.

  Lithium ion storage batteries are currently widely used as power sources for mobile devices. Lithium ion storage batteries are expected to be used for large power supplies such as electric vehicles and power storage because of their higher energy density than existing nickel-cadmium storage batteries and nickel-hydrogen storage batteries. In particular, non-aqueous electrolyte secondary batteries using transition metal composite oxides as electrode active materials are attracting attention because of their good cycle characteristics and high safety (for example, Non-Patent Document 1).

In such a non-aqueous electrolyte secondary battery, the electrode has a structure in which an electrode active material, a conductive additive, and a binder (binder) for imparting shape stability to the electrode active material are dispersed in a solvent. The kneaded and kneaded materials are pasted on a current collector, molded and dried.
For example, polyvinylidene fluoride is used as the binder, and this binder is dispersed in N-methyl-2-pyrrolidone which is an organic solvent. When an organic solvent is used as a dispersant, it is necessary to recover the solvent in addition to the cost of the solvent itself.

Therefore, water is used as a solvent, and a binder such as a styrene-butadiene copolymer that is easily dispersed in water may be used as the binder (for example, Patent Document 1). Had a problem in the mixing properties of the electrode active material and the binder.
Therefore, Patent Document 2 uses lithium manganese composite using water as a dispersion solvent to which a water-soluble polymer called carboxymethyl cellulose is added as a dispersion stabilizer, and using polytetrafluoroethylene (PTFE) as a binder. Oxide-based electrode active materials such as oxide (Example 11), lithium / nickel / manganese / cobalt composite oxide (Example 12), and lithium titanium composite oxide (Example 13) are prepared.

Patent Document 3 discloses a mixed powder of a conductive material and a material in which a coating material such as Al ₂ O ₃ is adhered in the form of particles or layers on the surface of a lithium / nickel composite oxide (core material) as an electrode active material. The electrode active material mixture paste is prepared by mixing with an aqueous binder in which the water-soluble polymer is dissolved and the water-dispersible polymer is dispersed.

JP-A-4-342966 JP 2011-258333 A JP 2011-146360 A

Takami, Kosugi, Honda "New Rechargeable Battery SCiBTM for Hybrid Vehicles with Excellent Durability and Safety" Toshiba Review Vol.63, No.12, pp.54-57 (2008)

However, in Patent Document 2, when a conductive additive is mixed with an oxide electrode active material, how effective is an aqueous solvent with a water-soluble polymer added as a dispersion stabilizer for the dispersion of the electrode active material. No example is shown.
As a result of intensive studies by the inventor, when a conductive additive is mixed, particularly when a carbon-based powder is mixed as a conductive additive, separation of different kinds of particles is likely to occur due to particle density and hydrophilicity problems. I understood that.

  Moreover, the electrode active material used in the Example of patent document 3 is restricted to lithium nickel nickel cobalt oxide. Further, in Patent Document 3, since a metal oxide such as Al, B, Ga, In, Mg, Si, and Zr is attached to the surface of the electrode active material as a coating material, the unit area and unit thickness of the electrode There is also a problem that the capacity per unit is reduced and the energy density of the battery is lowered.

  The present invention has been made in view of the above-described circumstances, and in order to manufacture a battery electrode having excellent shape stability, an electrode active material mixture that can be manufactured in a short time, an electrode manufactured using the electrode, and a non-electrode It aims at providing a water electrolyte secondary battery.

The electrode active material mixture for a non-aqueous electrolyte secondary battery of the present invention is used to produce an electrode for a non-aqueous electrolyte secondary battery, and includes at least an electrode active material, a conductive additive, a binder, a polyether, Water is included as a solvent for dispersing the electrode active material, the conductive additive, the binder, and the polyether, and the electrode active material is any one of (1) to (3) below.
(1) Li _{1 + x} A _y Mn _2-xy O ₄ (0 ≦ x ≦ 0.34, 0 <y ≦ 0.6, A is a group consisting of Al, Mg, Zn, Ni, Co, Fe and Cr At least one selected from)
_{(2) Li [Li (1/3} ) -x A y Ti (5/3) + xy] O 4 (0 ≦ x ≦ 1 / 3,0 ≦ y ≦ 1/2, A is Al, Mg, Zn , At least one selected from the group consisting of Ni, Co, Fe, Cr or Nb),
(3) Ti _x A _y O ₂ (0.8 ≦ x + y ≦ 1.2, A is at least one selected from the group consisting of Al, Mg, Zn, Ni, Co, Fe, Cr, or Nb).

The polyether is preferably polyethylene glycol (PEG), polypropylene glycol (PPG), polybutylene glycol (PBG) or a mixture thereof.
The surface of the electrode active material may be coated with the polyether.
The conductive aid may be a carbon-based powder. Examples of the carbon-based powder include natural graphite, artificial graphite, vapor grown carbon fiber, carbon nanotube, acetylene black, ketjen black, and furnace black. Thus, when carbon-based powder is mixed as a conductive additive, according to the present invention, separation of different kinds of particles caused by particle density and hydrophilic problems can be suppressed, and a uniform mixture can be obtained in a short time. It can be.

The binder is at least one of polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, styrene-butadiene copolymer, polyacrylic ester, polyvinyl alcohol, carboxymethyl cellulose, and polyimide. It is preferable.
Depending on the type of the electrode active material, it may be suitably used for the positive electrode of the battery, or may be suitably used for the negative electrode of the battery.

  Furthermore, according to this invention, the electrode for nonaqueous electrolyte secondary batteries obtained from the said electrode active material mixture is provided. Moreover, according to this invention, the nonaqueous electrolyte secondary battery provided with it is provided.

  According to the present invention, the electrode active material mixture contains any one of the electrode active materials specified in the above (1) to (3), a conductive additive, a binder, water, and a polyether, so that a short time can be obtained. Thus, the dispersed state is improved, and an electrode having good shape stability and battery performance can be produced.

Embodiments of the present invention will be described below with reference to the accompanying drawings.
The scope of the present invention is defined by the terms of the claims, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.
<1. Electrode>
The electrode active material mixture of the present invention contains at least an electrode active material, a conductive additive, a binder (binder), polyether, and water.

The electrode active material is a transition metal oxide and / or transition metal oxide capable of inserting / extracting lithium ions, and (1) Li _{1 + x} A _y Mn _2-xy O ₄ (0 ≦ x ≦ 0.34, 0 <y ≦ 0.6, A is at least one selected from the group consisting of Al, Mg, Zn, Ni, Co, Fe and Cr), (2) Li [Li _{(1/3) −} consisting _{x A y Ti (5/3) +} xy] O 4 (0 ≦ x ≦ 1 / 3,0 ≦ y ≦ 1/2, A is Al, Mg, Zn, Ni, Co, Fe, Cr or Nb At least one selected from the group), (3) Ti _x A _y O ₂ (0.8 ≦ x + y ≦ 1.2, A is from the group consisting of Al, Mg, Zn, Ni, Co, Fe, Cr, or Nb) Any one of at least one selected) is used. These electrode active materials have the feature that there is almost no volume change accompanying charging / discharging.

Although not particularly limited, in (1), the metal A is preferably an oxide of aluminum or nickel.
In the above (2) and (3), it is preferable that the metal of A is not included (y = 0). Or when the metal of A is included, the oxide whose metal of A is niobium is preferable.
The polyether is preferably polyethylene glycol (PEG), polypropylene glycol (PPG), polybutylene glycol (PBG) or mixtures thereof. In the present invention, the mixing ratio of the polyether to the total solvent is preferably 0.5 to 5% by weight, and more preferably 0.5 to 3%. Two or more kinds of polyethers may be mixed and used.

  A binder that can be dispersed in water is used. For example, although not particularly limited, polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), styrene-butadiene copolymer (SBR), polyacrylic acid ester, polyvinyl alcohol (PVA), At least one selected from the group consisting of carboxymethyl cellulose (CMC), polyimide (PI) and derivatives thereof can be used. You may add a dispersing agent and a thickener to these. In the present invention, the amount of the binder contained in the electrode is preferably 1 part by weight or more and 30 parts by weight or less, more preferably 1 part by weight or more and 15 parts by weight or less with respect to 100 parts by weight of the electrode active material. If it is the said range, the adhesiveness of an electrode active material and a conductive support material will be maintained, and adhesiveness with a collector can fully be acquired.

  The electrode contains a conductive additive. Although it does not specifically limit as a conductive support material, A carbonaceous material and / or metal microparticles are preferable. Examples of the carbon-based material include natural graphite, artificial graphite, vapor-grown carbon fiber, carbon nanotube, acetylene black, ketjen black, and furnace black. Examples of the metal fine particles include copper, aluminum, nickel, and an alloy containing at least one of these. Further, the surface of the electrode active material or the surface of fine particles of inorganic material may be plated. These carbon-based materials and metal fine particles may be used alone or in combination of two or more.

The amount of the conductive additive contained in the negative electrode is preferably 1 part by weight or more and 30 parts by weight or less, more preferably 1 part by weight or more and 15 parts by weight or less with respect to 100 parts by weight of the electrode active material. If it is the said range, the electroconductivity of an electrode will be ensured.
Examples of the current collector used in the electrode for the nonaqueous electrolyte secondary battery of the present invention include copper, aluminum, nickel, titanium, an alloy containing at least one of these, or a polymer having conductivity. Examples of the shape include a foil shape, a mesh shape, a punching shape, an expanded shape, and a foam structure. The porosity of the current collector is defined as “the total volume of the pores existing in the unit volume including the current collector”.

  Here, the mesh shape is a woven fabric or non-woven fabric of metal or conductive polymer fibers. The thickness of the fiber is preferably 50 μm or more and 2000 μm or less. When the thickness is less than 50 μm, the current collector tends to be easily broken. On the other hand, when a fiber thicker than 2000 μm is used, the opening becomes too large to make the porosity described later, and it tends to be difficult to hold the electrode active material mixture by the mesh.

  The punching shape is a plate in which holes such as a circle, a rectangle, or a hexagon are formed, and a metal made of metal is punching metal. Since it is plate-shaped, the porosity corresponds to the hole area ratio (the ratio of the total area of the holes per unit area of the plate in plan view). The hole area ratio is determined by the ratio between the hole diameter and the bone (metal part), the hole shape, and the hole arrangement. The shape of the hole is not particularly limited, but from the viewpoint of increasing the hole area ratio, a round hole zigzag type (open angle of the zigzag type is 60 °, for example) and a square hole parallel type are preferable.

The expanded shape is a staggered cut made on a plate and stretched to form a mesh. Expanded metal is made of metal. The porosity of the expanded metal corresponds to the hole area ratio, which is determined by the hole diameter / bone ratio, the hole shape, and the hole arrangement.
The foam structure has a three-dimensional network structure like a sponge, and the pores are continuous or dispersed. The structure is determined by the pore size and porosity. The shape and diameter of the continuous holes are not particularly limited, but a structure having a high specific surface area is preferable.

The metal used for the current collector of the present invention is only required to be stable at the electrode operating potential. When the operating potential is 0.7 V or less on the basis of lithium, copper and its alloys are preferable, and when 0.7 V or more, aluminum and its alloys are used. Is preferred.
The device for producing the electrode active material mixture of the present invention is not particularly limited, but since the electrode active material, conductive additive, binder, polyether and water can be uniformly mixed, agitation granulator, ball mill, planetary mixer, jet It is preferable to use a mill or a thin film swirl mixer. The mixing method of the electrode active material mixture is not particularly limited, but may be prepared by mixing the electrode active material, the conductive additive, and the polyether, and then adding a binder dispersed in water. You may make by adding water, after mixing an auxiliary material, polyether, and a binder. Preferably, a method in which an electrode active material, a conductive additive, and a polyether are mixed and then a binder dispersed in water is added and mixed is desirable. In this way, a slurry-like electrode active material mixture is obtained.

An electrode for a non-aqueous electrolyte secondary battery can be produced by supporting a current collector after removing water from the electrode active material mixture of the present invention. That is, after filling and applying the electrode active material mixture containing water to the pores and the outer surface of the current collector, the electrode is produced by removing the water.
The method for supporting the electrode active material mixture on the current collector is not particularly limited. For example, the electrode active material mixture is dispersed on the current collector and pressurized to form an electrode, and then water is removed. A sheet is formed only from the substance mixture, and an electrode is formed by pressure bonding to the current collector to remove the mixed solvent, a method in which the electrode active material mixture is applied with a doctor blade, a die coater, etc., and then water is removed. A method of removing water after adhering to the electric body and a method of removing water after impregnating the current collector in the electrode active material mixture are preferable. In particular, a method of forming an electrode by pressure, pressure bonding or the like is preferable. A method of removing the mixed solvent is preferable because it is easy to dry using an oven or a vacuum oven. As the atmosphere, air at room temperature or high temperature, an inert gas, a vacuum state, or the like can be given.

  There is a method of preparing the electrode active material mixture of the present invention after previously coating the surface of the electrode active material with polyether. In this case, a solid electrode having a solid content concentration of 80% or more, a sheet is formed only from the electrode active material mixture, and after pressure-bonded to the current collector, a mixed electrode is removed to obtain a good electrode. By setting the solid content concentration to 80% or more, a part of the surface polyether is dissolved and the lubricity is improved. Polyether coating can be performed by using a tumbling fluidized coating apparatus (MP-25, manufactured by Paulek) to scatter the active material into the container and spray the aqueous polyether solution into the container. The coating thickness is preferably 1 nm or more and 1 μm or less.

The obtained electrode may be used as a negative electrode of a nonaqueous electrolyte secondary battery or may be used as a positive electrode. When used as a positive electrode, lithium ions may be inserted in advance chemically and electrochemically.
<2. Capacity ratio and area ratio of negative electrode to positive electrode>
As for the ratio of the electric capacity of a positive electrode and a negative electrode in the secondary battery produced using the electrode for nonaqueous electrolyte secondary batteries manufactured from the electrode active material mixture of the present invention, it is desirable to satisfy the following formula (a).

0.7 ≦ B / A ≦ 1.3 (a)
However, in said formula (a), A shows the electrical capacity per 1 cm < ² > of positive electrodes, B shows the electrical capacity per 1 cm < ² > of negative electrodes.
When B / A is less than 0.7, the potential of the negative electrode may become a potential at which the negative electrode current collector reacts with lithium or a lithium deposition potential during overcharge, while B / A is 1.3. If it is larger, a side reaction may occur because there are many negative electrode active materials not involved in the battery reaction.

The area ratio between the positive electrode and the negative electrode in the nonaqueous electrolyte secondary battery of the present invention is not particularly limited, but preferably satisfies the following formula (b).
1 ≦ D / C ≦ 1.2 (b)
However, in said formula (b), C shows the area of a positive electrode, D shows the area of a negative electrode. When D / C is less than 1, for example, when B / A = 1, the capacity of the negative electrode is smaller than that of the positive electrode, so that the potential of the negative electrode may become a lithium deposition potential during overcharge. On the other hand, if D / C is greater than 1.2, the negative electrode active material not involved in the battery reaction may cause a side reaction because the portion of the negative electrode that is not in contact with the positive electrode is large. Although control of the area of a positive electrode and a negative electrode is not specifically limited, For example, in the case of electrode preparation, it can carry out by controlling the coating width.

The area ratio between the separator and the negative electrode used in the nonaqueous electrolyte secondary battery of the present invention is not particularly limited, but preferably satisfies the following formula (c).
1 ≦ F / E ≦ 1.5 (c)
However, in said formula (c), E shows the area of a negative electrode and F shows the area of a separator. When F / E is less than 1, the positive electrode and the negative electrode are in contact with each other. When F / E is greater than 1.5, the volume required for the exterior increases, and the capacity density and output density of the battery may decrease.

<3. Separator>
Examples of the separator used in the nonaqueous electrolyte secondary battery of the present invention include porous materials and nonwoven fabrics. The material of the separator is preferably one that does not dissolve in the organic solvent that constitutes the electrolytic solution. Specifically, a polyolefin polymer such as polyethylene or polypropylene, a polyester polymer such as polyethylene terephthalate, cellulose, or glass. Inorganic materials.

The thickness of the separator is preferably 1 to 500 μm. If it is less than 1 μm, it tends to break due to insufficient mechanical strength of the separator and cause an internal short circuit. On the other hand, when it is thicker than 500 μm, the load characteristics of the battery tend to be reduced due to the increase in the internal resistance of the battery and the distance between the positive and negative electrodes. A more preferable thickness is 10 to 300 μm.
<4. Non-aqueous electrolyte>
The non-aqueous electrolyte used in the non-aqueous electrolyte secondary battery of the present invention is not particularly limited, but a polymer is impregnated with an electrolytic solution in which a solute is dissolved in a non-aqueous solvent, or an electrolytic solution in which a solute is dissolved in a non-aqueous solvent. A gel electrolyte or the like can be used.

  The non-aqueous solvent preferably includes a cyclic aprotic solvent and / or a chain aprotic solvent. Examples of the cyclic aprotic solvent include cyclic carbonates, cyclic esters, cyclic sulfones and cyclic ethers. Examples of the chain aprotic solvent include chain carbonates, chain carboxylic acid esters and chain ethers. In addition to the above, a solvent generally used as a solvent for nonaqueous electrolytes such as acetonitrile may be used. More specifically, dimethyl carbonate, methyl ethyl carbonate, dimethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethylene carbonate, propylene carbonate, butylene carbonate, γ-butyrolactone, 1,2-dimethoxyethane, sulfolane, dioxolane, propionic acid Methyl and the like can be used. These solvents may be used alone or as a mixture of two or more. However, in view of the ease of dissolving the solute described below and the high conductivity of lithium ions, a mixture of two or more of these solvents. Is preferably used. A gel electrolyte in which an electrolyte is impregnated in a polymer can also be used.

The solute is not particularly limited. For example, LiClO ₄ , LiBF ₄ , LiPF ₆ , LiAsF ₆ , LiCF ₃ SO ₃ , LiBOB (Lithium Bis (OxAlato) Borate), LiN (SO ₂ CF ₃ ) _2, etc. are dissolved in the solvent. It is preferable because it is easy to do. The concentration of the solute contained in the electrolytic solution is preferably 0.5 mol / L or more and 2.5 mol / L or less. If it is less than 0.5 mol / L, the desired lithium ion conductivity may not be exhibited. On the other hand, if it is higher than 2.5 mol / L, the solute may not be dissolved any more. The non-aqueous electrolyte may contain a trace amount of additives such as a flame retardant and a stabilizer.

<5. Non-aqueous electrolyte secondary battery>
The positive electrode and the negative electrode of the nonaqueous electrolyte secondary battery of the present invention may be in the form in which the same electrode is formed on both sides of the current collector, and the positive electrode is formed on one side of the current collector and the negative electrode is formed on one side. In other words, in the case of a bipolar type, in order to prevent a liquid junction between the positive electrode and the negative electrode through the current collector, the conductive auxiliary material and / or the insulating material is between the positive electrode and the negative electrode. Is arranged. In the case of a bipolar electrode, a separator is disposed between the positive electrode side and the negative electrode side of the adjacent bipolar electrode, and the positive electrode and An insulating material is disposed around the negative electrode.

  The nonaqueous electrolyte secondary battery of the present invention may be one obtained by winding or laminating a separator disposed between the positive electrode side and the negative electrode side. The positive electrode, the negative electrode, and the separator are impregnated with a nonaqueous electrolyte that is responsible for lithium ion conduction. When a non-aqueous electrolysis gel is used, the electrolyte may be impregnated in the positive electrode and the negative electrode, or may be in a state only between the positive electrode and the negative electrode. If the positive electrode and the negative electrode are not in direct contact with the gel electrolyte, the separator need not be used.

The amount of the nonaqueous electrolyte used in the nonaqueous electrolyte secondary battery of the present invention is not particularly limited, but is preferably 0.1 mL or more per 1 Ah of battery capacity. If it is less than 0.1 mL, the conduction of lithium ions accompanying the electrode reaction may not catch up, and the desired battery performance may not be exhibited.
The nonaqueous electrolyte may be added to the positive electrode, the negative electrode, and the separator in advance, or may be added after winding or laminating a separator disposed between the positive electrode side and the negative electrode side. When using a gel-like non-aqueous electrolyte, it may be gelled after impregnation with a monomer, or may be placed between the positive electrode and the negative electrode after gelling in advance.

  The non-aqueous electrolyte secondary battery of the present invention may be wound or laminated with a laminate film after the laminate is wound, or may be rectangular, elliptical, cylindrical, coin-shaped, button-shaped, or sheet-shaped. It may be packaged with a metal can. The exterior may be provided with a mechanism for releasing the generated gas or the like. Further, a mechanism for injecting an additive for recovering the function of the deteriorated nonaqueous electrolyte secondary battery from the outside of the battery may be provided. The number of stacked layers can be stacked until a desired battery capacity is exhibited. In the case of stacking, pressure may be applied in the stacking direction of the electrodes. Pressure may be applied inside the cell or may be applied from the outside of the exterior.

  The nonaqueous electrolyte secondary battery of the present invention can be made into a secondary battery module by connecting a plurality of nonaqueous electrolyte secondary batteries. The module of the present invention can be manufactured by connecting in series or in parallel as appropriate depending on the desired size, capacity, and voltage. Further, a control circuit may be attached to the secondary battery module in order to confirm the state of charge of each battery and improve safety.

(1) is prepared electrode active material of the electrode _{Li 1.1 Al 0.1 Mn 1.8 O 4} ; LiNi 0.5 Mn 1.5 O 4; Li 4 Ti 5 O 12; TiO 2 (B) is For each 100 parts by weight, 5.6 parts by weight of conductive additive (acetylene black), 5.6 parts by weight in terms of solid content of various binders, and 1.2 parts by weight of PEG (polyethylene glycol) are mixed. Thus, an electrode active material mixture was prepared.

Li _1.1 Al _0.1 Mn _1.8 O ₄ is Li _{1 + x} A _y Mn _2-xy O ₄ (0 ≦ x ≦ 0.34, 0 <y ≦ 0.6, A is Al, This corresponds to the case of A = Al, x = 0.1, and y = 0.1 in at least one selected from the group consisting of Mg, Zn, Ni, Co, Fe, and Cr. The LiNi _0.5 Mn _1.5 O ₄ corresponds to the case of A = Ni, x = 0, y = 0.5.

The Li ₄ Ti ₅ O ₁₂ is “Li [Li _{(1/3) -x} A _y Ti _{(5/3) + xy} ] O ₄ (0 ≦ x ≦ _1/3, 0 ≦ y ≦ 1/2, A corresponds to the case of x = 0 and y = 0 in “at least one selected from the group consisting of Al, Mg, Zn, Ni, Co, Fe, Cr and Nb)”. The TiO ₂ (B) is Ti _x AyO ₂ (0.8 ≦ x + y ≦ 1.2, A is at least one selected from the group consisting of Al, Mg, Zn, Ni, Co, Fe, Cr and Nb) This corresponds to the case of x = 1 and y = 0.

The electrode active material Li _1.1 Al _0.1 Mn _1.8 O ₄ (LAMO) is described in the literature ("Lithium Aluminum Manganese Oxide Having Spinel-Framework Structure for Long-Life Lithium-Ion Batteries" Electrochemical and Solid-State Letters. Volume9, Issue12, Pages A557 (2006)). That is, an aqueous dispersion of manganese dioxide, lithium carbonate, aluminum hydroxide, and boric acid was prepared, and a mixed powder was prepared by a spray drying method. At this time, the amounts of manganese dioxide, lithium carbonate and aluminum hydroxide were adjusted so that the molar ratio of lithium, aluminum and manganese was 1.1: 0.1: 1.8. Next, the mixed powder was heated at 900 ° C. for 12 hours in an air atmosphere, and then again heated at 650 ° C. for 24 hours. Finally, the powder was washed with water at 95 ° C. and dried to prepare an electrode active material.

LiNi _0.5 Mn _1.5 O ₄ (LiNiMO) as an electrode active material is the literature (“Solid-state redox potentials for Li [Me1 / 2Mn3 / 2] O4 (Me: 3d-transition metal) having spinel-framework” It was made by the method described in "structure: a series of 5 volt materials for advanced lithium-ion batteries" Journal of Power Sources, Vol. 81-82, pp. 90-94 (1999)). That is, lithium hydroxide, manganese oxide hydroxide, and nickel hydroxide were first mixed so that the molar ratio of lithium, manganese, and nickel was 1: 1.5: 0.5. Next, the mixture was heated at 550 ° C. in an air atmosphere, and then heated again at 750 ° C. to prepare an electrode active material.

Li ₄ Ti ₅ O ₁₂ (LTO), an electrode active material, has been published in the literature ("Zero-Strain Insertion Material of Li [Li1 / 3Ti5 / 3] O4 for Rechargeable Lithium Cells" J. Electrochem. Soc., Volume 142, Issue 5 , pp. 1431-1435 (1995)). That is, first, titanium dioxide and lithium hydroxide are mixed so that the molar ratio of titanium and lithium is 5: 4, and then this mixture is heated at 800 ° C. for 12 hours in a nitrogen atmosphere to obtain an electrode active material. Produced.

TiO ₂ (B: bronze type) as an electrode active material is described in the literature (“TiO 2 (B) as a promissing high potential negative electrode for large-size lithium-ion batteries” Journal of Power Sources 189, 580 (2009)). Prepared by the method described. That is, potassium carbonate and anatase TiO ₂ were mixed at a molar ratio of 1: 4, and K ₂ Ti ₄ O ₉ was obtained by firing twice at 1000 ° C. for 24 hours in air, and then in 1M hydrogen chloride solution. Ion exchange was performed by soaking for 3 days, and it was prepared by dehydration and drying at 500 ° C. for 30 minutes.

A method for mixing each electrode active material and a method for producing the electrode are shown below.
First, the electrode active material and the conductive additive were mixed using an automatic mortar. Transfer the mixed powder to a stainless steel bowl, add polyether and binder dispersed in water, pre-mix using alumina pestle, add water to adjust the solid content concentration to 75%, about 5 to 15 minutes, By mixing again, a slurry-like electrode active material mixture was prepared.

  A sheet was prepared by passing the electrode active material mixture described above through a gap roll. The sheet was again passed through a gap roll together with aluminum expanded metal (aperture 1 mm × 2 mm, thickness 0.1 mm), and water was removed by vacuum drying at 170 ° C. After drying, the thickness of the electrode containing aluminum expanded metal was approximately 0.5 mm.

Li _1.1 Al _0.1 Mn _1.8 O ₄ (LAMO) and LiNi _0.5 Mn _1.5 O ₄ (LiNiMO) were used as positive electrode active materials. Li ₄ Ti ₅ O ₁₂ (LTO) and TiO ₂ (B) were used as negative electrode active materials.
The average particle diameter of the electrode active material measured by a laser diffraction scattering method particle size distribution analyzer was LAMO = 16 μm, LiNiMO = 11 μm, LTO = 7 μm, TiO ₂ (B) = 1 μm.

(2) Production of half battery A half battery was produced as follows.
The obtained electrode (working electrode) / separator / lithium metal were laminated in this order. Lithium metal was used as an electrode by pressing a metal on a stainless steel sheet. ^Two separators of PP microporous membrane (thickness 25 μm, area 20 cm ² ) were used as the separator. An aluminum tab serving as a lead electrode was vibration welded to the working electrode. A nickel tab was used for the extraction electrode of the lithium electrode. Put the laminate in a bag-like aluminum laminate sheet, put 1 mL of non-aqueous electrolyte (propylene carbonate / ethyl methyl carbonate = 3/7 vol%, LiPF ₆ 1 mol / L) in the bag, then only the extraction electrode A half cell was made by exposing and heat sealing the outlet of the bag.

(3) Measurement (3-1) Positive electrode First, PTFE is used as the binder, and PEG (Examples 1 and 4), PPG (Examples 2 and 5), or PBG (Examples 3 and 6) is used as the polyether. A half cell including a positive electrode using Li metal as a counter electrode was prepared and measured.

  Moreover, what coated PEG on the positive electrode active material (Examples 7 and 8) was also produced, it was set as the electrode similarly to the above, and the half-cell test was done. Coating was performed using a tumbling fluidized coating apparatus (MP-25, manufactured by Paulek). Coating was performed by repeating the process of spraying and drying a 5% aqueous PEG solution in a tank in which the active material was scattered. The coated material was prepared by forming a sheet with only the electrode active material mixture, pressing it onto the current collector, and then removing the mixed solvent.

With such a half-cell sandwiched between the metal plates from the outside, the voltage range was set to 3 to 5 V, and a charge / discharge cycle test was conducted at a current value (1/8 C rate) at which charging or discharging ended over 8 hours. A charge / discharge test apparatus (HJ1005SD8, manufactured by Hokuto Denko) was used for the cycle, and the number of cycles was 200.
Table 1 shows the measurement results of the capacity retention rate.

From the results of Table 1, when the polyether was not mixed (Comparative Examples 1 to 4), the capacity retention rate was not good. When the polyether was mixed (Examples 1 to 3, 4 to 6, 7 to 8), it was found that electrode formation with a uniform appearance was possible by mixing for a short time (5 minutes). Moreover, in the Example, the capacity maintenance rate exceeded 90%, and the result that it was favorable was also obtained.
Even when the active material surface was coated and the electrode was formed by pressurizing a low-moisture mixture, the mixing was facilitated and the dispersion was improved.

(3-2) Negative Electrode Next, a half cell including a negative electrode (LTO or TiO ₂ (B)) with Li metal as a counter electrode was prepared and measured. Since PEG was used as the polyether and the operating potential was lower than that of the positive electrode, PTFE, styrene-butadiene rubber (SBR), acrylic, polyvinyl alcohol (PVA), and polyimide (PI) were used as the binder. A charge / discharge cycle test was conducted in the same manner as in (3-1) except that the voltage range was 1 to 3V. The results are shown in Table 2.

As shown in Table 2, when a mixture was prepared using LTO as the negative electrode material and PTFE as the binder in a mixing time of 5 minutes (Comparative Example 6), the electrode active material dropped from the current collector to form an electrode. I couldn't.
When the water-soluble polymer PEG was contained (Example 9), the electrode active material did not fall even at a mixing time of 5 minutes, and the appearance was uniform and the performance was good. Moreover, even if it used binders other than PTFE by mixing PEG (Examples 10-13), electrode formation was possible and the battery performance was also favorable.

When TiO ₂ (B) is used for the negative electrode material, PTFE is used for the binder, a water-soluble polymer PEG is used, and a mixture is prepared in a mixing time of 5 minutes (Example 14), electrode formation is possible and battery performance is also improved. It was good. The capacity retention rate is lower than that in Example 9 because of the difference in electrode active material.
From these facts, by preparing a mixture by adding PEG, it becomes possible to produce an electrode that has good electrode active material dispersion, good electrode shape stability, and good battery performance. I understand.

Claims (9)

Used to produce an electrode for a non-aqueous electrolyte secondary battery, at least an electrode active material, a conductive aid, a binder, a polyether, and the electrode active material, a conductive aid, a binder, and a polyether An electrode active material mixture which contains water as a solvent for dispersing the water and the electrode active material is any one of the following (1) to (3).
(1) Li _{1 + x} A _y Mn _2-xy O ₄ (0 ≦ x ≦ 0.34, 0 <y ≦ 0.6, A is a group consisting of Al, Mg, Zn, Ni, Co, Fe and Cr At least one selected from)
_{(2) Li [Li (1/3} ) -x A y Ti (5/3) + xy] O 4 (0 ≦ x ≦ 1 / 3,0 ≦ y ≦ 1/2, A is Al, Mg, Zn , At least one selected from the group consisting of Ni, Co, Fe, Cr or Nb),
(3) Ti _x A _y O ₂ (0.8 ≦ x + y ≦ 1.2, A is at least one selected from the group consisting of Al, Mg, Zn, Ni, Co, Fe, Cr, or Nb).   The electrode active material mixture according to claim 1, wherein the polyether is one or a mixture selected from the group consisting of polyethylene glycol, polypropylene glycol, and polybutylene glycol.   The electrode active material mixture according to claim 1 or 2, wherein the surface of the electrode active material is coated with the polyether.   The electrode active material mixture according to claim 1, wherein the conductive additive is a carbon-based powder.   The binder is at least one of polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, styrene-butadiene copolymer, polyacrylate, polyvinyl alcohol, carboxymethylcellulose, and polyimide. The electrode active material mixture according to claim 1, which is a seed.   The electrode active material mixture according to any one of claims 1 to 5, wherein the electrode active material is used for a positive electrode of a battery.   The electrode active material mixture according to any one of claims 1 to 5, wherein the electrode active material is used for a negative electrode of a battery.   The electrode for nonaqueous electrolyte secondary batteries produced by apply | coating the electrode active material mixture of any one of Claims 1-7 on a collector, and removing a solvent.   A non-aqueous electrolyte secondary battery produced using the electrode for a non-aqueous electrolyte secondary battery according to claim 8.