JP2012109237A - Electrode plate for nonaqueous electrolyte secondary battery, nonaqueous electrolyte secondary battery, battery pack, and method for manufacturing electrode plate for nonaqueous electrolyte secondary battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrode plate for a nonaqueous electrolyte secondary battery capable of being used for a long time under extreme conditions and showing excellent output and input characteristics, and a battery and a battery pack using the same.SOLUTION: An electrode plate for a nonaqueous electrolyte secondary battery comprises a collector, and an electrode active material layer on at least a portion of the surface of the collector. The electrode active material layer contains electrode active material particles and a binder. The electrode active material particles and the collector, and the electrode active material particles among themselves are adhered by the binder. The binder contains a metal oxide and silicon.

Description

  The present invention relates to an electrode plate used for a non-aqueous electrolyte secondary battery, a non-aqueous electrolyte secondary battery, a battery pack, and a method for producing an electrode plate for a non-aqueous electrolyte secondary battery.

  A non-aqueous electrolyte secondary battery represented by a lithium ion secondary battery has a high energy density and a high voltage, and is gradually charged when the battery is charged before being completely discharged, which is called a memory effect at the time of charge / discharge. Since there is no phenomenon in which the battery capacity decreases, it is used in various fields such as portable devices, notebook computers, and portable devices.

Currently, as a measure to prevent global warming, efforts to reduce CO ₂ emissions are being carried out on a global scale. By reducing the dependence on oil and allowing it to travel with a low environmental load, it can greatly reduce CO ₂ emissions. There is an urgent need to develop and promote next-generation clean energy vehicles represented by plug-in hybrid vehicles and electric vehicles that can contribute. If non-aqueous electrolyte secondary batteries can be used as the driving force for these next-generation clean energy vehicles, there is no need to rely on gasoline, which can greatly contribute to CO ₂ reduction and greatly prevent global warming. Can contribute. On the other hand, in order to use a non-aqueous electrolyte secondary battery as a driving force for a next-generation clean energy vehicle, it is necessary to be able to be used stably over a long period of time.

  Currently, various proposals of non-aqueous electrolyte secondary batteries include a positive electrode plate, a negative electrode plate, a separator, and a non-aqueous electrolyte solution. The positive electrode plate is generally provided with an electrode active material layer in which positive electrode active material particles are fixed to the surface of a current collector such as a metal foil. Moreover, as a negative electrode plate, what is equipped with the electrode active material layer by which a negative electrode active material particle adheres to the collector surface, such as copper and aluminum, is common.

  In order to manufacture the electrode plate which is the positive electrode plate or the negative electrode plate, first, the electrode active material particles which are the positive electrode active material particles or the negative electrode active material particles, the resin binder, or further, the conductive material or other materials as necessary. The material is kneaded and / or dispersed in a solvent to prepare a slurry-like electrode active material layer forming liquid. And an electrode plate provided with an electrode active material layer is formed by applying an electrode active material layer forming liquid on the current collector surface, then drying to form a coating film on the current collector, and pressing (for example, Patent Document 1 or Patent Document 2).

  At this time, the electrode active material particles contained in the electrode active material layer forming liquid are particulate metal compounds dispersed in the liquid, and as such, are applied to the surface of the current collector, dried, and pressed. Even if it is done, it will be hard to adhere to the surface of the current collector, and will peel off from the current collector immediately. Therefore, when forming the electrode active material layer, a resin binder is added to the electrode active material layer forming liquid, and the electrode active material particles are fixed on the current collector by the resin binder, and the electrode active material The particles are fixed to each other.

JP 2006-310010 A JP 2006-107750 A

  However, in the electrode plate formed by the method proposed in Patent Document 1 and Patent Document 2, the electrode active material particles, the current collector, and the electrode active material particles are fixed only by the resin binder. There is a problem that the impedance of the electrode active material layer becomes large and the output characteristics cannot be improved.

  In order to solve such problems, there is an attempt to replace all or part of the resin binder with a metal oxide, that is, to fix the electrode active material particles, the current collector and the electrode active material particles to each other with the metal oxide. Has been made. By using a metal oxide instead of the resin binder, the impedance of the electrode active material layer can be reduced by the amount of using the metal oxide, thereby improving the input / output characteristics.

  Under such circumstances, the present invention further advances the attempt to fix the above-mentioned electrode active material particles, current collector, and electrode active material particles to each other with metal oxide, and employs metal oxide fixation. By reducing the impedance of the electrode active material layer and improving the adhesion between the electrode active material layer and the current collector, the electrode active material layer does not peel from the current collector compared to the conventional case. Therefore, an electrode plate for a non-aqueous electrolyte secondary battery that can be used under severe conditions for a long period of time, a battery and a battery pack using the same, and a method for manufacturing the electrode plate for a non-aqueous electrolyte secondary battery The main issue is to provide

  The present invention for solving the above problems is an electrode plate for a non-aqueous electrolyte secondary battery comprising a current collector and an electrode active material layer formed on at least a part of the surface of the current collector. The electrode active material layer contains electrode active material particles and a binding material, and the electrode active material particles and the current collector, and the electrode active material particles are fixed by the binding material. The binder material includes a metal oxide and silicon.

Further, the present invention for solving the above-described problems is a non-aqueous electrolyte secondary comprising a current collector, a current collector, and an electrode active material layer formed on at least a part of the surface of the current collector. In the battery electrode plate, the electrode active material layer contains electrode active material particles and a binder, and the electrode active material particles, the current collector, and the electrode active material particles are The binder is fixed by a binder, and the binder contains a metal oxide and appears at 980 to 1100 cm ⁻¹ of the Si—O bond obtained when the infrared absorption spectrum of the electrode active material layer is measured. The half width at half maximum of the peak is 30 to 230 cm ⁻¹ . Further, the half width at half maximum of peak appearing in the Si-O bond 1000～1100Cm ^-1 obtained when measuring the infrared absorption spectrum of the electrode active material layer may be a 30~90cm ^-1.

  Another invention for solving the above-described problems is a non-aqueous electrolyte secondary battery comprising at least an electrode plate, a separator, and a non-aqueous electrolyte, wherein the electrode plate is the non-aqueous electrolyte described above. It is an electrode plate for electrolyte secondary batteries.

  Further, another invention for solving the above-described problem includes at least a storage case, a nonaqueous electrolyte secondary battery including a positive electrode terminal and a negative electrode terminal, and a protection circuit having an overcharge and overdischarge protection function, A battery pack configured by storing the non-aqueous electrolyte secondary battery and the protection circuit in the storage case, wherein the non-aqueous electrolyte secondary battery is the non-aqueous electrolyte secondary battery. It is characterized by.

  Another invention for solving the above problems is a method for producing an electrode plate for a non-aqueous electrolyte secondary battery, wherein the electrode active material particles, the metal element-containing compound, and the silicon element-containing compound are: An electrode active material layer-forming liquid contained is applied to at least a part of the current collector to form a coating film, and the coating film is heated by the metal element-containing compound and the silicon element-containing compound. A heating step of heating at a temperature equal to or higher than the decomposition temperature.

  According to the electrode plate for a nonaqueous electrolyte secondary battery of the present invention, an electrode plate having excellent output characteristics over a long period of time can be obtained. Further, the same effects as described above can be obtained even in a battery or battery pack using the electrode plate of the present invention. Furthermore, according to the manufacturing method of this invention, the electrode plate for nonaqueous electrolyte secondary batteries which has the said effect can be provided.

It is sectional drawing of the positive electrode plate for nonaqueous electrolyte secondary batteries of this invention. It is a cyclic voltammogram which shows the result of the cyclic voltammetry test using the metal oxide which shows alkali metal ion insertion elimination reaction. It is a cyclic voltammogram which shows the result of the cyclic voltammetry test using the metal oxide which does not show alkali metal ion insertion elimination reaction. It is the schematic which shows an example of the nonaqueous electrolyte secondary battery of this invention. It is a sectional exploded view showing an example of a battery pack of the present invention. 3 is a chart showing IR measurement results of Example 1. 14 is a chart showing IR measurement results of Example 13. 10 is a chart showing IR measurement results of Comparative Example 3. It is mapping data by TEM-EDX of Example 1. It is mapping data by TEM-EDX of Example 1.

  Hereinafter, a nonaqueous electrolyte secondary battery electrode plate of the present invention, a nonaqueous electrolyte secondary battery and a battery pack using the electrode plate, and a method for producing a nonaqueous electrolyte secondary battery electrode plate will be described. To do.

  As shown in FIG. 1, the electrode plate for a non-aqueous electrolyte secondary battery according to the present invention comprises a current collector 1 and an electrode active material layer 2 formed on at least a part of the surface of the current collector. Is done.

  Here, the electrode plate 10 for a nonaqueous electrolyte secondary battery according to the first embodiment of the present invention includes a current collector 1 and an electrode active material layer formed on at least a part of the surface of the current collector 1. 2, the electrode active material layer 2 contains electrode active material particles 21 and a binder material 22 containing a metal oxide and silicon. The current collector 1 and the electrode active material particles 21 are characterized by being fixed by the binder 22.

The electrode plate 10 for a non-aqueous electrolyte secondary battery according to the second embodiment of the present invention includes a current collector 1 and an electrode active material layer 2 formed on at least a part of the surface of the current collector 1. The electrode active material layer 2 includes electrode active material particles 21 and a binder material 22 containing a metal oxide, and the electrode active material particles 21 and the current collector 1 and the electrode active material particles 21 are fixed to each other by the binding material 22. Furthermore, the half-width of the peak appearing at 980 to 1100 cm ⁻¹ of the Si—O bond obtained when the infrared absorption spectrum of the electrode active material layer 2 is measured is 30 to 230 cm ^−1. is doing.

  According to the electrode plate for a nonaqueous electrolyte secondary battery of the first embodiment and the second embodiment, the impedance of the electrode active material layer can be reduced by the metal oxide contained in the binder material. . Furthermore, by improving the adhesion between the electrode active material layer 2 and the current collector 1, the electrode active material layer 2 is not peeled off from the current collector 1 as compared with the prior art, and thus is severe for a long period of time. It becomes possible to provide the electrode plate 10 for a non-aqueous electrolyte secondary battery that can be used under circumstances.

By using the electrode plate for a nonaqueous electrolyte secondary battery of the first embodiment and the second embodiment, the reason for the adhesion between the current collector and electrode active material particles is not clear, but at least, In the first embodiment, it is presumed that the presence of silicon contained in the binding material contributes to the improvement of adhesion. Also in the second embodiment, it can be seen that the electrode active material layer contains silicon element and oxygen element, and these elements are bonded to each other (Si-O bond) in the layer. How the bond acts on the binding substance, that is, how the electrode active material particles and the current collector and the electrode active material particles adhere to each other is not necessarily clear. . However, since the Si—O bond having a peak appearing at 980 to 1100 cm ⁻¹ having a half width at half maximum in the above range is present in the electrode active material layer, as a result, the electrode active material layer 2, the current collector 1, It is presumed that the adhesion of the material is improved. Hereinafter, the electrode plate for a non-aqueous electrolyte secondary battery of the present invention will be described separately for the first embodiment and the second embodiment as necessary.

  The electrode plate for a nonaqueous electrolyte secondary battery of the present invention (hereinafter sometimes referred to as the electrode plate of the present invention) can be used as a positive electrode plate or a negative electrode plate of a nonaqueous electrolyte secondary battery. Below, when using as a positive electrode plate, it divides and demonstrates in detail when using as a negative electrode plate. In the following description, the electrode plate of the present invention used for the positive electrode is referred to as a positive electrode plate, and the electrode plate of the present invention used for the negative electrode is referred to as a negative electrode plate. The material particles may be described with positive and negative polarities such as positive electrode active material layers, positive electrode active material particles, negative electrode active material layers, and negative electrode active material particles.

<< Positive electrode plate >>
FIG. 1 is a cross-sectional view of a positive electrode plate for a non-aqueous electrolyte secondary battery of the present invention.

  As shown in FIG. 1, the positive electrode plate 10 has a configuration in which a positive electrode active material layer 2 is provided on a positive electrode current collector 1.

<Positive electrode current collector>
The positive electrode current collector 1 used for the positive electrode plate 10 of the present invention is not particularly limited as long as it is generally used as a positive electrode current collector of a positive electrode plate for a non-aqueous electrolyte secondary battery. For example, a positive electrode current collector formed of a simple substance such as an aluminum foil or a nickel foil or an alloy can be preferably used. Note that the positive electrode current collector 1 used for the positive electrode plate 10 is subjected to surface processing on the surface on which the positive electrode active material layer 2 is scheduled to be formed (the surface of the positive electrode current collector 1) as necessary. Body 1 may be sufficient. As the positive electrode current collector 1 whose surface is processed on the surface, a positive electrode current collector in which a conductive substance is laminated on the surface of a material having a current collecting function, chemical polishing treatment, corona treatment, oxygen plasma treatment are used. Examples thereof include a positive electrode current collector made. That is, the positive electrode current collector 1 has not only a current collector formed of only a material having a current collecting function, but also a surface on which a substance for ensuring conductivity is laminated, or some surface treatment. Also included are those made. The surface of the current collector in the present invention means the surface of a material having a current collecting function in the current collector 1 formed only from a material having a current collecting function, and has a current collecting function. In the case where surface processing or a conductive material is laminated on the entire surface of the material, the surface processing surface or the surface of the conductive material is referred to. In addition, in the case where a part of the surface of the material having a current collecting function is subjected to a surface processing treatment or a conductive material, the surface processing surface, the surface of the conductive material, or these surfaces A portion where a processing treatment or a conductive substance is not stacked (that is, a surface of a material having a current collecting function).

  The thickness of the positive electrode current collector 1 is not particularly limited as long as it is generally a thickness that can be used as a current collector of a positive electrode plate for a nonaqueous electrolyte secondary battery, but is preferably 10 to 100 μm, and is preferably 15 to 50 μm. More preferably.

<Positive electrode active material layer>
The positive electrode active material layer 2 contains positive electrode active material particles 21, and positive electrode active material particles 21, a current collector 1, and a binder material 22 for fixing the positive electrode active material particles 21 to each other.

  The layer thickness of the positive electrode active material layer 2 is not particularly limited, and is generally about 300 nm to 200 μm.

  Moreover, it is preferable that the positive electrode active material layer 2 has voids to such an extent that the nonaqueous electrolyte solution can permeate, and the porosity is preferably 10% or more and 70% or less. The porosity can be measured with Autopore IV 9500 manufactured by Shimadzu Corporation. Hereinafter, the positive electrode active material particles 21 and the binder material 22 will be specifically described.

(Positive electrode active material particles)
The positive electrode active material particles 21 can be appropriately selected and used as chargeable / dischargeable positive electrode active material particles, and the positive electrode active material particles 21 are not particularly limited. Examples of the positive electrode active material particles 21 in the lithium ion secondary battery include LiCoO ₂ , LiMn ₂ O ₄ , LiNiO ₂ , LiFeO ₂ , Li ₄ Ti ₅ O ₁₂ , LiFePO ₄ , LiNi _1/3 Mn _1/3 Co. Examples include positive electrode active material particles such as lithium transition metal composite oxides such as _1/3 O ₂ and LiNi _0.80 Co _0.15 Al _0.05 O ₂ .

  The particle diameter of the positive electrode active material particles 21 is not particularly limited, and those having an arbitrary size can be appropriately selected and used. However, as the particle diameter of the positive electrode active material particles is smaller, the surface area per unit weight can be increased and the rate characteristics can be improved. Therefore, when higher rate characteristics are required, the positive electrode active material particles 21 have a small particle size, specifically less than 10 μm, preferably 5 μm or less, particularly preferably 1 μm or less.

  In addition, the particle diameters of the positive electrode active material particles 21 shown in the present invention and the present specification and the negative electrode active material particles described later are average particle diameters (volume-median particle diameter: measured by laser diffraction / scattering particle size distribution measurement). D50). The particle diameters of the positive electrode active material particles and the negative electrode active material particles are obtained by identifying the measured electron microscope observation data using a particle recognition tool and obtaining the shape data obtained from the recognized particle image. And a particle size distribution graph can be prepared and calculated from the particle size distribution graph. The particle size distribution graph can be created, for example, by using an image analysis type particle size distribution measurement software (manufactured by Mount Tech Co., Ltd., MAC VIEW) based on an electron microscope observation result.

(Binder)
As shown in FIG. 1, the positive electrode active material layer 2 constituting the positive electrode plate 10 contains a binder material 22, and the positive electrode active material particles 21, the current collector 1, and the positive electrode active material particles 21 are It is fixed by the binding substance 22.

(Binder material in the first embodiment)
The binding substance 22 in the first embodiment includes a metal oxide and silicon as essential components.

  Whether or not the binder material 22 contains a metal oxide and silicon is determined by using a transmission electron microscope (TEM) and scanning electron transmission microscopy (STEM) with an EDX detector for nano-order elemental analysis. Can be confirmed by elemental mapping indicated by X and X-ray diffraction (XRD). Specifically, a metal oxide contained in the electrode active material layer is identified by X-ray diffraction, and a substance that adheres the objects to be adhered to each other in a first fixing mode and a second fixing mode to be described later. Confirm by the above element mapping. At this time, when the presence of the metal element and silicon can be confirmed at the same location or a nearby location, and the confirmed metal element is a metal of a metal oxide identified by X-ray diffraction, a binding substance It can be judged that 22 contains a metal oxide and silicon. Further, the binder 22 may be in a form in which silicon is doped into a metal oxide, or in a form in which the metal oxide and silicon are present independently.

"Silicon"
The binder material 22 contains silicon as an essential component. Silicon may be an elemental silicon, a silicon compound, or a combination of these compounds. Examples of the silicon compound include silicon oxide, silicon nitride, silicon phosphate compound, silicon sulfide, silicon carbide, and silicon fluoride, but other silicon compounds may be used.

  There is no particular limitation on the content of metal oxide and silicon, but when the total mass of silicon and metal oxide contained in all the binding materials 22 is 100%, the total mass of silicon element or silicon compound is 10 to 50% is preferable. By setting the content of the silicon element or silicon compound within the above range, it is possible to further improve the adhesion between the current collector 1, the positive electrode active material particles 21, and the positive electrode active material particles.

  As described above, the content of silicon or silicon compound contained in the binding substance 22 is not limited to the substance that adheres the adherends to each other in the first fixing mode and the second fixing mode. It can be confirmed by elemental mapping shown by nano-order elemental analysis with an EDX detector by scanning transmission electron microscopy (STEM method) using a scanning electron microscope (TEM). Also, only the binder containing silicon or silicon compound is separately synthesized under the same conditions as the binder contained in the actual electrode active material layer, and the content is determined from the composition of silicon or silicon compound obtained by ICP emission analysis. Can also be calculated.

"Metal oxide"
In addition, the binder material 22 contains a metal oxide as an essential component together with the silicon. The metal oxide may be a metal oxide that exhibits an alkali metal ion insertion / release reaction, or may be a metal oxide that does not exhibit an alkali metal ion insertion / release reaction.

As the metal oxide exhibiting an alkali metal ion insertion / release reaction, any metal oxide exhibiting the insertion / release reaction can be appropriately selected and used, and is not particularly limited. Examples of such a metal oxide include a composite oxide of at least one metal selected from cobalt, nickel, manganese, iron, and titanium and lithium, such as LiCoO ₂ , LiMn ₂ O ₄ , LiNiO. ₂ , LiFeO ₂ , Li ₄ Ti ₅ O ₁₂ , LiFePO ₄ , LiNi _1/3 Mn _1/3 Co _1/3 O ₂ , LiNi _0.9 Co _0.1 O ₂ , LiNi _0.80 Co _0.15 Al _0.05 O ₂ , etc. Examples thereof include metal composite oxides.

  In the case of the binder 22 containing a metal oxide that exhibits an alkali metal ion insertion / release reaction, the binder 22 itself can also function as an active material, so that the capacity of the positive electrode plate 10 can be increased. There is an advantage that you can.

  On the other hand, as a metal oxide that does not exhibit an alkali metal ion insertion / extraction reaction, an oxide of a metal element that is generally understood to be a metal, and a metal oxide that does not exhibit the reaction is appropriately selected and used. There is no particular limitation. Examples of the metal element include Li, Be, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Cs, Ba, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Examples include Fr, Ra, and Ce.

  When the binding material 22 includes a metal oxide that does not exhibit alkali metal ion insertion / release reaction, the binding material 22 does not electrochemically react with alkali metal ions such as lithium ions. As a result, there is an advantage that no expansion or reaction product due to the electrochemical reaction of the metal oxide occurs, and as a result, deterioration due to expansion or deficiency of the metal oxide in the positive electrode active material layer 2 can be suppressed. is there.

  Although the reason is not clear, among the above metal elements, particularly when a binder containing an oxide of a metal element belonging to the third to fifth periods is present in the positive electrode active material layer, it is better. This is preferable because it shows improved input / output characteristics.

  Among metal oxides containing metal elements belonging to the third to fifth periods, titanium oxide is inexpensive and easy to handle, and is excellent when contained in the positive electrode active material layer. It is preferable because it can show the effect of improving the input / output characteristics. In particular, when a binder material containing titanium oxide is present in the positive electrode active material layer, it is possible to exhibit a high charge / discharge rate (discharge capacity retention rate) of 80% or more at a discharge rate of 50C, such as an automobile. It is possible to cope with large-scale equipment.

  The metal oxide in the present invention is a metal oxide in which oxygen is bonded to any one of the above-described metal elements, or a composite metal containing two or more metal elements selected from the above-described metal elements Any of oxides may be used. For example, examples of metal oxides in which oxygen is bonded to one metal element include sodium oxide, magnesium oxide, aluminum oxide, silicon oxide, potassium oxide, calcium oxide, scandium oxide, titanium oxide, vanadium oxide, chromium oxide, and oxide. Examples thereof include manganese, iron oxide, cobalt oxide, nickel oxide, zinc oxide, gallium oxide, strontium oxide, yttrium oxide, zirconium oxide, molybdenum oxide, ruthenium oxide, tantalum oxide, tungsten oxide, and cerium oxide.

  Examples of composite metal oxides containing two or more kinds of metal elements that can be used as metal oxides include cerium oxide doped with gadolinium, zirconium oxide doped with yttrium, and iron. And a mixed oxide of titanium and titanium, an oxide in which indium and tin are mixed, nickel oxide doped with lithium, and the like.

  Moreover, in this invention, the metal oxide which shows an alkali metal ion insertion-elimination reaction and the metal oxide which does not show an alkali metal ion insertion-release reaction can also be used together.

The presence or absence of an alkali metal ion insertion / elimination reaction of the metal oxide can be confirmed by an electrochemical measurement (cyclic voltammetry: CV) method. The CV test will be described below. For example, in the case where the electrode potential is within an appropriate voltage range of the active material, for example, lithium ions are assumed as alkali metal ions, and the binding material 22 is LiMn ₂ O ₄ , after sweeping from 3.0 V to 4.3 V, The work of returning to 3.0 V again is repeated about 3 times. The scanning speed is preferably 1 mV / sec. For example, in the case of LiMn ₂ O ₄ , as shown in FIG. 2, an oxidation peak corresponding to an alkali metal ion desorption reaction of LiMn ₂ O ₄ appears in the vicinity of about 3.9 V, and an alkali metal in the vicinity of about 4.1 V. A reduction peak corresponding to the ion insertion reaction appears, whereby the presence or absence of an alkali metal ion insertion / desorption reaction can be confirmed. As shown in FIG. 3, when no peak appears, it can be determined that there is no alkali metal ion insertion / desorption reaction.

(Binder material in the second embodiment)
The binding material 22 in the second embodiment includes a metal oxide as an essential component and does not contain silicon as an essential component. Is different. Further, the metal oxide contained in the binding material 22 of the second embodiment is the same as the metal oxide contained in the first binding material 22 described above, and the description thereof is omitted here.

  In the positive electrode plate of the first embodiment and the second embodiment of the present invention, the positive electrode active material particles 21, the positive electrode current collector 1, and the positive electrode active material particles 21 are fixed together by a binding material 22. In this case, the following two aspects are included. The first fixing mode is between the adherends (for example, between the positive electrode active material particles 21, between the positive electrode active material particles 21 and the positive electrode current collector 1, or when using a conductive material, This is a mode in which the binder 22 is interposed between the positive electrode active material particles 21 and the conductive material particles, and the both are fixed. In the second fixing mode, the objects to be bonded are in direct contact with each other and the objects to be bonded are fixed to each other by the presence of the binding substance 22 surrounding the contact portion. In the present invention, in the positive electrode active material layer, either one of the first fixing mode and the second fixing mode, or both modes are present. In particular, as the particle diameter of the positive electrode active material particles 21 contained in the positive electrode active material layer becomes smaller, the second fixing mode tends to increase.

  The binding material 22 may be present in the positive electrode active material layer in a shape that fixes the objects to be bonded in the first fixing mode or the second fixing mode. There is no particular limitation on the size and shape. For example, the binding material 22 is a fine particulate metal oxide, and a large number of the fine particulate binding materials 22 are formed of one of the positive electrode active material particles 21 or two or more aggregates. It may exist so as to surround the entire surface or a part thereof.

  In particular, it is preferable that the positive electrode active material layer 2 includes a portion connected by continuous crystal lattices in part of the adjacent binder materials 22. With this configuration, film adhesion can be improved and rate characteristics can be improved. As described above, the binding material 22 in the present invention is for fixing the positive electrode active material particles 21 to each other, and is connected by continuous crystal lattices in at least a part of the binding materials 22. It is presumed that the film adhesion of the positive electrode active material layer 2 is improved by including the portion. And it seems that this improvement in film adhesion contributes to the improvement in rate characteristics.

  Further, from the viewpoint of improving the film adhesion of the positive electrode active material layer 2, it is more desirable that the portion where the crystal lattices of the adjacent binder materials 22 are continuous exist significantly in the positive electrode active material layer 2. In the present invention, whether or not the crystal lattices of the binder materials are continuous can be confirmed by observing the crystal lattice of the cross section of the adjacent binder material in the positive electrode active material layer with a transmission electron microscope. .

  In order to configure the positive electrode active material layer of the present invention so as to include a portion where crystal lattices in adjacent binder materials 22 are continuous, a method for producing a positive electrode plate for a non-aqueous electrolyte secondary battery of the present invention to be described later It is desirable to manufacture according to According to the production method of the present invention, on the positive electrode current collector, the metal element-containing compound present around the positive electrode active material particles undergoes a reaction such as thermal decomposition or oxidation, and binds around the positive electrode active material particles. A binding substance that is a substance is generated. At this time, if adjacent binder substances or a part of the precursor thereof are bonded, the crystal growth of the two easily proceeds simultaneously in the bonded portion. As a result of the simultaneous progress of crystal growth in the joint portion, the positive electrode active material layer of the present invention is configured to include a portion where crystal lattices in adjacent binder materials are continuous.

  Alternatively, the binder 22 may be non-particulate and may be a continuous body that fills the space between the positive electrode active material particles 21 leaving a void. Alternatively, the binding material 22 may form a continuous coating layer in the form of a film, a pleat, or a hump that surrounds two or more aggregates of the positive electrode active material particles 21. Further, when the surface of the binding material 22 is observed at a scanning electron microscope level, for example, the surface of the binding material 22 is observed in a smooth state, has numerous innumerable protrusions, has a grainy feel, or these The surface condition is not limited at all. That is, the binding material 22 in the present invention surrounds at least a part of the positive electrode active material particles 21 and the binding materials 22 are connected to each other, or the binding material 22 is a continuous body. In addition, the binding material What is necessary is just to comprise the positive electrode active material layer 2 by connecting the binding material 22 in the vicinity of the positive electrode current collector 1 to the surface of the positive electrode current collector 1.

  Moreover, in this invention, even if the location where the positive electrode electrical power collector 1, the positive electrode active material particle 21, and the positive electrode active material particle 21 are adhere | attached exists with the resin-made binder which can function as a binder. Good. That is, it is not prohibited that the positive electrode plate of the present invention contains a resin binder. The resin binder functions as a binder, but the resin binder is the binder 22 of the present invention, that is, a binder 22 containing a metal oxide and silicon, or a metal oxide. In the present invention, the binder 22 does not include a resin binder.

  Further, when the positive electrode plate of the present invention contains a resinous binder, a binding material 22 containing a metal oxide and silicon, or a metal oxide, and a resinous binder that can function as a binding material, The rate characteristic improves as the ratio of the binding substance 22 to the total mass increases. In consideration of such points, when the total mass of the binding material 22 and the resin binder that can function as the binding material is 100% by mass, the binding material 22 is 50% by mass or more and 100% by mass. It is preferable that it is in the range of% below. Of course, even if it is outside this range, it goes without saying that the rate characteristics are improved by the amount of the binder 22 contained in the positive electrode plate.

  In the present invention, the mixing ratio of the positive electrode active material particles 21 and the binder material 22 contained in the positive electrode active material layer 2 is not particularly limited, but the content of the binder material 22 is too small. In such a case, the positive electrode current collector 1, the positive electrode active material particles 21, and the positive electrode active material particles 21 may not be able to increase the adhering strength to a desired level, and the improvement in rate characteristics may be sufficiently satisfied. There is a risk that it will not be possible. Therefore, considering this point, the mass ratio of the binder material 22 is preferably 1 part by mass or more and 100 parts by mass or less when the mass ratio of the positive electrode active material particles 21 is 100 parts by mass.

  Further, the positive electrode active material layer 2 may be any material as long as it satisfies the requirement that the positive electrode active material particles 21 and the binder material 22 are included, but further additives may be added without departing from the spirit of the present invention. May be formed. For example, according to the present invention, good conductivity can be exhibited without using a conductive material exemplified by a conductive carbon material such as carbon black, but better conductivity is desired. Depending on the case or the type of active material particles, a conductive material may be used.

Next, the Si—O bond of the second embodiment of the present invention will be specifically described.
<Si-O bond>
The positive electrode plate 10 for a non-aqueous electrolyte secondary battery according to the second embodiment of the present invention is a binder in which the positive electrode current collector 1, the positive electrode active material particles 21, and the positive electrode active material particles 21 include a metal oxide. It is fixed by the substance 22. Furthermore, the half-width of the peak appearing at 980 to 1100 cm ⁻¹ of the Si—O bond obtained when measuring the infrared absorption spectrum of the positive electrode active material layer 2 is 30 to 230 cm ^−1. ing.

  From this, it can be seen that the layer contains silicon (Si) element and oxygen (O) element, and these elements are bonded to each other in the layer (Si-O bond) It is not always clear how the bond acts on the binding material 22, that is, how the positive electrode active material particles 21 and the current collector 1 and the positive electrode active material particles 21 are fixed to each other. is not. However, the presence of Si—O bonds having a half-width peak in the above range in the positive electrode active material layer 2 results in an improvement in the adhesion between the positive electrode active material layer 2 and the current collector 1. It becomes possible.

Note that whether or not the peak appearing at 980 to 1100 cm ⁻¹ is a Si—O bond peak is 980 when confirming the silicon element and oxygen element in X-ray photoelectron spectroscopy and measuring the infrared absorption spectrum. It can be specified by comprehensively judging the presence of a peak around ˜1100 cm ⁻¹ . That is, when the presence of silicon element and oxygen element is confirmed by X-ray photoelectron spectroscopy, and a peak exists in the vicinity of 980 to 1100 cm ⁻¹ when the infrared absorption spectrum is measured, this peak is expressed by Si−. It can be identified as a peak of O bond.

  From the above, it is clear that the positive electrode plate of the second embodiment contains silicon element in the positive electrode active material layer 2, which means that silicon is contained in the binder material 22. This does not mean that it does not matter whether the binder material 22 contains silicon.

  When the structure of the positive electrode active material layer 2 as a whole is such that such a characteristic peak appears in the infrared absorption spectrum measurement, the Si—O bond that causes the peak is formed by the binding material described above. 22 directly or indirectly, or directly or indirectly acting on the positive electrode active material particles 21 and the current collector 1, and each of silicon (Si) and oxygen (O) is singly used. It is presumed that the adhesion between the positive electrode active material layer 2 and the current collector 1 can be improved as a result.

Here, in the present invention, if the half-width of the peak appearing at 980 to 1100 cm ⁻¹ of the Si—O bond obtained by infrared absorption spectrum measurement is 30 to 230 cm ⁻¹ , the above-described effects can be obtained. but from the viewpoint of further improvement in adhesion, with a peak of Si-O bonds appear to 1000～1100Cm ^-1, preferably half width at half maximum of the peak is 30～90Cm ^-1, of the peak half width at half maximum Is more preferably 50 to 70 cm ⁻¹ .

  Further, in the present invention, any positive electrode active material layer that can confirm the predetermined peak when the infrared absorption spectrum measurement is performed on the positive electrode active material layer 2 may be used, and the predetermined peak is generated. It is not particularly limited what is a specific material having a Si—O bond and what is a starting material for finally generating the Si—O bond.

  In addition, the Si—O bond included in the positive electrode active material layer 2 includes, for example, a compound containing silicon such as silicon oxide, silicon oxide carbide, silicon oxynitride, and silicon oxyfluoride included in the positive electrode active material layer 2. Although it may originate, it is not limited to this, The silicon | silicone which exists in the positive electrode active material layer 2 may be the bond shown between arbitrary oxygen in the positive electrode active material layer 2 containing the positive electrode collector 1 surface. That's fine.

Although it does not specifically limit about the manufacturing method of the positive electrode plate of the 2nd Embodiment of this invention, The manufacturing method of this invention mentioned later can be illustrated as a preferable aspect. In the production method of the present invention to be described later, the compound containing silicon, which is a factor indicating the half width at half maximum of the Si—O bond peak represented by the infrared absorption spectrum, is subjected to the heating step as described above. It is a compound containing silicon that can remain, and does not include, for example, a silane coupling agent in which the half-width of the peak is generally less than 30 cm ⁻¹ .

The positive electrode plate according to the first embodiment of the present invention and the positive electrode plate according to the second embodiment have been described above. The positive electrode plate having the characteristics of both the first embodiment and the second embodiment, Specifically, the binder material 22 contains a metal oxide and silicon, and appears at 980 to 1100 cm ⁻¹ of the Si—O bond obtained when the infrared absorption spectrum of the positive electrode active material layer 2 is measured. The advantageous effects of the present application described above can be exhibited even in a positive electrode plate having a half width at half maximum of 30 to 230 cm ⁻¹ .

<< Method for Producing Positive Electrode Plate >>
Next, the manufacturing method of the positive electrode plate of this invention is demonstrated. In the positive electrode plate of the first embodiment, a positive electrode active material layer forming liquid containing positive electrode active material particles, a metal element-containing compound, and a silicon element-containing compound is formed on at least a part of the current collector. A coating step of coating to form a coating film, and a heating step of heating the coating film at a temperature at which the metal element-containing compound and the silicon element-containing compound are thermally decomposed or more. It can be produced by producing a binding material containing oxide and silicon, and fixing the current collector, the positive electrode active material particles, and the positive electrode active material particles together with the binding material.

The positive electrode plate according to the second embodiment of the present invention includes a positive electrode active material layer forming liquid containing positive electrode active material particles, a metal element-containing compound, and a silicon element-containing compound on a current collector. An application step of forming a coating film by applying to at least a part, and a heating step of heating the coating film at a temperature equal to or higher than the temperature at which the metal element-containing compound and the silicon element-containing compound are thermally decomposed. When a binder material containing a metal oxide is generated by the process, the current collector, the positive electrode active material particles, and the positive electrode active material particles are fixed to each other by the binder material, and an infrared absorption spectrum is measured. half width at half maximum of peak appearing in the Si-O bond 980～1100Cm ^-1 the resulting, can be produced by forming a positive electrode active material layer is 30~230cm ^-1. Incidentally, Si-O bonds of the peak obtained when measuring the infrared absorption spectrum with appear in 1000～1100Cm ^-1, the half width at half maximum of the peak, to form a positive electrode active material layer is 30～90Cm ^-1 Thus, it is possible to manufacture a positive electrode plate having a higher adhesion between the current collector and the positive electrode active material layer.

<Application process>
The coating step forms a coating film by applying a positive electrode active material layer forming liquid containing positive electrode active material particles, a metal element-containing compound, and a silicon element-containing compound to at least a part of the current collector. It is a process to do. Hereinafter, the positive electrode active material particles, the metal element-containing compound, and the silicon element-containing compound contained in the positive electrode active material layer forming liquid will be described.

(Positive electrode active material particles)
As the positive electrode active material particles, the positive electrode active material particles described in the positive electrode plate of the present invention can be used as they are, and the description thereof is omitted here.

(Metal element-containing compounds)
The metal element-containing compound contained in the positive electrode active material layer forming liquid is a precursor for producing a metal oxide contained in the binder material 22 described in the positive electrode plate of the present invention. Therefore, any metal element-containing compound may be used as long as it is applied on the substrate in a state of being added to the positive electrode active material layer forming liquid and a metal oxide is generated when the heating process is performed.

  As a metal element-containing compound for producing a metal oxide exhibiting an alkali metal ion insertion / elimination reaction, a lithium element-containing compound and any metal element selected from cobalt, nickel, manganese, iron or titanium are used. One or two or more metal element-containing compounds can be preferably used. The metal element-containing compound may be an inorganic metal element-containing compound in which no carbon is contained in the compound, or an organometallic element-containing compound constituted by containing carbon in the compound. Also good. In the present invention and the present specification, the inorganic metal element-containing compound and the organic metal-containing compound may be simply referred to as a metal element-containing compound.

  In addition, examples of the metal element-containing compound include carbonates, chlorides, nitrates, sulfates, perchlorates, acetates, phosphates, bromates, and the like of other metal elements such as lithium element or cobalt. Can do. Among them, in the present invention, carbonates, chlorides, nitrates, and acetates are preferable because they are easily available as general-purpose products. In particular, nitrate is preferably used because it has good film forming properties for a wide variety of positive electrode current collectors.

For example, as a metal element-containing compound for producing LiCoO ₂ as a metal oxide exhibiting an alkali metal ion insertion / elimination reaction, a Li element-containing compound and a Co element-containing compound can be used in combination as main raw materials, Furthermore, other raw materials can be used in combination as required. Examples of the Li element-containing compound include lithium carbonate, lithium citrate tetrahydrate, lithium perchlorate trihydrate, lithium acetate dihydrate, lithium nitrate, and lithium phosphate. Examples of the Co element-containing compound include cobalt carbonate, cobalt (II) chloride hexahydrate, cobalt (II) formate dihydrate, cobalt (III) acetylacetonate, and cobalt (II) acetylacetonate dihydrate. , Cobalt (II) acetate tetrahydrate, cobalt (II) oxalate dihydrate, cobalt (II) nitrate hexahydrate, cobalt (II) ammonium hexahydrate, cobalt (III) nitrite Examples thereof include sodium and cobalt (II) sulfate heptahydrate. The combination ratio (Li: Co = X: 1) of the Li element-containing compound and the Co element-containing compound used as the main raw material is not particularly limited, but is preferably 1 ≦ X <2, and preferably 1 ≦ X ≦ 1. 2 is more preferable.

Moreover, as a metal element-containing compound for producing LiNiO ₂ as a metal oxide exhibiting an alkali metal ion insertion / release reaction, a Li element-containing compound and a Ni element-containing compound can be used in combination as main raw materials, Furthermore, other raw materials can be used in combination as required. Examples of the Li element-containing compound are the same as in the case of producing LiCoO ₂ described above. Examples of the Ni element-containing compound include nickel carbonate, nickel (II) chloride hexahydrate, and nickel (II) acetate. Tetrahydrate, nickel (II) perchlorate hexahydrate, nickel (II) bromide trihydrate, nickel (II) nitrate hexahydrate, nickel (II) acetylacetonate dihydrate, Examples thereof include nickel (II) hypophosphite hexahydrate and nickel (II) sulfate hexahydrate. The combination ratio (Li: Ni = X: 1) of the Li element-containing compound and Ni element-containing compound used as the main raw material is not particularly limited, but is preferably 1 ≦ X <2, and preferably 1 ≦ X ≦ 1. 2 is more preferable.

In addition, as a metal element-containing compound for producing LiMn ₂ O ₄ as a metal oxide exhibiting an alkali metal ion insertion / release reaction, a Li element-containing compound and a Mn element-containing compound may be used in combination as main raw materials. In addition, other raw materials can be used in combination as required. Examples of the Li element-containing compound are the same as in the case of producing LiCoO ₂ described above. Examples of the Mn element-containing compound include manganese carbonate, manganese (III) acetate dihydrate, and manganese (II) nitrate. Examples include hexahydrate, manganese (II) sulfate pentahydrate, manganese (II) oxalate dihydrate, and manganese (III) acetylacetonate. The combination ratio (Li: Mn = X: 1) of the Li element-containing compound and the Mn element-containing compound used as the main raw material is not particularly limited, but is preferably 0.5 ≦ X <1, 0.5 ≦ More preferably, X ≦ 0.6.

In addition, as a metal element-containing compound for producing LiFeO ₂ as a metal oxide exhibiting an alkali metal ion insertion / release reaction, a Li element-containing compound and a Fe element-containing compound can be used in combination as main raw materials, Furthermore, other raw materials can be used in combination as required. Examples of the Li element-containing compound are the same as in the case of producing LiCoO ₂ described above. Examples of the Fe element-containing compound include iron (II) chloride tetrahydrate, iron (III) citrate, and acetic acid. Examples include iron (II), iron (II) oxalate dihydrate, iron (III) nitrate nonahydrate, iron (II) lactate trihydrate, and iron (II) sulfate heptahydrate. . The combination ratio (Li: Fe = X: 1) of the Li element-containing compound and the Fe element-containing compound used as the main raw material is not particularly limited, but is preferably 1 ≦ X <2, and preferably 1 ≦ X ≦ 1. 2 is more preferable.

In addition, as a metal element-containing compound for producing Li ₄ Ti ₅ O ₁₂ as a metal oxide exhibiting an alkali metal ion insertion / release reaction, a Li element-containing compound and a Ti element-containing compound are used in combination as a main raw material. In addition, other raw materials can be used in combination as required. Examples of the Li element-containing compound are the same as in the case of producing LiCoO ₂ described above, and examples of the Ti element-containing compound include titanium tetrachloride and titanium acetylacetonate. The combination ratio (Li: Ti = X: 1) of the Li element-containing compound and the Ti element-containing compound used as the main raw material is not particularly limited, but is preferably 0.8 ≦ X <2, and 0.8 ≦ More preferably, X ≦ 1.2.

  On the other hand, examples of the metal element-containing compound that does not show an alkali metal ion insertion / release reaction include Li, Be, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, and Ni. Cu, Zn, Ga, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Cs, Ba, Hf, Ta, W, Re, Os, Ir , Pt, Au, Hg, Tl, Pb, Bi, Fr, Ra, and a compound containing one or more metal elements selected from a general metal element group such as Ce, Examples thereof include compounds that become metal oxides that do not exhibit alkali metal ion insertion / elimination reaction by thermal decomposition.

  Further, although the reason is not clear, among the metal elements exemplified above, in particular, when a metal element-containing compound containing a metal element belonging to 3 to 5 cycles is used, the input / output of the produced positive electrode plate This is preferable because the characteristics tend to be higher.

  Moreover, as a metal element containing compound containing a metal element, for example, a metal salt can be preferably used. Examples of the metal salt include chlorides, nitrates, sulfates, perchlorates, phosphates and bromates of the above metal elements. Above all, chlorides, nitrates, and acetates are easily available as general-purpose products. In addition, these metal element-containing compounds are dissolved in a solvent, and a coating solution is applied onto a current collector to form a coating film. When heated, chlorine ions, nitrate ions, and acetate ions can be easily eliminated from the coating film, so that these can be particularly preferably used.

  Moreover, you may use the organometallic compound which is a compound containing a metal and carbon as a metal element containing material. The organometallic compound includes both a metal complex containing a carbon element and a metal salt containing a carbon element. More specifically, the organometallic compound contains any one kind or two or more kinds of metallic elements and carbon selected from a general metallic element group as listed in the above metallic element-containing compound. Any compound may be used. In addition, in the organometallic compound, it is preferable that a metal element belonging to 3 to 5 cycles among the metal element group is contained, similarly to the metal element-containing compound.

  Examples of the metal salt containing the carbon element include acetate and oxalate. Among them, in the present invention, acetate is preferably used because it is easily available as a general-purpose product.

  Examples of the metal complex containing the carbon element include ethoxide, acetylacetonate, and lactate.

  Note that materials other than the metal element-containing compounds specifically exemplified above can be appropriately selected and used as long as they do not depart from the spirit of the present invention. That is, in the positive electrode active material layer provided on the positive electrode plate for a non-aqueous electrolyte secondary battery manufactured by the manufacturing method, the positive electrode active material particles are fixed on the current collector and the positive electrode active material particles are fixed to each other. Any material can be used as long as it is a product that can produce a metal oxide that does not exhibit an alkali metal ion insertion / elimination reaction.

  One kind of the metal element-containing compound described above may be used alone, or two or more kinds may be used in combination. In addition, a metal element-containing compound for producing a metal oxide that exhibits an alkali metal ion insertion / release reaction and a metal element-containing compound for producing a metal oxide that does not exhibit an alkali metal ion insertion / release reaction are combined. May be used.

  In the positive electrode active material layer forming liquid described above, the ratio of the total amount of one or more metal element-containing compounds added in the solvent is 0.01 to 5 mol / L, particularly 0.1 to 5 mol / L. 2 mol / L is preferred. By setting the concentration to 0.01 mol / L or more, the positive electrode current collector and the positive electrode active material layer can be satisfactorily adhered, and the positive electrode active material particles can be fixed. In addition, by setting the concentration to 5 mol / L or less, it is possible to maintain a good viscosity that allows the coating liquid to be satisfactorily applied to the surface of the positive electrode current collector, and form a uniform coating film. be able to.

(Silicon element-containing compound)
In the positive electrode plate produced by the production method of the present invention, the silicon-containing compound is a compound capable of imparting a predetermined silicon or silicon-containing compound contained in the binder material, or a predetermined silicon contained in the positive electrode active material layer. Any compound that can impart a compound containing silicon may be used. Specific examples include organic silicon-containing compounds such as silane coupling agents, alkyl silicates, and siloxanes, and inorganic silicon-containing compounds such as polysilane and silicic acid. However, since the heating temperature in the heating step of the production method of the present invention is equal to or higher than the thermal decomposition temperature of the silicon-containing compound, any silicon-containing compound is treated with silicon after pyrolysis or a compound containing silicon. Since it can be contained in the active material layer or the binder material, it is not limited to the above examples, and various silicon-containing compounds can be used. From the viewpoint of good compatibility with the solvent, an organic silicon-containing compound is preferred. In the present invention, the organic silicon-containing compound means a compound containing silicon and carbon, and the inorganic silicon-containing compound means a compound containing silicon and not containing carbon.

  Among organic silicon-containing compounds, silicon-containing compounds having a hydrolyzable group are more preferable for the following reasons. That is, since the hydrolyzable group adheres well to the surface of the inorganic compound, it is expected that the hydrolyzable group adheres well to the surface of the positive electrode active material particles during the manufacturing process. And, the adhesion to the positive electrode active material particles by the hydrolyzable group is expected to improve the adhesion between the adjacent positive electrode active material particles or the current collector (first action). ). As another function, the positive electrode active material particles and the current collector, and the positive electrode active material particles contain this silicon by covering the silicon element bonded to the hydrolyzable group and generating a binder. The effect | action fixed favorably by a binder is anticipated (2nd effect | action). Therefore, from the viewpoint of enjoying the first action and / or the second action described above, among the organic silicon-containing compounds, a silicon-containing compound having a hydrolyzable group such as a silane coupling agent and an alkyl silicate. Is preferred.

  In the present specification, the term “adhesion” used for the hydrolyzable group and the reactive functional group is an interaction between the hydrolyzable group and the positive electrode active material particle or the hydrolyzable group and the current collector. Means a state in which the two are bound together, and may be, for example, a chemical bond, but is not limited thereto.

  In particular, the silane coupling agent has a hydrolyzable group (for example, an ethoxy group or a methoxy group) capable of generating a silanol group (Si-OH) and an alcohol by hydrolysis on one end side of the molecular structure. On the end side, the reactive functional group was selected from the group consisting of vinyl group, epoxy group, styryl group, methacryloxy group, acryloxy group, amino group, ureido group, chloropropyl group, mercapto group, polysulfide group, and isocyanate group. Has a functional group. The reactive functional group adheres well to the current collector, metal element-containing compound, positive electrode active material particles, or optionally added resin. That is, the reactive functional group is likely to be combined with the raw material before thermal decomposition. Therefore, the silane coupling agent is bonded to the raw material being thermally decomposed by the hydrolyzable group at one end, and is bonded to the raw material before the thermal decomposition by the reactive functional group at the other end. Although the silane coupling agent itself is thermally decomposed by heating in the heating process, the adhesion between the raw materials in the manufacturing process is promoted, and finally, the current collector, the positive electrode active material particles, and the positive electrode active material It is assumed that the adhesion between the particles can be improved. As a result, it is presumed that excellent adhesion is exhibited in the manufactured positive electrode plate of the present invention. Therefore, a silane coupling agent is preferably selected as at least one silicon-containing compound of one or more silicon-containing compounds in the production method of the present invention.

  It is preferable that the silane coupling agent has a vinyl group, a methacryloxy group, and an amino group as reactive functional groups from the viewpoint of improving the adhesion between the current collector and the positive electrode active material layer.

  About the addition amount of a silane coupling agent, it is preferable to add in the range of 1 weight% or more and 25 weight% or less with respect to the positive electrode active material layer forming liquid whole quantity. With the addition amount of the silane coupling agent being within this range, while suppressing the possibility that inhibition of the generation of the active material during the heating of the coating film is suppressed, the formed positive electrode active material layer and the current collector The effect that the adhesiveness can be enhanced can be further enhanced.

  Examples of silyl isocyanate that is a silane coupling agent include, but are not limited to, methyl triisocyanate silane and tetraisocyanate silane.

  Examples of the alkyl silicate include, but are not limited to, tetramethoxysilane, polymethoxysiloxane, and tetra-n-propoxysilane.

  The addition amount of the silicon-containing compound is preferably in the range of 1% by weight to 25% by weight with respect to the total amount of the positive electrode active material layer forming liquid. Adhesion between the positive electrode active material layer to be formed and the current collector while suppressing the possibility that the inhibition of the generation of the active material is suppressed when the coating film is heated because the addition amount of the silicon-containing compound is within this range. The effect that the property can be enhanced can be further enhanced.

  In the case of using a silane coupling agent, the stock solution may be used as it is, using water or IPA as a solvent, dissolving and hydrolyzing the silane coupling agent in this, and adjusting the concentration appropriately. You may use what we did.

  In addition, the positive electrode active material layer forming liquid may contain a conductive material, an organic substance that is a viscosity adjusting agent of the coating liquid, or other additives within a range not departing from the gist of the present invention. The solvent for dispersing or dissolving the metal element-containing compound may be any solvent that can dissolve the metal element-containing compound, and a conventionally known solvent can be appropriately selected and used. For example, water, lower alcohols such as NMP (N-methyl-2-pyrrolidone), methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, 2-butanol, t-butanol, acetylacetone, diacetyl And ketones such as benzoylacetone, ketoesters such as ethyl acetoacetate, ethyl pyruvate, ethyl benzoylacetate and ethyl benzoylformate, toluene, ethylene glycol, diethylene glycol, polyethylene glycol, and mixed solvents thereof.

  There is no particular limitation on the method for coating the positive electrode active material layer forming liquid on the current collector, and a general coating method can be appropriately selected and used. For example, the coating liquid can be applied by a printing method, spin coating, dip coating, bar coating, spray coating, or the like. In addition, when the surface of the current collector is porous, has a large number of irregularities, or has a three-dimensional structure, it can be manually applied in addition to the above method.

  Moreover, there is no limitation in particular about the coating amount of a positive electrode active material layer formation liquid, However, It is preferable to apply in the range in which the thickness after a heating becomes the thickness of the positive electrode active material layer demonstrated above.

<Heating process>
The heating step is a step of heating the coating film formed on the current collector in the coating step at a temperature at which the metal element-containing compound and the silicon element-containing compound are thermally decomposed.

  About the heating temperature in a heating process, what is necessary is just the temperature which can thermally decompose the metal element containing compound used in a positive electrode active material layer, and a silicon element containing compound, Therefore It can set suitably according to these kinds it can. The temperature at which the metal element-containing compound and the silicon element-containing compound can be thermally decomposed is a temperature at which both the metal element-containing compound and the silicon element-containing compound are thermally decomposed. In other words, it is the higher temperature among the temperatures at which both the metal element-containing compound and the silicon element-containing compound are thermally decomposed. Further, the temperature equal to or higher than the temperature for thermal decomposition is a temperature equal to or higher than the thermal decomposition start temperature.

  The thermal decomposition start temperature can be determined by measuring the thermal decomposition temperature using an automatic TG / DTA simultaneous measurement device DTG-60A manufactured by Shimadzu Corporation. The thermal decomposition start temperature is the temperature at which the weight of the metal element-containing compound is reduced by 10% by weight from the weight at the start of heating when the metal element-containing compound is heated at a temperature increase rate of 10 ° C./min. . The same applies to the thermal decomposition start temperature of the silicon element-containing compound.

  Further, the heating atmosphere in the heating step is not particularly limited, and can be appropriately determined in consideration of the material used for manufacturing the positive electrode plate, the heating temperature, the oxygen potential of the metal element, and the like. For example, an air atmosphere is preferable in that a special atmosphere adjustment is not necessary and the heating process can be easily performed. In particular, when an aluminum foil is used as the positive electrode current collector, the heating step can be preferably performed because there is no possibility that the aluminum foil is oxidized even if the heating step is performed in an air atmosphere.

  On the other hand, when a copper foil is used as the positive electrode current collector, it is not desirable because it is oxidized when the heating step is performed in an air atmosphere. Therefore, in such a case, it is preferable to heat in an inert gas atmosphere, a reducing gas atmosphere, or a mixed gas atmosphere of an inert gas and a reducing gas. When the heating step is performed in an atmosphere that does not contain sufficient oxygen gas, the oxidation of the metal element in the metal element-containing compound is performed by oxygen and metal in the compound contained in the positive electrode active material layer forming liquid. Since it needs to be realized by bonding with an element, it is necessary to use a compound containing an oxygen element in the compound to be used.

  In the production method of the present invention, the inert gas atmosphere or the reducing gas atmosphere is not particularly limited to a specific atmosphere, and the production method of the invention can be appropriately carried out under these conventionally known atmospheres. Examples of the active gas atmosphere include argon gas, nitrogen gas, and reducing gas atmosphere, such as hydrogen gas, carbon monoxide gas, or a gas atmosphere in which the inert gas and the reducing gas are mixed.

  The positive electrode plate of the present invention may further contain a resin component such as a resin binder in the positive electrode active material layer produced as described above. The method of adding a resin component to the positive electrode active material layer includes, for example, applying a resin mixed solution to the surface of the positive electrode active material layer, or immersing the positive electrode plate in a resin mixed solution tank, A method of removing the solvent of the resin mixed solution impregnated in the positive electrode active material layer by infiltrating the voids of the positive electrode active material layer and then drying, and leaving only the resin component inside the positive electrode active material layer. Can be mentioned.

<< Negative Electrode Plate >>
Next, the negative electrode plate for a non-aqueous electrolyte secondary battery of the present invention will be described. As described in the above “positive electrode plate”, the electrode plate of the present invention can be used as a positive electrode plate or a negative electrode plate of a non-aqueous electrolyte secondary battery. The negative electrode plate for a nonaqueous electrolyte secondary battery of the present invention has the same configuration as the positive electrode plate for a nonaqueous electrolyte secondary battery of the present invention shown in FIG. 1, and the positive electrode current collector in FIG. The structure of the negative electrode plate of the present invention can be described by replacing 1 with a negative electrode current collector, replacing the positive electrode active material layer 2 with a negative electrode active material layer, and replacing the positive electrode active material particles 21 with negative electrode active material particles. . The negative electrode plate can also have the same configuration as that of the first and second embodiments described in the above “positive electrode plate”.

  Similar to the positive electrode plate of the present invention described above, silicon contained in the binder material, or a predetermined Si-O bond present in the negative electrode active material layer acts directly or indirectly on the binder material, or the negative electrode active material By acting directly or indirectly on the particles and the negative electrode current collector, finally, the negative electrode active material layer and the negative electrode current collector are more closely attached.

<Negative electrode current collector>
The negative electrode current collector is not particularly limited, and a conventionally known negative electrode current collector used for a negative electrode plate for a nonaqueous electrolyte secondary battery can be appropriately selected and used. For example, a negative electrode current collector formed of a simple substance such as an aluminum foil, a nickel foil, or a copper foil or an alloy can be preferably used. Similarly to the positive electrode current collector 1, the negative electrode current collector includes a material in which a material for ensuring conductivity is laminated on the surface and a material in which some surface treatment is performed.

  The thickness of the negative electrode current collector is not particularly limited as long as it is a thickness that can generally be used as a negative electrode current collector of a negative electrode plate for a non-aqueous electrolyte secondary battery, but is preferably 5 to 200 μm, preferably 10 to 50 μm. More preferably.

<Negative electrode active material layer>
The negative electrode active material layer contains negative electrode active material particles, negative electrode active material particles and a current collector, and a binding material for fixing the negative electrode active material particles to each other. In the first embodiment of the negative electrode plate of the present invention, the binding material contains a metal oxide and silicon, and in the second embodiment, a metal oxide is contained.

  The layer thickness of the negative electrode active material layer is not particularly limited, but the layer thickness is preferably 50 μm to 150 μm in order to obtain a high capacity while improving rate characteristics. By setting the thickness of the negative electrode active material layer in the above range, the distance between the negative electrode active material layer and the negative electrode current collector can be shortened, and the impedance of the negative electrode plate can be lowered.

  Moreover, it is preferable that the negative electrode active material layer has voids to the extent that the nonaqueous electrolyte solution can permeate similarly to the positive electrode active material layer.

(Negative electrode active material particles)
The negative electrode active material layer constituting the negative electrode plate contains negative electrode active material particles. The negative electrode active material particles are not particularly limited, and conventionally known negative electrode active material particles can be appropriately selected and used in the field of non-aqueous electrolyte secondary batteries. For example, natural graphite, artificial graphite, amorphous carbon, carbon black, carbon materials obtained by adding different elements to these components, metallic lithium and its alloys, tin, silicon and their alloys, and oxides of silicon and titanium cobalt And materials capable of occluding and releasing alkali metal ions, such as nitrides of manganese, iron, and cobalt. Among these, carbon materials are particularly suitable as negative electrode active material particles because of their low cost, easy handling, large energy that can be taken out per unit mass, low discharge potential, and good flatness. is there.

  The shape of the negative electrode active material particles is not particularly limited, and for example, a scale shape, a flat shape, a spindle shape, or a spherical shape can be used. Further, the particle size of the negative electrode active material particles is not particularly limited, and those having an arbitrary size can be appropriately selected and used in consideration of the thickness of the designed negative electrode active material layer. In addition, like the positive electrode active material particles described above, the rate and configuration can be improved by reducing the particle diameter of the negative electrode active material particles. Therefore, the particle diameter of the negative electrode active material particles is preferably less than 10 μm, preferably 5 μm or less, and particularly preferably 1 μm or less.

(Binder)
The negative electrode active material layer constituting the negative electrode plate contains a binder, and the negative electrode active material particles, the current collector, and the negative electrode active material particles are fixed together by the binder material. In the first embodiment of the negative electrode plate of the present invention, the binder material contains a metal oxide and silicon as essential components, and in the second embodiment, the binder material is a metal as an essential component. Contains oxides.

  As the metal oxide contained in the binder, an alkali metal, an alkaline earth metal, or a metal oxide of a transition metal belonging to the fourth period of the periodic table can be preferably used. Alkali metals and alkaline earth metals are stable even when used for the negative electrode plate of a non-aqueous electrolyte secondary battery because of their low redox potential. In addition, transition metals belonging to the fourth period of the periodic table are chemically stable, can form a plurality of oxidation numbers, and form a plurality of complexes even with the same element. Therefore, the convenience as the metal contained in the negative electrode plate is high. Examples of such metal oxides include copper, nickel, and lithium oxides. Further, in the first embodiment of the negative electrode plate of the present invention, the silicon contained in the binder material is the same as the silicon contained in the binder material of the first embodiment of the positive electrode plate of the present invention described above. Explanation here is omitted.

(Other materials)
The negative electrode active material layer may be any material as long as it satisfies the above-described requirements for including the negative electrode active material particles and the binder material. However, the negative electrode active material layer may be formed by adding further additives without departing from the spirit of the present invention. Also good. For example, in the present invention, it is possible to exert good conductivity without using a conductive material, but depending on the case where better conductivity is desired or depending on the type of negative electrode active material particles, the conductive material may be It may be used.

  For the same reason as described for the positive electrode plate, a metal oxide and silicon, or a binder containing a metal oxide, and a resin binder may also be used in the negative electrode plate.

<Si-O bond>
The Si—O bond in the second embodiment of the negative electrode plate of the present invention is the same as the Si—O bond in the second embodiment of the positive electrode plate, and a detailed description thereof is omitted here.

  When the negative electrode plate described above is used for the nonaqueous electrolyte secondary battery of the present invention, the positive electrode plate may be a conventionally known positive electrode plate, for example, positive electrode active material particles and positive electrode current collector, and positive electrode active material. A positive electrode plate formed by fixing substance particles with a resin binder may be used, or may be used in combination with the positive electrode plate described above.

  The manufacturing method of the negative electrode plate of the present invention described so far is not particularly limited, like the positive electrode plate of the present invention described above, but the negative electrode plate of the present invention is manufactured with high yield by the following method. Can do. Hereinafter, the manufacturing method of a negative electrode plate is demonstrated concretely.

<< Method for Manufacturing Negative Electrode Plate >>
The method for producing a negative electrode plate for a non-aqueous electrolyte secondary battery of the present invention has the same characteristics as the above-described “method for producing a positive electrode plate”. Each step will be described below.

  In the negative electrode plate of the first embodiment, a negative electrode active material layer forming liquid containing negative electrode active material particles, a metal element-containing compound, and a silicon element-containing compound is formed on at least a part of a current collector. A coating step of coating to form a coating film, and a heating step of heating the coating film at a temperature at which the metal element-containing compound and the silicon element-containing compound are thermally decomposed or more. It can be produced by producing a binding material containing oxide and silicon, and fixing the current collector, the negative electrode active material particles, and the negative electrode active material particles together with the binding material.

Moreover, the negative electrode plate of the second embodiment of the present invention includes a negative electrode active material layer forming liquid containing negative electrode active material particles, a metal element-containing compound, and a silicon element-containing compound on a current collector. An application step of forming a coating film by applying to at least a part, and a heating step of heating the coating film at a temperature equal to or higher than the temperature at which the metal element-containing compound and the silicon element-containing compound are thermally decomposed. When a binder material containing a metal oxide is generated by the process, the current collector, the negative electrode active material particles, and the negative electrode active material particles are fixed to each other by the binder material, and an infrared absorption spectrum is measured. half width at half maximum of peak appearing in the Si-O bond 980～1100Cm ^-1 the resulting, can be produced by forming a negative electrode active material layer which is 30~230cm ^-1. Incidentally, Si-O bonds of the peak obtained when measuring the infrared absorption spectrum with appear in 1000～1100Cm ^-1, the half width at half maximum of the peak, to form a positive electrode active material layer is 30～90Cm ^-1 Thus, it is possible to manufacture a negative electrode plate having a higher adhesion between the current collector and the negative electrode active material layer.

<Application process>
The coating process forms a coating film by applying a negative electrode active material layer forming liquid containing negative electrode active material particles, a metal element-containing compound, and a silicon element-containing compound to at least a part of the current collector. It is a process to do. Hereinafter, the negative electrode active material particles, the metal element-containing compound, and the silicon element-containing compound contained in the negative electrode active material layer forming liquid will be described. In addition, about a silicon element containing compound, the silicon element containing compound demonstrated with the manufacturing method of the positive electrode plate of this invention mentioned above can be used as it is, and description here is abbreviate | omitted.

(Negative electrode active material particles)
As the negative electrode active material particles, the negative electrode active material particles described in the negative electrode plate of the present invention can be used as they are, and the description thereof is omitted here.

(Metal element-containing compounds)
The metal element-containing compound contained in the negative electrode active material layer forming liquid is a precursor for producing a metal oxide contained in the binder material described in the negative electrode plate of the present invention. Therefore, any metal element-containing compound may be used as long as it is applied on the substrate in a state of being added to the negative electrode active material layer forming liquid and a metal oxide is generated when the heating process is performed.

  Specific examples of such metal element-containing compounds include metal element chlorides, carbonates, nitrates, acetates, perchlorates, phosphates, bromates and the like, and these metals. Examples thereof include salt hydrates. Among them, chlorides, carbonates, nitrates and acetates are easily available as general-purpose products, and these are dissolved in a solvent, and a coating solution is applied onto a current collector to form a coating film. When heated, chlorine ions, carbonate ions, nitrate ions, and acetate ions can be easily eliminated from the coating film, so that these can be used particularly preferably.

  For example, when the metal element is copper, copper chloride, copper carbonate (II), copper nitrate, copper acetate, copper acetate (II) monohydrate, etc. can be mentioned, and when the metal element is nickel Can include nickel chloride, nickel carbonate, nickel nitrate, nickel acetate, nickel (II) nitrate hexahydrate, nickel acetate (II) tetrahydrate, etc., when the metal element is lithium , Lithium chloride, lithium carbonate, lithium nitrate, lithium acetate, lithium acetate trihydrate and the like.

  The solvent used in preparing the negative electrode active material layer forming liquid may be any solvent that can dissolve the metal element-containing compound described above, and is the same as the solvent that can be used in the positive electrode active material layer forming liquid. Can be used.

  In the negative electrode active material layer forming liquid described above, the total ratio of one or two or more metal element-containing compounds added to the solvent is 0.01 to 20 mol / L, particularly 0.1 to 0.1 mol. 10 mol / L is preferable. By setting the concentration to 0.01 mol / L or more, the negative electrode current collector and the negative electrode active material layer can be satisfactorily adhered, and the negative electrode active material particles can be sufficiently fixed. In addition, by setting the concentration to 20 mol / L or less, it is possible to maintain a satisfactory viscosity to the extent that the coating solution can be satisfactorily applied to the negative electrode current collector surface, and to form a uniform coating film. Can do.

  The method for coating the negative electrode active material layer forming liquid on the negative electrode current collector is not particularly limited, and a method similar to the coating method used for producing the positive electrode plate can be appropriately selected and used. The same applies to the thickness of the coating amount.

(Heating process)
About a heating process, what is necessary is just to be the same as the manufacturing method of the positive electrode plate of the said invention, Therefore Therefore description here is abbreviate | omitted. In the formation of the negative electrode plate, for example, when a copper foil or the like is used as the current collector, it is preferable to perform heating in a nitrogen atmosphere or the like.

  Moreover, the negative electrode which reduced the metal oxide contained in a binder substance to a metal by giving a reduction process with respect to the binder substance formed by the above, and made negative electrode active material particles adhere with this reduced metal A plate may be manufactured.

  As a reduction treatment method, a reduction treatment method in which a reduction treatment is performed in a hydrogen plasma atmosphere, a reduction gas obtained by diluting hydrogen, carbon monoxide, or the like with hydrogen, carbon monoxide, or an inert gas such as nitrogen, helium, argon, or the like. And a reduction treatment method in which reduction is performed in the reducing gas atmosphere can be suitably used. As the reducing gas, one kind of reducing gas may be used alone, or two or more kinds of gases may be mixed and used.

  Further, the negative electrode plate formed through the reduction treatment does not contain an oxide in the negative electrode active material layer, and does not cause a reduction reaction during initial charging. Thereby, it is possible to prevent the charge reaction from being hindered by the reduction reaction during the initial charge and the initial charge / discharge efficiency from being lowered.

<< Non-aqueous electrolyte secondary battery >>
Next, the nonaqueous electrolyte secondary battery of the present invention using the positive electrode plate and / or the negative electrode plate of the present invention described above will be described.

  FIG. 4 is a schematic view showing an example of the non-aqueous electrolyte secondary battery of the present invention.

  As shown in FIG. 4, the non-aqueous electrolyte secondary battery 100 of the present invention includes a positive electrode plate 10 in which a positive electrode active material layer 2 is provided on one side of a positive electrode current collector 1, and a combination thereof. A negative electrode plate 50 in which a negative electrode active material layer 54 is provided on one side of the negative electrode current collector 55 and a separator 70 provided between the positive electrode plate 10 and the negative electrode plate 50. The container is housed in a container composed of 81 and 82, and is sealed in a state where the container is filled with a nonaqueous electrolytic solution 90 containing a lithium compound as an electrolyte. Here, the nonaqueous electrolyte secondary battery 100 of the present invention is characterized in that one or both of the positive electrode plate 10 and the negative electrode plate 50 is the electrode plate of the present invention described above.

  Hereinafter, configurations other than the positive electrode plate and / or the negative electrode plate described above, specifically, a separator and a nonaqueous electrolytic solution containing a lithium compound will be described.

(Separator)
There is no limitation in particular about the separator 70, A conventionally well-known separator can be suitably selected and used in the field | area of a nonaqueous electrolyte secondary battery. For example, a three-layer structure in which a lithium ion permeable polyethylene film having micropores is sandwiched between porous lithium ion permeable polypropylene films can be suitably used. This also serves as a safety mechanism that suppresses migration of lithium ions when the temperature in the non-aqueous electrolyte secondary battery rises, the polyethylene film softens at about 130 ° C. and the micropores collapse. Then, by sandwiching the polyethylene film with a polypropylene film having a higher softening temperature, the polypropylene film retains its shape even when the polyethylene film is softened, thereby preventing contact / short circuit between the positive electrode plate 10 and the negative electrode plate 50. In addition, the battery reaction can be reliably suppressed and safety can be ensured.

(Nonaqueous electrolyte)
The non-aqueous electrolyte 90 used in the present invention is not particularly limited as long as it is generally used as a non-aqueous electrolyte for a non-aqueous electrolyte secondary battery. When used, a nonaqueous electrolytic solution in which a lithium salt is dissolved in an organic solvent is preferably used.

Examples of the lithium salt include inorganic lithium salts such as LiClO ₄ , LiBF ₄ , LiPF ₆ , LiAsF ₆ , LiCl, and LiBr; LiB (C ₆ H ₅ ) ₄ , LiN (SO ₂ CF ₃ ) ₂ , LiC ( Organic compounds such as SO ₂ CF ₃ ) ₃ , LiOSO ₂ CF ₃ , LiOSO ₂ C ₂ F ₅ , LiOSO ₂ C ₄ F ₉ , LiOSO ₂ C ₅ F ₁₁ , LiOSO ₂ C ₆ F ₁₃ , and LiOSO ₂ C ₇ F ₁₅ Typical examples include lithium salts.

  Examples of the organic solvent used for dissolving the lithium salt include cyclic esters, chain esters, cyclic ethers, and chain ethers.

  As a structure of the nonaqueous electrolyte battery 100 manufactured using the positive electrode plate 10, the negative electrode plate 50, the separator 70, and the nonaqueous electrolyte solution 90, a conventionally known structure can be appropriately selected and used. For example, the structure which winds said positive electrode plate 10 and the negative electrode plate 50 in the shape of a spiral via the separator 70, and accommodates in a battery container is mentioned. As another aspect, a structure in which the positive electrode plate 10 and the negative electrode plate 50 cut into a predetermined shape are stacked and fixed via a separator 70, and this is housed in a battery container may be employed. In any structure, after the positive electrode plate 10 and the negative electrode plate 50 are accommodated in the battery container, the lead wire attached to the positive electrode plate is connected to the positive electrode terminal provided in the outer container, while being attached to the negative electrode plate. A non-aqueous electrolyte secondary battery is manufactured by connecting the lead wire to a negative electrode terminal provided in the exterior container, and further filling the battery container with a non-aqueous electrolyte and then sealing the battery container.

<< Battery pack >>
Next, a battery pack 200 configured using the nonaqueous electrolyte secondary battery 100 of the present invention will be described with reference to FIG.

  FIG. 5 is a schematic exploded view showing an example of the battery pack 200 of the present invention.

  As shown in FIG. 5, the battery pack 200 is configured by storing the nonaqueous electrolyte secondary battery 100 in a resin container 36 a, a resin container 36 b, and an end case 37. Further, a protection circuit for preventing overcharge and overdischarge between one end face of the nonaqueous electrolyte secondary battery, which is a face including the positive electrode terminal 32 and the negative electrode terminal 33, and the end case 37. A substrate 34 is provided.

  The protection circuit board 34 includes an external connection connector 35. The external connection connector 35 is connected to an external connection window 38a provided in the resin container 36a and an external connection window 38b provided in the end case 37. Inserted and connected to external terminals. The protection circuit board 34 is mounted with a charge / discharge safety circuit (not shown) for controlling charge / discharge, a wiring circuit for connecting the external connection terminal and the nonaqueous electrolyte secondary battery 100, and the like. .

  For the battery pack 200, a configuration of a conventionally known battery pack is appropriately selected except that the nonaqueous electrolyte secondary battery 100 of the present invention using the positive electrode plate 10 and / or the negative electrode plate 50 of the present invention is used. Can do. Although not shown, the battery pack 200 includes a positive electrode lead plate connected to the positive electrode terminal 32, a negative electrode lead plate connected to the negative electrode terminal 33, and an insulator between the nonaqueous electrolyte secondary ground 100 and the end case 37. Etc. may be provided as appropriate.

  In addition, the non-aqueous electrolyte secondary battery 100 of the present invention using the positive electrode plate 10 and / or the negative electrode plate 50 of the present invention is not only used for a battery pack, but also in the protection circuit, It may be used in a mode in which a function such as a battery temperature monitor is provided and the protection circuit is attached to the nonaqueous electrolyte secondary battery. In such an embodiment, the battery pack can be used as a secondary battery having a protection function and a protection circuit without constituting a battery pack, and is highly versatile. In addition, some aspects demonstrated above are only illustrations, and do not limit use of the positive electrode plate 10 and / or the negative electrode plate 50 of this invention, or the nonaqueous electrolyte secondary battery 100 of this invention at all. Absent.

  Next, the present invention will be described more specifically with reference to examples and comparative examples. Hereinafter, unless otherwise specified, parts or% is based on mass.

Example 1
Li (CH ₃ COO) · 2H ₂ O [molecular weight: 102.02]: 1.0 g added to methanol: 1.0 g and Mn (CH ₃ COO) ₂ · 4H ₂ O [molecular weight: 245.09] : Lithium complex oxidation in which 5 g is added to methanol: 5 g in an amount of Li (CH ₃ COO): Mn (CH ₃ COO) = 2.1 g: 9.8 g It was set as the raw material solution which produces | generates a thing. Next, the raw material solution: 8 g, the positive electrode active material (LiMn ₂ O ₄ ): 10 g having an average particle size of 4 μm, acetylene black (Denka Black, manufactured by Denki Kagaku Kogyo Co., Ltd.): 1.2 g, carbon fiber (Showa Denko) VGCF manufactured by KK): 0.25 g, silane coupling agent (3-glycidoxypropyltrimethoxysilane (KBM403 manufactured by Shin-Etsu Chemical Co., Ltd.)): 1.5 g, and resin hydroxyethyl cellulose: 0.2 g of pure water : Thickener aqueous solution dissolved in 9.8 g: 10 g and methanol solvent were mixed, and kneaded with an Excel auto homogenizer (Nihon Seiki Seisakusho Co., Ltd.) at a rotation speed of 8000 rpm for 15 minutes to obtain an electrode active material layer forming solution Prepared. An aluminum plate having a thickness of 15 μm was prepared as a current collector, and the electrode mass of the finally obtained electrode active material layer was adjusted to 91.7 g / m ² and prepared on the one side of the current collector as described above. The electrode active material layer forming solution was applied with an applicator to form an electrode active material layer forming coating film. Subsequently, the coating film was pressed using a roll press machine (manufactured by Sank Metal Co., Ltd .: mechanical type 1 ton) under the conditions of applied pressure: 0.1 ton / cm and pressing speed of 10 mm / second. Next, the current collector with the electrode active material layer-forming coating film formed on the surface was placed in a normal temperature electric furnace (Muffle furnace, manufactured by Denken, P90), and from room temperature to 450 ° C. over 20 minutes. Then, a positive electrode plate for a non-aqueous electrolyte secondary battery in which an appropriate electrode active material layer was laminated as a positive electrode active material layer on the current collector was obtained. The positive electrode plate was taken out of the electric furnace and allowed to stand until it reached room temperature, and then cut into a predetermined size (a disk having a diameter of 15 mm) using a press machine to obtain the positive electrode plate of Example 1. In addition, it was 60 micrometers when the thickness of the electrode active material layer was measured 10 points | pieces in arbitrary locations using the micrometer, and the average value was computed.

(Example 2)
A positive electrode plate of Example 2 was obtained in the same manner as in Example 1 except that the amount of the silane coupling agent used in Example 1 was changed to 2 g. In addition, when the thickness of the electrode active material layer was measured at 10 arbitrary points using a micrometer and the average value was calculated, it was 61 μm.

(Example 3)
In the same manner as in Example 1, except that 2 g of a silane coupling agent (3-aminopropyltriethoxysilane (KBE903 manufactured by Shin-Etsu Chemical Co., Ltd.)) was added instead of the silane coupling agent of Example 1, A positive electrode plate of Example 3 was obtained. In addition, it was 60 micrometers when the thickness of the electrode active material layer was measured 10 points | pieces in arbitrary places using the micrometer, and the average value was computed.

Example 4
Instead of the silane coupling agent of Example 1, except that 1 g of a silane coupling agent (N-2- (aminoethyl) -3-aminopropyltriethoxysilane (KBE603 manufactured by Shin-Etsu Chemical Co., Ltd.)) was added, The positive electrode plate of Example 4 was obtained in the same manner as Example 1. In addition, when the thickness of the electrode active material layer was measured at 10 arbitrary points using a micrometer and the average value was calculated, it was 62 μm.

(Example 5)
In place of the silane coupling agent of Example 1, 2 g of a silyl isocyanate compound (Origatix SI-310 manufactured by Matsumoto Fine Chemical Co., Ltd.) was added, and the positive electrode plate of Example 5 was prepared in the same manner as Example 1. Obtained. In addition, when the thickness of the electrode active material layer was measured at 10 arbitrary points using a micrometer and the average value was calculated, it was 61 μm.

(Example 6)
Li (CH ₃ COO) · 2H ₂ O [molecular weight: 102.02]: 10 g, Co (NO ₃ ) ₂ · 6H ₂ O [molecular weight: 290.9]: 30 g, and methanol: 20 g A raw material solution was prepared by mixing to produce a lithium composite oxide exhibiting lithium ion insertion / extraction. Next, 10 g of the above raw material solution, 10 g of a positive electrode active material LiMn ₂ O ₄ having an average particle size of 4 μm, 1.2 g of acetylene black (Denka Black, manufactured by Denki Kagaku Kogyo Co., Ltd.), carbon fiber (VGCF manufactured by Showa Denko KK) 0.25 g, silane coupling agent (3-glycidoxypropyltrimethoxysilane (KBM403, manufactured by Shin-Etsu Chemical Co., Ltd.)): 2 g and resin hydroxyethyl cellulose: 0.2 g dissolved in pure water: 9.8 g Aqueous adhesive solution: 10 g and a solvent (methanol) were mixed, and kneaded with an Excel auto homogenizer (Nihon Seiki Seisakusho Co., Ltd.) at a rotation speed of 8000 rpm for 15 minutes to prepare an electrode active material layer forming liquid.

Next, an aluminum plate having a thickness of 15 μm is prepared as a current collector, and the electrode mass of the electrode active material layer finally obtained is 84.6 g / m ² on the one surface side of the current collector. The electrode active material layer forming liquid prepared in this manner was applied with an applicator to form a coating film for forming an electrode active material layer. Subsequently, the coating film was pressed using a roll press machine (manufactured by Sank Metal Co., Ltd .: mechanical type 1 ton) under the conditions of applied pressure: 0.1 ton / cm and pressing speed of 10 mm / second. Next, the current collector with the electrode active material layer-forming coating film formed on the surface was placed in a normal temperature electric furnace (Muffle furnace, manufactured by Denken, P90), and from room temperature to 450 ° C. over 20 minutes. Heating was performed to obtain a positive electrode plate for a non-aqueous electrolyte secondary battery in which an electrode active material layer was laminated on a current collector. This positive electrode plate was taken out from the electric furnace and allowed to stand until it reached room temperature, and then cut into a predetermined size (a disk having a diameter of 15 mm) using a press machine to obtain a positive electrode plate of Example 6. In addition, it was 57 micrometers when the thickness of the electrode active material layer was measured 10 points | pieces using the micrometer, and the average value was computed.

(Example 7)
On the positive electrode plate for a non-aqueous electrolyte secondary battery produced in Example 1, 0.9 g of PVDF (manufactured by Kureha, KF # 1320): 10 g was dissolved in NMP (manufactured by Mitsubishi Chemical Corporation) as an organic solvent: 10 g. A positive electrode plate of Example 7 was obtained in the same manner except that the PVDF resin solution was applied with an applicator and dried at 120 ° C. for 10 minutes. In addition, it was 60 micrometers when the thickness of the electrode active material layer was measured 10 points | pieces in arbitrary locations using the micrometer, and the average value was computed.

(Example 8)
10 g of positive electrode active material (LiMn ₂ O ₄ ) having an average particle size of 4 μm, 1.28 g of acetylene black (manufactured by Denki Kagaku Co., Ltd., Denka Black), 0.25 g of carbon fiber (manufactured by Showa Denko KK, VGCF), di 3 g of isopropoxy titanium bis (triethanolamate) (TC400 manufactured by Matsumoto Fine Chemical Co., Ltd.), 2 g of silane coupling agent (3-methacryloxypropyltrimethoxysilane (KBM503 manufactured by Shin-Etsu Chemical Co., Ltd.)), and 0.3 g of resin ethyl cellulose 3 g of a resin solution in which 2.7 g of isopropyl alcohol was dissolved and 6 g of a solvent propylene glycol monomethyl ethyl acetate were mixed and kneaded with an Excel auto homogenizer (Nihon Seiki Seisakusho Co., Ltd.) at a rotation speed of 8000 rpm for 15 minutes. A material layer forming solution was prepared. An aluminum plate having a thickness of 15 μm is prepared as a current collector, and an electrode prepared as described above is formed on one surface side of the current collector in such an amount that the electrode mass of the electrode active material layer finally obtained is 55 g / m ² The active material layer forming liquid was applied with an applicator to form an electrode active material layer forming coating film. Subsequently, the coating film was pressed using a roll press machine (manufactured by Sank Metal Co., Ltd .: mechanical type 1 ton) under the conditions of applied pressure: 0.1 ton / cm and pressing speed of 10 mm / second. Next, the current collector with the electrode active material layer-forming coating film formed on the surface was placed in a normal temperature electric furnace (Muffle furnace, Denken, P90), and from room temperature to 400 ° C. over 20 minutes. After heating, a positive electrode plate for a non-aqueous electrolyte secondary battery of the present invention in which an appropriate electrode active material layer as a positive electrode active material layer was laminated on the current collector was obtained. And after taking out the said positive electrode plate from an electric furnace and leaving it to room temperature, it cut | judged to the predetermined | prescribed magnitude | size (a 15 mm diameter disc) using the press machine, and obtained the positive electrode plate of Example 8. In addition, it was 42 micrometers when the thickness of the electrode active material layer was measured 10 points | pieces in arbitrary places using the micrometer, and the average value was computed.

Example 9
Instead of adding diisopropoxy titanium bis (triethanolaminate) (TC400 manufactured by Matsumoto Fine Chemical Co., Ltd.) in Example 8, 2 g of diisopropoxy titanium bis (ethylacetoacetate) (TC750 manufactured by Matsumoto Fine Chemical Co., Ltd.) was added. A positive electrode plate of Example 2 was obtained in the same manner as Example 8. In addition, it was 44 micrometers when the thickness of the electrode active material layer was measured 10 points | pieces in arbitrary places using the micrometer, and the average value was computed.

(Example 10)
A positive electrode plate of Example 10 was obtained in the same manner as in Example 8 except that a silyl isocyanate compound (Orgatechs SI-310 manufactured by Matsumoto Fine Chemical Co., Ltd.) was used instead of the silane coupling agent of Example 8. In addition, when the thickness of the electrode active material layer was measured at 10 arbitrary points using a micrometer and the average value was calculated, it was 40 μm.

(Example 11)
On the positive electrode plate for a non-aqueous electrolyte secondary battery produced in Example 8, 0.9 g of PVDF (manufactured by Kureha, KF # 1320): 10 g was dissolved in NMP (manufactured by Mitsubishi Chemical Corporation) as an organic solvent: 10 g. A positive electrode plate of Example 11 was obtained in the same manner except that the PVDF resin solution was applied with an applicator and dried at 120 ° C. for 10 minutes. In addition, it was 48 micrometers when the thickness of the electrode active material layer was measured 10 points | pieces in arbitrary places using the micrometer, and the average value was computed.

(Example 12)
A positive electrode plate of Example 12 was obtained in the same manner as Example 8 except that 0.02 g of the silane coupling agent of Example 8 was used. In addition, it was 47 micrometers when the thickness of the electrode active material layer was measured 10 points | pieces in arbitrary places using the micrometer, and the average value was computed.

(Example 13)
In place of the silane coupling agent in Example 8, inorganic silicate was dispersed in a water dispersion solvent, except that 2 g of Snowtech XS made by Nissan Chemical Co. was used. 13 positive electrode plates were obtained. In addition, when the thickness of the electrode active material layer was measured at 10 arbitrary points using a micrometer and the average value was calculated, it was 45 μm.

(Comparative Example 1)
A positive electrode plate of Comparative Example 1 was obtained in the same manner as Example 6 except that no silane coupling agent was added. In addition, it was 60 micrometers when the thickness of the electrode active material layer was measured 10 points | pieces in arbitrary places using the micrometer, and the average value was computed.

(Comparative Example 2)
A positive electrode plate of Comparative Example 2 was obtained in the same manner as Example 8 except that no silane coupling agent was added. In addition, it was 44 micrometers when the thickness of the electrode active material layer was measured 10 points | pieces in arbitrary places using the micrometer, and the average value was computed.

(Comparative Example 3)
A positive electrode plate of Comparative Example 3 was obtained in the same manner as in Example 8 except that the heating temperature was heated to 150 ° C. over 20 minutes. In addition, it was 43 micrometers when the thickness of the electrode active material layer was measured 10 points | pieces in arbitrary places using the micrometer, and the average value was computed.

(Comparative Example 4)
Diisopropoxytitanium bis (triethanolaminate) (TC400 manufactured by Matsumoto Fine Chemical Co., Ltd.), resin solution obtained by dissolving 0.3 g of resin ethylcellulose in 2.7 g of isopropyl alcohol, and 6 g of solvent propylene glycol monomethylethyl acetate Using a solution in which 4 g of PVDF resin (manufactured by Kureha Co., KF # 1100) and 36 g of NMP (Mitsubishi Chemical Co., Ltd.), which is an organic solvent, are added and mixed as a dressing, the solid content concentration is 55% by mass. The positive electrode plate of Comparative Example 4 in the same manner as in Example 8, except that the mixture was dispersed and kneaded so as to be heated and heated from room temperature to 150 ° C. over 20 minutes and held at 150 ° C. for 10 minutes. Got. In addition, when the thickness of the electrode active material layer was measured at 10 arbitrary points using a micrometer and the average value was calculated, it was 45 μm.

(Measurement of half width at half maximum by IR)
The surface of the positive electrode active material layer in the positive electrode plate of each Example and Comparative Example was measured using IRμs manufactured by SPECTRA TECH, measurement mode: μ-ATR, ATR crystal: Ge, resolution: 4 cm ⁻¹ , integration number: 128 times, Measurement was performed under the conditions of a measurement wavenumber region of 650 cm ^{−1 to} 4000 cm ⁻¹ , and the half width at half maximum of the peak appearing from 980 to 1100 cm ⁻¹ was measured by Gaussian fitting. Measurements, along with the peak of the binding of Si-O appears in 980～1100Cm ^-1, the half width at half maximum of the peak, where is in the range of 30 cm ^-1 or more 90cm ^-1 or less as ○, outside the range Some cases were marked with x. The measurement results are shown in Table 1. As a reference, the infrared absorption spectrum chart in the measurement of the half width at half maximum of Example 1 is shown in FIG. 6A, and after the electrode active material layer forming liquid is applied during the manufacturing process of Example 1, heating is performed. FIG. 6B shows a chart of the infrared absorption spectrum before the process. Moreover, the chart of the infrared absorption spectrum in the measurement of the half width at half maximum of Example 13 is shown in FIG. 7, and the chart of the infrared absorption spectrum in the measurement of the half width at half maximum of Comparative Example 3 is shown in FIG.

From the chart shown in FIG. 6B, a peak of 3-glycidoxypropyltrimethoxysilane, which is a silane coupling agent, was confirmed at 1080 cm ⁻¹ . From the chart shown in FIG. 6A, a Si—O bond peak was confirmed at 991 cm ⁻¹ in the binding material formed by heating at a temperature higher than thermal decomposition, but 3-glycidoxypropyl. No trimethoxysilane peak was observed. From the chart shown in FIG. 7, a Si—O bond peak was confirmed at 990 cm ⁻¹ . Further, from the chart shown in FIG. 8, a peak of Si was confirmed at 1056.2 cm ^−1, and a peak of 3-methacryloxypropyltrimethoxysilane as a silane coupling agent was confirmed at 1102 cm ^−1. The peak of O bond was not confirmed.

(X-ray diffraction)
The metal oxide contained in the electrode active material layer in each Example and Comparative Example was analyzed using an X-ray diffractometer. The analysis results are shown in the binding substance column of Table 1. The electrode active material particles of Examples 1 to 5 and the metal oxide contained in the binder material are both lithium manganate and the same material, but this lithium manganate is contained in the binder material. It can be specified by confirming the metal element by TEM-EDX described later.

(Analysis by X-ray photoelectron spectroscopy)
Moreover, about the electrode active material layer in each Example and a comparative example, the analysis (XPS composition analysis) by X-ray photoelectron spectroscopy was performed. As the XPS composition analyzer, ESCA3400 (manufactured by Shimadzu Corporation) was used. From this analysis result, it was confirmed that silicon element was present in the electrode active material layer in all Examples.

(Confirmation of silicon element, metal element and oxygen by TEM-EDX)
About each Example and the comparative example, each electrode active material layer mapped silicon, a metallic element, and oxygen by the TEM-EDX (Energy Dispersive X-ray Spectroscopy) method. As a result, it was confirmed in all Examples that the silicon element was present at the same location as the metal element.

  For reference, FIGS. 9 and 10 show mapping data of the first embodiment. FIG. 9 is mapping data indicating the presence of a binding substance that fixes the current collector and the electrode active material particles, and FIG. 9A is mapping data for confirming the presence of silicon. FIG. 9B is mapping data for confirming the presence of oxygen, and FIG. 9C is mapping data for confirming the presence of the metal element. FIG. 10 is mapping data indicating the presence of a binding substance that fixes the electrode active material particles to each other. FIG. 10A is mapping data for confirming the presence of silicon, and FIG. ) Is the mapping data for confirming the presence of oxygen, and FIG. 10C is the mapping data for confirming the presence of the metal element. 9 and 10, the symbol X is a current collector, the symbol Y is an electrode active material particle, and the symbol Z is a region indicating the presence of a binding substance. 9 (a), 9 (b), 10 (a) and 10 (b), the location where the current collector and the electrode active material particles are fixed, and the electrode active material particles are fixed. The presence of silicon and oxygen was confirmed in the locations. Further, as can be seen from the mapping data of FIG. 9C and FIG. 10C, the electrode active material particles Y, the location where the current collector and the electrode active material particles are fixed, and the electrode active material The presence of manganese was confirmed at the location where the particles were fixed, that is, at the same location as silicon.

  The metal element present in the same location as the silicon element by the confirmation of silicon, oxygen, and metal element by TEM-EDX (Energy Dispersive X-ray Spectroscopy) method and the metal oxide confirmed by the X-ray diffraction, It can be identified as a metal element constituting a metal oxide. That is, in all the Examples, it was confirmed that the current collector, the electrode active material particles, and the electrode active material particles were fixed by silicon element and metal oxide. On the other hand, since no silicon element-containing compound was used in Comparative Examples 1 and 2, the presence of silicon element was not confirmed. Further, in Comparative Example 4, PVdF was used instead of the metal element-containing compound, and the presence of silicon element was confirmed at the same location as carbon, oxygen, and fluorine that are components of PVdF. In Comparative Example 3, the presence of the metal element and silicon can be confirmed, but the presence of the metal oxide was not confirmed by the IR, and therefore no metal oxide was present at the same location as the silicon element. I understand.

(Confirmation of film formation)
In the above examples and comparative examples, when the electrode plate was cut out on the disc without any problem, it was evaluated that the film forming property of the electrode active material layer was good. On the other hand, a part of the electrode active material layer is peeled off or the active material particles are dropped from the current collector in the above-described hollowing process, and the processing is poor, so that it can be used as a working electrode of a tripolar coin cell described later. When the tolerable disk is not formed, it is evaluated that the film forming property of the electrode active material layer is poor. The film forming properties are shown in Table 2.

(Evaluation of adhesion)
The adhesion test was carried out as follows, the peelability of the electrode active material layer was measured on the current collector, and evaluated as follows. When cellophane tape (manufactured by Nichiban Co., Ltd., CT-15) is attached to the surface of the electrode active material layer of the positive electrode plates of Examples 1 to 13 and Comparative Examples 1 to 4, and then peeled off, the electrode active material layer is placed on the cellophane tape side. When the transfer amount was less than 30%, ◯, when it was 30% or more and less than 90%, Δ, and when it was 90-100%, it was marked as x. In addition,% shows the area of the transferred film in the cellophane tape. The evaluation results of the adhesion strength are also shown in Table 2.

(Bending test)
Using a bending tester (SEPRO) with a shaft diameter of 20 mm, the film strength of the electrode active material layers of the positive electrode plates of Examples 1 to 13 and Comparative Examples 1 to 4 was measured, and when the film was bent, there was a crack in the film. What did not enter was set as (circle), what entered 1-2 cracks was set as (triangle | delta), and what entered 3 or more cracks was set as x. The evaluation results of the bending test are also shown in Table 1.

(Battery characteristics evaluation)
<Production of tripolar coin cell>
Lithium hexafluorophosphate (LiPF ₆ ) is added as a solute to a mixed solvent of ethylene carbonate (EC) / dimethyl carbonate (DMC) (volume ratio = 1: 1), and the concentration of LiPF _{6 as} the solute is 1 mol. The non-aqueous electrolyte was prepared by adjusting the concentration to be / L. Using Examples 1 to 5 and Comparative Example 1 prepared as described above as the positive electrode plate as the working electrode, using the metal lithium plate as the counter electrode plate and the reference electrode plate, and using the non-aqueous electrolyte solution prepared above as the non-aqueous electrolyte solution The tripolar coin cell was assembled and subjected to the following charge / discharge test and cycle test.

(Initial charging test)
The test cell was charged at a constant current (1300 μA) under a 25 ° C. environment until the voltage reached 4.3 V, and after the voltage reached 4.3 V, the voltage did not exceed 4.3 V. As described above, the current (discharge rate: 1C) was reduced until it became 5% or less, and the battery was charged at a constant voltage, fully charged, and then suspended for 10 minutes. Here, the “1C” means a current value (current value reaching the discharge end voltage) at which constant current discharge is performed using the tripolar coin cell and discharge is completed in one hour.

(Initial discharge test)
Thereafter, the fully charged test cell was subjected to a constant current (1300 μA) (discharge rate: 1 C) until the voltage changed from 4.3 V (full charge voltage) to 3.0 V (discharge end voltage) in an environment of 25 ° C. ), The cell voltage (V) is taken on the vertical axis, the discharge time (h) is taken on the horizontal axis, a discharge curve was prepared, and the initial discharge capacity (μAh) of the positive electrode plate was determined.

(Calculation of initial charge / discharge efficiency)
Initial charge / discharge efficiency% = {(initial charge capacity) / (initial discharge capacity)] × 100 Table 2 shows the results of the above examples and comparative examples.

(Cycle test)
Similarly to the initial charge / discharge test, the test cell after the initial charge / discharge test is performed twice, and the average value of the discharge capacity at this time is used as the initial value during the cycle test, and the same charge / discharge test as in the initial charge / discharge test is performed. Table 2 shows the number of cycles when the discharge test was repeated and the discharge capacity was 95% or less of the initial value.

As is clear from Tables 1 and 2, the current collector and the electrode active material particles and the electrode active material particles are fixed to each other with a binder containing metal oxide and silicon, or the current collector and the electrode active material The material particles and the electrode active material particles are fixed to each other with a binder containing a metal oxide, and the Si—O bond 980 to 1100 cm ⁻¹ obtained when the infrared absorption spectrum of the electrode active material layer is measured. The half-width of the peak that appears in the example is 30 to 230 cm ⁻¹ , the electrode plate of the example is compared with each comparative example provided with an electrode plate that does not satisfy the conditions of the present invention, film formability, adhesion, bending test It was confirmed that excellent effects were exhibited in all of the above. In particular, the peak of the half width at half maximum appearing in the Si-O bond 1000～1100Cm ^-1 obtained when measuring the infrared absorption spectrum of the electrode active material layer, the electrode plate in an exemplary 30～90Cm ^-1 is It was confirmed that excellent adhesion was exhibited. It was also confirmed that the initial charge / discharge efficiency and cycle characteristics were also improved.

  On the other hand, the electrode plates of Comparative Examples 1 and 2 in which the binder material does not contain silicon or silicon compound, and the half width is not included in the scope of the present application, and Comparative Examples 3 and 4 in which the binder material does not contain a metal oxide. The results were inferior to the electrode plates of the examples in all of the film formability, adhesion, and bending test. Moreover, it became a result inferior to the electrode plate of an Example also about the cycle number.

DESCRIPTION OF SYMBOLS 1 ... Positive electrode collector 2 ... Positive electrode active material layer 10 ... Positive electrode plate 32 ... Positive electrode terminal 33 ... Negative electrode terminal 34 ... Protection circuit board 35 ... External connection connector 36a, 36b ... Resin container 37 ... End case 38a, 38b ... External connection window 54 ... Negative electrode active material layer 55 ... Negative electrode current collector 70 ... Separator 81, 82 ... Exterior 90 ... non-aqueous electrolyte 100 ... non-aqueous electrolyte secondary battery 200 ... battery pack

Claims (10)

A non-aqueous electrolyte secondary battery electrode plate comprising a current collector and an electrode active material layer formed on at least a part of the surface of the current collector,
The electrode active material layer is
Contains electrode active material particles and binder,
The electrode active material particles and the current collector, and the electrode active material particles are fixed by the binder,
The electrode plate for a non-aqueous electrolyte secondary battery, wherein the binding material contains a metal oxide and silicon. A non-aqueous electrolyte secondary battery electrode plate comprising a current collector and an electrode active material layer formed on at least a part of the surface of the current collector,
The electrode active material layer is
Contains electrode active material particles and binder,
The electrode active material particles and the current collector, and the electrode active material particles are fixed by the binder,
The binder material includes a metal oxide,
Non-aqueous electrolysis, wherein the half-value half-width of the peak appearing at 980 to 1100 cm ⁻¹ of the Si—O bond obtained when the infrared absorption spectrum of the electrode active material layer is measured is 30 to 230 cm ^−1. Electrode plate for liquid secondary battery. Claim 2, wherein the electrode active material layer of the peak appearing in 1000～1100Cm ^-1 of Si-O bonds obtained when measuring the infrared absorption spectrum half width at half maximum, characterized in that it is a 30～90Cm ^-1 The electrode plate for non-aqueous electrolyte secondary batteries as described in 2. A non-aqueous electrolyte secondary battery comprising at least an electrode plate, a separator, and a non-aqueous electrolyte,
The electrode plate includes a current collector and an electrode active material layer formed on at least a part of the surface of the current collector,
The electrode active material layer contains electrode active material particles and a binder,
The electrode active material particles and the current collector, and the electrode active material particles are fixed by the binder,
The non-aqueous electrolyte secondary battery, wherein the binding material contains a metal oxide and silicon. A non-aqueous electrolyte secondary battery comprising at least an electrode plate, a separator, and a non-aqueous electrolyte,
The electrode plate includes a current collector and an electrode active material layer formed on at least a part of the surface of the current collector,
The electrode active material layer contains electrode active material particles and a binder,
The electrode active material particles and the current collector, and the electrode active material particles are fixed by the binder,
The binder material includes a metal oxide,
Non-aqueous electrolysis, wherein the half-value half-width of the peak appearing at 980 to 1100 cm ⁻¹ of the Si—O bond obtained when the infrared absorption spectrum of the electrode active material layer is measured is 30 to 230 cm ^−1. Liquid secondary battery. Claim half width at half maximum of the peak appearing in the Si-O bond 1000～1100Cm ^-1 obtained when measuring the infrared absorption spectrum of the electrode active material layer, characterized in that it is a 30~90cm ^-1 5 A nonaqueous electrolyte secondary battery according to 1. A storage case, a non-aqueous electrolyte secondary battery including a positive electrode terminal and a negative electrode terminal, and a protection circuit having an overcharge and over-discharge protection function are provided, and the storage case includes the non-aqueous electrolyte secondary battery and the protection A battery pack configured to contain a circuit,
The non-aqueous electrolyte secondary battery includes at least an electrode plate, a separator, and a non-aqueous electrolyte,
The electrode plate includes a current collector and an electrode active material layer formed on at least a part of the surface of the current collector,
The electrode active material layer contains electrode active material particles and a binder,
The electrode active material particles and the current collector, and the electrode active material particles are fixed by the binder,
The battery pack, wherein the binding material contains a metal oxide and silicon. A storage case, a non-aqueous electrolyte secondary battery including a positive electrode terminal and a negative electrode terminal, and a protection circuit having an overcharge and over-discharge protection function are provided, and the storage case includes the non-aqueous electrolyte secondary battery and the protection A battery pack configured to contain a circuit,
The non-aqueous electrolyte secondary battery includes at least an electrode plate, a separator, and a non-aqueous electrolyte,
The electrode plate includes a current collector and an electrode active material layer formed on at least a part of the surface of the current collector,
The electrode active material layer contains electrode active material particles and a binder,
The electrode active material particles and the current collector, and the electrode active material particles are fixed by the binder,
The binder material includes a metal oxide,
A battery pack, wherein a half-value half-width of a peak appearing at 980 to 1100 cm ⁻¹ of an Si—O bond obtained when an infrared absorption spectrum of the electrode active material layer is measured is 30 to 230 cm ⁻¹ . Claim 8 half width at half maximum of the peak appearing in the Si-O bond 1000～1100Cm ^-1 obtained when measuring the infrared absorption spectrum of the electrode active material layer, characterized in that it is a 30～90Cm ^-1 The battery pack described in 1. An application step of applying an electrode active material layer forming liquid containing electrode active material particles, a metal element-containing compound, and a silicon element-containing compound to at least a part of the current collector to form a coating film; ,
A heating step of heating the coating film at a temperature equal to or higher than a temperature at which the metal element-containing compound and the silicon element-containing compound are thermally decomposed;
The manufacturing method of the electrode plate for nonaqueous electrolyte secondary batteries characterized by including.