JP2012109205A - Electrode plate for nonaqueous electrolyte secondary battery, nonaqueous electrolyte secondary battery, and battery pack - Google Patents

Abstract

An electrode plate for a non-aqueous electrolyte secondary battery having an electrode active material layer on a current collector, wherein the electrode active material layer has excellent adhesion and excellent input / output characteristics. An electrode plate for a liquid secondary battery is provided, and a non-aqueous electrolyte secondary battery using the electrode plate for a non-aqueous electrolyte secondary battery as a positive electrode plate and / or a negative electrode plate is provided. It aims at providing the nonaqueous electrolyte secondary battery and battery pack which used the electrode plate for liquid secondary batteries for the positive electrode plate and / or the negative electrode plate.
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 comprising: An active material particle containing a crystalline metal compound and a binder formed from a metal oxide are formed, and the crystalline metal compound is selected from a semi-metal element and a typical metal element It is doped with a seed or two or more elements, or the metal oxide forming the binding material is doped with one or more elements selected from metalloid elements and typical metal elements An electrode plate for a non-aqueous electrolyte secondary battery.
[Selection figure] None

Description

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

A non-aqueous electrolyte secondary battery represented by a lithium ion secondary battery has a high energy density and a high voltage, and has a memory effect during charging / discharging (when the battery is charged before it is completely discharged, Since there is no phenomenon in which the capacity decreases, it is used in various fields such as portable devices and large devices. Currently, efforts are being made to reduce CO ₂ emissions on a global scale, and this plug-in can greatly contribute to reducing CO ₂ emissions by reducing the dependence on oil and allowing it to travel with low environmental impact. There is an urgent need to develop and disseminate clean energy vehicles such as hybrid vehicles and electric vehicles. The development and popularization of these clean energy vehicles requires the use of driving power independent of gasoline. Non-aqueous electrolyte secondary batteries represented by lithium ion secondary batteries are expected as the driving force.

  The nonaqueous electrolyte secondary battery is formed of a positive electrode plate, a negative electrode plate, a separator, and an organic electrolyte. As said positive electrode plate and negative electrode plate, what is equipped with the electrode active material layer formed by apply | coating an electrode active material layer forming liquid on the collector surface, such as metal foil, is generally used. The electrode active material layer forming liquid is an active material particle, resin binder, and conductive material that can be charged / discharged by exhibiting insertion and desorption of alkali metal ions such as lithium, or other materials as required. And kneaded and / or dispersed in an organic solvent to prepare a slurry. The conductive material may be omitted when the active material particles also exhibit a conductive effect. Then, an electrode active material layer forming liquid is applied to the surface of the current collector, then dried to form a coating film on the current collector, and an electrode plate having the electrode active material layer is manufactured by pressing as necessary. The method is general (for example, paragraphs [0019] to [0026] of Patent Document 1 and claim 1 of Patent Document 2 and paragraphs [0051] to [0055]).

  The active material particles contained in the electrode active material layer forming liquid are particulate compounds dispersed in the forming liquid, and are not easily fixed to the current collector surface only by being applied to the current collector surface. Material. Accordingly, even when an electrode active material layer forming liquid not containing a resin binder is applied to a current collector and dried to form a coating film, the coating film is easily peeled off from the current collector. Therefore, an electrode active material layer in a conventional electrode plate is generally formed by fixing active material particles on a current collector through a resin binder, and the resin binder The material was essentially an essential constituent.

JP 2006-310010 A JP 2006-107750 A

  As described above, in recent years, non-aqueous electrolyte secondary batteries have been further developed for fields that require high input / output characteristics such as electric vehicles, hybrid vehicles, and power tools. In addition, secondary batteries used in relatively small devices such as mobile phones are also expected to have improved input / output characteristics because the devices tend to be multifunctional. In connection with this, the improvement of the input / output characteristic of an electrode plate has been a subject of the nonaqueous electrolyte secondary battery. However, in the conventional electrode plate in which the active material particles are fixed on the current collector only with the resin binder, the resin binder becomes an electric resistance, which hinders the improvement of the input / output characteristics of the electrode plate. Had a problem. Further, the conventional electrode plate in which the active material particles are fixed on the current collector only with the conventional resin binder has a problem that the adhesion of the electrode active material layer to the current collector is insufficient. It was. From the above problems, it was suggested that the discharge capacity retention rate was lowered (that is, the cycle characteristics were lowered) due to repeated use in the electrode active material layer.

  The present invention has been accomplished in view of the above circumstances. That is, the present invention includes an electrode active material layer in which the problem depending only on the resin binder is solved, the adhesion of the electrode active material layer is improved, and the non-aqueous electrolyte solution having excellent input / output characteristics. An object is to provide an electrode plate for a secondary battery, a non-aqueous electrolyte secondary battery using the electrode plate, and a battery pack in which the non-aqueous electrolyte secondary battery is housed.

The gist of the present invention is the invention described in the following (1) to (17).
(1) 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 formed including active material particles exhibiting alkali metal ion insertion and desorption, and a binder containing a metal oxide,
The electrode plate for a non-aqueous electrolyte secondary battery (hereinafter referred to as the first electrode), wherein the active material particles are doped with one or more elements selected from metalloid elements and typical metal elements May be referred to as an aspect).
(2) The metal oxide contained in the binder is doped with one or more elements selected from a semi-metal element and a typical metal element. The electrode plate for nonaqueous electrolyte secondary batteries as described.
(3) 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 is formed including active material particles exhibiting alkali metal ion insertion and desorption, and a binder containing a metal oxide,
An electrode for a non-aqueous electrolyte secondary battery, wherein the metal oxide contained in the binder is doped with one or more elements selected from metalloid elements and typical metal elements Board.
(4) The non-aqueous electrolyte according to (3), wherein the active material particles are doped with one or more elements selected from a metalloid element and a typical metal element. Secondary battery electrode plate.
(5) The non-aqueous solution according to any one of (1) to (4) above, wherein the metal oxide contained in the binding substance is a metal oxide capable of inserting and releasing alkali metal ions Electrode plate for electrolyte secondary battery.
(6) One or more elements selected from the above metalloid elements and typical metal elements are selected from the group consisting of Al, B, Si, P, Na, Mg, Ca, and Sn Alternatively, the electrode plate for a non-aqueous electrolyte secondary battery according to any one of (1) to (5) above, wherein the electrode plate is at least two types.
(7) The electrode active material layer is characterized in that the active material particles are fixed to each other by the binding material, and the active material particles are fixed to the current collector by the binding material. The electrode plate for a non-aqueous electrolyte secondary battery according to any one of (1) to (6) above.
(8) The electrode for a nonaqueous electrolyte secondary battery according to any one of (1) to (7), wherein the binder material covers at least a part of the surface of the active material particles. Board.

(9) A nonaqueous 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,
In the electrode active material layer, a plurality of nuclei are formed in a state where active material particles exhibiting alkali metal ion insertion / release are dispersed, and a plurality of metal oxides including a metal oxide are surrounded by the nuclei With an enclosure of
The plurality of enclosures are connected to each other in a part of adjacent enclosures, or continuous without distinction,
The enclosure in the vicinity of the current collector is connected to the current collector surface,
The electrode plate for a non-aqueous electrolyte secondary battery (hereinafter referred to as “electrode plate”), wherein the active material particles as the core are doped with one or more elements selected from metalloid elements and typical metal elements , Sometimes referred to as a second aspect).
(10) The metal oxide contained in the enclosure is doped with one or more elements selected from metalloid elements and typical metal elements, as described in (9) above Electrode plate for non-aqueous electrolyte secondary battery.
(11) 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,
In the electrode active material layer, a plurality of nuclei are formed in a state in which active material particles exhibiting alkali metal ion insertion and desorption are dispersed, and a plurality of metal oxides including a metal oxide are surrounded. With an enclosure,
The plurality of enclosures are connected to each other in a part of adjacent enclosures, or continuous without distinction,
The enclosure in the vicinity of the current collector is connected to the current collector surface,
An electrode plate for a non-aqueous electrolyte secondary battery, wherein the metal oxide contained in the enclosure is doped with one or more elements selected from a metalloid element and a typical metal element.
(12) The active material particles as the core are doped with one or more elements selected from a metalloid element and a typical metal element. Electrode plate for non-aqueous electrolyte secondary battery.
(13) The nonaqueous electrolytic solution according to any one of (9) to (12) above, wherein the metal oxide contained in the enclosure is a metal oxide capable of inserting and releasing alkali metal ions. Secondary battery electrode plate.
(14) There is a region where the crystal structure of the nucleus and the crystal structure of the envelope are discontinuously joined at the interface between the nucleus and the envelope surrounding the nucleus. The electrode plate for a non-aqueous electrolyte secondary battery according to any one of (9) to (13) above,
(15) One or more elements selected from Al, B, Si, P, Na, Mg, Ca, and Sn are selected from the above-mentioned metalloid elements and typical metal elements The electrode plate for a nonaqueous electrolyte secondary battery according to any one of (9) to (14) above, which is as described above.

(16) A nonaqueous electrolyte secondary battery comprising at least a positive electrode plate, a negative electrode plate, a separator provided between the positive electrode plate and the negative electrode plate, and an electrolyte solution containing a nonaqueous solvent,
Either the positive electrode plate or the negative electrode plate, or both are electrode plates for a non-aqueous electrolyte secondary battery according to any one of (1) to (15) above. Secondary battery (hereinafter sometimes referred to as a third embodiment).
(17) In a battery pack in which a nonaqueous electrolyte secondary battery having at least a positive electrode terminal and a negative electrode terminal and a protection circuit having an overcharge and overdischarge protection function are stored in a storage case.
The non-aqueous electrolyte secondary battery comprises at least a positive electrode plate, a negative electrode plate, a separator provided between the positive electrode plate and the negative electrode plate, and an electrolyte solution containing a non-aqueous solvent. And
One of the positive electrode plate and the negative electrode plate, or both of them is the electrode plate for a nonaqueous electrolyte secondary battery according to any one of (1) to (15). Hereinafter, it may be referred to as a fourth aspect).

  In the electrode plate for a non-aqueous electrolyte secondary battery according to the first aspect and the second aspect of the present invention, the active material particles (nuclear bodies) in the electrode active material layer are selected from metalloid elements and typical metal elements. To improve the adhesion of the electrode active material layer to the current collector by adding a metal oxide to at least a part of the binding material (enclosure). I was able to. In addition, the first and second aspects of the present invention are also excellent in cycle characteristics.

  In the electrode plate for a non-aqueous electrolyte secondary battery according to the first and second aspects of the present invention, the metal oxide contained in the binder (enclosure) in the electrode active material layer is a metalloid element and The active material particles (nuclear bodies) are doped with one or two or more elements selected from typical metal elements, and the active material particles (nuclear bodies) are fixed on the current collector by the binder (enclosure). It was possible to improve the adhesion of the electrode active material layer to the electric body. In addition, the first and second aspects of the present invention are also excellent in cycle characteristics.

  The electrode plate for a non-aqueous electrolyte secondary battery according to the first and second aspects of the present invention comprises an electrode active material layer having a binder (enclosure) containing active material particles (nuclear bodies) and a metal oxide. ) And the input / output characteristics can be improved.

  Further, the nonaqueous electrolyte secondary battery according to the third aspect, in which the electrode plate for a nonaqueous electrolyte secondary battery according to the first aspect or the second aspect is used as a positive electrode plate and / or a negative electrode plate, The battery pack of the 4th aspect in which the water electrolyte secondary battery was accommodated is the improvement of the adhesiveness in the electrode plate for nonaqueous electrolyte secondary batteries of the 1st aspect or the 2nd aspect, and the outstanding entrance / exit characteristic. In addition, it is possible to provide an excellent nonaqueous electrolyte secondary battery and battery pack reflecting the cycle characteristics.

It is a cyclic voltammogram which shows the result of the cyclic voltammetry test using the metal oxide which shows lithium ion insertion / extraction. It is a cyclic voltammogram which shows the result of the cyclic voltammetry test using the metal oxide which does not show lithium ion insertion elimination. (3A) is a schematic view showing a cross-section when the electrode plate for a non-aqueous electrolyte secondary battery in the present invention is cut substantially perpendicular to the current collector surface, and (3B) is an electrode active material layer of the electrode plate. It is a schematic diagram which shows the surface. It is a schematic sectional drawing in one form of the lithium ion secondary battery of this invention. It is a schematic exploded view in one embodiment of the battery pack of this invention. 2 is a scanning electron micrograph (magnification 10,000 times) obtained by photographing the surface of the electrode active material layer of the electrode plate of Example 1. FIG. 10 is a scanning electron micrograph (magnification 10,000 times) obtained by photographing the surface of the electrode active material layer of the electrode plate of Example 6. FIG. (8A) to (8D) are schematic cross-sectional views showing exemplary embodiments of the current collector used in the present invention.

[1] Nonaqueous electrolyte secondary battery electrode plate (first embodiment), [2] Nonaqueous electrolyte secondary battery electrode plate (second embodiment), [3] Non A method for producing an electrode plate for a water electrolyte secondary battery, [4] a non-aqueous electrolyte secondary battery (third aspect), and [5] a battery pack (fourth aspect) will be described in this order.
The electrode plate for a non-aqueous electrolyte secondary battery according to the present invention will be described as being divided into a positive electrode plate and a negative electrode plate, if necessary, and unless otherwise specified, an electrode plate for a non-aqueous electrolyte secondary battery and Is used to include both positive and negative electrode plates. The electrode plates for the non-aqueous electrolyte secondary battery of the first and second embodiments are sometimes referred to as “electrode plate I of the present invention” and “electrode plate II of the present invention”, respectively. The plates I and II are sometimes collectively referred to as the “electrode plate of the present invention”. The nonaqueous electrolyte secondary battery of the third aspect is sometimes referred to as “secondary battery of the present invention”, and the battery pack of the fourth aspect is sometimes referred to as “battery pack of the present invention”.

  The electrode plate for a non-aqueous electrolyte secondary battery according to the first and second aspects of the present invention is such that the alkali metal ions move between the positive electrode and the negative electrode through the non-aqueous electrolyte, thereby charging and discharging. It means an electrode plate that can be used for a possible secondary battery. Examples of the alkali metal include lithium and sodium, but are not limited thereto. For example, when the nonaqueous electrolyte secondary battery electrode plate of the present invention is an electrode plate for a lithium ion secondary battery, an active material particle that is a metal compound capable of inserting and removing lithium ions is selected, and In the case of an electrode plate for a sodium ion secondary battery, an active material particle that is a metal compound capable of inserting and releasing sodium ions is selected. The description of the electrode plate for a non-aqueous electrolyte secondary battery according to the first aspect and the second aspect of the present invention described below will be made mainly using an electrode plate for a lithium ion secondary battery as an example, The alkali metal ion secondary battery will be described.

[1] Electrode plate for non-aqueous electrolyte secondary battery (first aspect)
The electrode plate I for nonaqueous electrolyte secondary batteries of the first aspect (electrode plate I of the present invention) includes a current collector and an electrode active material layer formed on at least a part of the surface of the current collector. An electrode plate for a non-aqueous electrolyte secondary battery comprising: an electrode active material layer comprising active material particles exhibiting alkali metal ion insertion and desorption; and a binding material containing a metal oxide. .
The electrode plate I of the present invention is characterized in that (i) the crystalline metal compound is doped with one or more elements selected from a semimetal element and a typical metal element, or (ii) The metal oxide forming the binder material is characterized by being doped with one or more elements selected from a metalloid element and a typical metal element. In addition, the electrode plate I of the present invention may be provided with the above two features (i) and (ii) at the same time.

The present inventors have found that an electrode active material layer containing at least active material particles containing a crystalline metal compound and a metal oxide that can be a binding material can be formed on the current collector surface. It was. This realized the escape of the electrode active material layer depending only on the resin binder.
In addition, the present inventors include an element selected from a semimetal element and a typical metal element in either or both of the active material particles and the metal oxide contained in the binder contained in the electrode active material layer. It has been found that the adhesion of the electrode active material layer to the current collector is improved by doping, and the present invention has been completed.

The mechanism for improving the adhesion is not clear, but the present inventors presume as follows. That is, the present inventors have increased the surface activity of the active material particles doped with an element selected from a metalloid element and a typical metal element, and include the active material grains or the metal oxides. It is presumed that the adhesion with the binding substance is improved.
Similarly, the present inventors have increased the surface activity of the binding material by doping the metal oxide contained in the binding material with an element selected from a semi-metal element and a typical metal element. It is assumed that the adhesion with the substance particles is improved. Alternatively, it is presumed that the above-mentioned doped binding substance can improve the adhesion to the current collector surface. The improvement in the adhesiveness is improved in the same manner even when both the active material particles and the metal oxide are doped with the above-described elements.

  In particular, the improvement in the adhesion of the electrode active material layer to the current collector in the electrode plate I of the present invention can advantageously affect processing characteristics such as winding, bending and cutting of the electrode plate. Therefore, the nonaqueous electrolyte secondary battery of the third aspect using the electrode plate for a nonaqueous electrolyte secondary battery of the present invention and the battery pack of the fourth aspect in which the nonaqueous electrolyte secondary battery is accommodated Thus, it is possible to expand the degree of freedom in designing to various forms as compared with the conventional art.

  Moreover, it is speculated that the improvement of the adhesion is also related to the improvement of the discharge capacity maintenance rate when the electrode plate I of the present invention is repeatedly used, that is, the improvement of cycle characteristics. More specifically, the present inventors have improved the above-mentioned adhesion by suppressing the deterioration of the crystal structure due to the expansion and contraction of the active material particles during the insertion and removal of alkali metal ions such as lithium. It is assumed that this contributes to improvement of cycle characteristics.

The above-described improvement in the adhesion of the electrode plate I of the present invention and the superiority of the input / output characteristics are as follows. This can be desirably reflected in the non-aqueous electrolyte secondary battery. In particular, the nonaqueous electrolyte secondary battery according to the third aspect using the electrode plate I of the present invention for both positive and negative electrodes is capable of high-speed charge / discharge, and is connected between the active material particles in the electrode active material layer and the active material particles. Desirable effects such as improved adhesion to the adherent and improved durability and cycle characteristics can be exhibited.
Similarly to the non-aqueous electrolyte secondary battery of the third aspect, the non-aqueous electrolyte secondary battery of the fourth aspect also accommodates the non-aqueous electrolyte secondary battery of the third aspect. The excellent properties of the electrode plate for the electrolyte secondary battery can be reflected well.

  In a typical example of the electrode plate I of the present invention, an electrode active material layer containing active material particles and a binder containing a metal oxide is laminated on a current collector. In a typical example of such an electrode plate, since the electrode active material layer is directly laminated on the current collector by the binding material, the movement of electrons between the electrode active material layer and the current collector is extremely low. To be smooth. The electrode plate I of the present invention has excellent input / output characteristics. At least one of the factors enabling such high input / output is that the electrode active material layer containing the metal oxide and active material particles contained in the binder material on the electrode plate is laminated on the current collector. It is thought to be caused by this.

  The various effects of the electrode plate I of the present invention described above and inferences relating thereto are the same for the electrode plate II of the present invention. That is, in the description of the various effects of the electrode plate I of the present invention described above, the effect of the electrode plate II of the present invention and the effect thereof are described using the active material particles as a nucleus described later and the binder as an envelope described later. Can be understood as an inference about.

(1) Electrode active material layer The electrode active material layer in the electrode plate I of the present invention is formed to contain active material particles exhibiting alkali metal ion insertion and desorption, and a binding material containing a metal oxide, (I) a feature that the active material particles are doped with one or more elements selected from a metalloid element and a typical metal element; or (ii) a metal oxide contained in the binder material It is characterized by being doped with one or more elements selected from metalloid elements and typical metal elements. Hereinafter, the electrode plate I of the present invention having the above feature (i) is referred to as an electrode plate (I-i), and the electrode plate I of the present invention having the above feature (ii) is referred to as an electrode plate (I-i). I-ii). The electrode plate for a non-aqueous electrolyte secondary battery according to the present invention is an electrode plate (I-i), and the metal oxide contained in the binder is selected from a semi-metal element and a typical metal element. And an electrode plate (I-ii), wherein the active material particles are selected from a semi-metal element and a typical metal element. The aspect doped with the element more than a seed | species is included.

(1-1) Active Material Particles As the active material particles contained in the electrode active material layer of the positive electrode plate and / or the negative electrode plate, an alkali metal such as lithium ion used in the electrode plate for a non-aqueous electrolyte secondary battery. Any active material particle that exhibits ion insertion / release is not particularly limited. For example, the active material particles may be a compound mainly including a crystalline metal compound that is sufficient to show insertion / extraction of alkali metal ions such as lithium ions, and may be a compound composed of a substantially crystalline metal compound. . In addition to the crystalline metal compound, other materials and elements other than metal elements may be included within a range in which the action of alkali metal ion insertion / extraction can be exhibited.
As another example, the active material particles used in the present invention may not contain a crystalline metal compound. For example, the active material particles used in the present invention may be a material that exhibits a crystal structure other than metal, such as graphite or hard carbon, and that is capable of inserting and releasing alkali metal ions. . Further, the presence or absence of crystallinity of the active material particles is not particularly limited as long as alkali metal ion insertion / extraction is possible.

  In the electrode plate I of the present invention, active material particles doped with one or two or more elements selected from a semimetal element and a typical metal element are selected, or active material particles before doping are selected. This may be appropriately determined in consideration of the specific implementation contents of the electrode plate (I-i) or the electrode plate (I-ii).

  The doped active material particles are one or more selected from a semi-metal element and a typical metal element while maintaining a crystalline state of the active material particles before being doped. It may be a metal compound or a material substituted with one of these elements. In other words, in the electrode plate I of the present invention, the crystal structure of the active material particles contained in the electrode active material layer is analyzed, and the metal compound or material recognized from the crystal structure is recognized as the crystal structure of the compound before doping. When a metal compound or material constituting the crystal structure includes a metalloid element and / or a typical metal element, the metalloid element and / or the typical metal element is understood as a doped metal element.

  Moreover, it does not ask | require whether the active material particle used for the electrode plate of this invention exists in a crystalline state. Therefore, as a different example of the doped active material particles, there is a metal compound or material including an amorphous state that does not show a crystalline state, while maintaining the amorphous state of the active material particles before being doped. It may be a metal compound or material in which some metal elements are substituted with one or more elements selected from metalloid elements and typical metal elements.

  The doped active material particles used in the electrode plate of the present invention may be in a mode in which the active material particles are regularly or irregularly doped with a metalloid element and a typical metal element. As a specific example of such an embodiment, the active material particles are formed of a metal compound capable of inserting and releasing alkali metal ions, or a material having a crystal structure such as graphite, and the active material particles are regularly or An example in which the above elements are doped irregularly is exemplified.

  Alternatively, the doped active material particles used in the electrode plate of the present invention may be an embodiment in which at least a part of the compound or material constituting the active material particles is doped with a metalloid element and a typical metal element. . As a specific example of such an embodiment, a film (hereinafter referred to as “dope”) that is formed of a compound or material doped with the above element covering the periphery of a compound or material that exhibits undoped alkali metal ion insertion / extraction. An example of active material particles formed by providing a “film” is also given. In addition, the compound or material which comprises the said film | membrane does not ask | require the presence or absence of an alkali metal ion insertion and desorption, in the limit which enables the effect | action of the alkali metal ion insertion and desorption of the compound or material coat | covered with the said dope film | membrane.

  The metalloid element is a non-metal in terms of element classification, but also indicates a tendency of a metal element. On the periodic table, elements such as boron, silicon, germanium, arsenic, antimony, selenium, tellurium and the like near the boundary with the metal element correspond to the metalloid element. The typical metal is a metal element of group 1, 2, 12, and 13 among metal elements that are easily converted to cations when a compound is formed. Examples of metalloid elements and typical metal elements suitable for the dope include one or more selected from Al, B, Si, P, Na, Mg, Ca, and Sn.

  The metalloid element or the typical metal element can be an element doped into a metal site other than the alkali metal of the alkali metal composite oxide such as lithium. Since these doped metalloid elements or typical metal elements are not doped at sites of alkali metals such as lithium, they do not participate in charging / discharging with alkali metals such as lithium, and therefore do not directly reduce the discharge capacity. . Such doped metal compounds are, for example, weighed, mixed and pulverized as oxides, hydroxides, etc., respectively, and then fired in air at a high temperature to obtain the desired lithium, etc. An alkali metal composite oxide can be obtained.

  The active material particles in the electrode active material layer are doped with one or more elements selected from a metalloid element and a typical metal element, so that the active material particles or between the active material particles and the binding material The adhesion of the electrode active material layer to the current collector can be improved. Moreover, the electrode plate for nonaqueous electrolyte secondary batteries of the present invention of the first and second aspects is also excellent in cycle characteristics. One of the factors for improving the cycle characteristics in the electrode plate of the present invention is that the active material particles doped as described above are contained in the electrode active material layer, thereby causing expansion and contraction during lithium ion desorption insertion. It is presumed that the deterioration of the crystal structure is suppressed.

  The active material particles exhibiting alkali metal ion insertion / release in the present invention will be described below by taking lithium ion insertion / release active material particles and sodium ion insertion / release active material particles as examples. The illustration does not limit the present invention at all, and the present invention can be applied to active material particles exhibiting other alkali metal ion insertion / release.

Active material particles capable of inserting and removing lithium ions (undoped active material particles):
When the electrode plate of the present invention is a positive electrode plate for a lithium ion secondary battery, the active material particles used are any active material particles that can be used for a positive electrode plate for a lithium ion secondary battery. May be selected. Examples of the positive electrode active material particles include those containing lithium composite oxides such as lithium cobaltate, lithium manganate, lithium nickelate, lithium ferrate, lithium titanate, lithium iron phosphate, and vanadium oxide. Can do. Specific formulas for _example, and the like _{LiCoO 2, LiMn 2 O 4,} LiNiO 2, LiFeO 2, LiTiO 2, Li 4 Ti 5 O 12, V 2 O 5, LiFePO 4. However, the above is an example and does not limit the present invention.
In addition, when the electrode plate of the present invention is a negative electrode plate for a lithium ion secondary battery, the active material particles used are any active material particles that can be used for a negative electrode plate for a lithium ion secondary battery. You may choose one. Examples of the negative electrode active material particles include those containing carbon materials such as lithium titanate such as Li ₄ Ti ₅ O ₁₂ and graphite. However, the above is an example and does not limit the present invention.

Active material particles capable of inserting and removing lithium ions (doped active material particles):
In the present invention, the active material particles doped with one or more elements selected from the metalloid element and the typical metal element are other than Li atoms in the lithium ion insertion / desorption active material particles. Some metal atoms may be doped with one or more elements selected from metalloid elements and typical metal elements.
As an example of the metal compound that may be included in the doped lithium ion insertion / desorption active material particles, when M is exemplified as the metalloid element or the typical metal element, LiM _X Co _1-X O ₂ , _{LiM X Mn 2-X O 4} , LiM X Ni 1-X O 2, LiM X Fe 1-X O 2, LiM X Ti 1-X O 2, LiM X Fe 1-X PO 4 and the like.
Specific examples of the active material particles doped with the metalloid element or the typical metal element include LiAl _X Mn _{2 -X} O ₄ , LiB _X Mn _{2 -X} O ₄ , and LiNa _X Mn ₂ as a lithium manganese composite oxide. _{-X O 4, LiMg X Mn 2} -X O 4 and the like, as the lithium-cobalt composite _{oxide, LiSi X Co 1-X O} 2, LiP X Co 1-X O 2, LiSn X Co 1-X O 2, LiCa _X Co _1-X O ₂ and the like can be mentioned. In addition, in said chemical formula, preferable X is 0.1 <= X <= 0.3.

  Examples of doped lithium ion active material particles that can be inserted and desorbed, and crystalline materials other than metal compounds include graphite doped with lithium element, graphite doped with boron element, and elemental fluorine. However, the present invention is not limited to this.

  When the doped active material particle capable of inserting and releasing lithium ions is an active material particle having a doped film, the doped film is made of the metal compound or material that is the doped active material particle described above. Alternatively, it may be formed, or may be formed of a doped metal oxide that does not exhibit desorption / desorption of alkali metal ions such as lithium, which will be described later as embodiment c.

Active material particles capable of inserting and removing sodium ions (undoped active material particles):
When the electrode plate of the present invention is a positive electrode plate for sodium ion secondary batteries, the active material particles used are any active material particles that can be used for positive electrode plates for sodium ion secondary batteries. May be selected. Examples of the positive electrode active material particles include those containing sodium complex oxides such as sodium cobaltate and sodium manganate. However, the above is an example and does not limit the present invention.
In addition, when the electrode plate of the present invention is a negative electrode plate for sodium ion secondary batteries, the active material particles used are any active material particles that can be used for the negative electrode plate for sodium ion secondary batteries. You may choose one. Examples of the negative electrode active material particles include those containing sodium metal, a sodium alloy, or a carbon material such as graphite or hard carbon, and more specifically, for example, sodium manganese nickelate (NaMn _{0. 5} Ni _0.5 O ₂ ), sodium nickel cobaltate (for example, NaNi _0.5 Co _0.5 O ₂ ) and the like, but are not limited thereto.

Active material particles capable of insertion / extraction of sodium ions (doped active material particles):
The active material particles capable of inserting / extracting sodium ions doped with one or more elements selected from a metalloid element and a typical metal element are Na atoms in the active material particles capable of inserting / extracting sodium ions. A part of metal atoms other than may be doped with one or more elements selected from metalloid elements and typical metal elements.
Examples of the metal compound that may be contained in the doped active material particles capable of insertion / extraction of sodium ions include sodium manganate (for example, NaAl _0.1 Co _{0) in} which a part of sodium manganate is replaced with aluminum and cobalt. _.2 Mn _0.7 O ₂ ), sodium manganese nickelate (for example, NaAl _0.1 Mn _0.5 Ni _0.4 O ₂ ) in which a part of nickel is replaced with aluminum, and a part of cobalt is replaced with aluminum. nickel sodium cobaltate (e.g. _{NaAl 0.1 Ni 0.5 Co 0.4 O 2} ) , and the like, but is not limited thereto.

  In addition, active sodium particles that can be doped with sodium ions, and examples of crystalline materials other than metal compounds include hard carbon doped with sodium element, hard carbon doped with boron element, Examples thereof include hard carbon doped with fluorine element, but are not limited thereto.

  Further, when the doped active material particles capable of inserting and desorbing sodium ions are active material particles provided with a doped film, the doped film is made of the metal compound or material that is the doped active material particle described above. It may be formed, or may be formed of a doped metal oxide which will be described later and is a metal oxide that does not show alkali metal ion insertion / extraction.

Active material particle size:
The particle diameter of the active material particles used for the electrode active material layer of the electrode plate I of the present invention is not particularly limited, and those having an arbitrary size can be appropriately selected and used. In particular, when active material particles having a small particle diameter are used, the total surface area of the active material particles in the electrode active material layer can be increased, and alkali metal ions such as lithium in one active material particle can be increased. Since the movement distance can be shortened, the input / output characteristics can be improved. Therefore, in order to obtain higher input / output characteristics, it is desirable to select one having a small particle size. Specifically, the particle diameter of the active material particles to be used is preferably less than 10 μm, more preferably 5 μm or less, and particularly preferably 1 μm or less. In a conventional slurry-like electrode active material layer forming liquid using a resin binder, when the active material particle diameter used is less than 10 μm, the coating suitability tends to be poor, and when it is 5 μm or less, the formation is performed. The fluidity of the liquid is remarkably deteriorated, making it difficult to apply to mass production equipment such as a printing press. Further, if it is 1 μm or less, it tends to be difficult to disperse the active material particles in the forming liquid. On the other hand, in the case of the active material particles used for the electrode active material layer of the electrode plate I of the present invention, the above-mentioned problems can be avoided, so that the particle diameter of the active material particles can be arbitrarily selected. . The particle diameter of the active material particles used for the electrode active material layer of the electrode plate I of the present invention means an average particle diameter (volume median particle diameter: D50) measured by laser diffraction / scattering particle size distribution measurement. To do.

  The particle diameter of the active material particles contained in the electrode active material layer is a plurality (for example, arbitrarily selected from the electron microscope observation results using image analysis type particle size distribution measurement software (manufactured by Mount Tech Co., Ltd., MAC VIEW). It can be obtained by measuring the longest diameter of about 10 active material particles and calculating the average value.

(1-2) Binder The binder contained in the electrode active material layer of the electrode plate I of the present invention is a binder containing a metal oxide, and forms a part of the electrode active material layer. And has an action of fixing the active material particles on the current collector. Such a binding substance is not particularly limited as long as it is a binding substance having the above action, but acts as a binding substance and is also involved in insertion and desorption of alkali metal ions such as lithium. More preferably, it also acts as an active material.

  That is, the binder is a compound mainly composed of a metal oxide, and in particular, may be a compound substantially composed of a metal oxide. Alternatively, the binder may contain a material other than a metal oxide, an element other than a metal element, and an element other than an oxygen element as long as the active material particles can be fixed on the current collector. These matters also apply to other aspects of the present invention described later.

  The metal oxide contained in the binder material in the electrode plate I of the present invention is (aspect a) a metal oxide that does not show insertion / extraction of alkali metal ions such as lithium and is not doped, (aspect b) lithium An alkali metal ion insertion and desorption such as, and an undoped metal oxide, (aspect c) an alkali metal desorption and desorption such as lithium, and a doped metal oxide ( Aspect d) Alkali metal ions such as lithium can be inserted and desorbed, and can be classified into four aspects: doped metal oxides. Which mode should be selected for the binding material may be appropriately determined in consideration of the specific implementation of the electrode plate (Ii) or the electrode plate (I-ii).

Note that in this specification, a description of a binder substance that is a metal oxide capable of inserting and removing lithium ions and includes a doped metal oxide (that is, the metal oxide shown in the above (aspect d)) By changing lithium to another alkali metal, the electrode plate of the present invention can be applied to an electrode plate for an alkali metal ion secondary battery other than the electrode plate for a lithium ion secondary battery.
Moreover, since the description of the metal oxide which is a metal compound regarding the doped active material particle | grains mentioned above is diverted suitably as for the metal oxide shown by the said aspect d, description is omitted here.
In addition, regarding “metalloid element and typical metal element” relating to the metal oxide contained in the binder, the matters described with respect to the above-described active material particles are diverted, and thus the description thereof is omitted here.

(I) Action of binder substance In the electrode plate for a nonaqueous electrolyte secondary battery according to the first aspect of the present invention, when the active material particles are fixed on the current collector by the binder substance, The following two fixing modes are included. That is, one aspect of the fixing is between the adherends (for example, between the active material particles, between the active material particles and the current collector surface, or when using a conductive material, the conductive material and the active material particles). Between the conductive material particles, etc.) via the metal oxide contained in the binding material (hereinafter sometimes referred to as “fixing mode 1”), the objects to be bonded are in direct contact with each other. The case where the adherends are fixed by surrounding the contact portion and the binding substance is present (hereinafter also referred to as “fixing mode 2”) is included. In many of the electrode plates I of the present invention, either one or both of the fixing modes 1 and 2 are present in the electrode active material layer. In particular, the sticking mode 2 tends to increase as the particle diameter of the active material particles and conductive material particles contained in the electrode active material layer decreases.

In the electrode plate I of the present invention, when either or both of the fixing modes 1 and 2 are present in the electrode active material layer, an excellent effect in terms of improving the conductivity is exhibited. In order to understand the above effect, attention is paid particularly to the adhesion between the conductive material particles in the electrode active material layer containing the conductive material particles. When the conductive material particles are fixed to each other according to the fixing mode 1, since the metal oxide is included in the binding substance, the exchange of electrons between the conductive material particles is larger than that of the conventional resin binder. Hard to become an obstacle. Further, when the conductive material particles are fixed by the fixing mode 2, the particles are in direct contact with each other, so that the flow of electrons is naturally smooth and excellent conductivity is exhibited. Such an effect can be said to be the same for the adhesion between the conductive material particles and the active material particles. In addition, even at the boundary between the current collector and the electrode active material layer, the current collector surface and the active material particles or the conductive material particles are fixed through the binder, or they are in direct contact with each other. Then, it is fixed by the presence of the binding substance around the contact portion. Therefore, for the same reason as described above, the flow of electrons between the current collector and the electrode active material layer becomes smooth.
That is, in the electrode plate I of the present invention, the metal oxide is present in the electrode active material layer as a binder, and various materials are included in the electrode active material layer according to the fixing mode 1 and / or the fixing mode 2. It is preferable that the fixing mode 1 and the fixing mode 2 are mixed, because it is possible to keep the electric resistance low by fixing. Even when the metal oxide is titanium oxide having a very low conductivity, the electron flow is smooth as compared with the resinous binder, and as a result, the electrode plate I of the present invention is excellent. It can exhibit the input / output characteristics. Therefore, the electrode active material layer in the electrode plate I may select an aspect that does not contain a conductive material, or an aspect that significantly reduces the content of the conductive material as compared with the conventional case. On the other hand, as described above, the electrode body I of the present invention can be charged and discharged without the use of a conductive material, and by further positively containing the conductive material in the electrode active material layer, the input / output characteristics of the electrode plate Can be significantly improved.

(B) Binder Substance Component The binder substance is not particularly limited as long as it contains a metal oxide having an action of fixing the active material particles on the current collector. In particular, when the binding material includes a metal oxide exhibiting alkali metal ion insertion / release, such as lithium, the binding material can also act as an active material, and the present invention substantially It is possible to contribute to an increase in the electrode capacity of the secondary battery. In the conventional electrode active material layer, the resin binder only has a binding action, but in the electrode plate I of the present invention, it has an action of fixing as a binding substance and is an alkali metal such as lithium. When a metal oxide exhibiting ion insertion / desorption is selected and contained in the electrode active material layer, the electrode capacity of the nonaqueous electrolyte secondary battery of the present invention can be increased. The metal oxide that forms the binding substance in the present invention includes a metal element-containing phosphate compound.

  Regarding the binding material in the electrode plate I of the present invention, a metal oxide doped with one or more elements selected from a semi-metal element and a typical metal element is selected or doped with the above elements Whether to select a non-metal oxide may be appropriately determined in consideration of the specific implementation contents of the electrode plate (I-i) or the electrode plate (I-ii).

Undoped metal oxide:
First, regarding a metal oxide contained in a binder, a metal oxide that is not doped with one or more elements selected from a semimetal element and a typical metal element will be described.

(Embodiment a) Embodiment of an undoped metal oxide that does not show insertion / extraction of an alkali metal such as lithium:
The metal oxide contained in the electrode active material layer may be a compound having an oxygen element bonded to a metal element. As long as such a condition is satisfied, oxidation of an element generally understood as a metal is performed. If it is a thing, it will not specifically limit. The oxide of the metal element is any of a metal oxide in which oxygen is bonded to any one of the metal elements, or a complex metal oxide containing two or more metal elements selected from the metal elements described above. It may be.
Specific examples of the metal oxide 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, One metal oxide of metal elements such as Pb, Bi, Fr, Ra, and Ce, or a composite metal oxide containing two or more metal elements can be used.

  Examples of metal oxides that do not exhibit insertion or desorption of alkali metal ions such as lithium among the metal oxides of the above elements include metal oxides in which oxygen is bonded to any one of the metal elements, sodium oxide, Magnesium oxide, aluminum oxide, silicon oxide, potassium oxide, calcium oxide, scandium oxide, titanium oxide, vanadium oxide, chromium oxide, manganese oxide, iron oxide, cobalt oxide, nickel oxide, zinc oxide, gallium oxide, strontium oxide, yttrium oxide , Zirconium oxide, molybdenum oxide, ruthenium oxide, tantalum oxide, tungsten oxide, cerium oxide, and the like. Examples of the composite metal oxide containing two or more metal elements include cerium oxide in which gadolinium is substituted. Yttrium substituted acid Zirconium, mixed oxides of iron and titanium, oxides of indium and tin are mixed, lithium and the like nickel oxide substituted.

(Aspect b) An aspect of an undoped metal oxide capable of insertion / extraction of an alkali metal such as lithium:
As the metal oxide of the aspect b, an alkali metal ion insertion / extraction contained in the active material particles described above can be used as appropriate, and the same metal oxide as the undoped metal oxide can be used.
That is, the metal oxide of aspect b is a compound having an oxygen element that binds to a metal element, and may be a metal oxide capable of alkali metal ion insertion and removal. There is no particular limitation as long as it is an oxide of an element generally understood as a metal.
In particular, when a lithium composite oxide is selected as the metal oxide of aspect b, the electrode plate of the present invention is desirable because it can be suitably used as an electrode plate in a lithium ion secondary battery. In particular, when the metal oxide is a composite oxide of at least one metal selected from cobalt, nickel, manganese, iron, and titanium, lithium ion secondary battery Since a suitable electrode plate can be provided, it is preferable. In the electrode active material layer in the electrode plate for a lithium ion secondary battery, the metal oxide can act as a binder and can also act as an active material, thereby improving the input / output characteristics and increasing the electrode capacity. An electrode plate can be provided. For the same reason, in the case of an alkali metal ion secondary battery other than lithium, any one or more metals selected from an appropriate alkali metal and cobalt, nickel, manganese, iron, and titanium are used. It is preferable that a composite slope such as is selected as the metal oxide contained in the binder.

The metal oxide in the above-described aspect b is similar to the metal compound contained in the active material particles described above, lithium cobaltate, lithium manganate, lithium nickelate, lithium ferrate, lithium titanate, lithium iron phosphate, Examples thereof include lithium composite oxides such as vanadium oxide. Specific formulas for _example, and the like _{LiCoO 2, LiMn 2 O 4,} LiNiO 2, LiFeO 2, LiTiO 2, Li 4 Ti 5 O 12, V 2 O 5, LiFePO 4. However, the above is an example and does not limit the present invention. Other examples of the metal oxide in the above-described embodiment b include lithium titanate such as Li ₄ Ti ₅ O ₁₂ exhibiting lithium ion insertion / extraction, but are not limited thereto.

  In the case where the electrode plate of the present invention is an electrode plate of an alkali metal ion secondary battery other than lithium, the metal oxide in aspect b is a metal oxide exhibiting alkali metal ion insertion / extraction other than lithium. You may select suitably.

In particular, the presence of a conductive metal oxide such as LiCoO ₂ or LiMn ₂ O ₄ as a binding material on the surface of the active material particles or between the active material particles can provide conductivity in the electrode active material layer. Since it can improve, the input-output characteristic of the electrode plate I of this invention can be improved. In addition, when the binder material has conductivity, the amount of conductive material added separately can be reduced, so that the amount of active material particles per volume can be increased. As a result, the electrode capacity Can be increased.

Doped metal oxide:
Next, metal oxides doped with one or more elements selected from metalloid elements and typical metal elements will be described with respect to metal oxides contained in the binder material. The doped metal oxide is one or two selected from a semimetal element and a typical metal element while maintaining a crystalline state of the metal oxide before doping. It means a metal oxide substituted with the above elements. At this time, it does not matter whether the metal oxide is crystalline or amorphous.

(Embodiment c) Embodiment of doped metal oxide that does not show insertion / extraction of an alkali metal such as lithium:
Examples of metal oxides that do not show insertion / extraction of alkali metals such as lithium ions and that are doped with one or more elements selected from metalloid elements and typical metal elements include: A part of any metal element in a metal oxide that does not exhibit alkali metal ion insertion / extraction, such as lithium, is replaced with one or more elements selected from metalloid elements and typical metal elements Things.

  Examples of doped metal oxides that do not exhibit alkali metal ion insertion / extraction, such as lithium, are based on titanium oxide, while maintaining the crystal structure of the titanium oxide, A silicon titanium oxide in which a part of the silicon is replaced by silicon can be given. Similarly, yttrium zirconium oxide can be used. However, the above examples do not limit the electrode plate I of the present invention.

(Aspect d) Aspects of doped metal oxide capable of insertion / extraction of an alkali metal such as lithium:
Examples of metal oxides that exhibit insertion / extraction of alkali metals such as lithium ions and that are doped with one or more elements selected from metalloid elements and typical metal elements are described above. Metal in which a part of an arbitrary metal element other than alkali metal such as lithium and one or more elements selected from metalloid elements and typical metal elements are substituted in the metal compound forming the active material particles An oxide is mentioned.

Examples of metal oxides which are doped metal oxides and exhibit alkali metal ion insertion / extraction such as lithium are the same as the above-described doped active material particles, and M is the above-mentioned metalloid element or typical metal element. As examples, LiM _X Co _1-X O ₂ , LiM _X Mn _{2 -X} O ₄ , LiM _X Ni _1-X O ₂ , LiM _X Fe _1-X O ₂ , LiM _X Ti _1-X O ₂ , LiM _X Fe _1-X PO ₄ and the like. Further, specific examples of the active material particles doped with the metalloid element or the typical metal element include LiAl _X Mn _{2 -X} O ₄ , LiB _X Mn _{2 -X} O ₄ , LiNa _X as a lithium manganese composite oxide. _{Mn 2-X O 4, LiMg} X Mn 2-X O 4 and the like, as the lithium-cobalt composite _{oxide, LiSi X Co 1-X O} 2, LiP X Co 1-X O 2, LiSn X Co 1-X O ₂ , LiCa _X Co _1-X O ₂ , and the like. In addition, in said chemical formula, preferable X is 0.1 <= X <= 0.3. Since the description about the metal oxide which is the aspect d can be suitably quoted from the description regarding the metal oxide contained in the doped active material particle | grains demonstrated above, further description is omitted here.

Identity between the metal compound contained in the active material particles and the metal oxide contained in the binder material:
When the metal oxide contained in the binder is a metal oxide capable of inserting and releasing alkali metals such as lithium, the metal compound contained in the active material particles combined with the metal oxide is May be the same or different.
When the metal compound mainly contained in the positive electrode active material particle and the metal oxide mainly contained in the binder material combined therewith are the same compound, and the metal compound mainly contained in the negative electrode active material particle, In the case where the metal oxide mainly contained in the binding material combined with is the same compound, it is preferable from the viewpoint of increasing the electrode capacity of the electrode plate. In particular, when the active material particles are lithium manganate particles and the binder material is also lithium manganate, it is desirable because the input / output characteristics are particularly excellent. At this time, the lithium metal manganate that is the active material particles and / or the lithium manganate that forms the binder material is doped with a metalloid element and / or a typical metal element.

  On the other hand, a device operated using a battery has a voltage standard for each device. In addition, an inherent potential (potential difference) also exists in the electrode plate of the battery, and this potential is mainly determined by the potential of the active material contained in the electrode active material layer. When active material particles and a metal oxide (binding material) that can be an active material are present in the electrode active material layer, the metal compound mainly contained in the active material particles and the metal oxide are the same. In the case of compounds, the potentials shown are also equal. As a result, the metal oxide also participates in the insertion / extraction of lithium ions at the time of charging / discharging as the active material particles as the active material, thereby increasing the electrode capacity of the electrode plate I of the present invention, and thus the present invention. It is possible to increase the capacity of the secondary battery electrode. On the other hand, in the case where the metal compound mainly contained in the active material particles is different from the metal oxide, and therefore has a different potential, the potential of the metal oxide and the device in which the battery is used Depending on voltage standards, the metal oxide may or may not act as an active material.

  In the electrode plate I of the present invention, the fact that the metal compound mainly contained in the active material particles and the metal oxide are the same compound means that the chemical composition of both is the same except for doped elements. To do. The metal compound mainly contained in the active material particles and the metal oxide mainly contained in the binder material mean compounds that control the crystal structure of the metal oxide forming the active material particles or the binder material. . The metal compound mainly contained in the active material particles recognized as the same compound and the metal oxide mainly contained in the binder material have not only the same composition ratio shown in the chemical composition but also the present invention. The electrode plate I may be different as long as the effect of the electrode plate I is not impaired. As another method for determining that the metal compound mainly contained in the active material particles and the metal oxide mainly contained in the binder material are the same compound by another means other than the analysis of chemical composition, a compound crystal It can be confirmed by the structure. That is, when a compound that is an active material particle and a compound that is a metal oxide are observed with a transmission electron microscope and the crystal structures of the two compounds are the same, they can be determined to be the same compound. . Here, the same crystal structure means that the crystal structure is included in the same crystal phase. In other words, when the active material particles and the metal oxide are not the same, the crystal structures of the two are located in different crystal phases, and the narrowly defined identity based on the difference in the contrast of the crystal lattices. Not intended.

(C) Charging / discharging potential of metal oxide In the electrode plate I of the present invention, when the metal oxide contained in the binder material is a metal oxide capable of inserting and releasing alkali metal ions, the metal oxide The conditions for making it act as an active material are demonstrated using a specific example below.
In the battery manufactured using the electrode plate I of the present invention, when the potential of the active material particles is 3.7 V and the potential of the metal oxide as the binding material is 4.5 V, the battery is When used in a 3.7 V device, the metal oxide does not contribute to charge / discharge (ie, does not act as an active material) because the metal oxide does not reach a voltage indicating insertion / extraction of lithium ions. On the other hand, in the battery manufactured using the electrode plate I of the present invention, when the potential of the active material particles is 3.7 V and the potential of the metal oxide as the binding material is 3.4 V, the battery is charged with a voltage. When this is used in a device having a standard of 3.7 V, the metal oxide exhibits insertion and desorption of lithium ions and contributes to charge and discharge (that is, acts as an active material). However, in the latter example, power loss is generated by the difference between the potential of the active material particles and the potential of the metal oxide.
Therefore, from the viewpoint of increasing the discharge capacity of the battery (hereinafter, the discharge capacity of the battery may be simply referred to as “battery capacity”), the metal oxide as the binding material in the electrode plate I of the present invention is lithium ion insertion. A metal oxide exhibiting desorption, preferably a metal oxide exhibiting a potential equal to or lower than that of the active material particles, and more preferably a metal oxide exhibiting a potential equal to that of the active material particles.

(1-3) Lithium ion insertion / desorption of binding material In the electrode plate I of the present invention, when attention is paid to one active material particle contained in the electrode active material layer, the binding material It may be present covering at least part of the surface. At this time, the binder may be present in a state having an exposed surface that can come into contact with the non-aqueous electrolyte. In this case, the binding material includes a binding material in which a part of the surface is exposed to be in contact with the non-aqueous electrolyte in the fixing mode 1 or 2, and other active material particles, a conductive material, a collection material, and the like. Also included is a binding material that is not in contact with an electric body or the like and covers only a part of the surface of one active material particle.
When a battery using the electrode plate I of the present invention is operated, a binding material that covers at least a part of the surface of the active material particles and has an exposed surface that can come into contact with the non-aqueous electrolyte is activated. In the case of acting as a substance, lithium ion insertion / extraction can also occur in the binder material prior to the active material particles or in parallel with the active material particles. Thus, when the binding material acts as an active material, it is presumed that the binding material compensates for lithium ions lost during charging, and is also preferable from the viewpoint of improving the input / output characteristics.

In the electrode plate I of the present invention, whether or not the binding substance exhibits lithium ion insertion / extraction is confirmed by an electrochemical measurement method (cyclic voltammetry method) (hereinafter sometimes referred to as CV test). can do.
Whether or not the binding substance exhibits lithium ion insertion / extraction depends on the action of the metal oxide contained in the binding substance. Specifically, the electrode potential is set and measurement is performed in an appropriate voltage range of the metal oxide contained in the binder. For example, if the metal oxide is LiMn ₂ O ₄ , the operation of sweeping from 3.0 V to 4.3 V and then returning to 3.0 V is repeated about three times. The scanning speed is preferably 1 mV / sec. For example, if the metal oxide is LiMn ₂ O ₄ , in the cyclic voltammogram, an oxidation peak corresponding to the Li elimination reaction of LiMn ₂ O ₄ appears in the vicinity of about 3.9 V, and Li in the vicinity of about 4.1 V. A reduction peak corresponding to the insertion reaction appears. The appearance of the peak confirms lithium ion insertion / desorption of LiMn ₂ O ₄ . FIG. 1 shows the second cycle result in the cyclic voltammogram when LiMn ₂ O ₄ is used. The appropriate voltage range means a voltage range in which the presence or absence of a peak indicating insertion / extraction of lithium ions in the metal oxide used in the test can be confirmed in the cyclic voltammetry test.

On the other hand, as an example of a metal oxide that does not exhibit lithium ion insertion / extraction, when a cyclic voltammetry test is similarly performed using iron oxide, no peak is detected in the cyclic voltammogram. FIG. 2 shows the results of the second cycle in the cyclic voltammogram when using iron oxide.
The presence or absence of lithium ion insertion / extraction of the metal oxide to be contained in the electrode active material layer can be confirmed as described above. Therefore, in manufacturing the electrode plate I of the present invention, it is determined in advance whether or not lithium ion insertion / extraction is exhibited, and then determined as a metal oxide contained in the binder in the electrode active material layer. it can. On the other hand, for example, the following confirmation can be performed as to whether or not the binder material in the already completed electrode plate contains a metal oxide exhibiting lithium ion insertion / extraction. That is, the electrode active material layer is scraped to prepare a sample, and the composition analysis of the sample is performed to estimate what kind of metal oxide is contained in the sample. Whether or not the metal oxide shows lithium ion insertion / extraction by forming a coating film made of the estimated metal oxide on a substrate such as glass and subjecting it to a cyclic voltammetry test. Can be confirmed. Alternatively, the electrode active material layer in the already completed electrode plate is observed with a transmission electron microscope, and the crystal lattice of the metal oxide contained in the binder is the same as the crystal lattice of the compound known as a conventionally known active material If so, it can be determined that the metal oxide contained in the binder is a metal oxide exhibiting lithium ion insertion / extraction. The above-mentioned confirmation by the CV test is the same even when the metal oxide contained in the binder is doped with one or more elements selected from a semi-metal element and a typical metal element. Can be implemented.

(1-4) Crystal lattice of binder material The electrode plate I of the present invention relates to the binder material contained in the electrode active material layer, and the crystal lattice is continuous in at least a part of the adjacent binder materials. It may also include locations connected by. As described above, the binding material is originally intended to fix the active material particles on the current collector, but when at least a part of the binding materials have a continuous crystal lattice, It is assumed that the film adhesion of the electrode active material layer is improved. This improvement in film adhesion is estimated to contribute to the improvement of the input / output characteristics of the electrode plate by smoothing the movement of electrons. Note that 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 electrode active material layer with a transmission electron microscope. Note that the crystal lattice of the binder material specifically means a crystal lattice of a metal oxide contained in the binder material.

  In order to form the electrode active material layer in the electrode plate I of the present invention so as to include a portion where crystal lattices between adjacent binder materials are continuous, the electrode plate of the present invention described later (as described above, the present invention It is desirable that the electrode plate I and the electrode plate II are manufactured according to the description of the manufacturing example. That is, the method for producing an electrode plate of the present invention comprises applying an electrode active material layer-forming liquid onto a current collector to form a coating film, and performing means such as heating from the coating film to form an electrode active material layer. Form. At that time, on the current collector, a metal element-containing compound present around the active material particles undergoes a reaction such as thermal decomposition or oxidation, and a metal oxide as a binding material is generated around the active material particles. Is done. At this time, if a part of the adjacent binding substances (or their precursors) are joined, the crystal growth of both tends to proceed simultaneously at the joined part. As a result of the simultaneous progress of crystal growth in the joint portion, the electrode active material layer of the electrode plate of the present invention is formed so as to include a portion where crystal lattices in adjacent binder materials are continuous.

(1-5) Ratio of active material particles and binder material In the electrode plate I of the present invention, the ratio of the metal oxide contained in the active material particles and the binder material in the electrode active material layer is not particularly specified, It can be appropriately determined in consideration of the type and size of the active material particles used, the type of metal oxide, the function required for the electrode, and the like. Note that, as described above, the metal oxide in the electrode active material layer of the electrode plate I of the present invention includes those that show insertion and desorption of alkali metal ions such as lithium. It can play a role as an active material as well as a binding material for fixing to the surface. Considering this point, it is preferable that the proportion of the binder material in the combined weight of the active material particles and the metal oxide contained in the binder material in the electrode active material layer is 3 to 30% by weight.

(1-6) Other materials in electrode active material layer The electrode active material layer in the electrode plate I of the present invention can be formed only from the binder material containing the active material particles and the metal oxide, As long as the effect of the electrode plate I of the present invention is not impaired, other additives can be further contained. For example, the electrode plate I of the present invention can exhibit good conductivity without using a conductive material, but when better conductivity is desired or the content of active material particles is increased. For example, a conductive material may be mixed. The use of a conductive material is expected to improve the output / input characteristics.

  As the conductive material, those usually used for electrode plates for non-aqueous electrolyte secondary batteries can be used, and examples thereof include carbon materials such as acetylene black and carbon black such as ketjen black. It is not limited to. The average particle size of the conductive material is preferably about 20 to 50 nm. As another conductive material, fine carbon fiber (for example, VGCF (registered trademark)) synthesized by a vapor phase method can be presented. The vapor grown carbon fiber can conduct electricity very well in the length direction and can improve the fluidity of electricity. Therefore, in addition to the particulate conductive material such as acetylene black, the combined use of carbon fibers can improve the conductive material addition effect. The average particle diameter can be obtained from the arithmetic average value actually measured with an electron microscope, as in the method of measuring the particle diameter of the active material particles.

When the conductive material is mixed in the electrode active material layer, the content is not particularly limited, but in general, the ratio of the conductive material is 5 to 20 parts by weight with respect to 100 parts by weight of the active material particles. It is desirable to contain.
In the electrode plate I of the present invention, it is possible to fix the active material particles on the current collector without using a resin binder. On the other hand, the electrode active material layer contains a resin component. The purpose is not to eliminate. For example, normally, when assembling a battery using an electrode plate, it is necessary to immerse the electrolyte in the pores of the electrode. In this case, in order to improve the permeability of the electrolyte, the electrode active material layer The resin component can be contained in the electrode active material layer in a proportion of 1 to 10% by mass. Alternatively, in the electrode plate I of the present invention, a resin binder may be mixed in the electrode active material layer in addition to the metal oxide as a binder. Thus, if necessary, the electrode plate I of the present invention may contain a resin material in the electrode active material layer.

(1-7) Thickness of electrode active material layer The thickness of the electrode active material layer in the electrode plate I of the present invention can be appropriately designed in consideration of the electrode capacity and input / output characteristics required for the electrode plate. In general, the thickness of the electrode active material layer is designed to be 200 μm or less, more specifically about 100 to 150 μm. Further, in the electrode plate I of the present invention, it is possible to form an electrode active material layer much thinner than in the prior art, and the thickness of the electrode active material layer depends on the particle diameter of the active material particles used. It is possible to form an electrode active material layer of about 300 nm to 200 μm. From the viewpoint of improving the input / output characteristics and improving the electrode capacity, the film thickness of the electrode active material layer is preferably 300 nm to 150 μm, and more preferably 500 nm to 100 μm. That is, when the thickness of the electrode active material layer is thin as in the above range, the active material particles used are those having a small particle diameter, and at least a particle diameter equal to or smaller than the film thickness of the electrode active material layer. means. In addition, when the thickness of the electrode active material layer is thin as in the above range, the distance between the active material particles and the current collector in the electrode active material layer is shortened, so that the resistance of the electrode plate can be lowered. become. In the electrode plate I of the present invention, the lower limit of the film thickness of the electrode active material layer mainly depends on the particle size of the active material particles used. Therefore, by reducing the particle size of the usable active material particles, It is possible to reduce the film thickness.

(2) Current collector The current collector used in the first aspect of the present invention is the same as the current collector used in the second aspect of the present invention to be described later, and the first aspect and the second aspect. Hereinafter, the current collector used in the present invention may be referred to as “the current collector of the present invention”.
The current collector of the present invention is generally used as a positive electrode current collector in a non-aqueous electrolyte secondary battery positive electrode plate or a negative electrode current collector in a non-aqueous electrolyte secondary battery negative electrode plate, There is no particular limitation. For example, the current collector is preferably formed of a single element such as an aluminum foil, a nickel foil, or a copper foil, or an alloy, or a highly conductive foil such as a carbon sheet, a carbon plate, or a carbon textile. Note that the current collector of the present invention may be a current collector that has been subjected to surface processing on the surface on which the electrode active material layer is to be formed, if necessary. Examples of the current collector that has been subjected to the surface processing treatment include those obtained by laminating a conductive material, those subjected to surface treatment such as chemical polishing treatment, corona treatment, and oxygen plasma treatment. Further, the surface of the current collector may be physically provided with any unevenness.

The current collector of the present invention will be described with reference to FIG. Note that (8A) to (8D) in FIG. 8 are examples of the current collector of the present invention, and the current collector of the present invention is not limited to the one illustrated in FIG.
As an example of the current collector, the current collector 1 used for the electrode plate 20 for a nonaqueous electrolyte secondary battery shown in (8A) is only the current collecting base material 3 such as a metal foil having a current collecting function. Can be used. Examples of the current collecting base 3 include the aluminum foil, nickel foil, and carbon sheet described above. In such a case, the electrode active material layer 2 is provided on at least a part of the surface 101 of the current collecting base material 3.
As an example of another current collector, the current collector 1 ′ used in the electrode plate 20 ′ for a nonaqueous electrolyte secondary battery shown in (8B) is a current collecting base material 3 having a current collecting function itself. A current collector 1 ′ in which an arbitrary conductive layer 4 having conductivity is provided on the upper surface can be used. The electroconductive layer 4 should just show electroconductivity of the grade which does not prevent the movement of the electron between the electrode active material layer 2 and the current collection base material 3. FIG. For example, the conductive layer 4 is a laminated layer containing copper or a copper alloy, a layer in which arbitrary conductive fine particles are deposited by plating or sputtering, or a layer in which one or more conductive thin films are provided. However, the present invention is not limited to these examples. In the current collector 1 ′, the surface of the conductive layer 4 becomes the surface 102 of the current collector 1 ′, and the electrode active material layer 2 is provided on at least a part of the surface 102. In (8B), an embodiment in which the arbitrary conductive layer 4 is one layer is shown. However, the configuration of the current collector 1 ′ is not limited to this, and the conductive layer 4 may have a stacked configuration in which two or more arbitrary conductive layers are stacked.

  As another example of the current collector, the current collector 1 ″ used for the electrode plate 20 ″ for the nonaqueous electrolyte secondary battery shown in FIG. 8 (8C) itself has a current collecting function. A current collector in which an arbitrary intermittent layer 5 formed intermittently is provided on the upper surface of the current collector base 3 can be used. The intermittent layer 5 may be a conductive layer similar to the conductive layer 4 described above, or may be a layer that does not exhibit conductivity. That is, in the electrode plate 20 ″ for the non-aqueous electrolyte secondary battery, the surface 103 of the current collector 1 ″ of the electrode active material layer 2 is provided with the surface 103 that is the surface of the intermittent layer 5 and the intermittent layer 5. And the surface 103 ′ which is the surface of the current collecting base 3 itself. At this time, the electrode active material layer 2 can be formed in contact with both the surface 103 and the surface 103 ′. In the electrode plate 20 ″ for a nonaqueous electrolyte secondary battery, the intermittent layer 5 may or may not have conductivity. Even if the intermittent layer 5 is a non-conductive layer, the electrode active material layer 2 is in direct contact with the current collector base 3 on the surface 103 ′ of the current collector 1 ″. And the current collector 1 ″ ensure the movement of electrons. However, from the viewpoint of reducing the electrical resistance of the negative electrode plate 20 ″ for the nonaqueous electrolyte secondary battery itself, it is preferable that the intermittent layer 5 also exhibits conductivity.

Further, when the intermittent layer 5 exhibits conductivity, the electrode active material layer 2 is selectively formed only on the surface of the current collector 1 ″ and on the intermittent layer 5, as indicated by (8D) in FIG. 'May be provided to constitute the electrode plate 20 ′ ″ for a non-aqueous electrolyte secondary battery. That is, the electrode active material layer 2 ′ may be selectively provided on at least a part of the surface 103 of the surface of the current collector 1 ″. Alternatively, although not shown, when the intermittent layer 5 does not exhibit conductivity, an electrode active material layer 2 ′ may be selectively provided on at least a part of the surface 103 ′ of the current collector 1 ″.
The current collector of the present invention may be only a current collecting base material having a current collecting function as exemplified above. In such an embodiment, the surface of the current collector on which the electrode active material layer is provided refers to the surface of the current collector substrate. Alternatively, the current collector of the present invention may have a current collecting base material having a current collecting function and an arbitrary laminated layer provided on the current collecting base material. In such an embodiment, the surface of the current collector on which the electrode active material layer is provided is within the range in which the movement of electrons is ensured in at least one region between the current collector base material and the electrode active material layer. It refers to the surface, or the surface of the current collecting base material where the laminated layer is not provided, or the surface of the current collecting base material where the surface of the laminated layer and the layered layer are not provided.

As the current collector of the present invention, one having a heat resistant temperature of 800 ° C. or lower, further 600 ° C. or lower, and particularly 400 ° C. or lower can be selected. The selection of the current collector is determined by the relationship with the temperature condition in the electrode active material layer forming step in the electrode plate manufacturing method of the present invention described later. In the manufacturing method, when the electrode active material layer forming step is a heating step, the electrode active material layer can be formed directly on the current collector at a heating temperature of, for example, 400 ° C. or less. Accordingly, the current collector can be selected to have a heat resistant temperature of 800 ° C. or lower, more preferably 600 ° C. or lower, and particularly 400 ° C. or lower, and an electrode active material layer is directly formed on the current collector. The electrode plate I or II of the present invention can be provided. The electrode active material layer directly provided on the current collector having low heat resistance of 400 ° C. or lower is preferably a combination in which the active material particles and the binding material are made of the same compound. It is not limited.
The thickness of the current collector is not particularly limited as long as it is generally a thickness that can be used as a current collector for a positive electrode plate or a negative electrode plate for a nonaqueous electrolyte secondary battery, but is preferably 10 to 200 μm. More preferably, it is 50 μm.

(3) Electrode plate I
The electrode plate I of the present invention can be used for either a positive electrode plate or a negative electrode plate of a nonaqueous electrolyte secondary battery, or for both a positive electrode plate and a negative electrode plate.
When the electrode plate I of the present invention is used as a positive electrode plate, the input / output performance is higher than when only the resin binder is used as the binder. In addition, the electrode plate I of the present invention can substantially increase the ratio of the active material in the electrode by designing the electrode plate I so that the binder material containing a metal oxide also acts as the active material. According to the above design, the electrode plate I of the present invention can increase the discharge capacity of the electrode plate (hereinafter, the discharge capacity of the electrode plate may be simply referred to as “electrode capacity”). Very good. Furthermore, the range of applications is wide in that many metal oxides can be applied to the binding material that forms a part of the electrode plate I of the present invention, and in addition, it is preferable because it can be used in combination with a conventional negative electrode plate. .

Further, when the electrode plate I of the present invention is used as a negative electrode plate, it is excellent in that the input / output performance is high and the electrode capacity can be increased as in the case of the positive electrode plate. In addition, the electrode plate I of the present invention has excellent adhesion between a metal substrate such as copper or aluminum and a metal oxide, and the metal oxide film present around the negative electrode active material particles is a solid electrolyte interface. ), And as a result, the cycle characteristics are favorable.
When the electrode plate I of the present invention is used for both positive and negative electrodes, desirable effects such as high-speed charge / discharge and improved cycle characteristics can be exhibited.

(4) Method for evaluating charge / discharge rate characteristics of electrode Measurement of discharge capacity retention rate:
The input / output characteristics of the electrode plate I of the present invention can be evaluated by determining the discharge capacity retention rate (%). The evaluation by measuring the discharge capacity retention rate is the same for the electrode plate II of the present invention described later. That is, the discharge capacity retention rate is an evaluation of discharge rate characteristics, and it is understood that an electrode plate with improved discharge rate characteristics generally has improved charge rate characteristics as well. Therefore, when a desirable discharge capacity maintenance rate is indicated, it is evaluated that the charge / discharge rate characteristics are improved. More specifically, the discharge rate 1C was set so that the theoretical value of the discharge capacity (mAh / g) of the active material particles would complete the discharge in 1 hour, and was actually measured at the set discharge rate of 1C. The discharge capacity (mAh / g) is set to a discharge capacity maintenance rate of 100%. Then, the discharge capacity (mAh / g) when the discharge rate is further increased is measured, and the discharge capacity retention ratio (%) can be obtained from the following formula 1.
(Formula 1)
Discharge capacity maintenance rate (%) =
[(Discharge capacity at each discharge rate (mAh / g)) / (Discharge capacity at 1 C (mAh / g))] × 100
The charge / discharge rate characteristics of the electrode plate I of the present invention vary depending on the type and particle diameter of the active material particles used, the amount of the metal oxide as the binder contained, the thickness of the electrode active material layer, and the like.

DC resistance measurement:
Alternatively, the input / output characteristics of the electrode plate I of the present invention can be evaluated by measuring the DC resistance value (Ω) of the manufactured electrode plate. The evaluation by measuring the DC resistance value is the same for the electrode plate II of the present invention described later. That is, a decrease in the DC resistance value of the electrode plate means an increase in output, and as a result, it can be understood that the input / output characteristics are improved. The DC resistance value can be measured by the following method.
The DC resistance value is measured using the electrode plate to be measured as the working electrode, using a metal lithium plate or the like as the counter electrode and reference electrode, and using a suitable electrolyte to assemble a tripolar coin cell. Using as a test cell, it can be calculated as follows.
When a discharge test is performed at two discharge rates (discharge rates 1C and 10C), a voltage value (mV) 10 seconds after the start of discharge is measured. For example, the voltage value (V1) (mV) when the discharge test is performed under the condition of the discharge rate 1C, and the voltage 10 seconds after the start of the discharge when the discharge test is performed under the condition of the discharge rate 10C. The value (V10) (mV) is measured. Based on these measured values (V1, V10) and the constant current values (I1, I10) (mA) corresponding to the discharge rates 1C, 10C, the DC resistance value (Ω) is calculated by the following equation 2. The When the resistance value is small in this test, it is evaluated that the flow of electrons and lithium ions is smooth and the input / output characteristics of the action plate are improved.
(Formula 2) DC resistance value (Ω) = (V1−V10) / (I10−I1)

[2] Nonaqueous electrolyte secondary battery electrode plate (second embodiment)
The electrode plate for nonaqueous electrolyte secondary batteries of the second aspect (electrode plate II of the present invention) comprises a current collector and an electrode active material layer formed on at least a part of the surface of the current collector. An electrode plate for a non-aqueous electrolyte secondary battery provided with the electrode active material layer including a plurality of nuclei dispersed in the electrode active material layer and a plurality of enclosures surrounding the nuclei. The plurality of enclosures are formed such that a part of adjacent enclosures are connected to each other or continuous without distinction, and the enclosure in the vicinity of the current collector is the current collector. It is connected to the surface.
In the electrode plate II of the present invention, (iii) one or two active material particles in which the core is an alkali metal ion insertion / extraction, and the active material particles are selected from a semimetal element and a typical metal element. On the other hand, the feature is that the enclosure contains a metal oxide, or the electrode plate II of the present invention has (iv) an activity in which the nucleus shows alkali metal ion insertion / extraction. On the other hand, the enclosure includes a metal oxide, and the metal oxide is doped with one or more elements selected from a metalloid element and a typical metal element. In addition, the electrode plate II of the present invention may have the above two features (iii) and (Iv) at the same time.
The electrode plate II of the present invention can be used for either a positive electrode plate or a negative electrode plate of a non-aqueous electrolyte secondary battery, or both a positive electrode plate and a negative electrode plate.

In the electrode plate II of the present invention, the components of the active material particles forming the nucleus are the same as the components of the active material particles described in the section of the electrode plate I of the present invention described in the first embodiment, The same applies to the particle size. In the electrode plate II of the present invention, the metal oxide contained in the enclosure is the same as the metal oxide contained in the binding material used in the electrode plate I of the present invention described in the first aspect. The compound has the same effect. The current collector forming the electrode plate II of the present invention is the same as the current collector forming the current collector of the electrode plate I of the present invention as described above.
Further, the active material particles capable of inserting / desorbing lithium ions (undoped active material particles) and the active material particles capable of inserting / desorbing lithium ions (doped active material) described in the electrode plate I of the present invention described above. Particles), active material particles capable of insertion / extraction of sodium ions (undoped active material particles), and active material particles capable of insertion / extraction of sodium ions (doped active material particles) are described in the electrode plate of the present invention. Applies to nuclei in II.
Further, as described in the electrode plate I of the present invention described above, (embodiment a) an embodiment of an undoped metal oxide that does not show insertion / extraction of an alkali metal such as lithium, (embodiment b) such as lithium An embodiment of an undoped metal oxide capable of insertion / extraction of an alkali metal, (Embodiment c) An embodiment of a doped metal oxide that does not show insertion / extraction of an alkali metal such as lithium (Embodiment d) The matter relating to the embodiment of the doped metal oxide, in which insertion and desorption of an alkali metal such as lithium is possible, is applied to the enclosure in the electrode plate II of the present invention.

  In addition, since the active material particles forming the nuclei are present on the current collector by being surrounded by the metal oxide contained in the enclosure, the effect of improving the input / output characteristics is described in the present invention. The electrode plate II is the same as the electrode plate I of the present invention described above. In addition, the electrode plate II of the present invention having a nucleus and an enclosure includes an electrode active material layer and a current collector because the enclosure in the vicinity of the current collector is connected to the surface of the current collector. The same is true for the smooth movement of electrons between and.

(1) Structure of electrode active material layer The structure of the electrode active material layer formed on the electrode plate II of the present invention will be described with reference to FIG. (3A) in FIG. 3 is a schematic view showing a cross section when the electrode plate II in the present invention is cut substantially perpendicular to the current collector surface, and (3B) is an electrode active material in the electrode plate II in the present invention. It is a schematic diagram which shows the surface of a layer.
In the structure of the electrode active material layer 2 of (3A) in FIG. 3, as shown in (3A), the electrode active material layer 2 includes a plurality of nuclei 6 dispersed in the electrode active material layer 2, and these There is a surrounding body 7 surrounding the plurality of core bodies 6. In the electrode active material layer 2, the nucleus 6 is formed from active material particles, and the enclosure 7 is formed including a metal oxide. The active material particles forming the core body 6 may be primary particles, secondary particles, or a mixture thereof. The enclosure 7 existing in the vicinity of the current collector 1 is connected to the surface of the current collector 1, whereby the electrode plate II (10) of the present invention having the electrode active material layer 2 directly on the current collector 1. Is completed. Further, the electrode active material layer 2 has voids 8 everywhere, so that when the battery is formed using the electrode plate II (10) of the present invention, the non-aqueous electrolyte passes through the voids 8. This facilitates penetration into the electrode active material layer 2.
(3B) in FIG. 3 is a schematic diagram showing the surface of the electrode active material layer 2. The surface of the electrode active material layer 2 is mainly covered with the enclosure 7, and the nucleus 6 is exposed in some places. In addition, voids 8 are present everywhere on the surface of the electrode active material layer 3.

  In the electrode active material layer 2, the surrounding body 7 surrounding the core body 6 is a plurality of surrounding bodies 7, and one surrounding body 7 surrounds one or a plurality of core bodies 6. Among the plurality of enclosures 7, a part of adjacent enclosures 7 may be connected to each other. Alternatively, the surrounding body 7 surrounding the core body 6 may be continuously connected without being distinguished from each other. Alternatively, in the electrode active material layer 2 in the electrode plate II of the present invention, the plurality of enclosures 7 and the enclosures 7 continuous without distinction may be mixed.

In the electrode active material layer 2, the envelope 7 is not particularly limited with respect to the aspect of the envelope 7 itself, for example, the size, shape, and distribution. For example, the enclosure 7 may be in the form of fine particles. In that case, an enclosure made up of a number of fine particulate metal oxides surrounds one or more of the electrode active materials as the core body 6 or the entire surface or part of the aggregate. It's okay. At this time, the particulate enclosures may be joined to each other.
The enclosure 7 may be non-particulate. At this time, the surrounding body 7 may be a continuous body in which the gap between the electrode active materials that are the core bodies 6 is embedded leaving the gap. The continuum surrounds a plurality of nuclei 6 with leaving a gap, but when the individual nuclei 6 are viewed, the entire surface of one nuclei 6 is surrounded by a wrapping 7 that is a continuum. It may be surrounded, or a surface that is not surrounded by the envelope 7 that is a continuous body may exist on the surface of one core body 6.

  The envelope 7 may constitute a continuous coating layer in the form of a film, a pleat, or a hump that surrounds two or more aggregates of the nuclei 6. The covering layer surrounds the plurality of nuclei 6 with leaving gaps, but when the individual nuclei 6 are viewed, the entire surface of one nuclei 6 forms an envelope 7 that forms the covering layer. It may be surrounded, or on the surface of one core body 6, there may be a surface that is not surrounded by the surrounding body 7 that is a covering layer. In addition, the surface of the enclosure 7 is densely populated with countless protrusions regardless of whether it is observed on a smooth surface, regular or irregular, for example, when magnified with a scanning electron microscope at a magnification of about 50,000 times. Or a combination thereof, and the surface state is not limited at all.

The shape of the surrounding body exemplified above and the manner in which the surrounding body surrounds the core body do not limit the electrode plate II of the present invention. That is, the envelope in the electrode active material layer of the electrode plate II of the present invention surrounds at least a part of the nucleus and the envelopes are connected to each other, or the envelope is a continuous body. Of these, any member may be used as long as the surrounding body in the vicinity of the current collector is connected to the surface of the current collector so that the nucleus is fixed on the current collector to constitute the electrode active material layer.
Regardless of whether the envelope in the electrode active material layer of the electrode plate II of the present invention has a particle shape or a non-particle shape, a part of the adjacent envelopes are connected to each other. In II, when the connection between the adjacent enclosures includes a portion where the crystal lattice is continuous, it is desirable because the film adhesion of the electrode active material layer is improved, thereby contributing to the improvement of the input / output characteristics. Whether or not the crystal lattice is continuous in at least a part of the enclosures is the same as the method for confirming whether or not the crystal lattice is continuous between the adjacent binding substances.

The structure of the electrode active material layer in the electrode plate II of the present invention can be constituted by a so-called double structure constituted by a nucleus and an enclosure. This double structure can be confirmed from a scanning electron micrograph. Moreover, the double structure can be understood from a method for manufacturing an electrode plate described later. That is, the method for producing an electrode plate is to apply an electrode active material layer-forming liquid containing electrode active material particles on a current collector to form a coating film, and to form a metal oxide that forms an enclosure within the coating film. Precipitate. At that time, on the current collector on which the coating film is formed, the existing electrode active material particles contained in the coating film form a nucleus, and a metal oxide that forms an enclosure around the nucleus so as to surround it. Is generated. As a result, the double structure is formed.
Regarding the above-mentioned double structure composed of the nucleus and the enclosure, there is one feature, particularly when focusing on the interface between the nucleus and the enclosure. The active material particles, which are substances forming the nucleus, may be formed including a crystalline metal compound or a crystalline material. Moreover, the aspect in which the metal oxide contained in an enclosure is an amorphous metal oxide, or the aspect which is a crystalline metal oxide is contained. In particular, when the enclosure exhibits lithium ion insertion / extraction, it is understood that the enclosure contains a crystalline metal oxide. Here, there is a region where both crystal lattices are continuous and a discontinuous region at the interface between the two formed when the crystalline nucleus is surrounded by an enclosure containing a crystalline metal oxide. Was confirmed. In particular, when the crystal lattice of the nucleus and the crystal lattice of the enclosure are different, the crystal lattices of both are discontinuous throughout the interface between the two. The continuity of the crystal lattice can be confirmed by observing the crystal lattice with a transmission electron microscope.

The present inventors have inferred that the presence of the above-described discontinuous region of the crystal lattice contributes to the improvement of cycle characteristics. The electrode plate for a non-aqueous electrolyte secondary battery has a cycle characteristic that is deteriorated or further destroyed while alkali metal ions such as lithium ions are repeatedly inserted into and released from the crystal structure of the active material particles. descend. It is considered that the deterioration and destruction of the crystal structure described above occurs along a continuous crystal lattice of the crystal structure. If there is a discontinuous region between the two crystal lattices, it is assumed that the deterioration of the crystal structure that occurs in each of the nuclei and the enclosure is less likely to affect each other. In addition, when a crack is about to be generated on the surface of the nucleus due to repeated insertion / desorption, there is a metal oxide contained in the surrounding body, so that the metal oxide is a metal oxide that does not insert / desorb lithium ions. Even if it exists, it is guessed that progress of a crack can be delayed. As a result, it is presumed that the cycle characteristics of the electrode plate II of the present invention are not easily lowered, and good cycle characteristics are exhibited. In other words, it is surmised that the double structure in the electrode plate II of the present invention contributes to the improvement of the cycle characteristics. In fact, it has been confirmed in Example 1 and the like that will be described later that the cycle characteristics of the present invention are improved as compared with the conventional electrode plate having no double structure.
The above-mentioned inference regarding the cycle characteristics in the electrode plate II of the present invention is based on the electrode plate II of the present invention having the feature (iii) or the feature (iv), the feature (iii), and the feature (iv) of the present invention. The same applies to any of the electrode plates II.

(2) Ratio of active material particles and metal oxide, other materials in electrode active material layer, thickness of electrode active material layer “Ratio between core and enclosure” in electrode plate II of the present invention The description of “ratio of substance particles to binding substance” applies. Further, the “other materials in the electrode active material layer and the thickness of the electrode active material layer in the electrode plate II of the present invention” are the same as those described in the “electrode plate I of the present invention” of the first aspect.
(3) Charging / discharging potential of metal oxide, insertion / extraction of lithium ion of metal oxide About “charge / discharge potential of metal oxide, insertion / extraction of lithium ion of metal oxide” in electrode plate II of the present invention, This is the same as described in “Electrode plate I of the present invention” in the first embodiment.
(4) Electrode plate II
The electrode plate II of the present invention can be used for either a positive electrode plate or a negative electrode plate of a non-aqueous electrolyte secondary battery, or for both a positive electrode plate and a negative electrode plate.
When the electrode plate II of the present invention is used as a positive electrode plate, it has no metal oxide contained in the enclosure, and has higher input / output performance than the case where only the resin binder is used. In addition, the electrode plate II of the present invention can substantially increase the proportion of the active material in the electrode by designing the metal plate contained in the enclosure to act as an active material. According to the above design, the electrode plate II of the present invention is very excellent in that the discharge capacity of the electrode plate can be increased. Further, the envelope forming part of the electrode plate II of the present invention is preferable in that it can be used in combination with a conventional negative electrode plate in that it can be used in combination with a conventional negative electrode plate in that many metal oxides can be applied.

Further, when the electrode plate II of the present invention is used as a negative electrode plate, it is excellent in that the input / output performance is high and the electrode capacity can be increased as in the case of the positive electrode plate. In addition, the electrode plate II of the present invention has excellent adhesion between a metal substrate such as copper or aluminum and a metal oxide, and the metal oxide film present around the negative electrode active material particles is a solid electrolyte interface. ), And as a result, the cycle characteristics are favorable. When the electrode plate II of the present invention is used for both positive and negative electrodes, high-speed charge / discharge is possible and desirable effects such as improved cycle characteristics are exhibited.
In addition, about the evaluation regarding the input / output characteristic of the electrode plate II of this invention which is a 2nd aspect, it is the same as that of the content described about the electrode plate I of this invention which is the 1st aspect mentioned above.

[3] Method for Producing Electrode Plate for Nonaqueous Electrolyte Secondary Battery The method for producing the electrode plate of the present invention (hereinafter sometimes referred to as the method for producing the electrode plate) will be described. The method for producing the electrode plate includes a metal element-containing compound that is a precursor of a metal oxide, a solvent and an active material particle that dissolves the metal element-containing compound, or an optional additive material. A forming solution is prepared. And the manufacturing method of this electrode plate has the application process (henceforth only an "application process") which apply | coats the said electrode active material layer forming liquid to the desired area | region of the collector surface, and forms a coating film. And an electrode active material layer forming step for forming an electrode active material layer from the coating film (hereinafter sometimes simply referred to as “electrode active material layer forming step”).
In the electrode active material layer forming step, the solvent contained in the coating film is removed and a metal element-containing compound contained in the coating film is reacted to generate a metal oxide. The active material particles can be fixed on the current collector, and an electrode active material layer containing the metal oxide and the active material particles can be formed on the current collector.

Moreover, after providing the arbitrary processes, such as a press process, between the said application | coating process and the said electrode active material layer formation process and removing the solvent in a coating film, you may implement an electrode active material layer formation process. . That is, in the electrode active material layer forming step, a metal element-containing compound contained in the coating film from which the solvent has been removed is reacted to generate a metal oxide, and the active material particles are collected by the metal oxide. The electrode active material layer containing the metal oxide and the active material particles may be formed on the current collector by being fixed on the current collector.
In the production method of the electrode plate, in the case of producing a positive electrode plate, in order to form a positive electrode active material layer on a current collector, the electrode active material layer forming liquid contains positive electrode active material particles and When a metal element-containing compound suitable for this is added and a negative electrode plate is produced, the negative electrode active material layer forming liquid contains a negative electrode active material in order to form a negative electrode active material layer on the current collector. Particles and metal element-containing compounds suitable for this are added. Hereinafter, in the manufacturing method of this electrode plate, “positive electrode” and “negative electrode” may be collectively referred to as “electrode”.

Unlike a conventional slurry-like electrode active material layer forming liquid using a resin binder, an electrode active material prepared by using a metal element-containing compound and active material particles used in the method for producing the electrode plate The layer-forming liquid exhibits a viscosity that can maintain good applicability to the current collector, regardless of the particle diameter of the active material particles contained therein. Therefore, with the conventional electrode active material layer forming liquid, it is possible to use active material particles having a small particle diameter, which has been difficult to use due to a significant increase in viscosity, by the method for producing the present electrode plate. In addition, the electrode plate manufacturing method has good applicability to the current collector of the electrode active material layer forming liquid, so that it can be applied to a desired thickness, and the electrode active material layer can be made thin. It becomes possible.
As described above, according to the method for manufacturing the electrode plate, both the use of active material particles having a small particle diameter and the thinning of the electrode active material, which are approaches to improving the input / output characteristics of the electrode plate, It can be easily realized. Therefore, according to the method for producing the electrode plate, the non-aqueous electrolyte with improved input / output characteristics can be obtained by using active material particles having a small particle diameter or by designing the thickness of the electrode active material layer to be small. An electrode plate for a secondary battery can be easily manufactured. However, the improvement of the input / output characteristics in the present electrode plate is not limited to the particle diameter of the active material particles and the thickness of the electrode active material layer, and can be shown in a wide range of designs.

Examples of the electrode active material layer forming step include, but are not limited to, a heating step, a reduced pressure drying step, a reduced pressure heating step, or a combination thereof, and an electrode active material applied on a current collector. It may be a step of implementing means capable of forming a coating film formed by the layer forming liquid as an electrode active material layer. For example, in the electrode active material layer forming step, a means for removing the solvent contained in the coating film is implemented, and then a means for reacting the metal element-containing compound is implemented. Two or more means may be included such as adding.
In the case where the electrode active material layer forming step is a heating step in which a heating means is carried out, the method for producing the electrode plate includes the electrode active material layer forming liquid in which the metal element-containing compound is dissolved on a current collector. It is applied and heated at a temperature not lower than the thermal decomposition start temperature of the metal element-containing compound and thermally decomposed, and the metal element contained therein is oxidized to produce a metal oxide. In the electrode active material layer forming step, the metal oxide formed on the current collector is coated on the current collector so as to embrace the active material particles contained in the electrode active material layer forming liquid. The active material particles can be fixed on the current collector. The active material particles contained in the electrode active material layer forming liquid, or further the conductive material particles, in addition to the fixing mode 1, as shown as the fixing mode 2, is a state in which the direct contact between the particles is satisfactorily maintained. The aspect fixed by is included.

  As described above, the factors that enable the fixed state as shown in the fixing modes 1 and 2 are that the metal element-containing compound is dissolved in the solvent and the active material particles in the manufacturing method of the present electrode plate. When forming an electrode active material layer by applying an electrode active material layer forming liquid mixed with the above to the current collector, the solvent is removed by means such as heating and the resulting metal oxide (binding material) Is presumed to be generated around the contact portion where the particles are in direct contact with each other. As a result, the electrode plate manufacturing method can manufacture an electrode plate that has good conductivity and can keep electric resistance low. In addition, in the manufacturing method of this electrode plate, the metal element containing compound contained in an electrode active material layer forming liquid is called a metal element containing compound including the thing melt | dissolved in the solvent.

(1) Active material particles The active material particles contained in the electrode active material layer forming liquid are the positive electrode active material particles already described in the above "electrode plate I of the present invention" and "electrode plate II of the present invention", or The same as the negative electrode active material particles. Therefore, in accordance with the description of the active material particles described above, the electrode plate manufactured by the method for manufacturing the present electrode plate is doped with one or more elements selected from a semi-metal element and a typical metal element. The active material particles to be selected may be determined depending on whether or not the active material particles are contained. In addition, the electrode active material layer forming liquid used for the manufacturing method of this electrode plate used the active material particle with a small average particle diameter compared with the electrode active material layer forming liquid using the conventional resin binder. Even in this case, the viscosity can be easily adjusted. In particular, the electrode active material layer forming liquid used in the manufacturing method of the present electrode plate is such that the coatability is reduced even if the active material particles have a particle size of 10 μm or less, and even 1 μm or less. It has a desirable feature that no increase in viscosity is observed. Therefore, a desired size can be selected for the particle diameter of the active material particles used.

(2) Metal element-containing compound The metal element-containing compound dissolved in the electrode active material layer forming liquid is contained in the electrode active material layer, and the active material particles are fixed to each other as a metal oxide contained in the binder. It is a precursor of a metal oxide that exhibits the action of causing the active material particles to adhere to the current collector. Therefore, the metal element-containing compound can be applied to the substrate in a state dissolved in a solution, and can generate the above-described metal oxide when heated at a temperature in the range of the thermal decomposition start temperature or higher. If it is a thing, it will not specifically limit. The “metal oxide contained in the binding substance” is a metal oxide that mainly forms the binding substance, and is substantially together with the metal oxide that is the binding substance and any element or material. Any metal oxide contained in the binder is included. In addition, it is desirable that the above arbitrary element or material contained in the binding substance is contained in the binding substance as long as the fixing action of the metal oxide can be exhibited.
As described above, the metal oxide contained in the binding substance in the electrode plate of the present invention may be a metal oxide that exhibits lithium ion insertion / extraction. Whether or not the metal oxide produced from the metal element-containing compound to be used exhibits lithium ion insertion / desorption is determined by applying a solution containing the metal element-containing compound on the substrate and heating it in a preliminary experiment. Thus, a metal oxide can be formed and confirmed by the cyclic voltammetry method.
In addition, as described above, the metal oxide contained in the binding material in the electrode plate of the present invention is a metal oxide doped with one or more elements selected from a semimetal element and a typical metal element. And embodiments that are undoped metal oxides.

When an undoped metal oxide is formed as the metal oxide contained in the binder, the metal element-containing compound is specifically 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, Fr, Ra, and Ce, one or two Any compound containing two or more metal elements may be used. The reason is not clear, but among the above metal elements, particularly when a metal element-containing compound containing a metal element belonging to 3 to 5 cycles is used, the input / output characteristics of the generated electrode plate are higher. It is preferable because of its tendency.
As the metal element-containing compound containing the metal element, for example, a metal salt is preferably used. Examples of the metal salt include chloride, nitrate, sulfate, perchlorate, acetate, phosphate, bromate, carbonate, and the like. Among these, it is preferable to use chlorides, nitrates, and acetates that are easily available, and it is particularly preferable to use inexpensive nitrates.
Specific examples of metal salts include magnesium chloride, aluminum nitrate, aluminum chloride, calcium chloride, scandium acetate, titanium tetrachloride, vanadium oxosulfate, ammonium chromate, chromium chloride, ammonium dichromate, chromium acetate, chromium nitrate. , Chromium sulfate, manganese nitrate, manganese sulfate, iron (I) chloride, iron (III) chloride, iron (II) acetate, iron (III) nitrate, iron (II) sulfate, ammonium iron (III) sulfate, cobalt chloride, nitric acid Cobalt, cobalt acetate, nickel chloride, nickel nitrate, nickel acetate, copper chloride, copper nitrate, zinc chloride, zinc acetate, zinc chloride, yttrium nitrate, yttrium chloride, zirconium chloride, zirconium nitrate, zirconium tetrachloride, silver chloride, Silver acetate, indium nitrate, indium acetate, tin sulfate, selenium chloride Cerium acetate, cerium nitrate, cerium oxalate, diammonium cerium nitrate, cerium sulfate, samarium chloride, samarium nitrate, lead chloride, lead acetate, lead nitrate, lead iodide, lead phosphate, lead sulfate, lanthanum chloride, acetic acid Lanthanum, lanthanum nitrate, gadolinium nitrate, strontium chloride, strontium acetate, strontium nitrate, niobium pentachloride, ammonium molybdate phosphate, molybdenum sulfide, palladium chloride, palladium acetate, palladium nitrate, antimony pentachloride, antimony trichloride, trifluoride Antimony, telluric acid, barium sulfite, barium chloride, barium chlorate, barium perchlorate, barium acetate, barium nitrate, tungstic acid, ammonium tungstate, tungsten hexachloride, tantalum pentachloride, hafnium chloride, sulfuric acid And the like can be given Funiumu.

  As described above, the metal element-containing compound used in the production method of the present invention may be an inorganic metal element-containing compound in which carbon is not contained in the compound, or carbon is contained in the compound. It may be an organometallic element-containing compound. As examples of organometallic compounds not exemplified above, titanium diisopropoxybis (acetylacetonate) and titanium chelating agents are also suitable. Hereinafter, the inorganic metal element-containing compound and the organic metal-containing compound may be collectively referred to as “metal element-containing compound”.

In addition, when the metal oxide contained in the binder material is an undoped metal oxide and exhibits a lithium ion insertion / extraction in the electrode active material layer, the metal element contains Examples of the compound include a combination of a lithium element-containing compound and one or more metal element-containing compounds containing any metal element selected from cobalt, nickel, manganese, iron or titanium. However, it is not limited to these.
Examples of the metal element-containing compound include chloride, nitrate, sulfate, perchlorate, acetate, phosphate, bromate, carbonate, etc. of other metal elements such as lithium element or cobalt. it can. Among these, chlorides, nitrates, and acetates can be suitably used because they are easily available as general-purpose products. In particular, nitrates are better used because they have good film-forming properties for various current collectors. Can do.

Hereinafter, the metal oxide on the current _collector, describes _{LiCoO 2, LiNiO 2, LiMn 2} O 4, LiFeO 2, Li 4 Ti 5 O 12 a metal element-containing compound to form, respectively.

For example, as a metal element-containing compound for generating LiCoO ₂ as a metal oxide on a current collector, a Li element-containing compound and a Co element-containing compound can be used in combination as main raw materials, and further necessary Depending on the case, other raw materials may be used in combination with the main raw material. Examples of the Li element-containing compound include lithium citrate tetrahydrate, lithium perchlorate trihydrate, lithium acetate dihydrate, lithium nitrate, and lithium phosphate. Examples of the contained compound include cobalt chloride (II) hexahydrate, cobalt (II) formate dihydrate, cobalt (III) acetylacetonate, cobalt (II) acetylacetonate dihydrate, cobalt acetate ( II) Tetrahydrate, Cobalt Oxalate (II) Dihydrate, Cobalt (II) Nitrate Hexahydrate, Cobalt (II) Ammonium Hexahydrate, Cobalt (III) Sodium Nitrate, and Cobalt Sulfate (II) The heptahydrate etc. are mentioned. 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.

Further, for example, as a metal element-containing compound for generating LiNiO ₂ as a metal oxide on a current collector, a Li element-containing compound and a Ni element-containing compound can be used in combination as main raw materials, If necessary, other raw materials can be used in combination with the main raw material. 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 chloride (II) hexahydrate and nickel acetate (II) tetrahydrate. , Nickel perchlorate (II) hexahydrate, nickel (II) bromide trihydrate, nickel (II) nitrate hexahydrate, nickel (II) acetylacetonate dihydrate, hypophosphorous acid Examples thereof include nickel (II) acid 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.

For example, as a metal element-containing compound for producing LiMn ₂ O ₄ as a metal oxide on a current collector, a Li element-containing compound and a Mn element-containing compound can be used in combination as main raw materials, If necessary, other raw materials can be used in combination with the main raw material. Examples of the Li element-containing compound are the same as in the case of producing LiCoO ₂ described above, and examples of the Mn element-containing compound include manganese acetate (III) dihydrate and manganese nitrate (II) 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.

For example, as a metal element-containing compound for generating LiFeO ₂ as a metal oxide on a current collector, a Li element-containing compound and a Fe element-containing compound can be used in combination as main raw materials, and further, if necessary Accordingly, other raw materials can be used in combination with the main raw material. 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 chloride (II) 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.

For example, as a metal element-containing compound for producing Li ₄ Ti ₅ O ₁₂ as a metal oxide on a current collector, a Li element-containing compound and a Ti element-containing compound can be used in combination as main raw materials, Furthermore, other raw materials can be used in combination with the main raw material 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 ≦ It is more preferable that X ≦ 1.

  In the electrode active material layer forming liquid described above, the total ratio of one or more metal element-containing compounds added in the solvent is preferably 0.01 to 5 mol / L, ˜2 mol / L is more preferred. When the concentration is 0.01 mol / L or more, the current collector and the electrode active material layer generated on the surface of the current collector are satisfactorily adhered, and the active material particles are fixed. Further, when the concentration is 5 mol / L or less, the electrode active material layer forming liquid can maintain a good viscosity enough to be applied to the current collector surface, and a uniform coating film is formed. Is done.

Next, a case where a metal oxide doped with one or more elements selected from a metalloid element and a typical metal element is described as the metal oxide contained in the binder.
In the case of forming a metal oxide doped with one or more elements selected from a semi-metal element and a typical metal element, a metal element to be further doped in the electrode active material forming liquid described above What is necessary is just to dissolve the metal element-containing compound for doping containing. In particular,
The metal oxide contained in the binder is a metal oxide capable of inserting and releasing lithium ions, and is doped with one or more elements selected from a semi-metal element and a typical metal element In the case of forming an oxide, for example, a lithium element-containing compound and one or more metal element-containing compounds containing any metal element selected from cobalt, nickel, manganese, iron, or titanium An electrode active material forming liquid can be prepared by dissolving a combination and a suitable metal element-containing compound for doping in a solvent and further containing active material particles and the like.

In the metal oxide contained in the binder, when it is desired to replace a part of the metal element other than alkali metal such as lithium with aluminum, aluminum nitrate, aluminum chloride or the like may be used as the metal element-containing compound for doping. it can.
Similarly, when it is desired to replace boron with a part of a metal element other than an alkali metal such as lithium, boric acid or the like is used, and with a part of a metal element other than an alkali metal such as lithium and magnesium. If you want to replace it with magnesium acetate, magnesium nitrate, etc., or if you want to replace some of the metal elements other than alkali metals such as lithium with sodium, then use sodium chloride, or alkali metals such as lithium. If you want to replace part of the metal element other than silicon with silicon, use silicic acid, and if you want to replace part of the metal element other than alkali metal such as lithium with phosphorus, use phosphoric acid. If you want to replace tin with some of the metal elements other than alkali metals such as lithium, use tin acetate, tin chloride, etc. When it is desired to replace a portion of calcium metal elements other than alkali metals can be used calcium chloride, calcium nitrate, calcium carbonate or the like, as doping metal element-containing compound. The compounding amount of the metal element-containing compound for doping may be appropriately determined in consideration of the substitution ratio of the metal element in the doped metal oxide to be formed.

(3) Other additives In addition to the above-mentioned active material particles and metal element-containing compound, the electrode active material layer forming liquid contains other materials as long as the conductive material or the effect of the electrode plate of the present invention is not impaired. These additives may be added. As the conductive material and other additives, the same materials as described in the description of the electrode active material layer of the electrode plate of the present invention can be used. When the conductive material is added to the electrode active material layer forming liquid, the active material particles generated on the current collector surface, or the active material particles and the total amount of metal oxides scheduled to be formed are 100 parts by weight. In addition, the addition amount of the conductive material is desirably 5 to 20 parts by weight. The description of 20 parts by weight is not intended to exclude the addition of the conductive material in excess of 20 parts by weight.

  It should be noted that the electrode active material layer in the electrode plate of the present invention does not prohibit impregnation with a resin material, particularly a resin binder, in addition to a binder containing a metal oxide. . Therefore, the step of impregnating the electrode active material layer with a resin material such as a resin binder may be further added after the electrode active material layer forming step described later, or in the electrode active material layer forming liquid. A resin material that can remain in the electrode active material layer may be added in advance.

(4) Solvent The solvent used for preparing the electrode active material layer forming liquid is not particularly limited. The following lower alcohols, diketones such as acetylacetone, diacetyl, and benzoylacetone, ketoesters such as ethyl acetoacetate, ethyl pyruvate, ethyl benzoylacetate, and ethyl benzoylformate, toluene, and mixed solvents thereof can be exemplified.
The electrode active material layer forming liquid requires active material particles, metal oxides, or other additives such as a conductive material, if necessary, in the electrode active material layer to be formed on the current collector. These compounding amounts are determined in consideration of being included in the amounts. At that time, the ratio of the materials contained in the electrode active material layer forming liquid (that is, the active material particles, the metal element-containing compound, the metal element-containing compound for doping dissolved as necessary, and any additive) is applied. It adjusts suitably in consideration of the applicability | paintability on a collector in a process, and the removal of the solvent in an electrode active material layer formation process. Generally, when the electrode active material layer forming liquid is 100% by weight, the total amount of solutes contained is adjusted to be 30 to 70% by weight. Next, the electrode active material layer forming liquid prepared as described above is applied onto a current collector to form a coating film. The current collector used in the method for producing the electrode plate is the current collector described in the “electrode plate I of the present invention” in the first aspect and the “electrode plate II of the present invention” in the second aspect. It is the same.

(5) Coating process In the coating process in the manufacturing method of this electrode plate, a well-known coating method can be suitably selected and implemented as a solution coating method. For example, the electrode active material layer forming liquid can be applied to any region of the current collector surface to form a coating film by printing, spin coating, dip coating, bar coating, spray coating, or the like. In addition, when the current collector surface is porous, has a large number of irregularities, or has a three-dimensional structure, the coating method is other than the above method, for example, a manual coating method. Is also possible. Note that the current collector used in the method for manufacturing the electrode plate can further improve the film forming property of the electrode active material layer by performing corona treatment, oxygen plasma treatment or the like in advance as necessary. preferable.

  The amount of the electrode active material layer forming liquid applied to the current collector can be arbitrarily determined according to the application of the electrode plate to be produced. Since the electrode active material layer in the manufacturing method of the electrode plate can be formed very thin as described above, when it is desired to reduce the thickness, the final electrode active material layer has a thickness of 300 nm to 150 μm. In particular, it may be applied thinly so as to be about 500 nm to 100 μm. As described above, a coating film for forming an electrode active material layer containing a metal element-containing compound that is a precursor of a metal oxide that is a binder is formed by applying an electrode layer forming solution to a substrate. The

  A pressing step may be further performed between the coating step and the electrode active material layer forming step or after the electrode active material layer forming step. The said press process can be implemented by drying the said coating film for electrode active material layer formation formed on the electrical power collector as needed, removing a solvent, and pressing it after that. Therefore, when performing an electrode active material layer formation process after a press process, a part or all of the solvent in a coating film may be removed beforehand before this electrode active material layer formation process. The pressing method can be carried out in the same manner as the press performed by applying a slurry-like electrode active material layer forming liquid containing a conventional resin binder on the current collector and drying it. However, it is not limited to this. Thus, the manufacturing method of this electrode plate can adjust the porosity of the electrode active material layer in the electrode plate finally manufactured by implementing a press process, and can also increase the energy density per volume. it can.

(6) Electrode active material layer formation process Next, about the electrode active material layer formation process for forming an electrode active material layer from the coating film formed in the said application | coating process, the heating process which heats this coating film is made into an example. explain. The heating step is performed for the purpose of thermally decomposing and oxidizing the metal element-containing compound present in the coating film, and removing the solvent contained in the coating film (but before the heating step). When carrying out the pressing step, the solvent is substantially removed beforehand by drying before pressing). When the metal element-containing compound for doping is dissolved in the electrode active material layer forming liquid, attention should be paid to the setting of the heating temperature so that the metal element-containing compound for doping is also thermally decomposed.
The heating method is not particularly limited as long as it is a heating method or a heating apparatus capable of heating the coating film at a heating temperature described later, and can be appropriately selected and carried out. Specific examples include a method of using a hot plate, an oven, a heating furnace, an infrared heater, a halogen heater, a hot air blower, or the like, or a combination of two or more. When the current collector to be used is planar, it is preferable to use a hot plate or the like for the heating step. In addition, when heating using a hot plate, it is preferable to install and heat the coating film surface side in a direction not in contact with the hot plate surface. The heating temperature varies depending on the type of the metal element-containing compound used. However, the metal element-containing compound is favorably thermally decomposed by heating the coating film in a temperature range of 150 ° C. to 800 ° C. An oxide is produced. It is understood that the metal oxide produced is a crystalline metal oxide when it exhibits insertion and desorption of alkali metal ions such as lithium.

  Here, generally, when producing a crystalline metal oxide, it is necessary to heat the coating film at a temperature of at least about 800 ° C. or higher. On the other hand, in the manufacturing method of the present electrode plate, the crystalline metal oxide is generated even at a low heating temperature of 700 ° C. or less, further 600 ° C. or less, particularly 400 ° C. or less. This is one of the characteristic points of the plate manufacturing method. Note that the crystalline metal oxide includes a microcrystalline state.

  The present inventors use the test liquid prepared in the same manner as the electrode active material layer forming liquid except that the electrode active material layer forming liquid and the active material particles are not included, to produce the electrode plate. Further research. That is, as the above test solution, a test solution containing a metal element-containing compound capable of producing a crystalline metal oxide exhibiting lithium ion insertion / release was prepared. Then, when the coating step and the heating step in the manufacturing method of the present electrode plate are carried out using the test solution, a crystalline metal oxide (hereinafter referred to as “metal oxide A”) exhibiting lithium ion insertion / release. ) Was generated. Similarly, by using an electrode active material layer-forming liquid containing active material particles, a crystalline metal oxide (hereinafter referred to as “battery” in this paragraph) that exhibits lithium ion insertion and desorption as a binding material is formed on a current collector. An electrode active material layer containing metal oxide B ”) was formed. Here, when the discharge capacities (μAh) of the metal oxide A and the metal oxide B were compared, it was found that the metal oxide B exhibits a discharge capacity superior to that of the metal oxide A. The discharge capacity (μAh) shown in the metal oxide B tends to be shown to a value very close to the theoretical value of the metal oxide B. The point that a metal oxide having such a high discharge capacity (that is, excellent crystallinity) can be produced at a heating temperature as low as 700 ° C. or less, further 600 ° C. or less, particularly 400 ° C. or less. This is a notable advantage of the method for producing the electrode plate.

The relationship between the heating temperature and the development of crystallinity of the metal oxide to be generated is estimated as follows. That is, since the active material particles are contained in the electrode active material layer forming liquid, the generated metal oxide follows the crystallinity of the active material particles, and is 700 ° C. or lower, further 600 ° C. In particular, it is presumed that lithium ion insertion / extraction is possible even at a heating temperature of 400 ° C. or less, and a highly crystalline metal oxide is obtained. In particular, when the chemical composition of the active material particles to be mixed with the generated metal oxide is the same, this follow-up action is assumed to be remarkable.
The heating step is carried out at a heating temperature of 400 ° C. or less, so that the selection range of the current collector is widened, and the electrode active material layer can be directly formed on various current collectors. Since cost merit is demonstrated from the point that temperature is low, it is preferable.
In addition, the heating temperature is preliminarily applied to a suitable substrate with a solution in which a metal element-containing compound to be used is dissolved and heated, and a film laminated on the substrate is scraped and used as a sample. By performing composition analysis and measuring the content ratio of the metal element and oxygen, it can be determined whether or not a metal oxide is formed. And when the metal oxide was produced | generated, it was confirmed that the used metal element containing compound was heated at the temperature more than thermal decomposition start temperature on a board | substrate. That is, in the method for producing the electrode plate, the “thermal decomposition start temperature of the metal element-containing compound” can be understood as a temperature at which the metal element-containing compound is decomposed by heating and the oxidation of the metal element starts.

  In the heating step, when determining the heating temperature, it is desirable to take into account the heat resistance of the current collector, active material particles, conductive material, and the like that are further used. For example, since the heat resistance of an aluminum foil generally used as a current collector for a positive electrode plate is around 660 ° C., the current collector may be damaged if the heating temperature exceeds 660 ° C. Therefore, the current collector, active material particles, and the like to be used may be determined in advance, and the metal element-containing compound may be selected from these heat resistance temperatures and thermal decomposition start temperatures in consideration of their heat resistance. That is, when an additive such as a conductive material is contained in the electrode active material layer forming liquid and the additive is to remain in the electrode active material to be formed, the additive It is preferable to select a temperature range below the heat resistant temperature. In addition, regarding the manufacturing method of this electrode plate, "heating temperature" means the highest temperature in a heating process. The heating mode in the heating step may be arbitrarily determined, for example, by gradually increasing the temperature, heating at a constant temperature, or heating at a stepped temperature.

  The electrode plate of the present invention may further contain a resin component in the electrode active material layer produced as described above. For example, the electrode active material layer may further contain a resin component by, for example, applying a resin mixed solution to the surface of the electrode active material layer or immersing an electrode plate in a resin mixed solution tank, A method of removing the solvent of the resin mixed solution impregnated in the electrode active material layer by allowing it to penetrate into the voids of the electrode active material layer and then drying it, and leaving only the resin component inside the electrode active material layer is mentioned. It is done. Thus, if it is the electrode plate of this invention which contains a resin component in an electrode active material layer, the bending tolerance of an electrode plate will improve by presence of a resin component, and it can improve a process characteristic. In particular, when the resin component is a conventionally used resin binder, the film adhesion of the electrode active material layer to the current collector can be further improved.

  Examples of resin materials contained in the resin mixture include conventional resin binders such as vinylidene fluoride resin (PVDF), styrene butadiene rubber (SBR), carboxymethoxycellulose (CMC), and the viscosity modifier. Although what can be selected can be selected, it is not limited to this. The resin material is appropriately selected to have a size that can penetrate into the voids in the electrode active material layer. Examples of the solvent for the resin mixture include lower alcohols having a total carbon number of 5 or less such as methanol, ethanol, isopropyl alcohol, propanol, and butanol, diketones such as acetylacetone, diacetyl, and benzoylacetone, ethyl acetoacetate, and pyrubin. Ketoesters such as ethyl acetate, ethyl benzoyl acetate, ethyl benzoylformate, pyrrolidones such as N-methylpyrrolidone (NMP), toluene, a mixed solvent thereof, water, and the like can be used. Can be mixed to prepare a resin mixed solution. The amount of the resin component contained in the electrode active material layer is desirably adjusted to such an extent that the input / output performance of the electrode plate is not deteriorated.

  In the manufacturing method of the electrode plate, when it is desired to form the electrode active material layer on both sides of the current collector, the coating step and the electrode active material layer forming step described above may be performed on both sides of the current collector. For example, the application step and the electrode active material layer formation step described above are performed on one side of the current collector to form an electrode active material layer, and then the application step and the electrode active material layer described above are performed on the other side. An electrode active material layer can be formed also on the back surface side by performing the forming step. Alternatively, the electrode active material layer may be formed on both sides of the current collector by performing the coating step sequentially or simultaneously on both sides of the current collector, and then simultaneously heating both sides of the current collector. it can.

[4] Non-aqueous electrolyte secondary battery (third embodiment)
The non-aqueous electrolyte secondary battery of the present invention (hereinafter also referred to as “secondary battery of the present invention”) includes at least a positive electrode plate, a negative electrode plate, and a separator provided between the positive electrode plate and the negative electrode plate. A non-aqueous electrolyte secondary battery comprising an electrolyte solution containing a non-aqueous solvent, wherein either one or both of the positive electrode plate and the negative electrode plate is the electrode plate of the present invention.
As illustrated in FIG. 4, the secondary battery of the present invention includes a positive electrode plate 50 in which an electrode active material layer 54 is provided on one surface side of a current collector 55 and one surface of the current collector 1 combined therewith. An electrode plate 10 provided with the electrode active material layer 2 on the side (that is, in FIG. 4, the electrode plate 10 is a negative electrode plate), and a separator 70 such as a polyethylene porous film is provided therebetween. It is done. These are housed in the outer casings 81 and 82 and sealed and manufactured in a state where the outer casings 81 and 82 are filled with the non-aqueous electrolyte 90, thereby forming the non-aqueous electrolyte secondary battery 100. The 4 is an illustration of the secondary battery of the present invention, and the secondary battery of the present invention is not limited to the non-aqueous electrolyte secondary battery shown in FIG.

(1) Electrode plate The nonaqueous electrolyte secondary battery of the present invention is characterized by using the above-described electrode plate for a nonaqueous electrolyte secondary battery of the present invention as at least one of a positive electrode plate and a negative electrode plate. In particular, conventionally, when the negative electrode plate is composed of a carbonaceous material, it has been common to add a large amount of conductive material to the positive electrode plate in order to increase the conductivity of the positive electrode plate accordingly. For this reason, the porosity of the positive electrode plate is lowered, and the permeability of the electrolytic solution is lowered, so that it is difficult to increase the output of the battery. However, since the electrode plate of the present invention is an electrode plate capable of high input / output, when this is used as a positive electrode plate, a large amount of conductive material is not used as in the prior art, or no conductive material is used at all. Good electrical conductivity and high input / output can be achieved.

Non-aqueous electrolyte secondary batteries do not insert and desorb lithium ions such as lithium metal and its alloys, tin, silicon, and their alloys as a negative electrode active material used for negative plates, not carbonaceous materials such as graphite. The aspect which comprises a negative electrode plate using the possible material is also included. In such a battery, a nonaqueous electrolyte secondary battery can be produced by positively using the electrode plate of the present invention as a negative electrode.
Moreover, a nonaqueous electrolyte secondary battery can also be comprised using the electrode plate of this invention for both a positive electrode plate and a negative electrode plate. In the nonaqueous electrolyte secondary battery of the present invention, when the electrode plate of the present invention is used in either the positive electrode plate or the negative electrode plate, the other electrode plate is used in the nonaqueous electrolyte secondary battery. The conventionally well-known electrode plate used can be used suitably.

  As a conventionally well-known positive electrode plate, in general, at least part of the current collector surface similar to the current collector used in the electrode plate of the present invention, positive electrode active material particles, conductive material, resin binder Although what was formed by apply | coating the positive electrode active material layer forming liquid to which etc. were added, drying, and pressing as needed may be used, it is not limited to this. On the other hand, as a conventionally known negative electrode plate, a copper foil such as an electrolytic copper foil or a rolled copper foil having a thickness of about 5 to 50 μm is used as a current collector, and a negative electrode active material layer is formed on at least a part of the current collector surface. Although what was formed by apply | coating a liquid, drying, and pressing as needed may be used, it is not limited to this. In the negative electrode active material layer forming liquid, generally active material particles containing carbonaceous material such as natural graphite, artificial graphite, amorphous carbon, carbon black, or those obtained by adding different elements to these components, or Active material particles including materials capable of inserting and removing lithium ions, such as metallic lithium and its alloys, tin, silicon, and alloys thereof, and other additions such as resin binders and conductive materials as required It is common for materials to be mixed.

(2) Non-aqueous electrolyte The non-aqueous electrolyte 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. A nonaqueous electrolytic solution in which 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 such as propylene carbonate and butylene carbonate, chain esters such as dimethyl carbonate and diethyl carbonate, cyclic ethers such as tetrahydrofuran and alkyltetrahydrofuran, and 1,2- Examples include, but are not limited to, chain ethers such as dimethoxyethane and 1,2-diethoxyethane.

(3) Structure of non-aqueous electrolyte secondary battery The structure of the non-aqueous electrolyte secondary battery of the present invention manufactured using the positive electrode plate, the negative electrode plate, the separator and the non-aqueous electrolyte solution is a conventionally known structure. It can be appropriately selected and employed. For example, the structure which winds a positive electrode plate and a negative electrode plate in the shape of a spiral via the separator like a polyethylene porous film, and accommodates in a battery container is mentioned. As another aspect, a structure may be employed in which a positive electrode plate and a negative electrode plate cut into a predetermined shape are stacked and fixed via a separator, and are accommodated in a battery container. In any structure of the positive electrode plate and the negative electrode plate, for example, after the positive electrode plate and the negative electrode plate 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, A non-aqueous electrolyte secondary battery is manufactured by connecting a lead wire attached to the negative electrode plate to a negative electrode terminal provided in the outer container, and further filling the battery container with a non-aqueous electrification solution and then sealing the battery container. be able to.

[5] Battery pack (fourth embodiment)
A battery pack according to a fourth aspect is a battery pack in which a non-aqueous electrolyte secondary battery having at least a positive electrode terminal and a negative electrode terminal and a protection circuit having overcharge and overdischarge protection functions are stored in a storage case. The non-aqueous electrolyte secondary battery comprises at least a positive electrode plate, a negative electrode plate, a separator provided between the positive electrode plate and the negative electrode plate, and an electrolyte containing a non-aqueous solvent. A battery is characterized in that either one or both of the positive electrode plate and the negative electrode plate is the electrode plate of the present invention.
The nonaqueous electrolyte secondary battery using the electrode plate of the present invention as a positive electrode plate and / or a negative electrode plate can be used as a so-called nonaqueous electrolyte secondary battery used in a battery pack. That is, the battery pack of the present invention uses the electrode plate of the present invention as a positive electrode plate and / or a negative electrode plate, and includes a nonaqueous electrolyte secondary battery including a positive electrode terminal and a negative electrode terminal, and a protection circuit having an overdischarge protection function. Are housed in a storage case. The battery pack of the present invention is equipped with a protection function for protecting the battery from, for example, overcharge, overdischarge, overcurrent, a short circuit of the battery peripheral circuit, a short circuit between the positive and negative electrodes, etc., in the nonaqueous electrolyte secondary battery itself. In addition, it may be a battery pack in which a protection circuit for preventing overcharge and overdischarge is housed and integrated in a storage case together with the non-aqueous electrolyte secondary battery. The battery pack of the present invention can be suitably used as a battery power supply device for a device that consumes a large amount of power relative to the scale of the device, such as a portable device such as a notebook computer, a camera, or a mobile phone.

  FIG. 5 shows a schematic exploded view of a battery pack 30 of the present invention using a lithium ion secondary battery 31 configured using the electrode plate of the present invention as one embodiment of the battery pack of the present invention. The battery pack 30 includes a lithium ion secondary battery 31 housed in a resin container 36a, a resin container 36b, and an end case 37. At this time, a protection circuit for preventing overcharge and overdischarge between one end face of the lithium ion secondary battery 31 and 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 protective circuit board 34 includes an external connection connector 35. The external connection connector 35 is inserted into an external connection window 38a provided in the resin container 36a and an external connection window 38b provided in the end case 37. Connected to an external terminal. The protection circuit board 34 includes a charge / discharge safety circuit (not shown) for controlling charge / discharge, a wiring circuit for connecting the external connection terminal and the lithium ion secondary battery 31, and the like. In addition, the battery pack 30 can employ | adopt the structure of a conventionally well-known battery pack suitably except using the lithium ion secondary battery 31 in which the electrode plate of this invention was used. Although not shown, the battery pack 30 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, an insulator, and the like between the lithium ion secondary battery 31 and the end case 37. , May be provided as appropriate.

  In addition, the non-aqueous electrolyte secondary battery of the present invention using the electrode plate of the present invention has functions such as overcurrent blocking and battery temperature monitoring in addition to the above-described protection circuit, in addition to the usage mode for battery packs. And the protection circuit may be used as an integrated and attached to the secondary battery itself. In this aspect, it 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 mentioned above are only illustrations, and do not limit use of the electrode plate of this invention or the nonaqueous electrolyte secondary battery of this invention at all.

[Example 1]
A positive electrode plate having a positive electrode active material layer formed on a positive electrode current collector was produced, and the positive electrode plate was evaluated.
(1) Production of positive electrode plate for nonaqueous electrolyte secondary battery A positive electrode active material layer forming liquid for forming an electrode active material layer in a positive electrode plate for a nonaqueous electrolyte secondary battery was prepared as follows.
As the metal element-containing compound _Firstly, Li and _{(CH 3 COO) · 2H 2} O to 1.6g, and 8.4g of _{Mn (NO 3) 2 · 6H} 2 O was added and mixed in water 50 g, methyl cellulose (Shin-Etsu 3 g of Chemical Industry Co., Ltd., trade name: 60SH4000), 40 g of LiAl _0.2 Mn _1.8 O ₄ particles as positive electrode active material particles, and acetylene black (manufactured by Denki Kagaku Kogyo Co., Ltd.) Product name: HS-100, particle diameter 48 nm) 5 g, vapor-phase synthetic carbon fiber (manufactured by Showa Denko KK, trade name: VGCF (registered trademark)) 0.5 g was added, and Excel Auto Homogenizer (Corporation) (Nippon Seiki Seisakusho) was stirred at 7000 rpm for 30 minutes to obtain a positive electrode active material layer forming liquid.

Next, an aluminum foil having a thickness of 15 μm as a positive electrode current collector was placed, and the positive electrode active material layer forming liquid was applied to one surface side of the positive electrode current collector with an applicator to form a coating film. Subsequently, it is pressed with a roll press, and the positive electrode current collector having the above-mentioned coating film is further taken from room temperature to 400 ° C. over 15 minutes using an electric furnace (muffle furnace, manufactured by Denken Co., Ltd., model: P90). The film was heated gradually to adjust the film thickness to 50 μm. In this manner, a positive electrode active material layer was formed on the positive electrode current collector to produce a positive electrode plate. The positive electrode plate was cut into a predetermined size (15 mmφ), and this was used as the positive electrode plate of Example 1.
In addition, the content (mg / 1.77 cm ² ) of active material particles per unit area in Example 1 was calculated from the amount of active material particles used and the like and shown in Table 3. In the examples and comparative examples, the heating atmosphere in the heating step was an atmospheric atmosphere unless otherwise specified. Confirmation that LiMn ₂ O _{4 as} a binding material was generated by the firing from the metal element-containing compound was not added separately to LiAl _0.2 Mn _1.8 O ₄ used for the positive electrode active material particles. A preliminary test for firing similar to the above was performed in the system, and it was confirmed by XRD measurement that LiMn ₂ O ₄ was formed.

(2) Evaluation of positive electrode plate The positive electrode active material layer formed on the positive electrode current collector was evaluated as follows. In addition, it is confirmed that the positive electrode plate of Example 1 is contained in the electrode plate I of this invention from Table 1 and Table 2 mentioned later. FIG. 6 shows a scanning electron micrograph (magnification 10,000 times) of the surface of the electrode active material layer of the positive electrode plate. From FIG. 6, a plurality of active material particles having an average particle diameter of 5 μm are dispersed. And a plurality of enclosures are formed in a state in which the metal oxide surrounds the plurality of nuclei, and the plurality of enclosures are formed by connecting a part of adjacent enclosures to each other. Or it is confirmed that the electrode plate II is included in the electrode plate II of the present invention from Table 1 and the like.

<1> Cyclic voltammetry test (CV test)
In order to confirm in advance whether or not the metal oxide, which is a binding material contained in the electrode active material layer in Example 1, exhibits lithium ion insertion / extraction, the following test was performed. That is, except that lithium manganate particles that are positive electrode active material particles are not used, a forming liquid is prepared in the same manner as the above positive electrode active material layer forming liquid used in Example 1, and this is used as in Example 1. A laminate was prepared as Reference Example 1. And the CV test was done using the above Reference Example 1. Specifically, the operation of first sweeping the electrode potential from 3.0 V to 4.3 V and then returning it to 3.0 V was repeated three times. The scanning speed was 1 mV / second. In the cyclic voltammogram showing the results of the second cycle, an oxidation peak corresponding to the Li elimination reaction of LiMn ₂ O ₄ was observed near 3.9 V, and a reduction peak corresponding to the Li insertion reaction was confirmed near 4.1 V. . This confirmed that the metal oxide contained in the electrode active material layer exhibits lithium ion insertion / extraction. The CV test was performed using VMP3 manufactured by Bio Logic.

<2> Adhesion test A test piece for measurement (width 15 mm, length 200 mm) was prepared from the positive electrode plate of Example 1 above, and a chuck-to-chuck distance of 150 mm, a test speed of 100 mm / min, and a 90-degree peeling method using Tensilon. The tensile strength was measured at The results are shown in Table 2.

<3> Evaluation of Film Formability In producing the positive electrode active material layer in Example 1, the positive electrode plate obtained above was processed to be rolled out into a disk shape of a predetermined size. In the processing operation, the positive electrode active material layer could be processed without problems such as peeling. From this, it was confirmed that the film forming property of the positive electrode active material layer was good. Also in the following examples and comparative examples, as described above, when the electrode plate can be pulled out into a disk shape without any defects, it is evaluated that the film forming property of the electrode active material layer is good. . On the other hand, part of the electrode active material layer is peeled off in the above-mentioned punching process, or the active material particles fall from the current collector, etc., and the processing is poor, and it is used as a working electrode of a tripolar coin cell to be described later In the case where a disk that can withstand the above is not formed, it is evaluated that the film forming property of the electrode active material layer is poor. The results are shown in Table 2.

<4> Production of tripolar coin cell To a mixed solvent of ethylene carbonate (EC) / dimethyl carbonate (DMC) (volume ratio = 1: 1), lithium hexafluorophosphate (LiPF ₆ ) is added as a solute, and the solute A non-aqueous electrolyte was prepared by adjusting the concentration so that the concentration of LiPF ₆ was 1 mol / L. Using the electrode plate of Example 1 as the working electrode plate as the positive electrode plate, the metal lithium plate as the counter electrode plate and the reference electrode plate, the non-aqueous electrolyte prepared above as the electrolytic solution, and the tripolar coin cell This was assembled as an example test cell 1. The example test cell 1 was subjected to the following charge / discharge test.

<5> Charge / Discharge Test In order to perform the charge / discharge test of the working electrode plate in the above-described example test cell 1, the example test cell 1 was first fully charged as in the following charge test.

<5-1> Charging test Example Test cell 1 was charged at a constant current (1124 μA) under a 25 ° C. environment until the voltage reached 4.3 V, and the voltage was 4.3 V (full charge voltage). ), The current (discharge rate: 1300μA, equivalent to about 1C) is reduced to 5% or less so that the voltage does not exceed 4.3V. And then rested 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. In addition, the constant current is a capacity that can be discharged in 1 hour (90 mAh / g in the case of lithium manganate in Example 1) in the working electrode plate in Example Test Cell 1 in 1 hour in this charge / discharge test. The current value is set to complete the discharge.

<5-2> Discharge test Thereafter, in the fully charged example test cell 1 in an environment of 25 ° C., the voltage was changed from 4.3 V (full charge voltage) to 3.0 V (discharge end voltage). Constant current discharge at a constant current (1300 μA) (discharge rate: equivalent to about 1 C), the cell voltage (V) on the vertical axis, the discharge time (h) on the horizontal axis, a discharge curve is created, and the positive electrode plate The discharge capacity (mAh) was determined and converted to the discharge capacity (mAh / g) per weight of the positive electrode plate. The calculated discharge capacity is shown as an electrode dose in Table 3. Based on the constant current discharge test performed at the constant current (1300 μA) (discharge rate: about 1 C, discharge end time: 1 hour) as described above, the constant current discharge was similarly performed at discharge rates 1 C and 10 C, respectively. A test was conducted. And DC resistance was measured as follows using the discharge capacity of the electrode plate for positive electrodes.

<5-3> DC Resistance Measurement The DC resistance value of Example 1 was calculated as follows using Example Test Cell 1 in accordance with the above description of DC resistance value measurement and Equation 2. That is, the voltage value (mV) 10 seconds after the start of discharge was measured in the case where the discharge test was performed using the example test cell 1 at two discharge rates (discharge rates 1C and 10C). The voltage value (V1) (mV) when the discharge test was performed under the condition of the discharge rate 1C, and the voltage value 10 seconds after the start of the discharge (when the discharge test was performed under the condition of the discharge rate 10C ( V10) (mV) was measured. Then, based on these measured values (V1, V10) and the constant current values (I1, I10) (mA) corresponding to the discharge rates 1C, 10C, the DC resistance value (Ω) is calculated by the above-described equation 2. did. The results are shown in Table 3.

<6> Content ratio of binder in electrode active material layer The ratio (% by weight) of the binder in the electrode active material layer was determined by calculation. Specifically, first, the theoretical value of the lithium metal oxide to be formed was calculated from the materials that generate the binding substance among the materials contained in the electrode active material layer forming liquid (that is, added). The weight (g) of the binding material was determined by the product of the molar amount of the Li source and the molecular weight of the binding material to be synthesized). Then, the calculated weight (g) of the binding material is the sum of the weight (g) of the added active material particles, the weight (g) of the binding material, and the weight (g) of the added conductive material. The ratio of the binding substance in the electrode active material layer was calculated. The results are shown in Table 2.

<7> Cycle characteristics A 1C1000 cycle characteristics test was performed as follows. In other words, the 1C 1000 cycle characteristic test was performed 1000 times with one charge and discharge as one cycle at the discharge rate 1C in the charge / discharge test described above. Then, the cycle characteristic evaluation was performed by dividing the discharge capacity after 1000 cycles (mAhr / g) by the discharge capacity after 1 cycle (mAhr / g) and multiplying by 100 to obtain the 1C1000 cycle discharge capacity maintenance ratio. Evaluated. The results are shown in Table 3.

[Examples 2 to 4]
Instead of 40 g of LiAl _0.2 Mn _1.8 O ₄ particles in Example 1 as positive electrode active material particles, 40 g of LiB _0.1 Mn _1.9 O ₄ particles and LiNa ₀ were used in Examples 2, 3, and 4, respectively. _.3 positive electrode plates of Examples 2, 3, and 4 in the same manner as described in Example 1 except that 40 g of Mn _1.7 O ₄ particles and 40 g of LiMg _0.1 Mn _1.7 O ₄ particles were used. Was made. Next, the obtained positive plates of Examples 2, 3, and 4 were evaluated in the same manner as in Example 1. It was confirmed that the positive plates of Examples 2, 3, and 4 were included in the electrode plate I of the present invention and the electrode plate II of the present invention, respectively, as described in Example 1.

[Example 5]
In Example 5, a metal oxide not showing lithium ion insertion / extraction was formed as a binder. That is, instead of “Li (CH ₃ COO) · 2H ₂ O and Mn (NO ₃ ) ₂ · 6H ₂ O” in Example 1 as a metal element-containing compound, “Y (NO ₃ ) ₃ · 6H ₂ O ”(5 g) was used, and a positive electrode plate of Example 5 was produced in the same manner as described in Example 1 except that the solvent and the added organic substance were changed to those shown in Table 1. It was confirmed that the positive electrode plate of Example 5 was included in the electrode plate I of the present invention and the electrode plate II of the present invention, respectively, as described in Example 1.

[Comparative Example 1]
Comparative Example as described in Example 1 except that 40 g of LiMn ₂ O ₄ particles were used instead of 40 g of LiAl _0.2 Mn _1.8 O ₄ particles in Example 1 as positive electrode active material particles. 1 positive electrode plate was produced.

[Examples 6 to 9]
Instead of “Li (CH ₃ COO) · 2H ₂ O 1.6 g and Mn (NO ₃ ) ₂ · 6H ₂ O 8.4 g” as the metal element-containing compound in Example 1, “Li (CH _{3 3} COO) · 2H ₂ O (10 g) and Co (NO ₃ ) ₂ · 6H ₂ O (29 g) ”as positive electrode active material particles in Example 1, 40 g of LiAl _0.2 Mn _1.8 O ₄ particles Instead, 40 g of LiSi _0.1 Co _0.9 O ₂ particles, 40 g of LiP _0.1 Co _0.9 O ₂ particles, 40 g of LiSn _0.1 Co _0.9 O ₂ particles, 40 g of LiCa _0.1 Co _0.9 O ₂ particles were used, respectively, and the heating conditions are shown in Table 1. Except having changed into the content shown, it carried out similarly to having described in the said Example 1, and produced the positive electrode plate of Examples 6, 7, 8, and 9. FIG. 7 shows a scanning electron micrograph (magnification 10,000 times) obtained by photographing the surface of the electrode active material layer of the positive electrode plate obtained in Example 6. In addition, it confirmed that the positive electrode plate of Examples 6-9 was contained in the electrode plate I of this invention and the electrode plate II of this invention similarly to having described in Example 1, respectively.

[Example 10]
A positive electrode plate was prepared by impregnating the electrode active material layer in the positive electrode plate of Example 1 with a resin binder as follows. That is, the positive electrode plate produced in the same manner as in Example 1 was immersed in a dipping tank filled with a resin mixed solution prepared as follows, and the resin mixed solution was sufficiently placed in the voids in the electrode active material layer of the positive electrode plate. Infiltrated. Thereafter, the positive electrode plate in which the resin mixed solution is immersed is taken out of the above-mentioned immersed layer, placed in an oven heated to 150 ° C. and dried for 15 minutes, and the liquid (hereinafter, NMP) contained in the resin mixed solution is removed. did. Thus, a positive electrode plate of Example 10 in which the resin binder remained in the electrode active material layer was produced. The resin mixed solution was prepared by using vinylidene fluoride resin (PVDF resin) as a resin material and mixing with N-methylpyrrolidone (NMP) so that the concentration of the PVDF resin was 0.1%. In addition, it was confirmed that the positive electrode plate of Example 10 was included in the electrode plate I of the present invention and the electrode plate II of the present invention in the same manner as described in Example 1.

[Example 11]
Using the negative electrode current collector, a negative electrode plate for a non-aqueous electrolyte secondary battery was formed as follows. First, 10 g of Li (CH ₃ COO) · 2H ₂ O, 71 g of (i-C ₃ H ₇ O) ₂ · Ti (C ₆ H ₁₄ O ₃ N) ₂ and 10 g of methanol as a metal element-containing compound In addition, 10 g of polyethylene oxide was mixed, and 40 g of Li ₄ Ti ₅ O ₁₂ particles were further mixed as negative electrode active material particles, and an Excel auto homogenizer (manufactured by Nippon Seiki Seisakusho Co., Ltd.) at a rotational speed of 7000 rpm. The negative electrode active material layer forming liquid was obtained by stirring for 30 minutes.

Next, an aluminum foil having a thickness of 15 μm as a negative electrode current collector was placed, and the negative electrode active material layer forming liquid was applied to one surface side of the negative electrode current collector with an applicator to form a coating film. Subsequently, it was pressed with a roll press machine, and the negative electrode current collector having the above coating film was further taken from room temperature to 550 ° C. for 15 minutes using an electric furnace (muffle furnace, manufactured by Denken Co., Ltd., model: P90). The film was heated gradually to adjust the film thickness to 50 μm. In this way, a negative electrode active material layer was formed on the negative electrode current collector to produce a negative electrode plate. The negative electrode plate was cut into a predetermined size (15 mmφ), and this was used as the negative electrode plate of Example 11.
From the amount of active material particles used and the like, the content (mg / 1.77 cm ² ) of active material particles per unit area in Example 11 was calculated and shown in Table 3.
The confirmation that Li ₄ Ti ₅ O _{12 as} a binding material was generated from the metal element-containing compound by the heating was performed separately in a system in which Li ₄ Ti ₅ O _{12 as} negative electrode active material particles was not added. A preliminary test for carrying out heating similar to the above was performed, and it was confirmed that Li ₄ Ti ₅ O ₁₂ was produced. As described in Example 1, the negative electrode plate of Example 11 was confirmed to be included in the electrode plate I of the present invention and the electrode plate II of the present invention.

[Examples 12 and 13]
A positive electrode plate was prepared in the same manner as in Example 1 except that the active material particles, metal element-containing compound, solvent, organic matter and heating conditions contained in the electrode active material layer forming liquid were changed to the contents shown in Table 1. This was designated as Example 12 and Example 13. Example 12 is a positive electrode plate made of a combination of undoped active material particles and a metal oxide (binding material) in which a part of manganese in lithium manganate is replaced with aluminum. Example 13 is a positive electrode plate in which both the active material particles and the metal oxide (binding material) are formed of a metal oxide in which a part of manganese in lithium manganate is replaced with aluminum. As described in Example 1, the positive plates of Examples 12 and 13 were confirmed to be included in the electrode plate I of the present invention and the electrode plate II of the present invention.

[Comparative Example 2]
Instead of “Li (CH ₃ COO) · 2H ₂ O 1.6 g and Mn (NO ₃ ) ₂ · 6H ₂ O 8.4 g” as the metal element-containing compound in Example 1, “Li (CH _{3 3} COO) · 2H ₂ O (10 g) and Co (NO ₃ ) ₂ · 6H ₂ O (29 g) ”as positive electrode active material particles in Example 1, 40 g of LiAl _0.2 Mn _1.8 O ₄ particles Instead, a positive electrode plate of Comparative Example 2 was produced in the same manner as described in Example 1 except that 40 g of LiCoO ₂ particles were used and gradually heated to 500 ° C. over 15 minutes. That is, Comparative Example 2 is a combination in which both the active material particles and the metal oxide (binder material) to be formed are not doped.

[Comparative Example 3]
NMP (46 g), 4 g of vinylidene fluoride resin as a resin binder, 40 g of LiAl _0.2 Mn _1.8 O ₄ particles as positive electrode active material particles, and acetylene black (Electrochemical Industry Co., Ltd.) as a conductive material Product name: HS-100, particle size 48 nm) 5 g, gas phase method synthetic carbon fiber (Showa Denko Co., Ltd., trade name: VGCF (registered trademark)) 0.5 g, added, dispersed, solid The slurry was dispersed and / or kneaded so as to have a partial concentration of 55% by weight to obtain a slurry-like positive electrode active material layer forming liquid.

  The positive electrode active material layer-forming liquid prepared above was applied onto a 15 μm-thick aluminum foil serving as a positive electrode current collector so that the film thickness after drying was 50 μm. Drying was performed in an air atmosphere to form a positive electrode active material layer. After pressing at 4 KN using a roll press machine, it was cut into a predetermined size (15φ) and vacuum-dried at 140 ° C. for 5 minutes to produce a positive electrode plate.

[Comparative Example 4]
A positive electrode plate was prepared in the same manner as in Comparative Example 3 except that the positive electrode active material particles used were LiMn ₂ O ₄ particles 40 g instead of LiAl _0.2 Mn _1.8 O ₄ particles 40 g. It was set as Comparative Example 4.

[Example 14]
A positive electrode plate was prepared in the same manner as in Example 6. And Example 6 was immersed in the immersion tank with which the resin liquid mixture prepared as follows was filled, and the said resin liquid mixture was fully osmose | permeated in the space | gap in the electrode active material layer of Example 6. FIG. Then, Example 6 was taken out from the said immersion layer, and it set in the oven heated at 150 degreeC, it was made to dry for 15 minutes, and the solvent of the resin liquid mixture was removed. Thus, a positive electrode plate in which the resin binder remained in the electrode active material layer was prepared, and this was used as Example 14. The resin mixed solution was prepared by using PVDF resin as a resin material and mixing it with an NMP solvent so that the concentration of PVDF was 0.1%.

[Example 15]
In Example 15, a metal oxide which does not show insertion / extraction of lithium ions as a binding material and was doped with aluminum was formed. That is, “Al (NO ₃ ) ₃ · 9H ₂ O” (0.5 g) was used as the metal element-containing compound in addition to “Y (NO ₃ ) ₃ · 6H ₂ O” (5 g) in Example 5. A positive electrode plate was produced in the same manner as described in Example 5 except that this was designated as Example 15. It was confirmed that the positive electrode plate of Example 15 was included in the electrode plate I of the present invention and the electrode plate II of the present invention, respectively, as described in Example 1.

  In each of Examples 1 to 5, 10, 12, 13, and 15, an improvement in adhesion was confirmed in the adhesion test with respect to Comparative Example 1 as a target. Moreover, as for Example 6-8, 14, the improvement of adhesiveness was confirmed in the adhesiveness test with respect to the comparative example 2 used as object. Also, high adhesion was confirmed for Example 11, which is an example of the negative electrode plate.

  In particular, the difference between Examples 12 and 13 and Comparative Example 1 is that Examples 12 and 13 are positive electrode active material particles and / or lithium manganate, which is a formed binding material, doped with aluminum. On the other hand, Comparative Example 1 is only that the positive electrode active material particles and / or the lithium manganate that is the formed binding material is not doped at all. However, due to this difference, it was confirmed that the adhesion test results changed greatly. On the other hand, in Comparative Examples 3 and 4 using PVDF, there is a difference in using active material particles in which lithium manganate is doped with aluminum in Comparative Example 3 and using active material particles containing lithium manganate that is not doped in Comparative Example 4. However, the adhesion shown was almost equivalent. From the results described above, a compound doped with one or more elements selected from metalloid elements and typical metal elements is used for the binding material formed from active material particles and / or metal oxides. It was speculated that the effect of improving the adhesiveness was not observed in the conventional electrode plate made only of the resin binder. That is, it is speculated that the effect of improving the adhesion by using the above-described doped compound is an excellent effect significantly shown in the electrode plate containing the binder formed by the metal oxide. It was done.

  Moreover, it was shown that Examples 1-15 are excellent also in the input / output characteristic and cycling characteristics.

1, 1 ′, 1 ″ current collector 2, 2 ′ electrode active material layer 3 current collecting base material 4 conductive layer 5 intermittent layer 6 core 7 envelope 8 voids 10, 20, 20 ′ non-aqueous electrolyte 2 Secondary battery electrode plate 20 ″, 20 ′ ″ Nonaqueous electrolyte secondary battery electrode plate 30 Battery pack 31 Lithium ion secondary battery 32 Positive electrode terminal 33 Negative electrode terminal 34 Protective circuit board 35 External connector 36a, 36b Resin Container 37 End case 38a, 38b External connection window 50 Nonaqueous electrolyte secondary battery electrode plate (positive electrode plate)
54 Electrode active material layer 55 Current collector 70 Separator 81, 82 Exterior 90 Non-aqueous electrolyte 100 Lithium ion secondary battery 101, 102, 103, 103 'Surface

The gist of the present invention is the invention described in the following (1) to (15).
(1) 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 formed including an active material particle containing a metal oxide exhibiting alkali metal ion insertion and desorption, and a binder containing a metal oxide,
The active material particles are doped with one or more elements selected from metalloid elements and typical metal elements ,
Metal oxide contained in the binder material, characterized in der Rukoto alkali metal ion intercalation and deintercalation possible metal oxide, a non-aqueous electrolyte secondary battery electrode plate (hereinafter, referred to as the first aspect Sometimes).
(2) The metal oxide contained in the binder is doped with one or more elements selected from a semi-metal element and a typical metal element. The electrode plate for nonaqueous electrolyte secondary batteries as described.
(3) 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 is formed including an active material particle containing a metal oxide exhibiting alkali metal ion insertion and desorption, and a binder containing a metal oxide,
The metal oxide contained in the binder is doped with one or more elements selected from metalloid elements and typical metal elements ,
Metal oxide contained in the binder material, characterized in der Rukoto alkali metal ion intercalation and deintercalation possible metal oxide, a non-aqueous electrolyte secondary battery electrode plate.
(4) The non-aqueous electrolyte according to (3), wherein the active material particles are doped with one or more elements selected from a metalloid element and a typical metal element. Secondary battery electrode plate.
( 5 ) One type selected from the group consisting of Al, B, Si, P, Na, Mg, Ca, and Sn, wherein one or more elements selected from the above metalloid elements and typical metal elements are used. Alternatively, the electrode plate for a non-aqueous electrolyte secondary battery according to any one of (1) to ( 4 ), wherein the electrode plate is a combination of two or more.
( 6 ) The electrode active material layer is characterized in that the active material particles are fixed to each other by the binding material, and the active material particles are fixed to the current collector by the binding material. The electrode plate for a non-aqueous electrolyte secondary battery according to any one of (1) to ( 5 ) above.
( 7 ) The electrode for a nonaqueous electrolyte secondary battery according to any one of (1) to ( 6 ), wherein the binder material covers at least a part of the surface of the active material particles. Board.

( 8 ) 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,
In the electrode active material layer, a metal in which a plurality of nuclei are formed in a state where active material particles containing a metal oxide exhibiting alkali metal ion insertion / release are dispersed and the plurality of nuclei are surrounded Comprising a plurality of enclosures comprising oxides;
The plurality of enclosures are connected to each other in a part of adjacent enclosures, or continuous without distinction,
The enclosure in the vicinity of the current collector is connected to the current collector surface,
The active material particles as the core are doped with one or more elements selected from metalloid elements and typical metal elements ,
Metal oxide contained in the enclosure is an alkali metal ion intercalation and deintercalation metal oxide capable der Rukoto non-aqueous electrolyte secondary battery electrode plate, wherein (hereinafter, may be referred to as the second aspect is there).
(9) the metal oxide contained in the enclosure, characterized in that it is doped with one or more elements selected from semi-metallic elements and typical metal elements, according to the above (8) Electrode plate for non-aqueous electrolyte secondary battery.
( 10 ) 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,
In the electrode active material layer, a plurality of nuclei are formed in a state where active material particles containing a metal oxide exhibiting insertion and desorption of alkali metal ions are dispersed, and the metal oxide is in a state of surrounding the plurality of nuclei A plurality of enclosures containing objects,
The plurality of enclosures are connected to each other in a part of adjacent enclosures, or continuous without distinction,
The enclosure in the vicinity of the current collector is connected to the current collector surface,
The metal oxide contained in the enclosure is doped with one or more elements selected from metalloid elements and typical metal elements ,
Metal oxide contained in the enclosure is an alkali metal ion intercalation and deintercalation metal oxide capable der Rukoto non-aqueous electrolyte secondary battery electrode plate according to claim.
( 11 ) The active material particles as the core are doped with one or more elements selected from a semi-metal element and a typical metal element, as described in ( 10 ) above Electrode plate for non-aqueous electrolyte secondary battery.
( 12 ) There is a region where the crystal structure of the nucleus and the crystal structure of the envelope are discontinuously joined at the interface between the nucleus and the envelope surrounding the nucleus. The electrode plate for a non-aqueous electrolyte secondary battery according to any one of ( 8 ) to ( 11 ) above,
( 13 ) One or two or more elements selected from Al, B, Si, P, Na, Mg, Ca, and Sn selected from the above-mentioned metalloid elements and typical metal elements The electrode plate for a nonaqueous electrolyte secondary battery according to any one of ( 8 ) to ( 12 ) above, which is as described above.

( 14 ) A nonaqueous electrolyte secondary battery comprising at least a positive electrode plate, a negative electrode plate, a separator provided between the positive electrode plate and the negative electrode plate, and an electrolyte containing a nonaqueous solvent,
Either the positive electrode plate or the negative electrode plate, or both are the electrode plates for a non-aqueous electrolyte secondary battery according to any one of (1) to ( 13 ). Secondary battery (hereinafter sometimes referred to as a third embodiment).
( 15 ) In a battery pack in which a nonaqueous electrolyte secondary battery having at least a positive electrode terminal and a negative electrode terminal and a protection circuit having an overcharge and overdischarge protection function are stored in a storage case, the nonaqueous electrolyte solution The secondary battery is a non-aqueous electrolyte secondary battery comprising at least a positive electrode plate, a negative electrode plate, a separator provided between the positive electrode plate and the negative electrode plate, and an electrolyte solution containing a non-aqueous solvent,
Either one of the positive electrode plate or the negative electrode plate, or both, is the electrode plate for a nonaqueous electrolyte secondary battery according to any one of (1) to ( 13 ). Hereinafter, it may be referred to as a fourth aspect).

The metal oxide contained in the binding substance in the electrode plate I of the present invention is (aspect b) an undoped metal oxide capable of inserting and releasing alkali metal ions such as lithium, (aspect d) Alkali metal ions such as lithium can be inserted and desorbed, and can be classified into two modes : doped metal oxides. Which mode should be selected for the binding material may be appropriately determined in consideration of the specific implementation of the electrode plate (Ii) or the electrode plate (I-ii). In the following, for reference, (aspect a) does not show insertion / extraction of alkali metal ions such as lithium and undoped metal oxide, (aspect c) does not show alkali metal desorption / desorption such as lithium, The description also includes a doped metal oxide.

[ Reference Example 5]
In Reference Example 5, a metal oxide showing no lithium ion insertion / extraction was formed as a binder. That is, instead of “Li (CH ₃ COO) · 2H ₂ O and Mn (NO ₃ ) ₂ · 6H ₂ O” in Example 1 as a metal element-containing compound, “Y (NO ₃ ) ₃ · 6H ₂ A positive electrode plate of Reference Example 5 was produced in the same manner as described in Example 1 except that O ”(5 g) was used and the solvent and the added organic substance were changed to those shown in Table 1. It was confirmed that the positive electrode plate of Reference Example 5 was included in the electrode plate I of the present invention and the electrode plate II of the present invention, respectively, as described in Example 1.

[ Reference Example 11]
Using the negative electrode current collector, a negative electrode plate for a non-aqueous electrolyte secondary battery was formed as follows. First, 10 g of Li (CH ₃ COO) · 2H ₂ O, 71 g of (i-C ₃ H ₇ O) ₂ · Ti (C ₆ H ₁₄ O ₃ N) ₂ and 10 g of methanol as a metal element-containing compound In addition, 10 g of polyethylene oxide was mixed, and 40 g of Li ₄ Ti ₅ O ₁₂ particles were further mixed as negative electrode active material particles, and an Excel auto homogenizer (manufactured by Nippon Seiki Seisakusho Co., Ltd.) at a rotational speed of 7000 rpm. The negative electrode active material layer forming liquid was obtained by stirring for 30 minutes.

Next, an aluminum foil having a thickness of 15 μm as a negative electrode current collector was placed, and the negative electrode active material layer forming liquid was applied to one surface side of the negative electrode current collector with an applicator to form a coating film. Subsequently, it was pressed with a roll press machine, and the negative electrode current collector having the above coating film was further taken from room temperature to 550 ° C. for 15 minutes using an electric furnace (muffle furnace, manufactured by Denken Co., Ltd., model: P90). The film was heated gradually to adjust the film thickness to 50 μm. In this way, a negative electrode active material layer was formed on the negative electrode current collector to produce a negative electrode plate. The negative electrode plate was cut into a predetermined size (15 mmφ), and this was used as the negative electrode plate of Reference Example 11.
The content (mg / 1.77 cm ² ) of active material particles per unit area in Reference Example 11 was calculated from the amount of active material particles used and the like and shown in Table 3.
The confirmation that Li ₄ Ti ₅ O _{12 as} a binding material was generated from the metal element-containing compound by the heating was performed separately in a system in which Li ₄ Ti ₅ O _{12 as} negative electrode active material particles was not added. A preliminary test for carrying out heating similar to the above was performed, and it was confirmed that Li ₄ Ti ₅ O ₁₂ was produced. As described in Example 1, the negative electrode plate of Reference Example 11 was confirmed to be included in the electrode plate I of the present invention and the electrode plate II of the present invention.

[ Reference Example 15]
Reference Example 15 was a metal oxide that did not show insertion / extraction of lithium ions as a binder, and a metal oxide doped with aluminum was formed. That is, “Al (NO ₃ ) ₃ · 9H ₂ O” (0.5 g) was used as the metal element-containing compound in addition to “Y (NO ₃ ) ₃ · 6H ₂ O” (5 g) in Example 5. A positive electrode plate was prepared in the same manner as described in Reference Example 5 except that this was referred to as Reference Example 15. It was confirmed that the positive electrode plate of Reference Example 15 was included in the electrode plate I of the present invention and the electrode plate II of the present invention, respectively, as described in Example 1.

In each of Examples 1 to 4 , 10, 12, and 13 , an improvement in adhesion was confirmed in the adhesion test with respect to Comparative Example 1 as a target. Moreover, as for Example 6-8, 14, the improvement of adhesiveness was confirmed in the adhesiveness test with respect to the comparative example 2 used as object.

Moreover, it was shown that Examples 1-4 , 6-10 , and 12-14 are excellent also in input-output characteristics and cycling characteristics.

Claims (17)

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 is formed including active material particles exhibiting alkali metal ion insertion and desorption, and a binder containing a metal oxide,
An electrode plate for a non-aqueous electrolyte secondary battery, wherein the active material particles are doped with one or more elements selected from metalloid elements and typical metal elements.   2. The non-aqueous solution according to claim 1, wherein the metal oxide contained in the binding material is doped with one or more elements selected from a metalloid element and a typical metal element. Electrode plate for electrolyte secondary battery. 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 is formed including active material particles exhibiting alkali metal ion insertion and desorption, and a binder containing a metal oxide,
The electrode for a non-aqueous electrolyte secondary battery, wherein the metal oxide contained in the binder material is doped with one or more elements selected from metalloid elements and typical metal elements Board.   4. The non-aqueous electrolyte secondary battery according to claim 3, wherein the active material particles are doped with one or more elements selected from metalloid elements and typical metal elements. 5. Electrode plate.   5. The non-aqueous electrolyte secondary battery according to claim 1, wherein the metal oxide contained in the binder is a metal oxide capable of inserting and releasing alkali metal ions. Electrode plate.   One or more elements selected from the metalloid element and the typical metal element are selected from the group consisting of Al, B, Si, P, Na, Mg, Ca, and Sn. It is the above, The electrode plate for nonaqueous electrolyte secondary batteries in any one of Claim 1 to 5 characterized by the above-mentioned.   The electrode active material layer is characterized in that the active material particles are fixed to each other by the binding material, and the active material particles are fixed to the current collector by the binding material. Item 7. The electrode plate for a non-aqueous electrolyte secondary battery according to any one of Items 1 to 6.   The electrode plate for a non-aqueous electrolyte secondary battery according to claim 1, wherein the binder material covers at least a part of the surface of the active material particles. 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,
In the electrode active material layer, a plurality of nuclei are formed in a state where active material particles exhibiting alkali metal ion insertion / release are dispersed, and a plurality of metal oxides including a metal oxide are surrounded by the nuclei With an enclosure of
The plurality of enclosures are connected to each other part of adjacent enclosures, or are continuous without distinction,
The enclosure in the vicinity of the current collector is connected to the current collector surface,
An electrode plate for a non-aqueous electrolyte secondary battery, wherein the active material particles as the core are doped with one or more elements selected from a metalloid element and a typical metal element.   The non-aqueous electrolysis according to claim 9, wherein the metal oxide contained in the enclosure is doped with one or more elements selected from a metalloid element and a typical metal element. Electrode plate for liquid secondary battery. 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,
In the electrode active material layer, a plurality of nuclei are formed in a state in which active material particles exhibiting alkali metal ion insertion and desorption are dispersed, and a plurality of metal oxides including a metal oxide are surrounded. With an enclosure,
The plurality of enclosures are connected to each other part of adjacent enclosures, or are continuous without distinction,
The enclosure in the vicinity of the current collector is connected to the current collector surface,
The electrode plate for a non-aqueous electrolyte secondary battery, wherein the metal oxide contained in the enclosure is doped with one or more elements selected from a metalloid element and a typical metal element.   The non-aqueous electrolyte according to claim 11, wherein the active material particles as the core are doped with one or more elements selected from a metalloid element and a typical metal element. Secondary battery electrode plate.   The electrode plate for a nonaqueous electrolyte secondary battery according to any one of claims 9 to 12, wherein the metal oxide contained in the enclosure is a metal oxide capable of inserting and releasing alkali metal ions. .   There is a region where the crystal structure of the nucleus and the crystal structure of the envelope are discontinuously joined at the interface between the nucleus and the envelope surrounding the nucleus. The electrode plate for a non-aqueous electrolyte secondary battery according to claim 9, wherein the electrode plate is a non-aqueous electrolyte secondary battery.   One or more elements selected from the metalloid elements and typical metal elements are one or more elements selected from Al, B, Si, P, Na, Mg, Ca, and Sn. The electrode plate for a non-aqueous electrolyte secondary battery according to claim 9, wherein the electrode plate is a non-aqueous electrolyte secondary battery. A non-aqueous electrolyte secondary battery comprising at least a positive electrode plate, a negative electrode plate, a separator provided between the positive electrode plate and the negative electrode plate, and an electrolyte solution containing a non-aqueous solvent,
Either one or both of the positive electrode plate and the negative electrode plate is the electrode plate for a non-aqueous electrolyte secondary battery according to any one of claims 1 to 15, wherein the non-aqueous electrolyte secondary battery is characterized in that . In a battery pack in which a non-aqueous electrolyte secondary battery having at least a positive electrode terminal and a negative electrode terminal and a protection circuit having overcharge and overdischarge protection functions are stored in a storage case,
The non-aqueous electrolyte secondary battery comprises at least a positive electrode plate, a negative electrode plate, a separator provided between the positive electrode plate and the negative electrode plate, and an electrolyte solution containing a non-aqueous solvent. And
Either one of this positive electrode plate or this negative electrode plate, or both are the electrode plates for nonaqueous electrolyte secondary batteries in any one of Claims 1-15, The battery pack characterized by the above-mentioned.