JP4971646B2 - Method for producing positive electrode mixture-containing composition, method for producing negative electrode mixture-containing composition, method for producing positive electrode for battery, method for producing negative electrode for battery, non-aqueous secondary battery and method for producing the same - Google Patents

Description

  The present invention relates to a method for producing a positive electrode mixture-containing composition, a method for producing a negative electrode mixture-containing composition, a method for producing a positive electrode for a battery, a method for producing a negative electrode for a battery, a non-aqueous secondary battery, and a method for producing the same. is there.

  In recent years, with the rapid spread of mobile devices such as mobile phones, the demand for non-aqueous secondary batteries having high energy density as the power source is rapidly expanding. In such a non-aqueous secondary battery, for the electrode, for example, a positive electrode formed by forming a positive electrode mixture layer containing a positive electrode active material on the current collector surface and a negative electrode mixture layer containing a negative electrode active material are collected. In general, an electrode body formed by laminating a negative electrode formed on the body surface via a separator and a nonaqueous electrolyte solution are loaded in a battery outer package.

  And in forming the mixture layer of each electrode, it contains an active material, a conductive additive, a binder, etc., and a positive and negative electrode mixture containing composition (paste, slurry, etc.) formed by dispersing this in a solvent. ) Is applied to the surface of the current collector and dried to remove the solvent.

  Various methods for preparing an electrode mixture-containing composition have also been proposed. For example, Patent Document 1 discloses a method in which an active material, a conductive additive, and a binder are mixed with a planetary mixer, and then the mixture is kneaded with an extruder and then the kneaded product and a solvent are mixed. Proposed.

  In Patent Document 2, a conductive auxiliary agent-containing dispersion obtained by kneading a conductive additive, a binder and a solvent with a twin screw extruder and an active material are further kneaded with a twin screw extruder. A method and a method of kneading a positive electrode active material, a conductive additive, a binder, and a solvent at once with a twin screw extruder have been proposed.

  Furthermore, as described in Patent Document 3, mechanical energy mainly composed of compressive force and grinding force is applied to the mixture of the active material and the conductive material, and the active material particles are subjected to mechanochemical reaction. It has been proposed to maintain contact between the active material particles and the conductive agent by rolling and coating a conductive material on the surface. Further, it has been proposed in Patent Document 4 that shear shearing acts to modify the surface of organic polymer particles with inorganic fine particles.

JP 2000-123879 (Claims etc.) JP 2004-14206 (Claims etc.) Japanese Patent Laid-Open No. 2001-68096 (Embodiments of the Invention, etc.) JP-A-10-202653 (Claims etc.)

  By the way, recently, in order to achieve further increase in capacity of the non-aqueous secondary battery, attempts have been made to increase the density of the electrode mixture layer and improve the filling amount of the active material. In order to increase the density of the electrode mixture layer, for example, a method in which the electrode mixture-containing composition is applied to the surface of the current collector and then compressed by a press treatment such as calendar molding can be employed. However, if the compressive force in the pressing process is too large, the current collector may be broken, and the productivity of the electrode is impaired. Therefore, in order to produce an electrode having a high-density electrode mixture layer with high productivity, it is preferable to prepare a high-density electrode mixture-containing composition that does not largely depend on the compression force in the press treatment. For this purpose, it is necessary to select a composition having high filling properties in advance.

  In order to increase the filling property of the electrode mixture-containing composition, the following problems must be solved. The electrode mixture-containing composition may contain a conductive assistant, but the conductive assistant generally has a ratio per weight compared to the active material in order to ensure a good electron conduction path of the active material. The surface area tends to be large and the bulk specific gravity tends to be small. Therefore, if the content of the conductive auxiliary agent is large, the battery performance is improved, but the density cannot be increased. If the content of the conductive auxiliary agent is small, the density can be increased but the battery performance is lowered.

  As a method for solving the above problem, for example, there is a method of adjusting the particle size or the like so that the composition is highly filled in advance. In general, high filling can be achieved by mixing large and small particle sizes in an appropriate ratio. However, this method has a problem that nonuniformity of the particle size causes nonuniformity of the electrochemical reaction and affects battery performance deterioration.

  The method disclosed in Patent Document 1 is characterized in that, particularly with respect to the positive electrode mixture-containing composition, it is possible to increase the density by dispersing the secondary agglomerated active material into the primary particles. As a contained composition amount, graphite as a conductive aid is as large as 26 parts by weight with respect to 100 parts by weight of lithium cobalt oxide as a positive electrode active material, and as described above, the bulk specific gravity is small as a conductive aid. The main effect is considered to be due to the secondary aggregate of graphite being dispersed in the primary particles.

  Moreover, in the method disclosed in Patent Document 2, the density of the positive electrode mixture-containing composition is increased by increasing the density and battery performance by sufficiently dispersing the conductive auxiliary agent in a small amount of 0.1 to 10% by mass. As in the technique of Patent Document 1, this is considered to be mainly due to the effect of dispersing the conductive auxiliary agent having a small bulk specific gravity.

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a non-aqueous secondary battery having a high capacity and suppressed deterioration of battery performance, a method for manufacturing the same, and the non-aqueous secondary battery. Methods for producing positive electrode for battery and negative electrode for battery, method for producing positive electrode mixture-containing composition for forming positive electrode for battery, and method for producing negative electrode mixture-containing composition for forming negative electrode for battery Is to provide.

  As a result of intensive studies on a technique for achieving a higher density of the electrode mixture layer while maintaining battery performance, the present inventors have applied shear, compression, friction energy, and the like to an irregularly mixed workpiece. This allows fine particles to disperse into primary particles and has a precise mixing function that maintains a controlled homogeneity, and causes a mechanochemical reaction to occur on the object to be processed. By preparing an electrode mixture-containing composition using a continuous shearing device having a function of modifying the surface so that the composite material particles are present, a highly filling composition is obtained, and this highly filling composition By using the product, the inventors have found that an electrode having a high-density electrode mixture layer can be produced with high productivity. In addition, the process which performs such precision mixing and mechanochemical reaction simultaneously is called "mechano union process" based on the trademark (registration No. 4673392) which the present inventor acquired about the mechanical equipment which has this function.

  That is, the non-aqueous secondary battery of the present invention is a non-aqueous secondary battery comprising a current collector formed by laminating a positive electrode and a negative electrode via a separator and a non-aqueous electrolyte, and at least of the positive electrode and the negative electrode One is the following positive electrode (a) or negative electrode (b).

Positive electrode (a):
Through a process in which at least the positive electrode active material or the positive electrode active material and the conductive auxiliary agent are precisely mixed by passing through a gap between the fixed disk and the rotating disk in multiple stages and processed by a continuous shearing device capable of causing a mechanochemical reaction. A positive electrode having a positive electrode mixture layer formed using a prepared positive electrode mixture-containing composition containing a positive electrode active material, a conductive additive and a binder.

Negative electrode (b):
At least the negative electrode active material and the negative electrode active material prepared by passing through a gap between the fixed disk and the rotating disk in multiple stages and processed by a continuous shearing device capable of causing a mechanochemical reaction, A negative electrode having a negative electrode mixture layer formed using a negative electrode mixture-containing composition containing an adhesive.

  Moreover, the manufacturing method of the non-aqueous secondary battery of this invention has the following positive electrode manufacturing process (A) and / or negative electrode manufacturing process (B), It is characterized by the above-mentioned.

Positive electrode manufacturing process (A):
Through a process in which at least the positive electrode active material or the positive electrode active material and the conductive auxiliary agent are precisely mixed by passing through a gap between the fixed disk and the rotating disk in multiple stages and processed by a continuous shearing device capable of causing a mechanochemical reaction. And a step of preparing a positive electrode mixture-containing composition containing a positive electrode active material, a conductive additive and a binder, and a step of producing a positive electrode having a positive electrode mixture layer using the positive electrode mixture-containing composition. .

Negative electrode manufacturing process (B):
The negative electrode active material and the binder are processed through a continuous shearing device that can mix at least the negative electrode active material by passing through a gap between the fixed disk and the rotating disk in multiple stages and can cause a mechanochemical reaction. It has the process of preparing the negative electrode mixture containing composition to contain, and the process of manufacturing the negative electrode which has a negative electrode mixture layer using the said negative electrode mixture containing composition.

  Further, the following inventions are also included in the present invention.

  At least positive electrode active material or positive electrode active material and conductive auxiliary agent are fixed in producing a positive electrode mixture-containing composition used for the production of a positive electrode for a battery, which contains a positive electrode active material, a conductive auxiliary agent and a binder. A method for producing a composition containing a positive electrode mixture, comprising a step of carrying out precision mixing by passing through a gap between a disk and a rotating disk in multiple stages and treating with a continuous shearing device capable of causing a mechanochemical reaction.

  In producing a negative electrode mixture-containing composition that contains a negative electrode active material and a binder and is used for the production of a negative electrode for a battery, at least the negative electrode active material is passed through the gap between the fixed disk and the rotating disk in multiple stages. A method for producing a composition containing a negative electrode mixture, which comprises a step of processing with a continuous shearing apparatus capable of producing a mechanochemical reaction with precision mixing.

  Through a process in which at least the positive electrode active material or the positive electrode active material and the conductive auxiliary agent are precisely mixed by passing through a gap between the fixed disk and the rotating disk in multiple stages and processed by a continuous shearing device capable of causing a mechanochemical reaction. The manufacturing method of the positive electrode for batteries characterized by having the process of forming a positive mix layer using the prepared positive mix containing composition containing a positive electrode active material, a conductive support agent, and a binder.

  At least the negative electrode active material and the negative electrode active material prepared by passing through a gap between the fixed disk and the rotating disk in multiple stages and processed by a continuous shearing device capable of causing a mechanochemical reaction, The manufacturing method of the negative electrode for batteries characterized by having the process of forming a negative mix layer using the negative mix containing composition containing an adhesive agent.

  The mechanochemical reaction referred to in this specification means that the surface of the material particles is modified by applying mechanical energy such as shear, compression and friction to a plurality of different material particles. Creating composite materials with new functions. The resulting composite material is a capsule type (the state where the surface of the core particle is completely covered with the adhering particles), a surface spot type (a state where the adhering particles are scattered on the surface of the core particle), and a dispersion type (the core particles and adhering particles Are kneaded shapes).

  The non-aqueous secondary battery of the present invention has a high capacity and good battery performance. Further, according to the method for producing a non-aqueous secondary battery of the present invention, the method for producing a positive electrode for a battery, the method for producing a negative electrode for a battery, the method for producing a positive electrode mixture-containing composition, and the method for producing a negative electrode mixture-containing composition Thus, the non-aqueous secondary battery of the present invention having a high capacity and good battery characteristics can be provided.

  FIG. 1 shows the structure of a continuous shearing device used in the present invention, that is, a continuous shearing device having a function of precisely mixing the object to be processed and causing a mechanochemical reaction in the object to be processed. A plan view of the fixed disk is shown in FIG. In the apparatus 1 of FIG. 1, the kneading part 3 is composed of a fixed disk 9 and a rotating disk 10 which are coaxially combined in multiple stages, and a concave groove (on both surfaces of the fixed disk 9 and the rotating disk 10. Cavity) is formed.

  A raw material (described later) of an electrode mixture-containing composition (a positive electrode mixture-containing composition or a negative electrode mixture-containing composition), which is an object to be processed, is supplied into the apparatus 1 from the quantitative feeder 5 and rotates the drive shaft 6. The raw material passes through the feed unit 2 by the feed screw 7 and is supplied to the kneading unit 3. In the kneading unit 3, when the rotating disk 9 rotates, the raw material introduced into the cavity of the fixed disk 10 and the cavity of the rotating disk 9 becomes the transfer pressure of the feed screw 7 and the transfer pressure of the intermediate screw 8. And the transfer pressure generated at the lead angle of the flight of the ridges forming the cavities of each disk. By these pressures, the action of compression, cavity shearing and split substitution is strongly generated between the cavities in the raw material of the electrode mixture-containing composition.

  In the continuous shearing device 1, by the above action, compared with other mechanical generators, precise mixing is performed in the first two disk zones, and mechanochemical reaction is performed more effectively in the subsequent combined disk zones. it can. As a result, the structure in which the compression pressure of the material sequentially acts as the kneading process progresses acts to increase the shear stress, and mechanical energy can be effectively applied.

  In addition, 4 in FIG. 1 is a discharge part, 12 is a jacket. Reference numeral 13 denotes a fan-shaped combined disk. The plan views of the disks constituting the fan-shaped combined disk are (a) (fixed disk) and (b) (rotary disk) in FIG. Reference numeral 14 denotes a chrysanthemum-shaped combination disk. The plan views of the disks constituting the chrysanthemum-shaped combination disk are (c) (fixed disk) and (d) (rotary disk) in FIG. Furthermore, 15 is a mortar type combination disk, and the plan views of the disks constituting the mortar type combination disk are (e) (fixed disk) and (f) (rotary disk) in FIG.

  In the continuous shearing device, the workpiece is passed through the gap between the fixed disk and the rotating disk in multiple stages, and there are many combinations of the fixed disk and the rotating disk. The number is preferably 4 or more in order to sufficiently exhibit the effects of mechanochemical reaction and precision mixing. If the number is too large, the size of the apparatus may increase, the temperature of the workpiece may increase, and the powder may be crushed. Therefore, 14 sets or less are preferable, and 6 sets or more and 12 sets or less are more preferable.

  For example, when preparing a positive electrode mixture-containing composition, the positive electrode active material and the conductive auxiliary agent, which are the raw materials of the composition, are put into the above-described apparatus, whereby the conductive auxiliary agent is rubbed against the positive electrode active material surface. Therefore, even with a small amount of a conductive aid, a highly dispersible state can be constructed. In addition, since the conductive auxiliary agent is rubbed against the surface of the active material, a solvent is added to the paste (slurry) necessary for application to the substrate (described later) and diluted and mixed. Since the conductive auxiliary agent is difficult to re-aggregate, a stable high-density positive electrode mixture-containing composition can be prepared. As described above, in addition to the dry mixing of the positive electrode active material and the conductive additive, wet mixing is also possible.

  In addition, for example, when preparing a positive electrode mixture-containing composition, the positive electrode active material powder itself that is a raw material of the composition can be physically fused to obtain high-density agglomerated particles that can be highly filled. . As described above, in order to make the active material itself highly packed, it is common to mix large particles and small particles in an appropriate ratio. There is a problem in that it causes non-uniformity and affects battery performance degradation. On the other hand, by processing the positive electrode active material using the above continuous shearing device, the active material of almost the same particle size is physically fused by the action of precision mixing and mechanochemical reaction, so that the high density Aggregated particles can be formed, and as a result, a high-density positive electrode mixture layer can be formed.

  In preparing the negative electrode mixture-containing composition, the negative electrode active material, which is a raw material of the composition, is treated using the continuous shearing device, so that the above-mentioned continuous mixture is prepared during the preparation of the positive electrode mixture-containing composition. The same result as the above effect by processing the positive electrode active material using a shearing device can be obtained.

The positive electrode active material according to the positive electrode mixture-containing composition is not particularly limited. For example, a lithium-containing metal oxide represented by LiMO ₂ or LiM ₂ O ₄ , and the element M is Co, Ni, Mn, What is at least one of metal elements such as Fe and Cu, more specifically, lithium such as lithium cobalt oxide such as LiCoO ₂ , lithium manganese oxide such as LiMnO _4, and lithium nickel oxide such as LiNiO ₂ -Containing metal oxides, or composite oxides having these as a basic structure (for example, different metal additives); metal oxides such as manganese dioxide, vanadium pentoxide, chromium oxide, or composite oxides having these as basic structures Metal sulfides such as titanium disulfide and molybdenum disulfide; These positive electrode active materials may be used individually by 1 type, for example, may use 2 or more types together as a mixture or a solid solution. In particular, when a lithium-containing composite oxide, such as LiCoO ₂ , LiMnO ₄ , or LiNiO ₂ , whose open circuit voltage during charging is 4 V or more on the basis of Li is used as the positive electrode active material, a battery having a higher energy density is formed. It is preferable because it is possible.

  The negative electrode active material according to the negative electrode mixture-containing composition is not particularly limited as long as it can dope and dedope lithium ions, but graphite, pyrolytic carbons, cokes, glassy carbons, organic polymers Carbon materials such as compound fired bodies, mesocarbon microbeads, carbon fibers, activated carbon, etc .; alloys such as Si, Sn, In, or oxides such as Si, Sn, In that can be charged and discharged at a low voltage close to Li; be able to. These negative electrode active materials may be used individually by 1 type, and may use 2 or more types together.

Examples of the conductive assistant include carbon black-based conductive assistants such as furnace black and ketjen black; acetylene black; flaky graphite; fibrous carbon; activated carbon; For example, if it is acetylene black and a carbon black type conductive support agent, that whose specific surface area is 50-2000 m < ² > / g is preferable. In the case of a graphite-based conductive additive such as scaly graphite, those having a specific surface area of 50 to 500 m ² / g are preferable. If a conductive auxiliary agent having a specific surface area that is too small is used, the contact area with the active material is reduced, so that the electrical conductivity may decrease and the internal resistance may increase. Moreover, when the conductive auxiliary agent whose specific surface area is too large is used, the required amount of the solvent in the electrode mixture-containing composition may increase, and it may be difficult to prepare a paste.

  In addition, although a conductive support agent is an essential raw material for preparation of a positive electrode mixture containing composition, it can be used as needed also in preparation of a negative electrode mixture containing composition. When using a conductive support agent for a negative electrode mixture containing composition, it is preferable to process a negative electrode active material and a conductive support agent using the said continuous shearing apparatus.

Examples of the binder related to the electrode mixture-containing composition include polytetrafluoroethylene, polyvinylidene fluoride (PVDF), polyethylene, polypropylene, polyethylene oxide, polyvinyl pyrrolidone, polyester resin, acrylic resin, phenol resin, epoxy resin, and the like. Resin-based binders; rubber-based binders such as ethylene-propylene-diene copolymer resins, styrene butadiene rubber (SBR), polybutadiene, and fluororubber; cellulose resins such as hydroxypropyl cellulose and carboxymethyl cellulose (CMC) Polysaccharides; and the like. These binders may be used alone or in combination of two or more. Among these, PVDF is particularly preferable. In preparing the electrode mixture-containing composition, the binder can also be used as a solution previously dissolved in a solvent.

  As the solvent for the electrode mixture-containing composition, for example, an aprotic organic solvent such as N-methyl-2-pyrrolidone (NMP), dimethylacetamide, dimethylformamide or the like may be used alone, or two or more kinds thereof may be used. May be used in combination.

  In preparing the positive electrode mixture-containing composition, it is sufficient that at least the positive electrode active material, or the positive electrode active material and the conductive additive are processed by the continuous shearing device, and the other steps are not particularly limited. However, for example, the following various methods can be employed.

(1) The positive electrode active material treated using the continuous shearing device is mixed with a conductive auxiliary agent, a binder and a solvent in a normal mixing method (for example, a mixing device such as a planetary mixer, the continuous shearing device, etc. A mixing method using an extruder or the like) to prepare a positive electrode mixture-containing composition.
(2) A mixture obtained by treating the positive electrode active material and the conductive additive using the continuous shearing device is mixed with a binder and a solvent by an ordinary mixing method (for example, the method exemplified above). A method for preparing a positive electrode mixture-containing composition.
(3) A method for preparing a positive electrode mixture-containing composition by kneading a positive electrode active material, a conductive additive, a binder and a solvent using the continuous shearing device.
(4) A method for preparing a positive electrode mixture-containing composition by mixing a positive electrode active material, a conductive additive, and a binder without using a solvent, using the continuous shear device.

  In preparing the positive electrode mixture-containing composition, the binder may be dissolved (or dispersed) in a solvent in advance as described above. In the method (1), the conductive additive, the binder and the solvent may be added and mixed at a time, or may be added and mixed in separate steps. Further, in the method (2), the binder and the solvent may be added and mixed at a time, or may be added and mixed in separate steps.

  Moreover, in the preparation of the negative electrode mixture-containing composition, it is sufficient that at least the step of treating the negative electrode active material with the above-described continuous shearing device is passed, and the other steps are not particularly limited. Can be adopted.

(1) The negative electrode active material treated using the above continuous shearing device is mixed with a binder and a solvent (further, if necessary, a conductive aid) and a normal mixing method [for example, preparation of a positive electrode mixture-containing composition] Various methods exemplified in Method Example (1)] to prepare a negative electrode mixture-containing composition by mixing.
(2) In the case of using a conductive additive, the mixture obtained by treating the negative electrode active material and the conductive additive using the continuous shearing device is mixed with a binder and a solvent and a normal mixing method (for example, the above-mentioned A method of preparing a negative electrode mixture-containing composition by mixing in an exemplified method).
(3) A method of preparing a negative electrode mixture-containing composition by kneading a negative electrode active material, a binder, and a solvent (and optionally a conductive auxiliary agent) using the continuous shearing device.
(4) A method in which a negative electrode mixture-containing composition is prepared by mixing the negative electrode active material and a binder (and further a conductive aid as required) without using a solvent, using the continuous shear device.

  In preparing the negative electrode mixture-containing composition, the binder may be dissolved (or dispersed) in a solvent in advance as described above. In the method (1), the conductive additive, the binder and the solvent may be added and mixed at a time, or may be added and mixed in separate steps. Further, in the method (2), the binder and the solvent may be added and mixed at a time, or may be added and mixed in separate steps.

  The solid content concentration of the positive electrode mixture-containing composition (content of components other than the solvent with respect to the total amount of the positive electrode mixture-containing composition) is preferably, for example, 50 to 85 mass%. In addition, the suitable content ratio of the positive electrode active material, the conductive additive, and the binder in the positive electrode mixture-containing composition will be described later.

  Moreover, it is preferable that solid content concentration (content of components other than the solvent with respect to the negative electrode mixture containing composition whole quantity) of the said negative electrode mixture containing composition shall be 35-70 mass%, for example. In addition, the suitable content rate of the negative electrode active material and binder (further a conductive support agent) in a negative electrode mixture containing composition is mentioned later.

  In preparing the positive electrode and the negative electrode according to the present invention, for example, after applying the positive electrode mixture-containing composition or the negative electrode mixture-containing composition to one or both sides of the current collector and drying to remove the solvent The thickness and density of the positive electrode mixture layer or the negative electrode mixture layer are adjusted by compressing by pressing. As a method for applying the positive electrode mixture-containing composition or the negative electrode mixture-containing composition, various known application methods such as an extrusion coater, a reverse coater, and a doctor blade can be employed. Moreover, an electrode can also be produced by press-molding the positive electrode mixture-containing composition or the negative electrode mixture-containing composition produced without using a solvent together with an expanded metal or a net.

  As the current collector used for the positive electrode and the negative electrode, for example, foils such as aluminum, copper, nickel, and stainless steel, expanded metal, and nets can be used. For example, as the positive electrode current collector, an aluminum foil is used as the negative electrode. A copper foil is particularly preferred as the current collector. The thickness of the current collector is, for example, 5 μm or more, more preferably 8 μm or more, and preferably 60 μm or less, more preferably 40 μm or less.

  Moreover, it is preferable to attach the lead body for connecting with the external terminal (a positive electrode terminal and a negative electrode terminal) of a battery to a positive electrode collector and a negative electrode collector by a well-known method.

  The active material content in the positive electrode mixture layer is 90% by mass or more, more preferably 95% by mass or more, and is 99% by mass or less, more preferably 98% by mass or less. If the active material content is too low, the capacity per unit volume of the positive electrode mixture layer and the capacity per unit volume will be reduced, so it may be difficult to increase the capacity of the battery, and if the active material content is too high, The conductivity of the positive electrode mixture layer may decrease, and the load characteristics of the battery may deteriorate.

  Further, the content of the conductive assistant in the positive electrode mixture layer is 0.1% by mass or more, more preferably 0.5% by mass or more, and 8% by mass or less, more preferably 5% by mass or less. desirable. If the conductive auxiliary agent content is too small, it may be difficult to ensure the conductivity in the positive electrode mixture layer. If the conductive auxiliary agent content is too high, the positive electrode active material content in the positive electrode mixture layer decreases. Therefore, since the unit mass of the positive electrode mixture layer and the capacity per unit volume are reduced, it may be difficult to increase the capacity of the battery.

  Furthermore, the binder content in the positive electrode mixture layer is 0.5% by mass or more, more preferably 1.0% by mass or more, and 3.0% by mass or less, more preferably 2.0% by mass or less. It is desirable that If the binder content is too small, the binding properties of the positive electrode active material and the conductive additive in the positive electrode mixture layer and the adhesion between the positive electrode mixture layer and the current collector may be insufficient. If the content of the adsorbent is too large, the content of the positive electrode active material in the positive electrode mixture layer decreases, causing a decrease in the unit mass of the positive electrode mixture layer and the capacity per unit volume. It can be difficult.

  Therefore, what is necessary is just to adjust each addition rate of a positive electrode active material, a conductive support agent, and a binder in the said positive mix mixture containing composition according to said suitable content ratio in the positive mix layer after formation.

  The active material content in the negative electrode mixture layer is 90% by mass or more, more preferably 95% by mass or more, and is 99% by mass or less, more preferably 98.5% by mass or less. If the active material content is too small, the capacity per unit volume and unit volume of the negative electrode mixture layer will be reduced, so that it may be difficult to increase the capacity of the battery, and if the active material content is too large, For example, since the binder content in the negative electrode mixture layer decreases, the binding property of the negative electrode active material and the like in the negative electrode mixture layer and the adhesion between the negative electrode mixture layer and the current collector may be insufficient. is there.

  The binder content in the negative electrode mixture layer is 1.5% by mass or more, more preferably 1.8% by mass or more, and 5% by mass or less, more preferably 3% by mass or less. desirable. If the binder content is too small, the binding properties of the negative electrode active material in the negative electrode mixture layer and the adhesion between the negative electrode mixture layer and the current collector may be insufficient, If the amount is too large, the content of the negative electrode active material in the negative electrode mixture layer decreases, causing a decrease in the unit mass of the negative electrode mixture layer and the capacity per unit volume, which makes it difficult to increase the capacity of the battery. Sometimes.

  Furthermore, when the negative electrode mixture layer contains a conductive additive, the conductive auxiliary agent content is 0.1% by mass or more, more preferably 0.5% by mass or more, and 3% by mass or less. Preferably it is 2 mass% or less. If the conductive auxiliary agent content is too low, the effect of using the conductive auxiliary agent may not be sufficiently obtained. If the conductive auxiliary agent content is too high, for example, the negative electrode active material content decreases. Since the unit mass of the negative electrode mixture layer and the capacity per unit volume are reduced, it may be difficult to increase the capacity of the battery.

  Therefore, in the above negative electrode mixture-containing composition, the respective addition rates of the positive electrode active material and the binder (further, the conductive auxiliary agent) are adjusted in accordance with the above-mentioned preferable content ratio in the negative electrode mixture layer after formation. That's fine.

  Next, the configuration of the non-aqueous secondary battery of the present invention will be described in detail. The non-aqueous secondary battery of the present invention only needs to have the positive electrode (the positive electrode for a battery according to the present invention) and the negative electrode (the negative electrode for a battery according to the present invention), and other configurations are not particularly limited. Various configurations of conventionally known non-aqueous secondary batteries can be employed.

  The nonaqueous secondary battery of the present invention is, for example, a spiral wound in a spiral shape with a separator interposed between a positive electrode (sheet positive electrode) and a negative electrode (sheet negative electrode) produced as described above. The electrode assembly or the laminated electrode assembly was inserted into a nickel-plated iron or stainless steel battery case or metal laminate film, and a non-aqueous electrolyte (hereinafter simply referred to as “electrolyte”) was injected. Then, it is produced through a sealing step. In addition, the battery generally incorporates a known explosion-proof structure for discharging the gas to the outside of the battery to prevent the battery from bursting when the internal pressure is increased to a predetermined pressure by the gas generated inside the battery. .

As the separator interposed between the positive electrode and the negative electrode, those having strength and capable of holding a large amount of electrolyte are preferable. From such a viewpoint, for example, the thickness is 10 to 50 μm and the porosity is 30 to 70. % Of microporous film and nonwoven fabric are suitable. Examples of the material for the separator include polyolefins such as polyethylene, polypropylene, and ethylene-propylene copolymer; polyesters such as polyethylene terephthalate and polybutylene terephthalate;

  As the electrolyte according to the battery of the present invention, a liquid electrolyte (hereinafter referred to as “electrolytic solution”) is usually used. As the electrolytic solution, an organic solvent-based nonaqueous electrolytic solution in which a solute is dissolved in an organic solvent is used. The solvent of the electrolytic solution is not particularly limited. For example, it is preferable to use a chain ester as a main solvent. Examples of chain esters suitable as the electrolyte solvent include chain esters such as dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (MEC), ethyl acetate (EA), and methyl propionate (MP). Those having a COO-bond are mentioned. The fact that these chain esters are the main solvent of the electrolytic solution means that these chain esters occupy more than 50% by volume in the total electrolyte solvent, The ester-like ester preferably accounts for 65% by volume or more, more preferably 70% by volume or more, and still more preferably 75% by volume or more in the total electrolyte solvent.

  However, from the viewpoint of improving the battery capacity, the electrolyte solvent is an ester having a higher dielectric constant than the chain ester alone (for example, an ester having a dielectric constant of 30 or more). The mixed solvent is preferably mixed. The amount of the ester having such a high dielectric constant in the total electrolyte solvent is, for example, preferably 10% by volume or more, and more preferably 20% by volume or more.

  Examples of the ester having a high dielectric constant include ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), γ-butyrolactone (γ-BL), ethylene glycol sulfite (EGS), and the like. . Among these, those having a cyclic structure such as EC and PC are preferred, cyclic carbonates are more preferred, and EC is particularly preferred.

  Examples of the solvent that can be used in addition to the chain ester and the ester having a high dielectric constant include 1,2-dimethoxyethane (1,2-DME), 1,3-dioxolane (1,3- DO), tetrahydrofuran (THF), 2-methyl-tetrahydrofuran (2-Me-THF), diethyl ether (DEE) and the like. In addition, amine-based or imide-based organic solvents, sulfur-containing or fluorine-containing organic solvents, and the like can also be used.

The solute of the electrolyte solution, for _{example, LiClO 4, LiPF 6, LiBF} 4, LiAsF 6, LiSbF 6, LiCF 3 SO 3, LiC 4 F 9 SO 3, LiCF 3 CO 2, Li 2 C 2 F 4 (SO 3 ) ₂ , LiN (CF ₃ SO ₂ ) ₂ , LiC (CF ₃ SO ₂ ) ₃ , LiC
_{n F 2n + 1 SO 3 (} n ≧ 2) , and the like, can be used in combination these singly or two or more. In particular, LiPF ₆ and LiC ₄ F ₉ SO ₃ are preferable because they can improve the charge / discharge characteristics of the battery. The concentration of the solute in the electrolytic solution is not particularly limited, but is, for example, 0.3 mol / l or more, more preferably 0.4 mol / l or more, and 1.7 mol / l or less, more preferably 1.5 mol. / L or less is desirable.

  The electrolyte solution preferably contains a compound having an alkyl group bonded to a benzene ring as an additive. A compound in which an alkyl group is bonded to a benzene ring can contribute to improvement of battery safety during overcharge. This is because when a non-aqueous secondary battery is overcharged, a compound in which an alkyl group is bonded to a benzene ring is oxidized and polymerized on the positive electrode side to generate a dimer abnormal oligomer or polymer on the positive electrode surface, It is considered that the safety against overcharging is improved by forming a film on the surface of the positive electrode with the oligomer or polymer.

  Examples of the compound having an alkyl group bonded to the benzene ring include cyclohexylbenzene, isopropylbenzene, n-butylbenzene, octylbenzene, toluene, xylene and the like. In particular, in the alkyl group bonded to the benzene ring, the carbon atom directly bonded to the benzene ring is bonded to at least one hydrogen atom from the viewpoint of improving battery safety during overcharge. More preferable. The alkyl group preferably has a certain length such as 4 or more carbon atoms, and preferably has a structure that is three-dimensionally bulky due to having a branched structure. For these reasons, cyclohexylbenzene is particularly preferred as the compound having an alkyl group bonded to the benzene ring.

  The larger the content of the compound having an alkyl group bonded to the benzene ring in the electrolytic solution, the greater the effect. However, when the content is too large, the ionic conductivity of the electrolytic solution tends to be lowered. Therefore, the content of the compound in which the alkyl group is bonded to the benzene ring in the electrolytic solution is, for example, 1% by mass or more, 10% by mass or less, and more preferably 5% by mass or less.

  Moreover, you may make the said electrolyte solution contain the additive which can contribute to the improvement of charging / discharging cycling characteristics, such as vinylene carbonate, with the compound which couple | bonded the alkyl group with the benzene ring. The content of the vinylene carbonate or the like in the electrolytic solution is, for example, 0.1% by mass or more, 5% by mass or less, and more preferably 2% by mass or less.

  In the battery of the present invention, a solid or gel electrolyte can be used as the electrolyte in addition to the above electrolyte. Examples of such electrolytes include known inorganic solid electrolytes and organic solid electrolytes mainly composed of polyethylene oxide, polypropylene oxide, or derivatives thereof.

  Hereinafter, the present invention will be described in detail based on examples. However, the following examples are not intended to limit the present invention, and all modifications made without departing from the spirit of the preceding and following descriptions are included in the technical scope of the present invention.

Example 1
<Preparation of positive electrode>
As a continuous shearing device capable of precisely mixing workpieces and causing mechanochemical reaction, "M-KCK-32 type" (hereinafter referred to as "M-KCK") manufactured by Asada Tekko Co., Ltd. Precise mixing and mechanochemicalization of the active material and conductive additive were performed. FIG. 1 is a schematic diagram of the structure of this M-KCK. As a positive electrode active material, LiCoO ₂ (average particle diameter: 10 μm): 100 parts by mass and acetylene black: 2.1 parts by mass as a conductive auxiliary agent were charged into a quantitative feeder in a powder supply unit, and M− Supplied to KCK. The rotation speed of the rotating shaft of M-KCK was 200 rpm, and the clearance between the rotating disk and the fixed disk was 1 mm. The number of combinations of fixed disks and rotating disks was six.

FIG. 3 shows a state of the mixture of the positive electrode active material and the conductive additive after the treatment. Through precise mixing and mechanochemical reaction, it was confirmed that acetylene black as a conductive auxiliary agent was attached as primary particles on the surface of LiCoO _{2 as} a positive electrode active material.

  The mixture of the positive electrode active material and the conductive additive after the above treatment with M-KCK is supplied to a planetary mixer, and NMP solution of PVDF (solid content concentration is 12% by mass) and NMP as a solvent are added thereto. The positive electrode mixture-containing composition was prepared by kneading for 60 minutes at a rotational speed of 20 rpm so that the solid content concentration of the finally obtained positive electrode mixture-containing composition was 80% by mass.

The positive electrode mixture-containing composition prepared by the planetary mixer is passed through a 70-mesh net to remove a large undispersed material, and then a positive electrode current collector which is an aluminum foil having a thickness of 15 μm using a reverse coater coating machine. It apply | coated uniformly on both surfaces of the body, and it dried and formed the positive mix layer. The coating amount after drying of the positive electrode mixture-containing composition was 23 mg / cm ² per side. The density of the positive electrode mixture layer before the press treatment was 2.78 g / cm ³ , and the density of the positive electrode mixture layer after the press treatment was 3.77 g / cm ³ . It cut | disconnected to the predetermined electrode width | variety, the aluminum lead body was welded to the exposed part of the electrical power collector, and the sheet-like positive electrode which has a positive mix layer on both surfaces was obtained.

<Production of negative electrode>
300 parts by mass of an aggregate-type artificial graphite material (average particle diameter: 18 μm) as a negative electrode active material, 300 parts by mass of a CMC aqueous solution (solid content concentration: 1.2% by mass) and an aqueous dispersion of SBR resin (solid content concentration: 40 parts by mass) 6.5 parts by mass was mixed and kneaded with a planetary mixer at a rotation speed of 20 rpm for 60 minutes to prepare a negative electrode mixture-containing composition (paste). Further, water was added to adjust the viscosity. The solid content concentration of the negative electrode mixture-containing composition was 45% by mass. This negative electrode mixture-containing composition was passed through a 70-mesh net to remove a large undispersed material, and then uniformly applied to both sides of a negative electrode current collector made of a strip-shaped copper foil having a thickness of 10 μm and dried. Thus, a negative electrode mixture layer was formed. The density of the negative electrode mixture layer before the press treatment was 1.10 g / cm ³ , and the density of the negative electrode mixture layer after the press treatment was 1.50 g / cm ³ . It cut | disconnected to the predetermined electrode width | variety, the nickel-made lead body was welded to the exposed part of an electrical power collector, and the sheet-like negative electrode which has a negative mix layer on both surfaces was obtained.

  In addition, the electrode mixture layer density before and after compression by the press treatment in the positive and negative electrodes was determined as follows (the same applies to all the following examples and comparative examples). The electrode was cut out at a predetermined area, and its weight was measured using an electronic balance having a minimum scale of 1 mg. The weight of the electrode mixture layer was calculated by subtracting the weight of the current collector from this weight. Further, the total thickness of the electrode is measured at 10 points with a micrometer having a minimum scale of 1 μm, the thickness of the electrode mixture layer is calculated by subtracting the thickness of the current collector from this thickness, and the electrode mixture is calculated from the average value and the area. The density of the electrode mixture layer was calculated by calculating the volume of the layer and dividing the weight of the electrode mixture layer by this volume.

<Preparation of electrolyte>
LiPF ₆ was dissolved in a mixed solvent in which MEC and EC were mixed at a volume ratio of 2: 1 so as to have a concentration of 1.2 mol / l, and further 2% by mass of cyclohexylbenzene was added to prepare an electrolytic solution. .

<Production of non-aqueous secondary battery>
The above positive electrode and negative electrode were dried. Thereafter, the positive electrode and the negative electrode were overlapped via a separator made of a microporous polyethylene film having a thickness of 20 μm, and this was wound in a spiral shape to obtain a wound electrode body. This wound electrode body was inserted into an aluminum rectangular can, and the positive electrode lead body was welded to a lid, and the negative electrode lead body was welded to a lead plate attached to a terminal attached to the lid via a packing. Thereafter, the lid and the can were seam welded. Thereafter, the electrolyte is injected from the electrolyte inlet provided on the lid, and the inlet is sealed, and then left at room temperature for 3 hours to fully impregnate the positive and negative electrodes and the separator with the electrolyte. A rectangular non-aqueous secondary battery having a thickness of 50 mm, a width of 34 mm, a thickness of 4.6 mm and a capacity of 900 mAh was produced.

Example 2
<Production of negative electrode>
As a negative electrode active material, 240 parts by mass of agglomerated artificial graphite material (average particle size: 18 μm) and 60 parts by mass of spherical natural graphite material (average particle size: 20 μm) were used as a quantitative feeder for a powder supply unit of M-KCK. The mixture was continuously mixed and precision-mixed and mechanochemicalized. The rotation speed of the rotating shaft of M-KCK was 100 rpm, and the clearance between the rotating disk and the fixed disk was 1 mm. The mixture of the negative electrode active material which performed M-KCK process is supplied to a planetary mixer, and 300 mass parts of CMC aqueous solution (solid content concentration: 1.2 mass%) and the aqueous dispersion (solid) of SBR type resin are added to this. (Minute concentration: 40% by mass) 6.5 parts by mass was mixed and kneaded with a planetary mixer to prepare a negative electrode mixture-containing composition (paste). Further, water was added to adjust the viscosity. The solid content concentration of the negative electrode mixture-containing composition was 55% by mass.

This negative electrode mixture-containing composition was passed through a 70-mesh net to remove a large undispersed material, and then uniformly applied to both sides of a negative electrode current collector made of a strip-shaped copper foil having a thickness of 10 μm and dried. Thus, a negative electrode mixture layer was formed. The density of the negative electrode mixture layer before the press treatment was 1.22 g / cm ³ , and the press pressure was adjusted so that the negative electrode mixture density after the press treatment was 1.65 g / cm ³ . Then, it cut | disconnected to the predetermined electrode width, the nickel-made lead body was welded to the exposed part of an electrical power collector, and the sheet-like negative electrode which has a negative mix layer on both surfaces was obtained.

  A nonaqueous secondary battery was produced in the same manner as in Example 1 except that the above sheet-like negative electrode was used.

Example 3
A positive electrode mixture-containing composition was prepared in the same manner as in Example 1 except that two kinds of LiCoO ₂ having an average particle diameter of 18 μm and 4 μm were mixed and used as the positive electrode active material. The solid content concentration of the finally obtained positive electrode mixture-containing composition was 82% by mass. A sheet-like positive electrode was produced in the same manner as in Example 1 except that the obtained positive electrode mixture-containing composition was used. Density of pressing before the positive electrode mixture layer is 2.81 g / cm ^3, the density of the positive electrode mixture layer after the pressing treatment was 3.80 g / cm ^3. A nonaqueous secondary battery was produced in the same manner as in Example 1 except that this sheet-like positive electrode was used.

Comparative Example 1
The same procedure as in Example 1 was performed except that mixing and kneading were performed using a planetary mixer at 30 rpm for 30 minutes without using M-KCK for mixing the positive electrode active material and the conductive additive. Thus, a positive electrode mixture-containing composition was prepared. In addition, it diluted in order to adjust to the viscosity suitable for the application | coating to the aluminum foil which is a collector, and solid content concentration of the final positive mix containing composition was 73 mass%. A sheet-like positive electrode was obtained in the same manner as in Example 1 except that this positive electrode mixture-containing composition was used. Density of pressing before the positive electrode mixture layer is 2.55 g / cm ^3, the density of the positive electrode mixture layer was 3.60 g / cm ^3. A nonaqueous secondary battery was produced in the same manner as in Example 1 except that this sheet-like positive electrode was used.

Comparative Example 2
As the positive electrode active material, a mixture of two types of LiCoO ₂ having an average particle diameter of 18 μm and 4 μm used in Example 3 was used, and without using M-KCK in the mixture of the positive electrode active material and the conductive assistant, Using a planetary mixer, mixing and kneading were carried out at 30 rpm for 30 minutes to prepare a positive electrode mixture-containing composition. In addition, it diluted in order to adjust to the viscosity suitable for application | coating to the aluminum foil which is a collector, and solid content concentration of the final positive electrode mixture containing composition was 70 mass%. A sheet-like positive electrode was obtained in the same manner as in Example 1 except that this positive electrode mixture-containing composition was used. Density of pressing before the positive electrode mixture layer is 2.75 g / cm ^3, the density of the positive electrode mixture layer after the pressing treatment was 3.76 g / cm ^3. A nonaqueous secondary battery was produced in the same manner as in Example 1 except that this sheet-like positive electrode was used.

Comparative Example 3
Mixing and kneading the mixture of the two types of negative electrode active materials for 30 minutes at 30 rpm using a planetary mixer without using M-KCK, and further to a copper foil as a current collector A negative electrode mixture-containing composition was prepared in the same manner as in Example 2, except that the solid content concentration of the final positive electrode mixture-containing composition was 43% by mass in order to adjust the viscosity to be suitable for the coating of A sheet-like negative electrode was obtained. The density of the negative electrode mixture layer before the press treatment was 1.15 g / cm ³ , and the press pressure was adjusted so that the density of the negative electrode mixture layer after the press treatment was 1.65 g / cm ³ . A nonaqueous secondary battery was produced in the same manner as in Example 1 except that this sheet-like negative electrode was used.

  The following battery characteristic evaluation was performed about the non-aqueous secondary battery of Examples 1-3 and Comparative Examples 1-3. First, when the charge / discharge current is indicated by C, a charge / discharge cycle test was performed in which 900 mA was set to 1C, the battery was charged to 4.2V with a current of 1C, and discharged to 2.75V at 1C. The discharge capacity at the 400th cycle was measured, and the discharge capacity at the 400th cycle was evaluated by a capacity maintenance ratio obtained by dividing this by the discharge capacity at the first cycle. Table 1 shows the discharge capacity at the first cycle (initial discharge capacity) and the capacity retention rate at the 400th cycle.

  A positive electrode (positive electrode according to Examples 1 to 3) obtained using a positive electrode mixture-containing composition prepared by subjecting a positive electrode active material and a conductive additive to precision mixing and mechanochemical treatment in advance was used before and after compression. The density of the positive electrode mixture layer is high. Furthermore, in the nonaqueous secondary batteries of Examples 1 to 3 having these positive electrodes, as can be seen from Table 1, both the initial discharge capacity and the capacity retention rate after 400 cycles are high, and high performance battery characteristics are obtained. Can be secured. As in Comparative Example 2, by using positive electrode active materials having different particle sizes, the density of the positive electrode mixture layer can be increased without performing precise mixing and mechanochemical treatment. In the battery of Comparative Example 2, the capacity retention rate after 400 cycles was low.

  Furthermore, the negative electrode obtained by using a negative electrode mixture-containing composition prepared by subjecting the negative electrode active material to precision mixing and mechanochemical treatment in advance (the negative electrode of Example 2) has a negative electrode mixture layer density before compression. It became high. Since the graphite material used for the negative electrode active material tends to be compressed and broken even with a small pressing pressure, it is preferable that the graphite material can be compressed and densified with the smallest possible pressing pressure. Therefore, the higher the negative electrode mixture layer density before compression, the better. Regarding the capacity retention rate after 400 cycles, the results obtained by applying precision mixing and mechanochemical treatment in advance show superior results, and can provide high-performance battery performance.

It is sectional drawing which shows roughly an example of the continuous shearing apparatus used by this invention. It is a top view which shows an example of a rotation disk and a fixed disk with the continuous shearing apparatus of FIG. In Example 1 of the present invention is a photograph showing the surface state of the LiCoO ₂ positive electrode active material was treated with a continuous shear device.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Continuous shear device 2 Feed part 3 Kneading part 4 Discharge part 5 Fixed feeder 6 Drive shaft 7 Feed screw 8 Intermediate screw 9 Rotating disk 10 Fixed disk 11 Kneading cylinder 12 Jacket 13 Fan-shaped combination disk 14 Chrysanthemum combination disk 15 Mortar type combination Disc 50 Positive electrode active material 60 Conductive aid

Claims (6)

In producing a positive electrode mixture-containing composition that contains a positive electrode active material, a conductive additive, and a binder, and is used to produce a positive electrode for a battery,
At least the positive electrode active material or the positive electrode active material and the conductive auxiliary agent are processed by a continuous shearing apparatus capable of causing a mechanochemical reaction by precisely mixing by passing the gap between the fixed disk and the rotating disk in multiple stages. The manufacturing method of the positive mix containing composition characterized by the above-mentioned. In producing a negative electrode mixture-containing composition that contains a negative electrode active material and a binder and is used in the production of a negative electrode for a battery,
A negative electrode active material containing at least a negative electrode active material, comprising a step of processing by a continuous shearing device capable of causing a mechanochemical reaction by precisely mixing by passing through a gap between a fixed disk and a rotating disk in multiple stages A method for producing the composition.   Through a process in which at least the positive electrode active material or the positive electrode active material and the conductive auxiliary agent are precisely mixed by passing through a gap between the fixed disk and the rotating disk in multiple stages and processed by a continuous shearing device capable of causing a mechanochemical reaction. The manufacturing method of the positive electrode for batteries characterized by having the process of forming a positive mix layer using the prepared positive mix containing composition containing a positive electrode active material, a conductive support agent, and a binder.   At least the negative electrode active material and the negative electrode active material prepared by passing through a gap between the fixed disk and the rotating disk in multiple stages and processed by a continuous shearing device capable of causing a mechanochemical reaction, The manufacturing method of the negative electrode for batteries characterized by having the process of forming a negative mix layer using the negative mix containing composition containing an adhesive agent. A non-aqueous secondary battery comprising a current collector formed by laminating a positive electrode and a negative electrode via a separator and a non-aqueous electrolyte, wherein at least one of the positive electrode and the negative electrode is the following positive electrode (a) or negative electrode ( b) A non-aqueous secondary battery.
Positive electrode (a):
Through a process in which at least the positive electrode active material or the positive electrode active material and the conductive auxiliary agent are precisely mixed by passing through a gap between the fixed disk and the rotating disk in multiple stages and processed by a continuous shearing device capable of causing a mechanochemical reaction. A positive electrode having a positive electrode mixture layer formed using a prepared positive electrode mixture-containing composition containing a positive electrode active material, a conductive additive and a binder.
Negative electrode (b):
At least the negative electrode active material and the negative electrode active material prepared by passing through a gap between the fixed disk and the rotating disk in multiple stages and processed by a continuous shearing device capable of causing a mechanochemical reaction, A negative electrode having a negative electrode mixture layer formed using a negative electrode mixture-containing composition containing an adhesive. The manufacturing method of the nonaqueous secondary battery characterized by having the following positive electrode manufacturing process (A) and / or negative electrode manufacturing process (B).
Positive electrode manufacturing process (A):
Through a process in which at least the positive electrode active material or the positive electrode active material and the conductive auxiliary agent are precisely mixed by passing through a gap between the fixed disk and the rotating disk in multiple stages and processed by a continuous shearing device capable of causing a mechanochemical reaction. A step of preparing a positive electrode mixture-containing composition containing a positive electrode active material, a conductive additive and a binder;
It has the process of manufacturing the positive electrode which has a positive mix layer using the said positive mix mixture containing composition.
Negative electrode manufacturing process (B):
The negative electrode active material and the binder are processed through a continuous shearing device that can mix at least the negative electrode active material by passing through a gap between the fixed disk and the rotating disk in multiple stages and can cause a mechanochemical reaction. A step of preparing a negative electrode mixture-containing composition,
It has the process of manufacturing the negative electrode which has a negative mix layer using the said negative mix mixture containing composition.

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