JP2009016265A - Electrode for lithium battery, manufacturing method of electrode for lithium battery, lithium battery, and manufacturing method for lithium battery - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrode (a positive electrode or a negative electrode) for a lithium battery and its manufacturing method capable of making a lithium battery having excellent battery performance such as high current load characteristics, and a lithium secondary battery and its manufacturing method using the same electrode and having the same battery performance. <P>SOLUTION: In the electrode for a lithium battery including an electrode active material A capable of occluding and releasing lithium ion, a carbon-based conductive auxiliary material B, and a binder C, an average particle size of the electrode active material A is 10 micrometers or less, a content of the carbon conductive auxiliary material B is 0.5 to 20% by mass, the carbon-based conductive auxiliary material B includes carbon fiber of an average fiber diameter of 5 to 200 nanometers and an average fiber length of 1 to 20 micrometers, and the carbon fiber exists in a non-condensed state to a range of 10 micrometers or more in length. The manufacturing method of an electrode for a lithium battery uses the electrode for a lithium battery, and further, the electrode for a lithium battery and its manufacturing method has the electrode for a lithium battery. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an electrode for a lithium battery and a method for producing the same. The present invention also relates to a lithium battery including the lithium battery electrode and a method for manufacturing the lithium battery.

  Lithium secondary batteries generate electrical energy through oxidation / reduction reactions when lithium ions are inserted / deintercalated from a positive electrode and a negative electrode. Lithium secondary batteries use a material capable of reversible insertion / desorption of lithium ions as an active material for a positive electrode and a negative electrode, and an organic electrolyte or a polymer electrolyte is filled between the positive electrode and the negative electrode. It will be.

  Lithium secondary batteries are widely used as power sources for mobile phones and mobile electronic devices because of their high energy density and light weight compared to conventional secondary batteries. When lithium secondary batteries were first introduced, there were problems such as insufficient battery capacity, insufficient charge / discharge cycle characteristics, and insufficient large current load characteristics. Since then, the improvement of each battery constituent material has led to a considerable improvement in battery characteristics, which has supported the recent high performance of mobile electronic devices. In recent years, the application of lithium secondary batteries to electric tools, electric bicycles, and the like that particularly require high current load characteristics has been advanced. In addition, lithium secondary batteries for use in automobiles have been actively studied.

  In order to improve the large current load characteristics, approaches from the structural design of electrode active materials, electrolytes, and batteries are considered, and various studies have been made. Since it is an electrode mainly composed of an electrode active material that contributes to the reaction of the lithium secondary battery, studies on electrode constituent materials have been actively conducted. A typical and highly effective method is to reduce the particle size of the active material.

For example, Non-Patent Document 1 reports a study on nano-size of LiCoO ₂ that is a positive electrode active material. However, in Non-Patent Document 1, generally, the smaller the particle size, the larger the interaction between particles, and a slurry (electrode forming material) composed of an electrode active material, a carbon-based conductive additive, a binder, a solvent, etc. During the preparation, there is a problem that the particles are easily aggregated and are difficult to form a uniform slurry.

  Since it is the resistance in the electrode, that is, the conductivity, that becomes a problem when a large current is passed, studies have been conducted on conductive aids and methods for dispersing conductive aids. Examples of the main conductive additive include carbon-based conductive additives such as acetylene black, furnace black, ketjen black, graphite fine powder, vapor grown carbon fiber, and carbon nanotube. Among such carbon-based conductive aids, carbon black-based materials such as acetylene black and graphite fine powder are dispersed because they are particulate and have the property of being easily entangled with the surface of the electrode active material. It is relatively easy and has been used for a long time.

  On the other hand, vapor grown carbon fibers and carbon nanotubes are more conductive than the carbon black materials described above because graphite crystals develop along the fiber axis and a single fiber can form a conductive path of about 10 μm. It is known for its high sex-imparting effect. Already, lithium-based secondary batteries using vapor grown carbon fiber as a conductive auxiliary material for electrodes have been put into practical use, supporting the improvement in performance of lithium-based secondary batteries.

  This vapor grown carbon fiber theoretically increases the distance that one fiber conducts electricity as the length of the fiber is longer, so if long fibers can be dispersed, the conductivity imparting effect is further enhanced, It is expected that large current load characteristics and charge / discharge cycle characteristics will be improved. However, due to the feature of the fiber shape, they are likely to be entangled with each other during the production of the electrode forming material, and spherical aggregates are formed in the electrode active material particles, and the dispersion state tends to deteriorate. As a result, the battery characteristics may be impaired.

  Various studies have so far been made on the method of dispersing the carbon-based conductive additive in the lithium-based secondary battery electrode. For example, Patent Document 1 discloses a method in which a positive electrode active material, a conductive additive, a binder dissolved in a solvent, and a solvent are added and kneaded with a kneader. Patent Document 2 discloses a method in which a conductive additive, a binder, and a solvent are added and primary kneaded, and then an active material and an additional solvent are added.

  In addition, Patent Document 3 discloses a positive electrode containing fibrous carbon, and describes a “positive electrode active material”, “conductive agent”, and “weight ratio of binder” as a method of manufacturing the positive electrode. . Similarly, Patent Document 4 discloses a technique in which a fibrous carbon material is added to a positive electrode, and describes “positive electrode active material”, “conductive agent”, and “weight ratio of binder”.

  Patent Document 5 includes a negative electrode active material, a conductive carbon material composed of vapor grown carbon fiber, and a binder, and the carbon fiber is present in a state where an aggregate having a size of 10 μm or more is not formed. A negative electrode for a secondary battery is disclosed. And as a manufacturing method for producing this negative electrode, a method is first disclosed in which a negative electrode active material and vapor grown carbon fiber are dry mixed, and then this mixture and a polyvinylidene fluoride binder are stirred and mixed. .

JP 2004-356004 A JP 2006-222073 A JP 2006-278079 A JP 2007-87841 A JP 2007-42620 A J. et al. Yamaki, et al. , Power Sources, 146 (2005) 27-32.

  However, in Patent Document 1, an electrode active material and a carbon-based conductive additive containing vapor grown carbon fiber are simply weighed in the same container, and a binder solution is added thereto to prepare a slurry. Even when an electrode was produced by applying the coating on the surface, agglomerates of vapor grown carbon fibers were present and a good dispersion state could not be obtained. In addition, when vapor-grown carbon fiber is applied as a conductive additive to the method of Patent Document 2, aggregates of vapor-grown carbon fiber are present in the electrode, and the battery characteristics are not good.

  In Patent Document 3 and Patent Document 4, only “positive electrode active material”, “conductive agent”, and “weight ratio of binder” are defined, and no other conditions are described. That is, it is extremely difficult to derive a good dispersion state of vapor grown carbon fiber (including fibrous carbon and fibrous carbon material) only under conditions such as weight ratio. It is difficult to improve battery characteristics such as improvement of the battery.

  Further, the device disclosed in Patent Document 5 is not designed for high speed / high shear mixing. Therefore, in the case where the agglomeration is easy to form due to the shape of the vapor grown carbon fiber or the active material particles are fine and easy to aggregate, the dispersion of the vapor grown carbon fiber is insufficient. In some cases, there is room for further study. In Example 7 of Patent Document 5, an example in which the average particle diameter of the active material is 25 μm is described. However, in the case of an active material having a smaller particle diameter, the dispersion of the carbon fiber is insufficient. was there.

  An object of the present invention is to provide a lithium-based battery electrode (positive electrode or negative electrode) that provides a lithium-based secondary battery excellent in battery characteristics such as a large current load characteristic, and a method for producing the same. Another object of the present invention is to provide a lithium secondary battery having the above characteristics using the electrode and a method for producing the same.

  As a result of intensive studies to achieve the above object, the present inventors have completed the present invention described below.

That is, the present invention
(1) An electrode active material capable of occluding and releasing lithium ions (A), a carbon-based conductive additive (B), and a binder (C) for a lithium-based battery, wherein the electrode active material (A) The average particle diameter is 10 μm or less, the content of the carbon-based conductive additive (B) is 0.5 to 20% by mass, the carbon-based conductive additive (B) has an average fiber diameter of 5 to 200 nm, an average An electrode for a lithium-based battery comprising carbon fibers having a fiber length of 1 to 20 μm and present in a state where the carbon fibers are not aggregated to a size of 10 μm or more.
(2) The electrode for a lithium battery according to (1), wherein the electrode active material (A) is an electrode active material for a positive electrode and is made of a lithium-containing metal oxide capable of inserting and extracting lithium ions.
(3) The electrode for a lithium-based battery according to (1), wherein the electrode active material (A) is an electrode active material for a negative electrode and is made of a carbon material capable of inserting and extracting lithium ions.
(4) The lithium-based battery electrode according to any one of (1) to (3), wherein the carbon fiber is a graphite-based carbon fiber that is heat-treated at a temperature of 2000 ° C. or higher.

(5) A method for producing an electrode for a lithium battery as described in (1) above, comprising the following sequential steps: (a) an electrode active material (A) and a carbon-based conductive additive (B) containing carbon fibers. A dry mixing step of dry mixing to obtain a dry mixture,
(B) an electrode-forming material preparation step of preparing an electrode-forming material by kneading the dry mixture, a solution or dispersion containing the binder (C), and a solvent;
(C) The manufacturing method of the electrode for lithium type batteries including the application | coating process which apply | coats the said electrode formation material on a collector.
(6) In the (a) dry mixing step, the electrode active material (A) and a carbon-based conductive additive containing the carbon fiber (A) so that the carbon fiber does not form an aggregate having a size of 10 μm or more ( The method for producing an electrode for a lithium battery according to (5), wherein B) is dry-mixed.
(7) The dry mixing in the (a) dry mixing step is a process of applying a shearing force so that the carbon fiber does not form an aggregate having a size of 10 μm or more by the mixing blade in the container having the mixing blade. A method for producing an electrode for a lithium battery according to (6).
(8) The method for producing an electrode for a lithium battery according to (7), wherein a peripheral speed of the mixing blade in the container is 20 m / s or more.
(9) The method for producing an electrode for a lithium battery according to any one of (5) to (8), wherein the electrode active material (A) is a lithium-containing metal oxide capable of inserting and extracting lithium ions.
(10) The method for producing an electrode for a lithium battery according to any one of (5) to (8), wherein the electrode active material (A) is a carbon material capable of inserting and extracting lithium ions.
(11) The method for producing an electrode for a lithium-based battery according to any one of (5) to (10), wherein the carbon fiber is a graphite-based carbon fiber that is heat-treated at a temperature of 2000 ° C. or higher.

(12) An electrode for a lithium battery obtained by the production method according to any one of (5) to (11).
(13) A lithium battery including the lithium battery electrode according to any one of (1) to (4) as a constituent element.
(14) A non-aqueous electrolyte solution and / or a non-aqueous polymer electrolyte, and the non-aqueous solvent used in these is an ethylene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, propylene carbonate, butylene carbonate, or vinylene carbonate. The lithium battery according to (13), which contains at least one selected from the group consisting of:
(15) A method for producing a lithium battery, comprising a step of producing an electrode to be used by the production method according to any one of (5) to (11).

  ADVANTAGE OF THE INVENTION According to this invention, the lithium battery electrode (positive electrode or negative electrode) which provides the lithium secondary battery excellent in battery characteristics, such as a large current load characteristic, and its manufacturing method can be provided. Moreover, the lithium secondary battery which has the said characteristic using the said electrode, and its manufacturing method can be provided.

[Electrode for lithium batteries]
The lithium battery electrode of the present invention includes an electrode active material (A) capable of occluding and releasing lithium ions, a carbon-based conductive additive (B), and a binder (C). There may be. The lithium battery in the present invention refers to a lithium secondary battery.

(Electrode active material (A))
In the present invention, the electrode active material (A) is applied to both a positive electrode active material (positive electrode active material) and a negative electrode active material (negative electrode active material) by appropriately selecting a constituent material. Can do.

<Positive electrode active material>
The positive electrode active material in the present invention is appropriately selected from one or two or more kinds of conventionally known materials (materials capable of occluding and releasing lithium ions) known as positive electrode active materials in lithium batteries. Of these, lithium-containing metal oxides that can occlude and release lithium ions are preferred.

  Examples of the lithium-containing metal oxide include a composite oxide containing lithium and at least one element selected from Co, Mg, Mn, Ni, Fe, Al, Mo, V, W, Ti, and the like. it can.

_{Specifically, Li x CoO 2, Li x} NiO 2, Li x MnO 2, Li x Co a Ni 1-a O 2, Li x Co b V 1-b O z, Li x Co b Fe 1-b _{O 2, Li x Mn 2 O} 4, Li x Mn c Co 2-c O 4, Li x Mn c Ni 2-c O 4, Li x Mn c V 2-c O 4, Li x Mn c Fe 2- _c O ₄ (where x = 0.02 to 1.2, a = 0.1 to 0.9, b = 0.8 to 0.98, c = 1.6 to 1.96, z = 2 .01 to 2.3)). Preferred lithium-containing metal _{oxides, Li x CoO 2, Li x} NiO 2, Li x MnO 2, Li x Co a Ni 1-a O 2, Li x Mn 2 O 4, Li x Co b V 1-b O _z (where x, a, b and z are the same as above). In addition, the value of x is a value before the start of charging / discharging, and increases / decreases by charging / discharging.

  The positive electrode active materials may be used alone or in combination of two or more. The average particle diameter of the positive electrode active material is 10 μm or less. When the average particle diameter exceeds 10 μm, the efficiency of the charge / discharge reaction under a large current is reduced. The average particle diameter is preferably 50 nm to 7 μm, and more preferably 1 to 7 μm.

<Negative electrode active material>
As the negative electrode active material, one or two or more kinds of conventionally known materials (materials capable of occluding and releasing lithium ions) known as negative electrode active materials can be selected and used in lithium batteries. . For example, as a material capable of inserting and extracting lithium ions, a carbon material; any of Si and Sn, or an alloy or oxide containing at least one of them can be used. Among these, a carbon material is preferable.

  Typical examples of the carbon material include natural graphite; artificial graphite produced by heat-treating petroleum-based and coal-based coke; hard carbon obtained by carbonizing a resin; mesophase pitch-based carbon material; When natural graphite or artificial graphite is used, one having a (002) plane spacing d (002) of the graphite structure by powder X-ray diffraction in the range of 0.335 to 0.337 nm from the viewpoint of increasing battery capacity. preferable.

  Natural graphite refers to a graphite material that is naturally produced as ore. Natural graphite is classified into two types, scaly graphite having a high degree of crystallinity and earthy graphite having a low degree of crystallinity, depending on its appearance and properties. The scaly graphite is further divided into scaly graphite having a leaf-like appearance and scaly graphite having a lump shape. There are no particular restrictions on the origin, properties, and types of natural graphite used as the graphite material. Further, natural graphite or particles produced using natural graphite as a raw material may be subjected to heat treatment.

  Artificial graphite refers to graphite made by a wide variety of artificial techniques and a graphite material close to a perfect crystal of graphite. As a typical example, a material obtained from a tar and coke obtained from dry distillation of coal, a residue obtained by distillation of crude oil, and the like, through a firing process of about 500 to 1000 ° C. and a graphitization process of 2000 ° C. or more is used. Can be mentioned. Kish graphite obtained by reprecipitation of carbon from dissolved iron is also a kind of artificial graphite.

  Using an alloy containing at least one of Si and Sn in addition to the carbon material as the negative electrode active material has a smaller electric capacity than when using each of Si and Sn alone or using each oxide. It is effective in that it can be done. Of these, Si-based alloys are preferable.

Examples of Si-based alloys include alloys of Si with at least one element selected from B, Mg, Ca, Ti, Fe, Co, Mo, Cr, V, W, Ni, Mn, Zn, Cu, and the like. Can be mentioned. Specifically, SiB ₄ , SiB ₆ , Mg ₂ Si, Ni ₂ Si, TiSi ₂ , MoSi ₂ , CoSi ₂ , NiSi ₂ , CaSi ₂ , CrSi ₂ , Cu ₅ Si, FeSi ₂ , MnSi ₂ , VSi ₂ , Examples include WSi ₂ and ZnSi ₂ .

  In the present invention, as the negative electrode active material, the aforementioned materials may be used alone or in combination of two or more. The average particle diameter of the negative electrode active material is 10 μm or less. When the average particle diameter exceeds 10 μm, the efficiency of the charge / discharge reaction under a large current is reduced. The average particle diameter is preferably 0.1 to 10 μm, and more preferably 1 to 7 μm.

  The average particle size of the electrode active material (A) (positive electrode active material, negative electrode active material) is the particle size at which the cumulative frequency of the particle size distribution measured using a laser diffraction particle size distribution meter is 50% by volume. It is.

(Carbon-based conductive additive (B))
The carbon-based conductive additive (B) according to the present invention includes carbon fibers having an average fiber diameter of 5 to 200 nm and an average fiber length of 1 to 20 μm.

  In general, the longer the fiber, the higher the conductivity imparting effect of the carbon fiber, but the fibers are easily entangled and the dispersibility is lowered. Further, the smaller the fiber diameter, the stronger the van der Waals force between the fibers, so that so-called bundles are easily formed, and the dispersibility is lowered. On the other hand, even if the fiber diameter is too large, the dispersibility is lowered.

  Therefore, when the average fiber diameter and average fiber length of the carbon fiber according to the present invention are out of the above ranges, the dispersibility is lowered, the conductivity imparting effect by the carbon fiber cannot be sufficiently obtained, and the large current load characteristic is improved. Cannot be achieved. The average fiber diameter of the carbon fibers is preferably 20 to 200 nm, and more preferably 50 to 200 nm. The average fiber length is more preferably 4 to 20 μm.

  The carbon fiber in the carbon-based conductive additive (B) is preferably contained in an amount of 1% by mass or more, more preferably 2% by mass or more, from the viewpoint of conductivity imparting effect. More preferably, the auxiliary material (B) is made of carbon fiber.

  The carbon fiber according to the present invention is not particularly limited as long as it has good electrical conductivity, but it has a high degree of crystallinity and is a vapor grown carbon fiber (carbon nanotube) in which graphene sheets are laminated in a direction perpendicular to the fiber axis. Are preferred).

<Gas grown carbon fiber>
The vapor grown carbon fiber can be produced by, for example, a method in which an organic compound gasified with iron serving as a catalyst is blown into a high temperature atmosphere. The crystal growth direction of vapor grown carbon fiber is almost parallel to the fiber axis, and the center part often has a hollow structure.

  Vapor-grown carbon fibers are in the state they are produced (fibers obtained by the above method and not subjected to any treatment), heat-treated at about 800 to 1500 ° C, or 2000 ° C or higher. Any of those graphitized at (preferably about 2000 to 3000 ° C.) can be used. It is preferable to use an electrode active material to be used and a material suitable for battery design, and heat treatment and further graphitization treatment are preferred because carbon crystallinity is advanced and high conductivity is obtained.

  In order to increase the degree of crystallinity, it is also effective to perform a graphitization treatment by mixing boron as a graphitization accelerator before graphitization. The boron source is not particularly limited, but the crystallinity can be easily increased by, for example, mixing powders such as boron oxide, boron carbide, and boron nitride with vapor grown carbon fiber before graphitization. At this time, boron remaining in the vapor grown carbon fiber is preferably 0.1 to 4,000 ppm. When the residual boron is 0.1 ppm or more, the effect of improving the crystallization degree is easily obtained, and when it is 4,000 ppm or less, boron that does not contribute to the promotion of crystallization and exists as a low-conductivity compound. It is possible to reduce the electrical conductivity of the vapor grown carbon fiber.

  Moreover, there exists a branched fiber as a preferable form of vapor grown carbon fiber. The branched portion has a hollow structure in which the entire fiber including the portion is in communication with each other, and the carbon layer constituting the cylindrical portion of the fiber is continuous. The hollow structure is a structure in which a carbon layer is wound in a cylindrical shape, and includes a structure that is not a complete cylinder, a structure having a partial cut portion, and a structure in which two stacked carbon layers are combined into one layer. Further, the cross section of the cylinder is not limited to a perfect circle but includes an ellipse or a polygon.

  Vapor grown carbon fibers often have irregularities or disturbances on the fiber surface, and thus have an advantage of improving the adhesion with the electrode active material. By improving the adhesion, the electrode active material and the vapor grown carbon fiber can be kept in a good adhesion state without dissociating, and the cycle life can be improved while maintaining the conductivity of the electrode.

  When the vapor grown carbon fiber contains a lot of branched fibers, a network can be formed in the electrode more efficiently. In addition, since the network between the electrode active material particles can be maintained well, the flexibility of the entire electrode can be increased.

  In the lithium battery electrode of the present invention, the content of the carbon-based conductive additive (B) in the electrode is 0.5 to 20% by mass. If the content is less than 0.5% by mass, the effect of maintaining the conductivity of the electrode is not sufficient, and the electrode characteristics are deteriorated such that the cycle life tends to be reduced. On the other hand, when it exceeds 20 mass%, it will become the cause of the fall of the current density of an electrode, and coatability. The content of the carbon-based conductive additive (B) is preferably 0.5 to 20% by mass, and more preferably 0.5 to 10% by mass.

  Moreover, the carbon fiber which concerns on this invention in a carbon-type conductive support material (B) exists in the state which is not aggregated to the magnitude | size of 10 micrometers or more. If the carbon fibers are aggregated to a size of 10 μm or more, the conductivity imparting effect is concentrated at that portion, and a non-uniform conductive state is formed as a whole electrode. As a result, the large current load characteristic and the charge / discharge cycle characteristic as the electrode for the lithium battery are also deteriorated. On the other hand, if the aggregate is smaller than 10 μm, or if no aggregate is formed, the carbon fiber is not uniformly dispersed in the electrode, and the carbon fiber is not localized. Does not adversely affect battery characteristics. From the viewpoint of further improving the large current load characteristics, the carbon fibers are preferably present in a state of not being aggregated to a size of 10 μm or more. Such a good dispersion state of the carbon fiber can be realized by the method for producing an electrode for a lithium battery of the present invention described later.

  As the entanglement between the carbon fibers proceeds, a substantially spherical aggregate is formed. The above-mentioned “state in which carbon fibers are not aggregated to a size of 10 μm or more” means a state in which aggregates of spherical carbon fibers grown to a diameter of 10 μm or more are not present on the electrode.

The shape of the aggregate as described above can be confirmed before being pressed by a press molding machine to form an electrode. It is possible to confirm its presence to form a part. For example, if the pressed electrode is observed from an oblique direction using a scanning electron microscope (SEM) at a minimum magnification (about 35 times) and an aggregate is present, the diameter of the semicircle of the protrusion (major axis) ) Can be measured to confirm an aggregate having a size of 10 μm or more.
Considering the conductivity imparting effect, the aggregates as described above are preferably 10 or less, more preferably 0 in the field of view of the lowest magnification of SEM (about 300 μm × 300 μm).

  In the carbon-based conductive additive (B), as carbon-based conductive additives other than the above carbon fibers, for example, carbon black-based materials such as acetylene black, furnace black, ketjen black, and graphite-based fine particles such as natural graphite and artificial graphite. Powder or the like can be used. The carbon black material and graphite fine powder are not particularly limited, but those having a small amount of metal impurities are preferable.

(Binder (C))
There is no restriction | limiting in particular as binder (C) in an electrode formation material, It can select suitably from a conventionally well-known material as a binder of a lithium battery electrode. Examples of such a binder (C) include polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer, and vinylidene fluoride-tetrafluoroethylene copolymer. Preferable examples include fluorine-containing polymer such as coalescence, styrene-butadiene copolymer rubber (SBR) and the like.

  The content of the binder (C) in the electrode is such that when PVDF is used as the binder (C), the electrode active material ( A) The range of 0.5-20 mass parts is preferable with respect to 100 mass parts, and the range of 1-10 mass parts is more preferable. On the other hand, when SBR is used as the binder (C), from the viewpoint of maintaining good electrical conductivity and sufficiently exhibiting the function as the binder, the amount of 0.1% relative to 100 parts by mass of the electrode active material (A). The range of 5-5 mass parts is preferable, and the range of 0.5-3 mass parts is more preferable.

[Method for producing electrode for lithium-based battery]
The above-described lithium battery electrode of the present invention is manufactured by the following method for manufacturing a lithium battery electrode of the present invention. The manufacturing method includes each step of a dry mixing step, an electrode forming material preparation step, and a coating step. Hereinafter, these steps will be described.

<(A) Dry mixing process>
The dry mixing step is a step of obtaining a dry mixture by dry mixing the electrode active material (A) and the carbon-based conductive additive (B) containing carbon fibers. In this step, it is preferable to perform dry mixing so that the carbon fiber does not form an aggregate having a size of 10 μm or more. If the aggregate is not formed in the process, the aggregate is less likely to be present in the lithium battery electrode, and it is possible to produce a lithium battery electrode with high battery characteristics such as a large current load characteristic. It becomes.

  In order to prevent the carbon fibers from forming aggregates having a size of 10 μm or more, for example, in a container having a mixing blade, the carbon fibers do not form aggregates having a size of 10 μm or more by the mixing blade. It is effective to apply a shearing force.

  In addition, as an apparatus used for dry mixing, a mixing apparatus in which a mixing blade rotates at a low speed causes the carbon fibers to form aggregates as described above in the electrode active material. Since the problem that an aggregate will remain arises, it is not preferable.

  In order to apply the shearing force as described above, for example, the peripheral speed of the mixing blade may be controlled. The collision between the mixtures in the mixing container serves to promote the dispersion, because the peripheral speed of the mixing blade greatly affects the collision situation. The peripheral speed is preferably 20 m / s or more, and more preferably 30 m / s or more.

  The dry mixing time is preferably selected so that the electrode active material (A) and the carbon-based conductive additive (B) are sufficiently and homogeneously mixed and an aggregate having a size of 10 μm or more is not formed. Less than minutes are preferable and less than 10 minutes are more preferable.

  Specific examples of the dry mixing apparatus include apparatuses designed for high-speed and high-shear mixing such as paddle mixers, hybridizers, mechano-fusions, nobilta, wonder blenders, and proshear mixers.

  In addition, content in the electrode for lithium-type batteries of a carbon-type conductive support material (B) shall be 0.5-20 mass%.

<(B) Electrode forming material preparation step>
The electrode forming material preparation step is a step of preparing an electrode forming material by kneading a dry mixture, a solution or dispersion containing the binder (C), and a solvent.

There is no restriction | limiting in particular as a solvent (a "dispersion medium" is included) used for preparation of the solution containing a binder (C), From the solvent conventionally used for formation of the electrode in a lithium-type battery, 1 or 2 is used. More than one species can be selected. Examples of such a solvent include N-methyl-2-pyrrolidone (NMP), methyl ethyl ketone, dimethylformamide, dimethylacetamide, N, N-dimethylaminopropylamine, and tetrahydrofuran. In particular, when PVDF is used as the binder (C), it is preferable to use N-methyl-2-pyrrolidone as the solvent.
Moreover, as a solvent added in order to provide fluidity | liquidity separately from the said solvent, the above can be used, and water can also be used for others.

  On the other hand, when SBR is used as the binder (C), a solution containing SBR can be prepared using N-methyl-2-pyrrolidone or water as a solvent. When water is used as a solvent, in order to impart viscosity to the resulting slurry, before adding the aqueous dispersion of SBR to the kneader, the aqueous thickener solution is added to the kneader and mixed with the dry mixture. It is preferable to keep it.

  Examples of the thickener include polyethylene glycols, celluloses, polyacrylamides, poly N-vinyl amides, poly N-vinyl pyrrolidones, and the like. Among these, celluloses such as polyethylene glycols and carboxymethyl cellulose (CMC) are preferable, and carboxymethyl cellulose (CMC) having a high affinity for SBR is particularly preferable. There are sodium salt type and ammonium salt type in CMC.

  The amount of the binder (C) used is preferably set as appropriate according to the type. By setting to an appropriate range, it is possible to achieve both a function as a binder and good conductivity of the obtained electrode.

  For example, when PVDF is used as the binder (C), it is preferably selected to be 0.5 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the electrode active material (A). .

  Moreover, when using SBR as a binder (C), it is preferably selected to be 0.5 to 5 parts by mass, more preferably 0.5 to 3 parts by mass with respect to 100 parts by mass of the electrode active material (A). Is done.

  There are no particular limitations on the kneader used for kneading, and examples include a planetary mixer, a defoaming kneader, a ball mill, a paint shaker, a vibration mill, and a Redige mixer.

  As a solution containing the binder (C), for example, when using a PVDF solution or an SBR solution containing N-methyl-2-pyrrolidone as a solvent, the dry mixture obtained in the dry mixing step by the kneader; The PVDF solution or SBR solution and optionally a solvent (preferably MMP or NMP) are kneaded to prepare an electrode-forming material comprising a slurry.

  On the other hand, when using, for example, an SBR aqueous dispersion containing water as a solvent as the solution containing the binder (C), after first mixing the dry mixture and the aqueous solution of the aforementioned thickener by the kneader. The mixture, the SBR aqueous dispersion, and optionally the solvent water are kneaded to prepare an electrode-forming material comprising a slurry.

  The amount of the solvent charged into the kneader is a viscosity suitable for applying the electrode forming material comprising the obtained slurry to the current collector, for example, 23 ° C., preferably 1,000 to 10,000 mPa · s. It is desirable to select it so that it is preferably 2,000 to 5,000 mPa · s.

<(C) Application process>
The application step is a step of applying the electrode forming material obtained through the electrode forming material preparation step onto the current collector.

  As the current collector, conventionally known materials such as aluminum, nickel, titanium and alloys thereof, stainless steel, platinum, and carbon sheets can be used. There is no particular limitation on the method of applying the electrode forming material onto these current collectors, and a conventionally known method such as a method of applying using a doctor blade or a bar coater can be employed. The electrode sheet obtained by coating in this manner is dried by a known method, and then molded to have a desired thickness and density by a known method such as a roll press or a pressure press. A lithium battery electrode is obtained.

  A positive electrode can be produced by using a lithium-containing metal oxide capable of inserting and extracting lithium ions as the electrode active material (A). Moreover, a negative electrode can be manufactured by using the carbon material which can occlude / release lithium ion as an electrode active material (A). Moreover, the carbon fiber used for the carbon-based conductive additive (B) is a graphite-based carbon fiber that is heat-treated at a temperature of 2000 ° C. or higher, thereby imparting high conductivity and high pressure resistance to the formed electrode. can do.

[Lithium battery and manufacturing method thereof]
The lithium-based battery of the present invention includes the above-described lithium-based battery electrode (positive electrode and / or negative electrode) of the present invention as a constituent element. Moreover, the manufacturing method of the lithium battery of this invention includes the process of manufacturing an electrode (a positive electrode and / or a negative electrode) with the manufacturing method of the lithium battery electrode of this invention mentioned above. A non-aqueous electrolyte and / or a non-aqueous polymer electrolyte can be used for the lithium battery of the present invention.

<Lithium battery>
(Non-aqueous electrolyte)
As the non-aqueous electrolyte solution, a non-aqueous solvent containing a lithium salt as a solute can be used. Examples of the lithium salt include generally known LiClO ₄ , LiBF ₄ , LiPF ₆ , LiAlCl ₄ , LiSbF ₆ , LiSCN, LiCl, LiCF ₃ SO ₃ , LiCF ₃ CO ₂ , LiN (CF ₃ SO ₂ ) _{2 and the} like. is there. These lithium salts may be used individually by 1 type, and may be used in combination of 2 or more types.

Non-aqueous solvents used in non-aqueous electrolytes include diethyl ether, dibutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether. , Ethylene glycol phenyl ether, ethers such as 1,2-dimethoxyethane; formamide, N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, N-methylacetamide, N, N -Dimethylacetamide, N-ethylacetamide, N, N-diethylacetamide, N, N-di Amides such as tilpropionamide and hexamethylphosphorylamide; sulfur-containing compounds such as dimethyl sulfoxide and sulfolane; dialkyl ketones such as methyl ethyl ketone and methyl isobutyl ketone; ethylene oxide, propylene oxide, tetrahydrofuran, 2-methoxytetrahydrofuran, 1,3-dioxolane and the like Preferred are organic ethers such as cyclic ethers of; carbonates such as ethylene carbonate and propylene carbonate; γ-butyrolactone; N-methylpyrrolidone; acetonitrile and nitromethane. Among these, ethylene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, propylene carbonate, butylene carbonate, and vinylene carbonate are more preferable. These solvents may be used alone or in a combination of two or more.
The concentration of the solute (lithium salt) in the nonaqueous electrolytic solution is preferably 0.1 to 5 mol / L, and more preferably 0.5 to 3 mol / L.

(Non-aqueous polymer electrolyte)
The non-aqueous polymer electrolyte includes a polymer compound that forms a matrix, a lithium salt, and optionally a plasticizer. Examples of the polymer compound include polyalkylene oxide derivatives such as polyethylene oxide and polypropylene oxide, and derivatives thereof. Polymers containing, polyvinylidene fluoride, polyhexafluoropropylene, polycarbonate, phosphate polymer, polyalkylimine, polyacrylonitrile, poly (meth) acrylate, polyphosphazene, polyurethane, polyamide, polyester, poly Examples thereof include derivatives such as siloxane and polymers containing the derivatives.

  Among the above polymer compounds, those containing oxyalkylene such as polyalkylene oxide, polyurethane, and polycarbonate, urethane, and carbonate structures in the molecule have good compatibility with various polar solvents and good electrochemical stability. preferable. From the viewpoint of stability, those having a fluorocarbon group such as polyvinylidene fluoride or polyhexafluoropropylene in the molecule are also preferred. These oxyalkylene, urethane, carbonate, and fluorocarbon groups may be contained in the same polymer. The repeating number of these groups should just be the range of 1-1000 respectively, and the range of 5-100 is preferable.

  On the other hand, examples of the lithium salt include the same compounds as those exemplified in the description of the non-aqueous electrolyte described above. The content of the lithium salt in the non-aqueous polymer electrolyte is preferably 1 to 10 mol / kg, and more preferably 1 to 5 mol / kg. As the plasticizer, the non-aqueous solvent exemplified in the above description of the non-aqueous electrolyte can be used.

<Method for producing lithium-based battery>
As the lithium-based battery of the present invention, a typical production method for a lithium ion secondary battery and a lithium polymer battery is shown below, but the present invention is not limited thereto.

  First, the sheet-like positive electrode and negative electrode for lithium battery (positive electrode sheet and negative electrode sheet) are respectively produced by the method for manufacturing an electrode for lithium battery of the present invention. The produced positive electrode sheet and negative electrode sheet are processed into a desired shape, combined, and laminated on the positive electrode sheet / separator / negative electrode sheet so that the positive electrode and the negative electrode do not touch, coin type, square type, cylindrical type, sheet type, etc. Store in a container. If there is a possibility that moisture or oxygen has been adsorbed during stacking and storage, it is again dried in an inert atmosphere under reduced pressure and / or a low dew point (-50 ° C. or lower), and then transferred to an inert atmosphere with a low dew point. Subsequently, a lithium ion secondary battery or a lithium polymer battery can be produced by injecting or mounting a nonaqueous electrolyte solution or a nonaqueous polymer electrolyte and sealing the container.

  Here, known separators can be used, but polyethylene and polypropylene porous microporous films are preferable from the viewpoint of being thin and having high strength. The porosity is preferably higher from the viewpoint of ionic conduction, but if it is too high, it will cause a decrease in strength and a short circuit between the positive electrode and the negative electrode, so it is usually used at 30 to 90%, preferably 50 to 80%. is there. Further, the thickness is preferably thin from the viewpoint of ion conduction and battery capacity, but if it is too thin, it may cause a decrease in strength or a short circuit between the positive electrode and the negative electrode, and thus it is usually used at 5 to 100 μm, preferably 5 to 50 μm. . These microporous films can be used in combination of two or more kinds or other separators such as a nonwoven fabric.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.

Various characteristics were evaluated according to the following methods.
[1] Average particle size:
Measurement was performed using a laser diffraction / scattering particle size distribution analyzer Microtrac HRA (manufactured by Nikkiso Co., Ltd.).

[2] Battery evaluation method:
(1) Production of Li-ion battery test cell (tripolar cell)
A triode cell was produced as follows. The following operation was carried out in a dry argon atmosphere with a dew point of -80 ° C or lower.
In a cell (with an inner diameter of about 18 mm) with a screw-in lid made of polypropylene, an electrode sample for evaluation (diameter φ16 mm) and a lithium metal foil were separated from a separator (polypropylene microporous film (Sellgard, Cellgard 2400), 25 μm). Further, a lithium metal foil for reference was laminated similarly with a separator interposed therebetween. An electrolytic solution was added thereto to obtain a test cell.

(2) Electrolyte solution A mixed product of 8 parts by mass of EC (ethylene carbonate) and 12 parts by mass of EMC (ethyl methyl carbonate) was dissolved in an amount of 1.0 mol / liter of LiPF ₆ as an electrolyte.

(3) Large current load test (tripolar cell; positive electrode evaluation)
Charging is performed from the rest potential to 4.2V by CC (constant current: constant current) at 0.22mA / cm ² (equivalent to 0.1C) and then switched to CV (constant voltage: constant voltage) charging at 2mV. Charging was stopped when the value dropped to 12 μA. The discharge was CC discharge from 0.1C equivalent to 2.0C equivalent and cut off at a voltage of 2.75V.

(4) Large current load test (tripolar cell; negative electrode evaluation)
Charging is performed from the rest potential to 2 mV with CC (constant current: constant current) at 0.22 mA / cm ² (equivalent to 0.1 C), then switched to CV (constant voltage: constant voltage) charging at 2 mV, and the current value is Charging was stopped when the voltage dropped to 12 μA.
The discharge was CC discharge from 0.1C equivalent to 2.0C equivalent and cut off at a voltage of 1.5V.

[3] Aggregation state of carbon fiber in electrode Observation of the aggregation state of carbon fiber was performed by the following method using a scanning electron microscope T-20 (manufactured by JEOL Ltd.).
The sample electrode was pressed at 1 t / cm ² and set on a sample stage for observation. The sample stage was tilted 30 to 60 ° from the horizontal state and adjusted so that the electrode surface could be seen widely at the minimum magnification (35 times). At that time, the presence or absence of an aggregate of carbon fibers having a diameter of 10 μm or more was observed at the protruding portion (swelled portion) of the sample surface. When an aggregate of carbon fibers is present, it can be determined by the fact that the part appears to be raised from the other part.

The types of materials and equipment used in the examples and comparative examples are shown below.
<Positive electrode active material>
LiCoO ₂ (C-5): manufactured by Nippon Chemical Industry Co., Ltd., average particle size: 5 μm.
<Negative electrode active material>
MCMB6-28: Osaka Gas Co., Ltd. average particle size: 6 μm.
<Gas grown carbon fiber>
VGCF: Showa Denko Co., Ltd.
Average fiber diameter (from SEM image analysis): 150 nm,
Average fiber length (from SEM image analysis): 8 μm,
Average aspect ratio: 53
Branching degree (calculated from the SEM image analysis, the number of branches per 1 μm fiber length; the same applies hereinafter): about 0.1 / μm,
X-ray C ₀ (crystallinity of graphite crystals determined by the Gakushin method): 0.6767 nm, Lc (crystallite size): 48.0 nm.
VGCF-S: Showa Denko Co., Ltd.
Average fiber diameter (from SEM image analysis): 120 nm,
Average fiber length (from SEM image analysis): 12 μm,
Average aspect ratio: 100
Branching degree: about 0.02 pieces / μm,
X-ray _{C 0: 0.6767nm, Lc: 48.0nm} .
<Binder>
KF-polymer (L # 1320): KF-polymer for positive electrode (L # 9210): for negative electrode The KF-polymer contains PVDF dissolved in NMP (N-methyl-2-pyrrolidone). . Both are made by Kureha Chemical Co., Ltd.
<Solvent>
NMP: Showa Denko Co., Ltd.

<Dry mixer>
Nobilta: Hosokawa Micron Co., Ltd. (peripheral speed: 30-50 m / s)
IKA mixer: made by Janke & Kunkel GmbH (mixing blade maximum rotation speed: 10,000 rpm (circumferential speed: 17 m / s))
<Slurry kneader>
TK-Hibismix f-Model. 03 type: made by Primics Co., Ltd.

Example 1
A total of 200 g of LiCoO ₂ and VGCF-S was weighed to a mass ratio of 98: 2, and placed in a Nobilta mixing container (effective volume: 500 mL), and dry mixed for 15 minutes. The peripheral speed of the mixing blade was 40 m / s.

  Thereafter, the mixed powder was transferred to TK-Hibismix, and KF-polymer (L # 1320) was added so that PVDF was 3% by mass in solid content, and kneading was performed. Then, it knead | mixed, adding NMP, and adjusted so that it might become the optimal coating viscosity.

The resulting slurry was applied onto an aluminum foil using an automatic coater and a doctor blade, then 30 minutes on a hot plate (80 ° C.) and then 1 hour in a vacuum dryer (120 ° C.). Drying was performed. After drying, it was punched to a predetermined size and pressed using a press molding machine. Thereafter, drying was performed again with a vacuum dryer (120 ° C.) for 12 hours. The press pressure was adjusted so that the final electrode density was 3.0 g / cm ³ .

  In this way, a positive electrode sample was prepared, and the dispersion state of VGCF-S was observed, and the battery was evaluated. The dispersion state and the battery evaluation results are shown in Table 1, and the battery evaluation results are graphed and shown in FIG.

Example 2
In Example 1, except that VGCF was used instead of VGCF-S, a positive electrode sample was prepared in the same manner as in Example 1, and the dispersion state of VGCF was observed and the battery was evaluated. The dispersion state and the battery evaluation result are shown in Table 1, and the battery evaluation result is graphed and shown in FIG.

Example 3
MCMB6-28 and VGCF were weighed in a total of 100 g so that the mass ratio was 98: 2, and placed in a Nobilta mixing container (effective volume: 500 mL), and dry mixed for 5 minutes. The peripheral speed of the mixing blade was 40 m / s. This was transferred to TK-Hibismix, and KF-Polymer L # 9210 was added so that PVDF was 5% by mass in solid content and kneaded. Then, it knead | mixed, adding NMP, and adjusted so that it might become the optimal coating viscosity.

The resulting slurry was applied onto a copper foil using an automatic coater and a doctor blade, then 30 minutes on a hot plate (80 ° C.) and then 1 hour in a vacuum dryer (120 ° C.). Drying was performed. After drying, it was punched to a predetermined size and pressed using a press molding machine. Thereafter, drying was performed again with a vacuum dryer (120 ° C.) for 12 hours. The press pressure was adjusted so that the final electrode density was 1.5 g / cm ³ .

  In this way, a negative electrode sample was prepared, the dispersion state of VGCF was observed, and battery evaluation was performed. The dispersion state and the battery evaluation result are shown in Table 2, and the battery evaluation result is graphed and shown in FIG.

Comparative Example 1
A total of 30 g of LiCoO ₂ and VGCF-S is weighed to a mass ratio of 98: 2 and placed in a mixing container (effective volume: 20 mL) of IKA mixer, and 10 at 10,000 rpm (peripheral speed: 17 m / s). Dry mixing was performed for 2 seconds. Thereafter, a positive electrode sample was manufactured through the same process as in Example 1.

  While observing the dispersion state of VGCF-S, the battery was evaluated. The dispersion state and the battery evaluation result are shown in Table 1, and the battery evaluation result is graphed and shown in FIG.

Comparative Example 2
A total of 30 g of LiCoO ₂ and VGCF are weighed to a mass ratio of 98: 2 and placed in a mixing container (effective volume: 20 mL) of an IKA mixer and dry at 10,000 rpm (peripheral speed: 17 m / s) for 10 seconds. Mixing was performed. Thereafter, a positive electrode sample was produced through the same process as in Example 1.
The dispersion state of VGCF was observed and the battery was evaluated. The dispersion state and the battery evaluation result are shown in Table 1, and the battery evaluation result is graphed and shown in FIG.

Comparative Example 3
VGCF and KF-polymer L # 9210 were added to TK-Hibis mix and kneaded. MCMB6-28 was added to this kneaded material and further kneaded. The solid content ratios of MCMB6-28, VGCF, and PVDF were adjusted to the same conditions as in Example 3.

  Next, the mixture was kneaded while adding NMP, and thereafter, the same process as in Example 3 was followed to produce a negative electrode sample.

  The dispersion state of VGCF was observed and the battery was evaluated. The dispersion state and the battery evaluation result are shown in Table 2, and the battery evaluation result is graphed and shown in FIG.

Comparative Example 4
MCMB6-28 and VGCF are weighed in a total ratio of 15 g so that the mass ratio is 98: 2, placed in an IKA mixer mixing vessel (effective volume: 20 mL), and 10,000 rpm (peripheral speed: 17 m / s) for 5 seconds. Dry mixing was performed. Thereafter, through the same process as in Example 3, a negative electrode sample was produced. In Comparative Example 4, a method based on the mixing method implemented in Example 7 of JP 2007-42620 A is adopted.

  The dispersion state of VGCF was observed and the battery was evaluated. The dispersion state and the battery evaluation result are shown in Table 2, and the battery evaluation result is graphed and shown in FIG.

As can be seen from Tables 1 and 2 and FIGS. 1 and 2, a lithium secondary battery having excellent large current load characteristics can be realized by the electrode and the electrode manufacturing method of the present invention.
In addition, “> 20” in the above table means that there are more than 20 aggregates of 10 μm or more.

It is a figure which shows the relationship between the discharge capacity and discharge current rate in an Example and a comparative example. It is a figure which shows the relationship between the discharge capacity and discharge current rate in an Example and a comparative example.

Claims (15)

An electrode for a lithium battery comprising an electrode active material (A) capable of inserting and extracting lithium ions, a carbon-based conductive additive (B) and a binder (C),
The electrode active material (A) has an average particle size of 10 μm or less,
Content of the said carbon-type conductive support material (B) is 0.5-20 mass%,
The carbon-based conductive additive (B) contains carbon fibers having an average fiber diameter of 5 to 200 nm and an average fiber length of 1 to 20 μm, and the carbon fibers are present in a state where they are not aggregated to a size of 10 μm or more. Battery electrode.   2. The electrode for a lithium-based battery according to claim 1, wherein the electrode active material (A) is an electrode active material for a positive electrode and is made of a lithium-containing metal oxide capable of inserting and extracting lithium ions.   2. The electrode for a lithium-based battery according to claim 1, wherein the electrode active material (A) is an electrode active material for a negative electrode and is made of a carbon material capable of inserting and extracting lithium ions.   The lithium-based battery electrode according to any one of claims 1 to 3, wherein the carbon fiber is a graphite-based carbon fiber that is heat-treated at a temperature of 2000 ° C or higher. It is a method of manufacturing the electrode for lithium type batteries of Claim 1, Comprising: The following sequential processes:
(A) a dry mixing step of dry mixing the electrode active material (A) and the carbon-based conductive additive (B) containing carbon fiber to obtain a dry mixture;
(B) an electrode-forming material preparation step of preparing an electrode-forming material by kneading the dry mixture, a solution or dispersion containing the binder (C), and a solvent;
(C) a coating step of coating the electrode forming material on a current collector;
The manufacturing method of the electrode for lithium type batteries containing this.   In the (a) dry mixing step, the electrode active material (A) and the carbon-based conductive additive (B) containing the carbon fiber so that the carbon fiber does not form an aggregate having a size of 10 μm or more; The method for producing an electrode for a lithium battery according to claim 5, wherein dry mixing is performed.   The dry mixing in the (a) dry mixing step is a process of applying a shearing force so that the carbon fiber does not form an aggregate having a size of 10 μm or more by the mixing blade in a container having a mixing blade. 6. A method for producing an electrode for a lithium battery according to 6.   The method for producing an electrode for a lithium-based battery according to claim 7, wherein a peripheral speed of the mixing blade in the container is 20 m / s or more.   The method for producing an electrode for a lithium battery according to any one of claims 5 to 8, wherein the electrode active material (A) is a lithium-containing metal oxide capable of inserting and extracting lithium ions.   The method for producing an electrode for a lithium battery according to any one of claims 5 to 8, wherein the electrode active material (A) is a carbon material capable of inserting and extracting lithium ions.   The method for producing an electrode for a lithium-based battery according to any one of claims 5 to 10, wherein the carbon fiber is a graphite-based carbon fiber that is heat-treated at a temperature of 2000 ° C or higher.   The electrode for lithium type batteries obtained by the manufacturing method of any one of Claims 5-11.   The lithium battery which contains the electrode for lithium batteries of any one of Claims 1-4 as a component.   Non-aqueous electrolyte solution and / or non-aqueous polymer electrolyte is used, and the non-aqueous solvent used for these is selected from ethylene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, propylene carbonate, butylene carbonate and vinylene carbonate The lithium battery according to claim 13, comprising at least one kind.   The manufacturing method of a lithium battery including the process of manufacturing the electrode to be used by the manufacturing method of any one of Claims 5-11.

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