JP2019114777A - Active material, electrode, and power storage element - Google Patents

Abstract

The present invention provides an active material used for a storage element having high energy density and high output characteristics.
An active material has porous carbon having a plurality of pores forming a three-dimensional network structure, and a conductive polymer, and at least a part of the plurality of pores in the porous carbon includes the conductive polymer. The conductive polymer is a polythiophene derivative, and the mass ratio of the porous carbon to the conductive polymer (porous carbon / conductive polymer) is 20/80 or more and 95/5 or less.
[Selected figure] Figure 2

Description

  The present invention relates to an active material, an electrode, and a storage element.

  In recent years, the storage element capable of increasing the energy density has been improved and spread with improved characteristics along with the miniaturization and high performance of portable devices, and further, the storage element has a larger discharge capacity and is excellent in safety. Development is also in progress, and mounting on electric vehicles etc. is also beginning. A lithium ion secondary battery is often used as such a storage element.

On the other hand, an electric double layer capacitor that can be charged and discharged at high speed without using a chemical reaction is used as a storage element of a hybrid car or the like. However, since the electric double layer capacitor has an energy density of 1 as compared to the lithium ion secondary battery, a heavy storage element is required to secure a sufficient discharge capacity, and is mounted in an automobile If that happens, it has been a hindrance to improving fuel efficiency.
As a storage element having both the high energy density of the lithium ion secondary battery and the high output characteristics of the electric double layer capacitor, a lithium ion is used as a carrier ion, using a positive electrode containing activated carbon and a negative electrode containing graphite Capacitors are attracting attention.

The lithium ion capacitor is prepared by doping lithium ions in advance with a chemical method or the like to a negative electrode material capable of inserting and extracting lithium ions, and lowering the negative electrode potential, thereby improving the withstand voltage and the energy density It can be higher than a double layer capacitor. A technique has been proposed for the purpose of further improving the energy density by mixing a polymer radical material in the positive electrode of the lithium ion capacitor (see, for example, Patent Document 1).
In addition, a non-aqueous electrolytic solution storage element using amorphous porous carbon having mesopores with a pore diameter of 2 nm or more connected in a three-dimensional network structure has been proposed as a positive electrode active material (see, for example, Patent Document 2) ).

  An object of the present invention is to provide an active material used for a storage element having high energy density and high output characteristics.

  The active material of the present invention as means for solving the above problems has porous carbon having a plurality of pores forming a three-dimensional network structure, and a conductive polymer, and the plurality of porous carbons in the porous carbon At least a portion of the pores contain the conductive polymer.

  According to the present invention, it is possible to provide an active material used for a storage element having high energy density and high output characteristics.

FIG. 1 is a cross-sectional enlarged view schematically showing an example of a cross section of porous carbon. FIG. 2 is a cross-sectional enlarged view schematically showing an example of a cross section of a part of the active material particles. FIG. 3 is a whole block diagram showing an example of a storage element to which the active material of the present invention is applied. FIG. 4 is a cross-sectional TEM image of porous carbon A particles used in Example 1. FIG. 5 is a cross-sectional SEM image of the positive electrode in Example 1. FIG. 6 is a C element mapping image of the positive electrode cross section in Example 1. FIG. 7 is an S element mapping image of the positive electrode cross section in Example 1. FIG. 8 is a diagram showing a discharge curve at 0.2 C and a discharge curve at 10 C in Example 1. FIG. 9 is a view showing a discharge curve at 0.2 C and a discharge curve at 10 C in Comparative Example 7.

(Active material)
The active material of the present invention has a porous carbon having a plurality of pores forming a three-dimensional network structure, and a conductive polymer, and at least a part of the plurality of pores in the porous carbon is the conductive It contains a polymer, and further contains other materials as required.

  Hereinafter, in the present invention, the electrode material means a material constituting an electrode such as an active material, a conductive additive, a binder, a thickener, a current collector and the like. Further, in the present invention, the active material refers to a substance directly involved in the expression of capacity in the storage element, that is, a substance having a function of storing or releasing ions in the storage element. Moreover, in the present specification, “storage” broadly refers to taking in ions in the material, “adsorption” that physically adsorbs the ions on the material surface, and “intercalation” in which the ions are inserted in the crystal structure of the material. These include “insertion” which inserts ions into the pores of the material, and the like.

In the prior art, when using a polymer having a high capacity as the active material, the active material of the present invention requires the addition of a large amount of a conductive aid because the conductivity of the polymer itself is low. Then, when mixing the activated carbon, the polymer, the conductive aid, and the binder, which are materials constituting the electrode, it becomes difficult to uniformly disperse the respective constituent materials, and the aggregation of the polymer and the conductive aid occurs. I will. When aggregation of the polymer or the conductive aid occurs, electron transfer between the polymer particles, between the polymer and the other material, or between the polymer and the current collector is suppressed, and a path (electron conductive path) through which electrons pass in the electrode is formed. Is insufficient, which results in the deterioration of output characteristics.
Furthermore, in the prior art, the conductive aid added in a large amount does not contribute to the development of capacity because it has no ability to insert and extract ions. Therefore, it is based on the finding that mixing a large amount of conductive support leads to relatively reducing the ratio of activated carbon and polymer functioning as an active material in the electrode, and also causes a reduction in the energy density of the storage element. It is a thing.

  The active material of the present invention sufficiently forms the conductive path in the electrode by including the conductive polymer in at least a part of the plurality of pores forming the three-dimensional network structure of the well-conductive porous carbon. can do. Furthermore, since the porous carbon itself also has the ability to insert and extract ions, it contributes to the expression of capacity, and hence there is no risk of lowering the energy density. Therefore, by using the electrode including the active material of the present invention, a storage element having high energy density and high output characteristics can be provided.

<Porous carbon>
As the porous carbon, porous carbon having a plurality of pores forming a three-dimensional network structure is used.
The phrase “the porous carbon has“ a plurality of pores forming a three-dimensional network structure ”” means that the porous carbon particles have a plurality of pores on the surface and inside, and adjacent pores are It means the state where it was connected mutually and connected three-dimensionally, and the communicating hole which has an opening part in the surface is formed.

As a method of confirming that the porous carbon has a plurality of pores forming a three-dimensional network structure, for example, observation is performed using SEM (Scanning Electron Microscope), TEM (Transmission Electron Microscope), etc. Methods etc.
The cross section of the porous carbon having the “a plurality of pores forming a three-dimensional network structure” can be shown as a schematic cross sectional view of FIG. 1 created based on a photograph by TEM. In addition, in FIG. 1, 101 shows a pore and 100 shows a carbon particle.
When the porous carbon has "a plurality of pores forming a three-dimensional network structure", when the conductive polymer is contained, the conductive carbon is uniformly contained in the porous carbon particles. It is advantageous in that it can be done.

The structure of the porous carbon “having a plurality of pores forming a three-dimensional network structure” will be further described.
In the porous carbon, any of micropores having a minimum diameter of less than 2 nm and mesopores having a minimum diameter of 2 nm or more (preferably 2 nm or more and 50 nm or less) may be present. The proportion of mesopores is preferably 25% or more. In the process of containing the conductive polymer in pores, if 25% or more of the pores forming the three-dimensional network structure are mesopores, since the mesopores are larger in pore diameter than the micropores It is advantageous in that the conductive polymer easily enters.
The proportion of mesopores can be calculated from the adsorption isotherm, and the adsorption isotherm can be created by measuring the adsorption amount of gas molecules when the material is kept at a constant temperature and the pressure is changed, for example It can be measured by an automatic specific surface area / pore distribution measuring apparatus (Tri Star II 3020, manufactured by Shimadzu Corporation).

The adsorption amount of gas molecules at a relative pressure (p / p ₀ ) of 0.3 or less of the adsorption isotherm is the adsorption amount of gas molecules attributable to micropores, and the relative pressure of 0.3 to 0.96 is attributable to mesopores Since the gas molecule adsorption amount is obtained, the ratio of mesopores can be calculated by the following equation 1.

[Equation 1]

There is no restriction | limiting in particular as direction of the opening of the pore in the said porous carbon, Although it can select suitably according to the objective, it is more preferable to form an opening in a random direction.
The term "random" indicates that the porous carbon has no specific regularity or rule with respect to the direction in which the conductive polymer is contained. If the pores are formed regularly in porous carbon, it will be difficult to mix the conductive polymer from various angles.

As a method for determining the state in which pores are formed in porous carbon, there is a method of adsorbing gas molecules whose adsorption occupancy area is known on the surface and determining the specific surface area of the sample from the amount of adsorption of the molecules, gas molecules A method called BET (Brunauer Emmett Teller) method for measuring pore distribution from condensation of is known.
The BET specific surface area of the porous carbon is preferably 800 m ² / g or more and 1,800 m ² / g or less, and more preferably 900 m ² / g or more and 1,500 m ² / g or less. When the BET specific surface area is in the above-mentioned preferable range, the amount of the pores formed is sufficient, and it is advantageous in that the storage and discharge of anions can be sufficiently performed to increase the discharge capacity. On the other hand, when the BET specific surface area is too large, such as activated carbon, to about 2,000 m ² / g, the reaction with the electrolyte proceeds too easily, and the decomposition of the electrolyte is promoted by repetition of charge and discharge and the long-term In fact, the discharge capacity may be reduced.
When the BET specific surface area of the active material is within the range as described above, the reaction with the electrolytic solution is reduced while the pores are formed in a sufficient amount, and the decomposition of the electrolytic solution is less likely to be promoted. A decrease in discharge capacity due to repeated discharges is suppressed.
The BET specific surface area can be determined, for example, using the BET (Brunauer Emmett Teller) method from the measurement results of the adsorption isotherm with an automatic specific surface area / pore distribution measuring apparatus (Tri Star II 3020, manufactured by Shimadzu Corporation) .

The bulk density of the porous carbon is preferably 0.1 g / cc or more and 1.0 g / cc or less, and more preferably 0.1 g / cc or more and 0.6 g / cc or less. If the bulk density is 0.1 g / cc or more, the thickness of the carbonaceous wall forming the pores is appropriate, a favorable pore structure is obtained, and the electrode density is increased when the electrode is formed. Thus, the discharge capacity per unit volume can be increased.
On the other hand, when the bulk density is higher than 1.0 g / cc, formation of mesopores becomes insufficient and the existing ratio of mesopores increases, so the anion storage amount decreases and a large discharge capacity is obtained. You can not get it.
The bulk density can be measured, for example, by a multifunctional powder physical property measuring instrument (Multitester MT-1001K, manufactured by Seishin Enterprise Co., Ltd.).

  The pore volume of the porous carbon is preferably 0.2 mL / g or more and 2.3 mL / g or less, and more preferably 0.5 mL / g or more and 2.3 mL / g or less. When the pore volume is 0.2 mL / g or more, mesopores rarely become independent pores, and a large discharge capacity can be obtained without inhibition of anion migration. On the other hand, if the pore volume of the carbon particles is 2.3 mL / g or less, the carbon structure does not become bulky, the energy density as an electrode can be increased, and the discharge capacity per unit volume can be increased. In addition, the carbonaceous wall forming the pores is not thin, and the shape of the carbonaceous wall can be maintained even after repeated insertion and extraction of anions, which is advantageous in that long-term cycleability is improved. .

It is preferable that a portion having a layered structure be present in the carbonaceous wall. The electrical resistivity of the carbonaceous wall is preferably 1.0 Ω · cm or less, and more preferably 1.0 × 10 ⁻¹ Ω · cm or less. Since the electrical conductivity in an electrode becomes favorable in the said electrical resistivity being 1.0 ohm * cm or less, a high output characteristic can be obtained. The smaller the electrical resistivity, the better. However, the electrical resistivity does not have to be 1.0 × 10 ^-1 Ω · cm or less. If the electrical resistivity is 1.0 Ω · cm or less, the conductive path in the electrode is sufficiently It can be formed.
The electrical resistivity can be measured, for example, by a powder resistance measurement system (MCP-PD51, manufactured by Mitsubishi Chemical Analytech Co., Ltd.).

  The pore volume of the porous carbon can be determined, for example, using the BJH (Barrett Joyner Hallender) method from the measurement results of the adsorption isotherm with an automatic specific surface area / pore distribution measuring device (Tri Star II 3020, manufactured by Shimadzu Corporation). It can be asked.

There is no restriction | limiting in particular as a median diameter by the volume based particle size distribution of the said porous carbon, Although it can select suitably according to the objective, 1 micrometer or more and 20 micrometers or less are preferable, and 1 micrometer or more and 10 micrometers or less are more preferable. It is advantageous at the point which can suppress that the volume density of an electrode falls large that the median diameter of porous carbon is in the said preferable range.
The median diameter can be measured, for example, by a laser diffraction scattering particle size distribution measurement method.

The porous carbon preferably has crystallinity.
As the crystallinity of the porous carbon, it is not necessary that all the carbonaceous matter has a crystalline structure having crystallinity, and an amorphous structure having no crystallinity may exist in part. , All may have an amorphous structure.
The term "having crystallinity" means a state (graphite layer) in which a hexagonal plate-like single crystal in which carbons are bonded by an sp2 hybrid orbital is formed in a layer. As a method of confirming that the porous carbon has crystallinity, for example, a method of observing a layered structure of graphite using a transmission electron microscope (TEM) or a peak of a spectrum by X-ray diffraction The method of confirmation etc. are mentioned. In particular, in the X-ray diffraction spectrum, it is preferable to confirm that it has a diffraction peak in the region of 25.00 or more and 27.00 or less of the Bragg angle 2θ, and in the region of the Bragg angle 2θ It is more preferable to confirm having.

  Here, the X-ray diffraction spectrum will be described. The X-ray diffraction spectrum can be obtained, for example, from measurement results using an X-ray diffraction apparatus (XRD: X-ray diffraction).

  When X-rays having a wavelength similar to the distance between atoms are incident on a material in which atoms are regularly arranged, the X-rays are scattered by electrons belonging to each atom. The scattered X-rays interfere with each other, and the reinforcement in a specific direction causes an X-ray diffraction phenomenon. By measuring the diffraction spectrum while changing the wavelength of the incident X-ray, the interstitial distance of the crystal structure of the substance can be measured. At this time, if the object to be measured is amorphous (amorphous), there is no regularity in the lattice distance, and the diffraction spectrum is only a gentle mountain or a flat in the entire measurement wavelength. However, in the crystallized portion, since the lattice distance shows regularity, a peak (maximum value) appears in the diffraction spectrum at a specific wavelength corresponding to the lattice distance. In the following description, such a specific maximum value is particularly referred to as a diffraction peak. That is, having a diffraction peak in the region of the Bragg angle 2θ indicates that at least a part of the carbon particles of porous carbon is crystallized. In other words, it indicates that a part of carbon particles is graphitized.

Also, the fact that there are two diffraction peaks indicates that two crystal structures having different lattice distances appear. Here, it is more preferable that the intensity ratio (Il / Ih)> 1 when the diffraction peak intensity on the low angle side among the two peaks is Il and the diffraction peak intensity on the high angle side is Ih. A large proportion of the low-angle-side diffraction peak intensity Il means that the carbon interlayer distance d in the graphitized region is large. If the strength ratio (Il / Ih) is larger than 1, anion intercalation occurs between porous carbon graphite layers when the positive electrode potential (vs. Li ^/ Li ⁺ ) reaches a region of 4.0 V or more. Even in this case, since the interlayer distance of the graphite layer is wide, the carbon layer structure is not broken and the carbon particles can be prevented from being broken.

  There is no restriction | limiting in particular as a shape of the said porous carbon, Although it can select suitably according to the objective, Particulate form or lump form is preferable. If the shape of the porous carbon is particulate or massive, it is easy to form a close-packed structure when made into an electrode, and the electrode density can be increased, so that the discharge capacity per unit volume can be increased. it can.

The porous carbon is not particularly limited, and one produced appropriately may be used, or a commercially available product may be used.
As said commercial item, Knobel (trademark) (made by Toyo Carbon Co., Ltd.) etc. are mentioned, for example.

As a method of producing the porous carbon, for example, a reinforcing material having a three-dimensional network structure and a starting material which is an organic substance as a carbon material forming source are formed and carbonized by firing at 2,000 ° C. or more. There is no restriction | limiting in particular as said organic substance, According to the objective, it can select suitably, For example, a polyimide, a phenol resin, an acrylic resin, the thermosetting resin of a pitch system etc. are mentioned.
Thereafter, by dissolving the muscle material with an acid or alkali, the trace in which the muscle material is dissolved becomes a plurality of mesopores forming a three-dimensional network structure, and can be formed intentionally.
There is no restriction | limiting in particular as said reinforcing material, According to the objective, it can select suitably, For example, acid or alkali-soluble metal, metal oxide, metal salt, metal containing organic substance etc. are mentioned.
The starting material is not particularly limited as long as it can be carbonized, and can be appropriately selected according to the purpose.
In addition, since the said starting material is an organic substance generally and discharge | releases a volatile substance at the time of carbonization, since a micropore is formed as an emission mark, it is difficult to manufacture the carbon particle in which the said micropore does not exist at all.

<Conductive polymer>
The conductive polymer is preferably a polymer capable of storing or releasing a cation or an anion in a redox reaction.
There is no restriction | limiting in particular as said conductive polymer, According to the objective, it can select suitably, For example, polythiophene or its derivative (s), polyaniline or its derivative, polypyrrole or its derivative, polyacetylene or its derivative, polycarbazole or its derivative Polyvinylpyridine or derivatives thereof, poly (n-vinylcarbazole) or derivatives thereof, polyfluorene or derivatives thereof, polyphenylene or derivatives thereof, poly (p-phenylenevinylene) or derivatives thereof, poly (pyridinevinylene) or derivatives thereof, poly An amine group, a hydroxy group, a nitrile, or the like, as appropriate, quinoxaline or a derivative thereof, polyquinoline or a derivative thereof, a polyoxadiazole derivative, a polyvasophenanthroline derivative, a polytriazole derivative, or a polymer thereof , Like those substituted with a substituent such as a carbonyl group. These may be used alone or in combination of two or more. Among these, polythiophene derivatives are preferable because they have high energy density.

As said polythiophene derivative, the polymer which has a repeating unit represented by following General formula (1) is preferable.
The polythiophene derivative having a repeating unit represented by the general formula (1) is a stabilized redox compound, and is a polymer accompanied by a redox reaction in at least one of a charge reaction and a discharge reaction.

  In the general formula (1), Z represents an atomic group forming a 5- to 9-membered heterocyclic ring containing an S element, an O element, or an Se element as a ring member. Since the S element, the O element or the Se element can have a large number of oxidation numbers, by including the S element, the O element or the Se element as a ring member, the transfer of electrons involved in the oxidation and reduction reactions is a multielectron reaction. It can be expected to progress. As a result, a high capacity per active material can be obtained, and a high energy density can be obtained when a polythiophene derivative is included as an active material of the storage element.

Ar represents an aromatic ring or an aromatic heterocycle.
Examples of the aromatic ring include benzene, biphenyl, naphthalene, anthracene, fluorene, pyrene, and derivatives thereof.
Examples of the aromatic heterocycle include pyridine, quinoline, thiophene, furan, oxazole, oxadiazole, carbazole, and derivatives thereof. Among these, thiophene and thiophene derivatives are preferable.

As a substituent of an aromatic ring or an aromatic heterocyclic ring, an alkyl group, an alkoxy group, or a halogen atom etc. are mentioned, for example.
As said alkyl group, a methyl group, an ethyl group, isopropyl group, or a butyl group etc. are mentioned, for example.
As said alkoxy group, a methoxy group, an ethoxy group, a propoxy group, or a butoxy group etc. are mentioned, for example.
As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom etc. are mentioned, for example.

n is preferably a natural number of 2 or more, more preferably a natural number of 10 to 100.
0 is preferably a natural number of 0 or more, and more preferably a natural number of 0 or 10 to 100.

  The polythiophene derivative having a repeating unit represented by the general formula (1) is preferably a polythiophene derivative having a repeating unit represented by the following general formula (2).

However, in the general formula (2), R represents a substituted or unsubstituted alkylene group or a substituted or unsubstituted branched alkylene group. p represents a natural number of 1 or more. Q represents an S element, an O element, or an Se element. Ar represents an aromatic ring or aromatic heterocycle which may have a substituent. n represents a natural number of 2 or more, and m represents a natural number of 0 or 2 or more.

  R represents a substituted or unsubstituted alkylene group or a substituted or unsubstituted branched alkylene group. As a group substituted by the said alkylene group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a thioalkyl group, an arylthio group, an alkylamino group, an arylamino group, or a halogen atom etc. are mentioned, for example.

As said alkyl group, a methyl group, an ethyl group, isopropyl group, or a butyl group etc. are mentioned, for example.
As said alkoxy group, that whose alkyl part is the said alkyl group is mentioned.
As said aryl group, a phenyl group, 4-toluyl group, 4-hydroxyphenyl group, 1-naphthyl group, or 2-naphthyl group etc. are mentioned, for example.
As said aryloxy group, that whose aryl part is said aryl group is mentioned, for example.
As said thioalkyl group, a methylthio group, an ethylthio group, or a butylthio group etc. are mentioned, for example.
As said arylthio group, a phenylthio group etc. are mentioned, for example.
Examples of the alkylamino group include diethylamino group, dimethylamino group, and hydroxyamino group.
Examples of the arylamino group include diphenylamino group and phenylnaphthylamino group.
As said halogen atom, a fluorine atom, a chlorine atom, or a bromine atom etc. are mentioned, for example.
p is a natural number of 1 or more representing the number of repeating units, and represents a natural number of 1 to 3.
Ar, m and n have the same meaning as in the above general formula (1).

  It is preferable that the polythiophene derivative which has a repeating unit represented by said General formula (1) is a polythiophene derivative which has a repeating unit represented by following General formula (3).

However, in the general formula (3), R represents a substituted or unsubstituted alkylene group or a substituted or unsubstituted branched alkylene group. p represents a natural number of 1 or more. Ar represents an aromatic ring or aromatic heterocycle which may have a substituent. n represents a natural number of 2 or more, and m represents a natural number of 0 or 2 or more.
Ar, m and n have the same meaning as the above general formula (1), and R and p have the same meaning as the above general formula (2).

  Here, specific examples of the polythiophene derivative having a repeating unit represented by the general formula (1) will be shown below, but it is not limited thereto. However, in the following formula, n represents a natural number of 2 or more, and m represents a natural number of 0 or 2 or more.

  Among the exemplified compounds of the polythiophene derivative exemplified above, the exemplified compounds (2), (3), (4), (5), (5), (8), (E) from the viewpoint of the magnitude of discharge capacity and ease of synthesis. 10), (11), (16), (26), (32), (36) and (44) are particularly preferred.

The polythiophene derivative is preferably a polymer having a repeating unit represented by the following general formula (61).
However, in the general formula (61), n1 and n2 each represent a natural number of 2 or more, n1 is more preferably a natural number of 10 to 100, and n2 is more preferably a natural number of 100 to 5,000.

The conductive polymer is preferably a polymer having a structure represented by the following general formula (4) in a repeating unit.
However, in the said General formula (4), Ar < ₁ >, Ar < ₂ > and Ar < ₃ > represent the aromatic ring or aromatic heterocycle which may have a substituent, respectively.
Examples of the aromatic ring include benzene, biphenyl, naphthalene, anthracene, fluorene, pyrene, and derivatives thereof.
Examples of the aromatic heterocycle include pyridine, quinoline, thiophene, furan, oxazole, oxadiazole, carbazole, and derivatives thereof. Among these, thiophene and thiophene derivatives are preferable.
As a substituent of an aromatic ring or an aromatic heterocyclic ring, an alkyl group, an alkoxy group, or a halogen atom etc. are mentioned, for example.
As said alkyl group, a methyl group, an ethyl group, isopropyl group, or a butyl group etc. are mentioned, for example.
As said alkoxy group, a methoxy group, an ethoxy group, a propoxy group, or a butoxy group etc. are mentioned, for example.
As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom etc. are mentioned, for example.

  Here, as the conductive polymer having a structure represented by the above general formula (4) in the repeating unit, the following exemplified compounds may be mentioned, but it is not limited thereto. However, in the following formula, n represents a natural number of 2 or more.

As said conductive polymer, the polymer which has a repeating unit represented by following General formula (5) is preferable.
However, in the general formula (5), R ₁ , R ₂ and R ₃ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted branched alkyl group. Ar ₁ , Ar ₂ and Ar _{3 each} represent an aromatic ring or aromatic heterocycle which may have a substituent. n represents a natural number of 2 or more.

As an alkyl group in R ₁ , R ₂ and R ₃ , for example, a methyl group, an ethyl group, a propyl group, a butyl group and the like can be mentioned.
As a branched alkyl group in R < ₁ >, R < ₂ > and R < ₃ >, an isopropyl group, an isobutyl group, a sec-butyl group, a tert- butyl group etc. are mentioned, for example.
As an aromatic ring in Ar ₁ , Ar ₂ and Ar ₃ , for example, benzene, biphenyl, naphthalene, anthracene, fluorene, pyrene or derivatives thereof can be mentioned.
Examples of the aromatic heterocyclic ring in Ar ₁ , Ar ₂ and Ar ₃ include pyridine, quinoline, thiophene, furan, oxazole, oxadiazole, carbazole, and derivatives thereof. Among these, thiophene and thiophene derivatives are preferable.

As a substituent of an alkyl group, a branched alkyl group, an aromatic ring or an aromatic heterocyclic ring, an alkyl group, an alkoxy group, or a halogen atom etc. are mentioned, for example.
As said alkyl group, a methyl group, an ethyl group, isopropyl group, or a butyl group etc. are mentioned, for example.
As said alkoxy group, a methoxy group, an ethoxy group, a propoxy group, or a butoxy group etc. are mentioned, for example.
As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom etc. are mentioned, for example.
n is preferably a natural number of 2 or more, more preferably a natural number of 100 to 5,000.

  Although the following exemplary compounds are mentioned as a conductive polymer represented by the said General formula (5), It is not limited to these. However, in the following formula, n represents a natural number of 2 or more.

As the conductive polymer, a polymer having a repeating unit represented by the following general formula (63) is preferable.
However, in the general formula (63), n is preferably a natural number of 2 or more, and more preferably a natural number of 100 to 5,000.

As the conductive polymer, a polymer having a repeating unit represented by the following general formula (65) is preferable.
However, in the general formula (65), n is preferably a natural number of 2 or more, and more preferably a natural number of 100 to 5,000.

  Here, the polythiophene derivative having a repeating unit represented by the general formula (1) can be obtained by polymerizing a thiophene derivative of the general formula (1A) or the general formula (1B) obtained by the following reaction .

However, in general formula (1A), Me represents a methyl group, and Z represents an atomic group forming a 5- to 9-membered heterocyclic ring containing an S element as a ring member.

The thiophene derivative represented by the general formula (1A) can be synthesized by the method described in Synthetic Communications 28 (12), 2237-2244 (1998). That is, it can be obtained by a nucleophilic substitution reaction using an acid catalyst of an alkoxy-substituted thiophene such as 3,4-dimethoxythiophene and a chalcogen element source such as dithiols and diols.
The reaction temperature is preferably 0 ° C to 150 ° C, and more preferably 50 ° C to 130 ° C.
Examples of the acid catalyst include acids (Brensted acid) such as sulfuric acid, hydrochloric acid, phosphoric acid, methanesulfonic acid, trichloroacetic acid, trifluoroacetic acid, p-toluenesulfonic acid and the like.
Examples of the reaction solvent include toluene, xylene, anisole, tetralin, methylcyclohexane, ethylcyclohexane, chlorobenzene, ortho-dichlorobenzene and the like.

The thiophene derivative represented by the general formula (1B) can be synthesized by the method described in Journal of Materials Chemistry 8 (8), 1719 to 1724 (1998). That is, by cyclizing the dibromo form of thione with sodium sulfide nonahydrate and oxidizing it with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) You can get it.
0 to 100 degreeC is preferable and, as for the reaction temperature in the case of cyclization, 10 to 40 degreeC is more preferable.
0 to 150 degreeC is preferable and, as for the reaction temperature in the case of oxidation, 80 to 130 degreeC is more preferable.

The polymerization of the polythiophene derivative can be carried out by oxidative coupling polymerization using an oxidizing agent.
Examples of the oxidizing agent include iron (III) chloride and metal salts of aromatic sulfonic acids.

  Examples of the metal salts of aromatic sulfonic acids include ferric o-toluenesulfonic acid, ferric m-toluenesulfonic acid, ferric p-toluenesulfonic acid, cupric o-toluenesulfonic acid, and m- Cupric toluene sulfonate, cupric p-toluene sulfonate, cobalt o-toluene sulfonate, cobalt m-toluene sulfonate, cobalt p-toluene sulfonate, manganese o-toluene sulfonate, manganese m-toluene sulfonate And p-toluenesulfonic acid manganese, ferric o-ethylbenzenesulfonic acid, ferric m-ethylbenzenesulfonic acid, ferric p-ethylbenzenesulfonic acid, ferric naphthalenesulfonic acid, derivatives thereof and the like. . These may be used alone or in combination of two or more.

Examples of the solvent for polymerization include alcohol solvents, halogenated hydrocarbons, aromatic hydrocarbons, acetonitrile, benzonitrile and the like. These may be used alone or in combination of two or more.
As said alcohol solvent, methanol, ethanol, butanol etc. are mentioned, for example.
As said halogenated hydrocarbon, chloroform, a dichloromethane, 1, 2- dichloroethane etc. are mentioned, for example.
Examples of the aromatic hydrocarbon include toluene, xylene, anisole, chlorobenzene, orthodichlorobenzene, nitrobenzene and the like.

The polythiophene derivative as the conductive polymer preferably has an oxidation potential at 3 V or more and 5 V or less in lithium metal electrode standard (vs. Li / Li ⁺ ), and more preferably one having an oxidation potential at 3 V or more and 4.5 V or less preferable.
When the active material of the present invention is used as a positive electrode active material of a storage element, the porous carbon starts to absorb anions at a potential of 3 V or more on a lithium metal electrode basis (vs. Li / Li ⁺ ). Therefore, if the oxidation potential (vs. Li ^/ Li ⁺ ) of the polythiophene derivative is 3 V or more, it can be driven at the same operating voltage as porous carbon, so the capacity of both porous carbon and polythiophene derivative particles is used can do. As a result, a larger capacity can be obtained as an active material.
Further, at a potential of 5 V or more based on the lithium metal electrode (vs. Li / Li ⁺ ), the non-aqueous solvent used in the non-aqueous electrolyte is oxidized and decomposed, so the oxidation potential of the polythiophene derivative (vs. Li / Li) ^{When +} ) is 5 V or more, the capacity at that potential can not be utilized. Therefore, the oxidation potential of the polythiophene derivative based on the lithium metal electrode (vs. Li / Li ⁺ ) is preferably 3 V or more and 5 V or less. The oxidation potential can be measured, for example, by a method of cyclic voltammetry (CV).

The polythiophene derivative as the conductive polymer is present in a state at least partially contained in the plurality of pores forming the three-dimensional network structure, and is contained in most of the plurality of pores Preferably, it is more preferably contained in all of the plurality of pores.
Since the resistance of the polythiophene derivative itself as the conductive polymer is high, the transfer of electrons accompanying the redox of the polythiophene derivative can not be carried out smoothly if there is no intervening material with high electrical conductivity, so the capacity is greatly reduced. Cause. However, as described above, the electrical conductivity of the polythiophene derivative is compensated by the porous carbon by including the polythiophene derivative in at least a part of the plurality of pores in the porous carbon having high electrical conductivity. Therefore, the electron transfer accompanying the oxidation-reduction of the polythiophene derivative is performed smoothly, so that the capacity of many polythiophene derivatives contained in the active material is expressed, and the energy density is enhanced.
Furthermore, since the polythiophene derivative is contained to the inside of porous carbon by the plurality of pores of the porous carbon forming a three-dimensional network structure, more polythiophene derivatives in the active material are effectively utilized. Therefore, it is advantageous in that the energy density can be further increased. Moreover, since more polythiophene derivatives can be contained in one porous carbon particle, it leads to an increase in the density of the active material 1 particles, which further contributes to the improvement of the energy density.

  20/80 or more and 95/5 or less are preferable, and, as for mass ratio (porous carbon / conductive polymer) of the said porous carbon and the said conductive polymer, 30/70 or more and 80/20 or less are more preferable. By setting the mass ratio of the porous carbon to the conductive polymer in this range, it is possible to balance the energy density and the output characteristics.

<Method of manufacturing active material>
The active material can be produced by applying shear force under predetermined conditions using the particle composite apparatus to the porous carbon and the conductive polymer.
Examples of the particle composite apparatus include Nobilta (registered trademark) and Mechanofusion (registered trademark) manufactured by Hosokawa Micron Corporation, a paint shaker apparatus manufactured by Asada Iron Works Co., Ltd., Miracle K. C. K (kneading and dispersing machine), Dry Star (registered trademark) made by Ashizawa Finetech Co., Ltd., Sigma Dry (registered trademark), MIRALO (registered trademark) made by Nara Machinery Co., Ltd., COMPOSI (registered trademark) made by Nippon Coke Co., Ltd. And the like.

  As a method for confirming that the conductive polymer is contained in at least a part of the plurality of pores forming the three-dimensional network structure, for example, SEM, TEM, EDS (Energy Dispersive X-ray Spectrometry), etc. The method of using and observing etc. are mentioned. The cross section of the active material can be shown as a schematic cross sectional view showing a part of the cross section of the active material particle of FIG. 2 created based on a photograph by SEM and an elemental mapping image by EDS. In FIG. 2, reference numeral 101 denotes a pore, and reference numeral 102 denotes a conductive polymer.

  Thus, in the active material of the present invention, by including the conductive polymer in at least a part of the plurality of pores of porous carbon, the conductive polymer itself has good electric conductivity. Therefore, since the more conductive polymers in the active material are effectively utilized, it is possible to efficiently use the high capacity that the conductive polymers originally have. As a result, the active material can have a high energy density.

The active material of the present invention can be used as either a positive electrode active material or a negative electrode active material, but is a positive electrode active material from the viewpoint of obtaining an electricity storage element having characteristics of high energy density and high output characteristics. Is preferred.
As described below, the active material of the present invention can be suitably used as an electrode of a storage element.

(electrode)
The electrode of the present invention contains the active material of the present invention and further has other members as required.
The electrode may be any of a positive electrode and a negative electrode, but a positive electrode is preferable from the viewpoint of obtaining a storage element having characteristics of achieving both high energy density and high output characteristics.

<Positive electrode>
The positive electrode is a flat electrode portion provided with a positive electrode current collector and a positive electrode material.
The positive electrode material contains a positive electrode active material, a binder, a conductive auxiliary, a thickener, and a conductive auxiliary, and further contains other components as needed.

-Positive electrode active material-
As a positive electrode active material, an anion can be stored or released, and it is preferable to use the active material of the present invention, but when using a positive electrode active material other than the active material of the present invention, from the viewpoint of safety and cost. And carbonaceous materials are preferred.
Examples of the carbonaceous material include graphite (graphite), thermal decomposition products of organic substances under various thermal decomposition conditions, activated carbon and the like.
Examples of graphite (graphite) include coke, artificial graphite, natural graphite, graphitizable carbon, non-graphitizable carbon and the like.
The positive electrode active material may be used singly or in combination of two or more. Moreover, you may use together the substance of that excepting the above, for example, a lithium metal oxide.
Examples of the lithium metal oxide include lithium cobaltate (LiCoO ₂ ), lithium nickelate (LiNiO ₂ ), lithium manganate (LiMn ₂ O ₄ ), olivine-type lithium iron phosphate (LiFePO ₄ ), and Li _p Ni Manganese-cobalt-nickel ternary oxide lithium (for example, LiNi _1/3 Co _1/3 Mn _1/3 O ₂ ) and the like that can be represented by a composition formula of _x Co _y Mn _z O ₂ can be mentioned.

-Binder and thickener-
The binder is a binder for binding the positive electrode active materials, or between the positive electrode active material and the positive electrode current collector, to maintain the electrode structure.
As a material of the binder, for example, it is preferable to use any of a fluorine-based binder, an acrylate-based latex, and carboxymethylcellulose (CMC).
Examples of the fluorine-based binder include polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE).
As materials for the binder, other than the above, for example, ethylene-propylene-butadiene rubber (EPBR), styrene-butadiene rubber (SBR), isoprene rubber, acrylate latex, carboxymethylcellulose (CMC), methylcellulose, hydroxymethylcellulose, ethylcellulose And polyacrylic acid, polyvinyl alcohol, alginic acid, oxidized starch, starch phosphate, casein and the like. These may be used alone or in combination of two or more.
The binder is not particularly limited as long as it is a solvent, an electrolytic solution, and a material stable to an applied potential used at the time of electrode production, and may be appropriately selected depending on the purpose.

-Conducting auxiliary agent-
In the present invention, the conductive aid refers to a conductive material which is dispersed in the electrode and used to reduce the resistance of the electrode, plays a role of assisting the conductivity between the electrode materials, and has a function of forming a conductive network. Have.
It is preferable that the said conductive support agent uses a carbonaceous material according to a metal material or a positive electrode active material. These may be used alone or in combination of two or more.
As a metal material used for the said conductive support agent, copper, aluminum, etc. are mentioned, for example.
As a carbonaceous material used for the said conductive support agent, acetylene black, ketjen black, artificial graphite, natural graphite, a graphene, a carbon nanofiber, a carbon nanotube etc. are mentioned, for example. Among these, acetylene black and ketjen black are preferable.

-Positive electrode current collector-
The positive electrode current collector is not particularly limited as long as it can be used for the storage element, and can be appropriately selected according to the purpose.
The material of the positive electrode current collector is made of a conductive material and is not particularly limited as long as it is stable against the applied potential, and can be appropriately selected according to the purpose. For example, nickel, aluminum, titanium, tantalum and the like can be mentioned. Among these, stainless steel and aluminum are preferable.
The type (shape and presence of processing) of the positive electrode current collector is not particularly limited as long as it can be used in the process of the positive electrode manufacturing method described later, and may be appropriately selected according to the purpose. For example, plain foil, hollow foil, edged foil, penetrating foil, projecting foil, expanded metal, etc. can be mentioned. Among these, plain foil, holey foil, edged foil, penetrating foil, and projecting foil are preferable.
A coating foil on which a carbonaceous material used for the conductive additive is applied in advance on the positive electrode current collector may be used as a positive electrode current collector. In this case, the carbonaceous material used as the coating layer may be the same carbonaceous material as the carbonaceous material used as the conductive aid described above for the conductive aid. Among these, acetylene black, ketjen black, artificial graphite and natural graphite are preferable.

<Method of manufacturing positive electrode>
As a manufacturing method of a positive electrode, a binder, a thickener, a conductive support agent, and a solvent are added to the positive electrode active material as needed, and a positive electrode material in a slurry form is applied on the positive electrode current collector and dried. Methods etc.
Examples of the solvent include water, aqueous solvents such as alcohol, and organic solvents such as N-methyl-2-pyrrolidone (NMP) and toluene.
The positive electrode active material may be formed into a sheet electrode by roll forming, or may be formed into a pellet electrode by compression forming.

<Negative electrode>
The negative electrode is a flat electrode portion provided with a negative electrode current collector and a negative electrode material.
The negative electrode material contains a negative electrode active material, a binder, a conductive auxiliary, a thickener, and a conductive auxiliary, and further contains other components as needed.

-Negative electrode active material-
The active material of the present invention can be used as the negative electrode active material, but when using a negative electrode active material other than the active material of the present invention, a carbonaceous material is preferable in terms of safety and cost.
As the carbonaceous material, for example, graphite (graphite), a thermal decomposition product of an organic substance under various thermal decomposition conditions, lithium metal oxide and the like can be mentioned.
Examples of the graphite (graphite) include coke, artificial graphite, natural graphite, graphitizable carbon, non-graphitizable carbon and the like.
However, the negative electrode active material is not particularly limited as long as it can occlude and release cations in a non-aqueous solvent system, and can be appropriately selected according to the purpose.
As a material used for the negative electrode active material, for example, a carbonaceous material capable of absorbing and desorbing lithium ion as a cation, a metal oxide, a metal or metal alloy capable of alloying with lithium, and a metal capable of alloying with lithium Composite alloy compounds of lithium-containing alloys and lithium, lithium metal nitride and the like can be mentioned.
Examples of the metal oxide include antimony tin oxide and silicon monoxide.
Examples of metals or metal alloys which can be alloyed with lithium include lithium, aluminum, tin, silicon, zinc and the like.
Examples of a composite alloy compound of lithium and an alloy containing lithium and an alloyable metal include lithium titanate and the like.
Examples of the metal lithium nitride include lithium cobalt nitride and the like.
The material used for these negative electrode active materials may be used individually by 1 type, and may use 2 or more types together. Among these, artificial graphite, natural graphite and lithium titanate are preferable.
In addition, as a cation, lithium ion is used widely.

-Conducting auxiliary agent-
As a conductive support agent used for a negative electrode, the same conductive support agent as the conductive support agent already demonstrated by the positive electrode can be used.

-Binder and thickener-
As the binder and the thickener used for the negative electrode, the same binder and thickener as those described above for the positive electrode can be used.
As said binder and a thickener, a fluorine-type binder, styrene butadiene rubber (SBR), carboxymethylcellulose (CMC) is preferable, for example.

<Negative current collector>
There is no restriction | limiting in particular as a negative electrode collector, According to the objective, it can select suitably.
The material of the negative electrode current collector is formed of a conductive material, and is not particularly limited as long as it is stable against an applied potential, and can be appropriately selected according to the purpose. Stainless steel, nickel, aluminum, copper and the like can be mentioned. Among these, stainless steel, copper and aluminum are particularly preferable.
The shape of the negative electrode current collector may be appropriately selected depending on the purpose other than flat plate shape.
The size of the negative electrode current collector is not particularly limited as long as it can be used for a storage element, and can be appropriately selected according to the purpose.

<< Method of manufacturing negative electrode >>
As a method of manufacturing the negative electrode, a negative electrode active material is optionally added with a binder, a thickener, a conductive auxiliary agent, a solvent, etc. to form a slurry, and the negative electrode material is applied onto the negative electrode current collector and dried. The method is used.
The negative electrode material in the form of a slurry is directly roll-formed to form a sheet electrode, the pellet electrode is formed by compression molding, a thin film of the negative electrode active material is formed on the negative electrode current collector by vapor deposition, sputtering, plating, etc. A method or the like may be used.
As a solvent used for the manufacturing method of a negative electrode, the solvent similar to the manufacturing method of a positive electrode can be used.

(Storage element)
The storage element of the present invention preferably has a positive electrode, a negative electrode, and an electrolytic solution, is disposed between the positive electrode and the negative electrode, and has a separator for holding the electrolytic solution, and further, as required, It has other members.
At least one of the positive electrode and the negative electrode is an electrode of the present invention.

<Electrolyte solution>
The electrolytic solution is preferably a non-aqueous electrolytic solution obtained by dissolving an electrolyte salt in a non-aqueous solvent.

-Non-aqueous solvent-
As said non-aqueous solvent, an aprotic organic solvent is preferable.
As said aprotic organic solvent, a carbonate type organic solvent is mentioned, for example, A low viscosity solvent is preferable.
Examples of the carbonate-based organic solvent include linear carbonates and cyclic carbonates. These may be used alone or in combination of two or more.
Among these, linear carbonates are preferable in that the solvency of the electrolyte salt is high.
Examples of the linear carbonate include dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC) and the like. These may be used alone or in combination of two or more. Among these, dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) are preferable.
When a mixed solvent of dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) is used, the mixing ratio of dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) is not particularly limited, and may be appropriately selected depending on the purpose. It can be selected.

Examples of cyclic carbonates include propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate (BC), vinylene carbonate (VC), fluoroethylene carbonate (FEC) and the like. These may be used alone or in combination of two or more. Among these, propylene carbonate (PC) and ethylene carbonate (EC) are preferable.
When a mixed solvent of ethylene carbonate (EC) as cyclic carbonate and dimethyl carbonate (DMC) as chain carbonate is used, the mixing ratio of ethylene carbonate (EC) and dimethyl carbonate (DMC) is not particularly limited. Instead, it can be selected appropriately according to the purpose.

Examples of ester-based organic solvents include cyclic esters and chain esters. Examples of the cyclic ester include γ-butyrolactone (γBL), 2-methyl-γ-butyrolactone, acetyl-γ-butyrolactone, γ-valerolactone and the like.
Examples of the chain ester include propionic acid alkyl ester, malonic acid dialkyl ester, acetic acid alkyl ester, formic acid alkyl ester and the like.
Examples of the acetic acid alkyl ester include methyl acetate (MA) and ethyl acetate.
Examples of the formic acid alkyl ester include methyl formate (MF) and ethyl formate.

As an ether type organic solvent, cyclic ether, chain | strand-shaped ether etc. are mentioned, for example.
Examples of the cyclic ether include tetrahydrofuran, alkyltetrahydrofuran, alkoxytetrahydrofuran, dialkoxytetrahydrofuran, 1,3-dioxolane, alkyl-1,3-dioxolane and 1,4-dioxolane.
Examples of the chain ether include 1,2-dimethoxyethane (DME), diethyl ether, ethylene glycol dialkyl ether, diethylene glycol dialkyl ether, triethylene glycol dialkyl ether, tetraethylene glycol dialkyl ether and the like.

-Electrolyte salt-
As an electrolyte salt used for a non-aqueous electrolyte solution, a lithium salt is preferable.
The lithium salt is not particularly limited as long as it dissolves in a non-aqueous solvent and exhibits high ion conductivity, and can be appropriately selected according to the purpose. For example, lithium hexafluorophosphate (LiPF ₆ ) Lithium perchlorate (LiClO ₄ ), lithium chloride (LiCl), lithium borofluoride (LiBF ₄ ), lithium arsenic hexafluoride (LiAsF ₆ ), lithium trifluorometasulfonate (LiCF ₃ SO ₃ ), lithium bistri fluoromethyl imide _{(LiN (C 2 F 5 SO} 2) 2), lithium bis perfluoro ethyl imide _{(LiN (CF 2 F 5 SO} 2) 2) , and the like. These may be used alone or in combination of two or more. Among these, LiPF ₆ and LiBF ₄ are preferable from the viewpoint of the size of the amount of occlusion of the anion in the electrode.
There is no restriction | limiting in particular as a density | concentration of electrolyte salt, Although it can select suitably according to the objective, It is 0.5 mol / L or more and 6 mol / L or less in nonaqueous solvent from the point of coexistence of discharge capacity and output. Is preferable, and 1 mol / L or more and 4 mol / L or less is more preferable.

<Separator>
The separator is provided between the positive electrode and the negative electrode in order to prevent a short circuit between the positive electrode and the negative electrode.
There is no restriction | limiting in particular as a material of the said separator, a shape, a magnitude | size, and a structure, According to the objective, it can select suitably.
Examples of the material of the separator include paper such as kraft paper, vinylon mixed paper, synthetic pulp mixed paper, cellophane, polyethylene graft film, polyolefin nonwoven fabric such as polypropylene meltblown nonwoven fabric, polyamide nonwoven fabric, glass fiber nonwoven fabric, micropore film, etc. It can be mentioned. Among these, from the viewpoint of electrolyte retention, one having a porosity of 50% or more is preferable.
As a shape of the separator, a non-woven fabric having a high porosity is preferable to a thin film type having micropores (micropores).
The average thickness of the separator is preferably 20 μm or more from the viewpoint of short circuit prevention and electrolyte solution retention.
The size of the separator is not particularly limited as long as it can be used for the non-aqueous electrolyte storage element, and can be appropriately selected according to the purpose.
The separator may have a single-layer structure or a laminated structure in which a plurality of separators are stacked.

<Method of Manufacturing Storage Element>
The method for producing the storage element is not particularly limited and may be appropriately selected according to the purpose. For example, the positive electrode, the negative electrode, and the separator, and, if necessary, other component members are assembled into an appropriate shape A method of storing in a container and filling an electrolytic solution can be mentioned.

The shape of the storage element of the present invention is not particularly limited, and in addition to the shape as shown in FIG. 3, it may be appropriately selected from various commonly adopted shapes according to the application. it can.
Examples of the shape include a cylinder type in which a sheet electrode and a separator are in a spiral shape, a cylinder type having an inside-out structure in which a pellet electrode and a separator are combined, and a coin type in which a pellet electrode and a separator are stacked.

The storage element of the present invention, as shown in FIG. 3, includes a positive electrode 1, a negative electrode 2 provided opposite to the positive electrode 1, a separator 3 disposed between the positive electrode 1 and the negative electrode 2, and non-aqueous electrolysis. And a liquid.
The storage element 10 includes a container 5 as an outer can that encloses and holds the positive electrode 1, the negative electrode 2, the separator 3, and the non-aqueous electrolyte, and a positive electrode wire 6 connected to the positive electrode 1 through the container 5. And the negative electrode wire 7 connected to the negative electrode 2 through the container 5 in the same manner. The non-aqueous electrolyte spreads throughout the container 5. Although FIG. 3 illustrates the case where the storage element 10 is a secondary battery, for example, a capacitor or the like may be used.

<Use>
The storage element of the present invention can be suitably used as, for example, a non-aqueous electrolyte secondary battery, a non-aqueous electrolyte capacitor, and the like.
There is no restriction | limiting in particular in the use of the said electrical storage element, It can use for various uses, For example, a laptop computer, a pen input personal computer, a mobile personal computer, an e-book player, a mobile telephone, a mobile fax, a mobile copy, a mobile printer, a headphone Stereo, video movie, LCD TV, handy cleaner, portable CD, mini disk, walkie-talkie, electronic notebook, calculator, memory card, portable tape recorder, radio, motor, lighting equipment, toy, game machine, watch, strobe, camera etc. Power supply, backup power supply etc. may be mentioned.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

  In order to confirm the formation state of the pore in the carbonaceous material used as a positive electrode active material in each Example and Comparative Example, the following evaluations were performed.

<Formation state of pores of porous carbon>
In the carbonaceous material used as a positive electrode active material in each example and comparative example, the presence or absence of a pore forming a three-dimensional network structure is observed by TEM (JEM-2100, manufactured by Nippon Denshi Co., Ltd.), and evaluated according to the following criteria did. The results are shown in Tables 1-1 to 5-2.
[Evaluation criteria]
○: A pore 101 forming a three-dimensional network structure as shown in FIG. 1 could be confirmed ×: A pore 101 forming a three-dimensional network structure as shown in FIG. 1 could not be confirmed

<Formation state of composite active material>
In the active material used as a positive electrode active material in each example and comparative example, an image mapped by SEM and EDS (SU 8230, manufactured by Hitachi High-Technologies Corporation) is observed, and the conductive material is formed in the pores of the porous carbon The following criteria evaluated the presence or absence of the composite active material in which the conductive polymer was contained. The results are shown in Tables 1-1 to 5-2.
[Evaluation criteria]
○: presence of the conductive polymer 102 in the pores 101 forming a three-dimensional network structure as shown in FIG. 2 ×: inside the pores 101 forming a three-dimensional network structure as shown in FIG. 2 The presence of the conductive polymer 102 can not be confirmed

Example 1
<Preparation of Active Material>
An exemplified compound (2) represented by the following formula, which is a polythiophene derivative as a conductive polymer, is prepared, and a porous carbon (porous carbon) having a plurality of pores forming a three-dimensional network structure as a carbonaceous material A) (Knobel: registered trademark, manufactured by Toyo Carbon Co., Ltd.) was prepared. A cross-sectional TEM image of porous carbon A particles is shown in FIG. The BET specific surface area of the porous carbon A particles was 1,000 m ² / g, the pore volume was 0.6 mL / g, and the average diameter of the pores was 3 nm.

However, n is a natural number of 2 or more.

  Next, porous carbon A and compound (2) were mixed at a mass ratio of 70/30, and filled in a vial containing zirconia beads. This was set in a paint shaker (manufactured by Asada Iron Works Co., Ltd.), and shaking was performed for 4 hours. After the treatment, the active material was recovered to obtain a particulate active material. The obtained particulate active material was designated as a positive electrode active material A.

<Fabrication of positive electrode>
-Preparation of positive electrode slurry-
When positive electrode active material A as a positive electrode active material, acrylate latex (TRD 202A, manufactured by JSR Corporation) as a binder, carboxymethyl cellulose (Daicel 2200, manufactured by Daicel Co., Ltd.) as a thickener, and the positive electrode active material A as 100 Mix using a planetary mixer (Hibismix 3D-2, made by Primix, Inc.) so that the mass ratio of solid content is 100: 3: 5, add water to prepare an appropriate viscosity, and prepare a positive electrode slurry The positive electrode material is obtained.

-Production of positive electrode-
Next, the obtained positive electrode material was apply | coated to the single side | surface using a doctor blade on plain aluminum foil with an average thickness of 20 micrometers as a positive electrode collector. The average of the basis weight after drying (the mass of the positive electrode active material A in the coated positive electrode) was 3.0 mg / cm ² . This was punched out to a diameter of 16 mm to make a positive electrode. A cross-sectional SEM image of the positive electrode is shown in FIG. Moreover, the image which element-mapd the cross section of the positive electrode by EDS is shown in FIG.6 and FIG.7. FIG. 6 is a mapping image of a carbon (C) element, and FIG. 7 is a mapping image of a sulfur (S) element, each showing the dispersion state of each element in the positive electrode.

<Separator>
As separators, two sheets of non-woven cellulose separator (average thickness 40 μm) punched into a diameter of 16 mm were prepared.

<Negative electrode>
As a negative electrode, a lithium metal foil (average thickness 100 μm) punched to a diameter of 16 mm was used.

<Non-aqueous electrolyte>
As a non-aqueous electrolytic solution, a mixed solution (manufactured by Kishida Chemical Co., Ltd.) of ethylene carbonate (EC): dimethyl carbonate (DMC) = 1: 2 (mass%) containing 1.0 mol / L of LiPF ₆ electrolyte is used. It was.

<Manufacture of non-aqueous electrolyte storage element>
After vacuum drying the positive electrode, the negative electrode, and the separator at 150 ° C. for 4 hours, in a dry argon atmosphere glove box, a 2032 coin cell as a storage element was assembled.
50 μL of the non-aqueous electrolyte was injected into the 2032 coin cell. Thus, the non-aqueous electrolyte storage element of Example 1 was produced.

  About the obtained non-aqueous-electrolyte electrical storage element of Example 1, the charge / discharge test was done as follows. The results are shown in Table 1-1.

<Charge / discharge test>
The obtained non-aqueous electrolyte storage element of Example 1 is held in a thermostatic chamber at 25 ° C., using an automatic battery evaluation apparatus (1024 B-7 V 0.1 A-4, manufactured by Electrofield Co., Ltd.) as follows: Charge-discharge test was conducted.
As the first charge and discharge process, first, constant current charge was performed to 4.4 V as a charge termination voltage at a current value in charge and discharge rate 0.2 C conversion.
Thereafter, charging was stopped for 24 hours, and then constant current discharge was performed up to 1.7 V as a discharge termination voltage at a current value in charge / discharge rate 1 C conversion.
In addition, the current value of 0.2 C conversion is a current value which discharges a non-aqueous electrolyte storage element having a capacity of a nominal capacity value at a constant current and ends the discharge in 5 hours. Further, a current value in 1 C conversion is a current value at which discharge is completed in one hour by constant current discharge of a non-aqueous electrolyte storage element having a capacity of a nominal capacity value.
After the aging process, charge and discharge shown in the following steps were performed.
[1]: Constant current charge up to 4.4 V at a current value of charge / discharge rate 0.2 C conversion [2]: Rest for 5 minutes [3]: Constant current up to 1.7 V at a current value of charge / discharge rate 0.2 C converted Discharge [4]: 5 minutes pause [5]: Charge / discharge rate 10 C constant current to 4.4 V Constant current charge [6]: 5 minutes pause [7]: Charge / discharge rate 10 C equivalent current In the above charge / discharge test, the discharge capacity at step [3] and the discharge capacity at step [7] were measured while performing the above-mentioned charge / discharge test. The discharge curve at 0.2 C and the discharge curve at 10 C in Example 1 are shown in FIG.
The discharge capacity is a conversion value (mAh / g) per 1 g of the positive electrode active material A. Further, the energy density per volume (Wh / L) of the non-aqueous electrolytic solution storage element was calculated using the following formula 2.

[Equation 2]

  Next, in order to evaluate the output characteristics, the capacity ratio of the discharge capacity at the time of 10 C discharge to the discharge capacity at the time of the 0.2 C discharge was determined using the following Equation 3. The fact that the capacity ratio shows a value closer to 100% means that the output characteristic is high because it indicates that the high C rate has a good electrical conductivity that can be handled. Do.

[Equation 3]

  Next, high energy density and high power were evaluated based on the evaluation criteria shown below. The results are shown in Table 1-1.

High energy density
[Evaluation criteria for high energy density]
○: energy density per volume is 31 Wh / L or more Δ: energy density per volume is 29 Wh / L or more and less than 31 Wh / L ×: energy density per volume is less than 29 Wh / L

<High output performance>
[High output evaluation criteria]
○: 60% or more of discharge capacity ratio at 10 C discharge to discharge capacity at 0.2 C discharge Δ: 50% to 60% capacity ratio of discharge capacity at 10 C discharge to discharge capacity at 0.2 C discharge Less than ×: The capacity ratio of discharge capacity at 10 C discharge to discharge capacity at 0.2 C discharge is less than 50%

(Example 2)
The non-aqueous electrolytic solution of Example 2 was carried out in the same manner as in Example 1 except that the exemplified compound (2) as the conductive polymer in Example 1 was changed to the exemplified compound (3) represented by the following formula. A storage element was manufactured and evaluated in the same manner as Example 1. The results are shown in Table 1-1.

However, n is a natural number of 2 or more.

(Example 3)
Non-aqueous electrolyte solution of Example 3 in the same manner as Example 1, except that Example Compound (2) as a conductive polymer in Example 1 is changed to Example Compound (4) represented by the following formula. A storage element was manufactured and evaluated in the same manner as Example 1. The results are shown in Table 1-1.

However, n is a natural number of 2 or more.

(Example 4)
The non-aqueous electrolytic solution of Example 4 was carried out in the same manner as Example 1, except that in Example 1, the exemplified compound (2) as the conductive polymer was changed to the exemplified compound (5) represented by the following formula. A storage element was manufactured and evaluated in the same manner as Example 1. The results are shown in Table 1-1.

However, n is a natural number of 2 or more.

(Example 5)
The non-aqueous electrolyte of Example 5 was carried out in the same manner as Example 1, except that Example Compound (2) as the conductive polymer in Example 1 was changed to Example Compound (8) represented by the following formula. A storage element was manufactured and evaluated in the same manner as Example 1. The results are shown in Table 1-1.

However, n is a natural number of 2 or more.

(Example 6)
The non-aqueous electrolyte of Example 6 was carried out in the same manner as Example 1, except that Example Compound (2) as the conductive polymer in Example 1 was changed to Example Compound (10) represented by the following formula. A storage element was manufactured and evaluated in the same manner as Example 1. The results are shown in Table 1-2.

However, n is a natural number of 2 or more.

(Example 7)
Non-aqueous electrolyte solution of Example 7 in the same manner as Example 1, except that in Example 1, the exemplified compound (2) as the conductive polymer is changed to the exemplified compound (11) represented by the following formula. A storage element was manufactured and evaluated in the same manner as Example 1. The results are shown in Table 1-2.

However, n is a natural number of 2 or more.

(Example 8)
The non-aqueous electrolyte of Example 8 in the same manner as in Example 1 except that the exemplified compound (2) as the conductive polymer in Example 1 is changed to the exemplified compound (16) represented by the following formula. A storage element was manufactured and evaluated in the same manner as Example 1. The results are shown in Table 1-2.

However, n is a natural number of 2 or more.

(Example 9)
The non-aqueous electrolyte of Example 9 was carried out in the same manner as Example 1, except that Example Compound (2) as the conductive polymer in Example 1 was changed to Example Compound (26) represented by the following formula. A storage element was manufactured and evaluated in the same manner as Example 1. The results are shown in Table 1-2.

However, n is a natural number of 2 or more.

(Example 10)
The non-aqueous electrolyte of Example 10 was carried out in the same manner as Example 1, except that Example Compound (2) as the conductive polymer in Example 1 was changed to Example Compound (32) represented by the following formula. A storage element was manufactured and evaluated in the same manner as Example 1. The results are shown in Table 1-2.

Here, n is a natural number of 2 or more, and m is a natural number of 0 or 2 or more.

(Example 11)
The non-aqueous electrolytic solution of Example 11 was carried out in the same manner as in Example 1 except that the exemplified compound (2) as the conductive polymer in Example 1 was changed to the exemplified compound (36) represented by the following formula. A storage element was manufactured and evaluated in the same manner as Example 1. The results are shown in Table 1-3.

Here, n is a natural number of 2 or more, and m is a natural number of 0 or 2 or more.

(Example 12)
The non-aqueous electrolyte of Example 12 in the same manner as Example 1, except that Example Compound (2) as the conductive polymer in Example 1 is changed to Example Compound (44) represented by the following formula. A storage element was manufactured and evaluated in the same manner as Example 1. The results are shown in Table 1-3.

Here, n is a natural number of 2 or more, and m is a natural number of 0 or 2 or more.

(Example 13)
Non-aqueous electrolyte storage battery of Example 13 in the same manner as Example 1, except that in Example 1, the exemplified compound (2) as the conductive polymer is changed to a compound (46) represented by the following formula. The device was manufactured and evaluated in the same manner as Example 1. The results are shown in Table 1-3.

However, n is a natural number of 2 or more.

(Example 14)
Non-aqueous electrolyte storage battery of Example 14 in the same manner as Example 1, except that in Example 1, the exemplified compound (2) as the conductive polymer is changed to the compound (47) represented by the following formula. The device was manufactured and evaluated in the same manner as Example 1. The results are shown in Table 1-3.

However, n is a natural number of 2 or more.

(Example 15)
Non-aqueous electrolyte storage battery of Example 15 in the same manner as Example 1, except that the exemplified compound (2) as the conductive polymer in Example 1 is changed to the compound (48) represented by the following formula. The device was manufactured and evaluated in the same manner as Example 1. The results are shown in Table 1-3.

However, n is a natural number of 2 or more.

(Example 16)
Non-aqueous electrolyte storage battery of Example 16 in the same manner as Example 1, except that the exemplified compound (2) as the conductive polymer in Example 1 is changed to the compound (49) represented by the following formula. The device was manufactured and evaluated in the same manner as Example 1. The results are shown in Table 1-4.

However, n is a natural number of 2 or more.

(Example 17)
Non-aqueous electrolyte storage battery of Example 17 in the same manner as Example 1, except that the exemplified compound (2) as the conductive polymer in Example 1 is changed to the compound (50) represented by the following formula. The device was manufactured and evaluated in the same manner as Example 1. The results are shown in Table 1-4.

However, n is a natural number of 2 or more.

(Example 18)
Non-aqueous electrolyte storage battery of Example 18 in the same manner as Example 1, except that Example Compound (2) as a conductive polymer in Example 1 is changed to a compound (51) represented by the following formula. The device was manufactured and evaluated in the same manner as Example 1. The results are shown in Table 1-4.

However, n is a natural number of 2 or more.

(Example 19)
Non-aqueous electrolyte storage battery of Example 19 in the same manner as Example 1 except that the exemplified compound (2) as the conductive polymer in Example 1 is changed to the compound (52) represented by the following formula. The device was manufactured and evaluated in the same manner as Example 1. The results are shown in Table 1-4.

However, n is a natural number of 2 or more.

Example 20
Non-aqueous electrolyte storage battery of Example 20 in the same manner as Example 1, except that Example Compound (2) as the conductive polymer in Example 1 is changed to the compound (53) represented by the following formula. The device was manufactured and evaluated in the same manner as Example 1. The results are shown in Table 1-4.

However, n is a natural number of 2 or more.

(Example 21)
Non-aqueous electrolyte storage battery of Example 21 in the same manner as Example 1, except that Example Compound (2) as a conductive polymer in Example 1 is changed to a compound (54) represented by the following formula. The device was manufactured and evaluated in the same manner as Example 1. The results are shown in Tables 1-5.

However, n is a natural number of 2 or more.

(Example 22)
Non-aqueous electrolyte storage battery of Example 22 in the same manner as Example 1, except that Example Compound (2) as a conductive polymer in Example 1 is changed to a compound (55) represented by the following formula. The device was manufactured and evaluated in the same manner as Example 1. The results are shown in Tables 1-5.

However, n is a natural number of 2 or more.

(Example 23)
Non-aqueous electrolyte storage battery of Example 23 in the same manner as Example 1, except that the exemplified compound (2) as the conductive polymer in Example 1 is changed to the compound (56) represented by the following formula. The device was manufactured and evaluated in the same manner as Example 1. The results are shown in Tables 1-5.

However, n is a natural number of 2 or more.

(Example 24)
Non-aqueous electrolyte storage battery of Example 24 in the same manner as Example 1, except that the exemplified compound (2) as the conductive polymer in Example 1 is changed to the compound (57) represented by the following formula. The device was manufactured and evaluated in the same manner as Example 1. The results are shown in Tables 1-5.

However, n is a natural number of 2 or more.

(Example 25)
Non-aqueous electrolyte storage battery of Example 25 in the same manner as Example 1, except that the exemplified compound (2) as the conductive polymer in Example 1 is changed to the compound (58) represented by the following formula. The device was manufactured and evaluated in the same manner as Example 1. The results are shown in Tables 1-5.

However, n is a natural number of 2 or more.

(Example 26)
Non-aqueous electrolyte storage battery of Example 26 in the same manner as Example 1, except that the exemplified compound (2) as the conductive polymer in Example 1 is changed to the compound (59) represented by the following formula. The device was manufactured and evaluated in the same manner as Example 1. The results are shown in Table 1-6.

However, n is a natural number of 2 or more.

(Example 27)
Non-aqueous electrolyte storage battery of Example 27 in the same manner as in Example 1 except that the exemplified compound (2) as the conductive polymer in Example 1 is changed to the compound (60) represented by the following formula The device was manufactured and evaluated in the same manner as Example 1. The results are shown in Table 1-6.

However, n is a natural number of 2 or more.

(Example 28)
Non-aqueous electrolyte storage battery of Example 28 in the same manner as Example 1, except that in Example 1, the exemplified compound (2) as the conductive polymer is changed to the compound (61) represented by the following formula. The device was manufactured and evaluated in the same manner as Example 1. The results are shown in Table 1-6.

However, n1 and n2 are natural numbers of 2 or more, respectively.

(Example 29)
Non-aqueous electrolyte storage battery of Example 29 in the same manner as Example 1, except that Example Compound (2) as the conductive polymer in Example 1 is changed to the compound (62) represented by the following formula. The device was manufactured and evaluated in the same manner as Example 1. The results are shown in Table 1-6.

However, n is a natural number of 2 or more.

(Example 30)
Non-aqueous electrolyte storage battery of Example 30 in the same manner as Example 1 except that in Example 1, the exemplified compound (2) as the conductive polymer was changed to the compound (63) represented by the following formula. The device was manufactured and evaluated in the same manner as Example 1. The results are shown in Table 1-6.

However, n is a natural number of 2 or more.

(Example 31)
Non-aqueous electrolyte storage battery of Example 31 in the same manner as Example 1, except that the exemplified compound (2) as the conductive polymer in Example 1 is changed to the compound (64) represented by the following formula. The device was manufactured and evaluated in the same manner as Example 1. The results are shown in Table 1-7.

However, n is a natural number of 2 or more.

(Example 32)
Non-aqueous electrolyte storage battery of Example 32 in the same manner as Example 1, except that the exemplified compound (2) as the conductive polymer in Example 1 is changed to the compound (65) represented by the following formula. The device was manufactured and evaluated in the same manner as Example 1. The results are shown in Table 1-7.

However, n is a natural number of 2 or more.

(Examples 33 to 38)
-Change of mass ratio of porous carbon to conductive polymer-
Example 1 except that the mass ratio (%) of the porous carbon A and the exemplary compound (2) which is a conductive polymer in Example 1 is changed as shown in Table 2-1 and Table 2-2, respectively The nonaqueous electrolytic solution storage elements of Examples 33 to 38 were produced in the same manner as in Example 1 and evaluated in the same manner as Example 1. The results are shown in Tables 2-1 and 2-2.

(Example 39)
-Modification of porous carbon-
Non-aqueous electrolyte storage element of Example 39 in the same manner as Example 1 except that porous carbon A was changed to porous carbon B (Kunobel: registered trademark, manufactured by Toyo Carbon Co., Ltd.) in Example 1. Were prepared and evaluated in the same manner as Example 1. The results are shown in Table 3. In addition, porous carbon B is porous carbon with high crystallinity, and the crystallinity was evaluated by acquiring an X-ray diffraction spectrum.

Acquisition of the X-ray diffraction spectrum was acquired by the X-ray-diffraction method which used the CuK alpha ray for X-ray source by X-ray-diffraction apparatus (XRD; Dicover8, product made by Bruker). The X-ray diffraction spectrum of porous carbon B has a high crystallinity because it has a diffraction peak derived from the regularity of the layer structure of graphite between Bragg angles 2θ = 25.00 and 27.00 or less It can be said that (high crystallinity) porous carbon. On the other hand, in the X-ray diffraction spectrum of the porous carbon A, a gentle mountain-like spectrum was confirmed in the region of 2θ. For this reason, it can be said that it is amorphous porous carbon. The BET specific surface area of porous carbon B particles was 1,130 m ² / g, the pore volume was 1.5 mL / g, and the average diameter of the pores was 5 nm.

(Examples 40 to 44)
-Combined use with other species active materials-
In Example 1, the positive electrode active material A in the preparation process of the active material is used as a first positive electrode active material, and activated carbon (Bellfine AP, manufactured by AT Electrode Co., Ltd.) is used as a second positive electrode active material. What mixed the substance and the 2nd positive electrode active material in the ratio shown in Table 4 was made into the positive electrode active materials B, C, D, E, and F, respectively. Nonaqueous electrolysis of Examples 40 to 44 in the same manner as in Example 1 except that the positive electrode active material A in the positive electrode slurry preparation step in Example 1 was changed to positive electrode active materials B, C, D, E, and F. A liquid storage element was manufactured and evaluated in the same manner as Example 1. The results are shown in Table 4. The BET specific surface area of activated carbon (BELLFINE AP, manufactured by AT Electrode Co., Ltd.) was 1,730 m ² / g.

(Comparative example 1)
In the same manner as in Example 1 except that porous carbon A is changed to activated carbon (BELLFINE AP, manufactured by AT Electrode Co., Ltd.) in Example 1, a non-aqueous electrolyte storage element of Comparative Example 1 is manufactured. And evaluated in the same manner as in Example 1. The results are shown in Table 5-1.

(Comparative example 2)
In the same manner as in Example 1 except that porous carbon A was changed to natural graphite (special CP, manufactured by Nippon Graphite Industry Co., Ltd.) in Example 1, a non-aqueous electrolyte storage element of Comparative Example 2 was manufactured. And evaluated in the same manner as in Example 1. The results are shown in Table 5-1.
The BET specific surface area of natural graphite (specially CP, manufactured by Nippon Graphite Industry Co., Ltd.) was 17 m ² / g.

(Comparative example 3)
Non-aqueous electrolyte solution of Comparative Example 3 in the same manner as Example 1 except that porous carbon A was changed to non-graphitizable carbon (Bellfine LN, manufactured by AT Electrode Co., Ltd.) in Example 1. A storage element was manufactured and evaluated in the same manner as Example 1. The results are shown in Table 5-1.
The BET specific surface area of non-graphitizable carbon (Bellefine LN, manufactured by AT Electrode Co., Ltd.) was 6 m ² / g.

(Comparative example 4)
A non-aqueous electrolytic solution storage element of Comparative Example 4 is manufactured in the same manner as in Example 1 except that porous carbon A is changed to mesoporous carbon (carbon mesoporous, manufactured by Sigma Aldrich) in Example 1. It evaluated similarly to Example 1. The results are shown in Table 5-2.
The BET specific surface area of mesoporous carbon (carbon mesoporous, manufactured by Sigma Aldrich) was 250 m ² / g, the pore volume was 0.3 mL / g, and the average diameter of the pores was 6 nm.

(Comparative example 5)
Non-aqueous electrolyte storage element of Comparative Example 5 in the same manner as Example 1 except that porous carbon A was changed to acetylene black (denka black powder, manufactured by Denki Kagaku Kogyo Co., Ltd.) in Example 1. Were prepared and evaluated in the same manner as Example 1. The results are shown in Table 5-2.
The BET specific surface area of acetylene black (Denka black powder, manufactured by Denki Kagaku Kogyo Co., Ltd.) was 70 m ² / g.

(Comparative example 6)
Non-aqueous electrolyte solution of Comparative Example 6 in the same manner as Example 1 except that porous carbon A was changed to ketjen black (EC 600 JD granular, made by Lion Specialty Chemicals Co., Ltd.) in Example 1. A storage element was manufactured and evaluated in the same manner as Example 1. The results are shown in Table 5-2.
The BET specific surface area of ketjen black (EC600 JD granular, manufactured by Lion Specialty Chemicals Co., Ltd.) was 1,300 m ² / g.

(Comparative example 7)
A non-aqueous electrolyte storage element of Comparative Example 7 was produced in the same manner as in Example 1 except that only the porous carbon A was used as the positive electrode active material in Example 1, and was evaluated in the same manner as Example 1. The results are shown in Table 5-2. The discharge curve at 0.2 C and the discharge curve at 10 C in Comparative Example 7 are shown in FIG.

(Comparative example 8)
A non-aqueous electrolytic solution storage element of Comparative Example 8 is manufactured in the same manner as Example 1 except that in Example 1, the positive electrode active material is only activated carbon (Bellfine AP, manufactured by AT Electrode Co., Ltd.). It evaluated similarly to Example 1. The results are shown in Table 5-2.

From the results of Tables 1-1 to 1-7, it is possible to use an active material containing a conductive polymer in at least a part of a plurality of pores of porous carbon having a plurality of pores forming a three-dimensional network structure as a positive electrode active material It has been found that Examples 1 to 32 used as each have high energy density and high output characteristics.
In particular, polythiophene derivatives of the exemplified compounds (1) to (44) which are conductive polymers used in Examples 1 to 12 are compounds having a large number of electrons, and the thiophene ring contained in the molecular skeleton of the polythiophene derivative has electrons It is easy to be stabilized in the released oxidation state. At the time of charge, electrons are drawn out to form cations, and in order to compensate for the cations, anions in the electrolytic solution approach and stabilize in this state. The reverse reaction proceeds at the time of discharge, but since the oxidation state accompanying charge and the stability at the reduction state accompanying discharge are high, the charge and discharge repetitive characteristics (cycle characteristics) are good. This is the same even when the C rate at the time of charge and discharge is high, and the redox reaction accompanying the charge and discharge proceeds reversibly.
Further, among the exemplified compounds (1) to (65) of the conductive polymer, the polythiophene derivative having the repeating unit represented by the above general formula (1) contains a plurality of sulfur atoms which can have a large number of oxidation numbers, so And since multiple electron reaction can be expected with reduction, it shows high capacity with charge and discharge.
Furthermore, since the polythiophene derivative has an oxidation potential (vs. Li ^/ Li ⁺ ) at a high potential and can perform charging and discharging in a high voltage region, the average voltage of the storage element is increased. As a result, the non-aqueous electrolytic solution storage element containing the polythiophene derivative exhibits high energy density.
In addition, since a very low resistance porous carbon A covers the periphery of the polythiophene derivative, good electrical conduction can be performed between the polythiophene derivative particles, and a large discharge occurs even at a high C rate. Capacitance can be obtained. As a result, high output characteristics are exhibited. This high output characteristic is manifested in Examples 1 to 32 even though the conductive auxiliary agent is not contained in the constituent material of the positive electrode, so that the porous carbon A is an electrode such as the conductive auxiliary agent. The composite active materials of Examples 1 to 32 have the functions of both an active material and a conductive aid as they are alone.

Compounds (46), (47) and (48), which are conductive polymers used in Examples 13 to 15, show a large value of discharge capacity as an active material because they contain S element in the molecular skeleton. However, because the disulfide bond (S-S bond) contained in the molecular skeleton proceeds with cleavage and recombination along with oxidation and reduction reactions, the stability and reversibility of the structure are somewhat insufficient. In particular, since the cleavage and recombination of the disulfide bond accompanying oxidation and reduction at high C rates is a more irreversible reaction, the discharge capacity slightly decreases and output characteristics slightly decrease at high C rates.
On the other hand, the compounds (49) to (65) which are conductive polymers used in Examples 16 to 32 are materials used as carrier transport materials of organic electrochromic (EL) elements and photosensitive drums. Due to its high electrical conductivity and high structural stability due to redox, it showed good energy density and high output characteristics.

Next, from the results of Tables 2-1 and 2-2, in Example 1 and Examples 33 to 38, the discharge capacity at 0.2 C decreases as the mass ratio of porous carbon A increases. all right. This is due to the decrease in the ratio of the conductive polymer exhibiting a high capacity, and in particular, when the mass ratio of the porous carbon A exceeds 95%, the energy density is sharply reduced. Therefore, the mass ratio of the porous carbon A is preferably 95% or less.
Further, in Example 1 and Examples 33 to 38, it was found that the capacity ratio of the discharge capacity at the time of 10 C discharge to the discharge capacity at the time of the 0.2 C discharge decreases with the decrease of the mass ratio of the porous carbon A . This is because the ratio of the conductive polymer to the porous carbon A is increased, and hence the proportion of the active material containing the conductive polymer in at least a part of the plurality of pores of the porous carbon A is decreased. is there. As a result, the electrical conductivity of the conductive polymer becomes poor, and in particular, when the mass ratio of porous carbon A is less than 20%, the capacity ratio of discharge capacity at 10 C discharge to discharge capacity at 0.2 C discharge is rapid. It will decrease. In order to obtain high output characteristics, the mass ratio of the porous carbon A is preferably 20% or more.

  Next, from the results in Table 3, it was found that in Example 1 and Example 39, even if the crystal structure of porous carbon was changed, it had high energy density and exhibited high output characteristics. This is because, even if the crystallinity of the porous carbon changes, the three-dimensionally distributed pore structure in the carbon particles continues to be maintained, and as a result, amorphous porous carbon is obtained. Even if the porous carbon having high crystallinity is used, it is possible to form a good complexed state with the conductive polymer.

  Next, from the results in Table 4, in Examples 40 to 44, even if other active material species (activated carbon) are used in combination with the composite active material of the present invention, they have high energy density and high output characteristics. It turned out to indicate. This is because the particle structure of the composite active material does not collapse even if another active material type and the composite active material are mixed and used, and the composite active material is used alone even in the presence of other active material types. And express the same function during charge and discharge.

From the results of Tables 5-1 and 5-2, comparing Example 1 with Comparative Examples 1 to 6, Example 1 using porous carbon A as a carbonaceous material in the active material has an energy density and an output of It turned out that it has high characteristics in characteristics. This is because the porous carbon A has a plurality of pores forming a three-dimensional network structure, and when having the pore structure, a plurality of fine particles are formed in preparation of the active material. At least a portion of the pores can contain a conductive polymer. In addition, porous carbon A can also store anions as it is charged. For this reason, a high energy density can be obtained because a large amount of capacity can be developed as compared to other carbonaceous materials.
It can be confirmed from the cross-sectional SEM image of the positive electrode shown in FIGS. 5 to 7 and the elemental mapping image by EDS that the conductive polymer is contained in the plurality of pores of the porous carbon A. FIG. 6 is an image in which the C element is mapped, and it is found that the particle shown in FIG. 5 is porous carbon A, since it corresponds to the position of the particle in the positive electrode shown in FIG. Further, FIG. 7 is an image in which the S element is mapped, and the bright spot in FIG. 7 indicates the existence position of the S element. Since the material containing the S element in the positive electrode material is only the polythiophene derivative, it is obvious that the polythiophene derivative is present at the position where the S element is present. That is, from FIGS. 5-7, it turned out that the electroconductive polymer is contained in the inside of the pore of porous carbon A, and it has confirmed that the inside of the positive electrode in Example 1 contained the active material.

  From the results in Table 5-2, when Example 1 and Comparative Example 7 are compared, Example 1 including the conductive polymer in the pores inside the porous carbon shows higher energy density. This is caused not only by the inclusion of the conductive polymer exhibiting high capacity, but also by the inclusion of the conductive polymer in the pores inside the porous carbon, the density of the positive electrode active material particles is increased. An increase in volume density is also a factor. Moreover, although it is considered as a comparison object to use only a conductive polymer for a positive electrode active material, since electrical conductivity is poor only with a conductive polymer, transfer of the electron accompanying charge and discharge is not performed. Therefore, since the capacity is not expressed, this example is not verified as a comparative example.

  Moreover, when Examples 40-44 and Comparative Example 8 are compared from the result of Table 5-2, the direction of Examples 40-44 which have the positive electrode active material A which contains a conductive polymer in the pore inside porous carbon is It shows high energy density. This is because the positive electrode active material A containing a conductive polymer having a higher capacity than activated carbon is contained in the electrode. In addition, Examples 40 to 44 show higher output characteristics, and a positive electrode active material A containing porous carbon with good electrical conductivity is mixed with another active material type (activated carbon) to obtain an electrode. It has also been shown that it has the effect of reducing the overall resistance. That is, even when used in combination with other active material species, the composite active material of the present invention exhibits a high energy density and a high output since it exhibits the capacity development function as an active material and the formation function of a conductive network such as a conductive additive. Characteristics can be realized.

  From the above results, it was found that by using the active material of the present invention for a storage element, it has high energy density and high capacity retention rate even at high rate discharge, so it has high output characteristics. .

The aspect of the present invention is, for example, as follows.
<1> porous carbon having a plurality of pores forming a three-dimensional network structure,
A conductive polymer,
It is an active material characterized in that at least a part of the plurality of pores in the porous carbon contains the conductive polymer.
<2> The active material according to <1>, wherein the porous carbon has a communicating hole having an opening on the surface.
<3> The active material according to any one of <1> to <2>, wherein the conductive polymer is a polythiophene derivative having a repeating unit represented by the following General Formula (1).
However, in the said General formula (1), Z represents the atomic group which forms the 5-9 membered heterocyclic ring which contains S element, O element, or Se element as a ring member. Ar represents an aromatic ring or aromatic heterocycle which may have a substituent. n represents a natural number of 2 or more, and m represents a natural number of 0 or 2 or more.
<4> The active material according to <3>, wherein the repeating unit represented by the general formula (1) is a repeating unit represented by the following general formula (2).
However, in the general formula (2), R represents a substituted or unsubstituted alkylene group or a substituted or unsubstituted branched alkylene group. p represents a natural number of 1 or more. Q represents an S element, an O element, or an Se element. Ar, n and m have the same meaning as in the above general formula (1).
<5> The active material according to <4>, wherein the repeating unit represented by the general formula (2) is a repeating unit represented by the following general formula (3).
However, in the general formula (3), R represents a substituted or unsubstituted alkylene group or a substituted or unsubstituted branched alkylene group. p represents a natural number of 1 or more. Ar, n and m have the same meaning as in the above general formula (1).
<6> The active material according to any one of <1> to <2>, wherein the conductive polymer has a structure represented by the following general formula (4) in a repeating unit.
However, in the said General formula (4), Ar < ₁ >, Ar < ₂ > and Ar < ₃ > represent the aromatic ring or aromatic heterocycle which may have a substituent, respectively.
<7> The active material according to any one of <1> to <2>, wherein the conductive polymer has a repeating unit represented by the following General Formula (5).
However, in the general formula (5), R ₁ , R ₂ and R ₃ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted branched alkyl group. Ar ₁ , Ar ₂ and Ar _{3 each} represent an aromatic ring or aromatic heterocycle which may have a substituent. n represents a natural number of 2 or more.
<8> The active material according to any one of <1> to <2>, wherein the conductive polymer has a repeating unit represented by the following general formula (63).
However, in said General Formula (63), n represents 2 or more natural numbers.
<9> The active material according to any one of <1> to <2>, wherein the conductive polymer has a repeating unit represented by the following general formula (65).
However, in the said General formula (65), n represents 2 or more natural numbers.
<10> The active material according to any one of <1> to <2>, wherein the conductive polymer is a polythiophene derivative having a repeating unit represented by the following general formula (61).
However, in the general formula (61), n1 and n2 each represent a natural number of 2 or more.
<11> The mass ratio (porous carbon / conductive polymer) of the porous carbon to the conductive polymer is 20/80 or more and 95/5 or less according to any one of <1> to <10>. Active material.
<12> The active material according to any one of <1> to <11>, wherein a bulk density of the porous carbon is 0.1 g / cc or more and 1.0 g / cc or less.
<13> The active material according to any one of <1> to <12>, wherein the plurality of pores in the porous carbon is a mesopore having a minimum diameter of 2 nm or more.
<14> The active material according to any one of <1> to <13>, wherein the porous carbon is composed of particulate or massive carbon.
<15> The active material according to any one of <1> to <14>, which is a positive electrode active material capable of inserting and extracting an anion.
<16> An electrode comprising the active material according to any one of <1> to <15>.
<17> a positive electrode, a negative electrode, and an electrolyte solution,
At least any one of the said positive electrode and the said negative electrode is an electrode as described in said <16>, It is an electrical storage element characterized by the above-mentioned.
<18> The storage element according to <17>, wherein the electrolytic solution is a non-aqueous electrolytic solution.
<19> The storage element according to any one of <17> to <18>, further including a separator that is disposed between the positive electrode and the negative electrode and that holds the electrolytic solution.

  In the active material according to any one of <1> to <15>, the electrode according to <16>, and the storage element according to any one of <17> to <19>, the various problems in the related art can be obtained. To achieve the object of the present invention.

DESCRIPTION OF SYMBOLS 1 positive electrode 2 negative electrode 3 separator 4 non-aqueous electrolyte 11 positive electrode collector 12 positive electrode active material 13 binder 14 conductive support agent 21 negative electrode collector 22 negative electrode active material

Patent No. 5228531 JP, 2016-58207, A

Claims (16)

Porous carbon having a plurality of pores forming a three-dimensional network structure,
A conductive polymer,
An active material, wherein at least a part of the plurality of pores in the porous carbon contains the conductive polymer.   The active material according to claim 1, wherein the porous carbon has a communicating hole having an opening on the surface. The active material according to any one of claims 1 to 2, wherein the conductive polymer is a polythiophene derivative having a repeating unit represented by the following general formula (1).
However, in the said General formula (1), Z represents the atomic group which forms the 5-9 membered heterocyclic ring which contains S element, O element, or Se element as a ring member. Ar represents an aromatic ring or aromatic heterocycle which may have a substituent. n represents a natural number of 2 or more, and m represents a natural number of 0 or 2 or more. The active material according to claim 3, wherein the repeating unit represented by the general formula (1) is a repeating unit represented by the following general formula (2).
However, in the general formula (2), R represents a substituted or unsubstituted alkylene group or a substituted or unsubstituted branched alkylene group. p represents a natural number of 1 or more. Q represents an S element, an O element, or an Se element. Ar, n and m have the same meaning as in the above general formula (1). The active material according to claim 4, wherein the repeating unit represented by the general formula (2) is a repeating unit represented by the following general formula (3).
However, in the general formula (3), R represents a substituted or unsubstituted alkylene group or a substituted or unsubstituted branched alkylene group. p represents a natural number of 1 or more. Ar, n and m have the same meaning as in the above general formula (1). The active material according to any one of claims 1 to 2, wherein the conductive polymer has a structure represented by the following general formula (4) in a repeating unit.
However, in the said General formula (4), Ar < ₁ >, Ar < ₂ > and Ar < ₃ > represent the aromatic ring or aromatic heterocycle which may have a substituent, respectively. The active material according to any one of claims 1 to 2, wherein the conductive polymer has a repeating unit represented by the following general formula (5).
However, in the general formula (5), R ₁ , R ₂ and R ₃ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted branched alkyl group. Ar ₁ , Ar ₂ and Ar _{3 each} represent an aromatic ring or aromatic heterocycle which may have a substituent. n represents a natural number of 2 or more. The active material according to any one of claims 1 to 2, wherein the conductive polymer has a repeating unit represented by the following general formula (63).
However, in said General Formula (63), n represents 2 or more natural numbers. The active material according to any one of claims 1 to 2, wherein the conductive polymer has a repeating unit represented by the following general formula (65).
However, in the said General formula (65), n represents 2 or more natural numbers. The active material according to any one of claims 1 to 2, wherein the conductive polymer is a polythiophene derivative having a repeating unit represented by the following general formula (61).
However, in the general formula (61), n1 and n2 each represent a natural number of 2 or more.   The active material according to any one of claims 1 to 10, wherein a mass ratio of the porous carbon to the conductive polymer (porous carbon / conductive polymer) is 20/80 or more and 95/5 or less.   The active material according to any one of claims 1 to 11, wherein a bulk density of the porous carbon is 0.1 g / cc or more and 1.0 g / cc or less.   The active material according to any one of claims 1 to 12, wherein the porous carbon comprises particulate or massive carbon.   The active material according to any one of claims 1 to 13, which is a positive electrode active material capable of inserting and extracting an anion.   An electrode comprising the active material according to any one of claims 1 to 14. A positive electrode, a negative electrode, and an electrolyte;
An electric storage device characterized in that at least one of the positive electrode and the negative electrode is an electrode according to claim 15.