JP2015050170A - Electrode material, power storage material including electrode material, and method of producing electrode material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrode material which enhances fast charge/discharge characteristics by smoothing movement of ions and movement of electrons in an electrolyte, and to provide a power storage device including the electrode material, and a method of producing the electrode material.SOLUTION: In an electrode material produced by compounding a metal compound and a carbon material, the carbon material contains an aggregate of fibrous carbon, and the electrode material includes a meso hole formed between the fibrous carbons by a metal compound grating-coupled to the fibrous carbon, and a macro hole formed in the aggregate of the fibrous carbons.

Description

  The present invention relates to an electrode material obtained by combining an electrode active material and a carbon material, a method for producing the electrode material, and an electricity storage device including the electrode material.

  As an electrode using a metal compound, a lithium ion secondary battery using a metal compound for each of a positive electrode and a negative electrode, a material capable of reversibly adsorbing / desorbing lithium ions to a positive electrode and activated carbon as a positive electrode (such as graphene and a metal compound) ) And the like. These power storage devices are used as power sources for information devices such as mobile phones and laptop computers, and for regenerative energy applications such as in-vehicle.

  In recent years, as a charging method for an electric vehicle or the like, wireless power feeding for innovatively improving convenience has been studied, and maintenance of the power feeding method and power transmission is progressing. For use in this wireless power supply application, power storage devices that can receive large currents at high speed with low resistance are particularly demanded, and further improvements in power storage devices such as lithium ion secondary batteries and lithium ion capacitors (high speed) Improvement of charge / discharge characteristics) is demanded.

  For the purpose of improving the high-speed charge / discharge characteristics of the electricity storage device, the surface of a specific lithium-containing composite oxide is a kind selected from carbon nanotubes, graphene, and carbon black having an average dispersed particle size of 0.2 μm or less Although a positive electrode active material for a lithium ion secondary battery coated with the above carbon material (known document 1) is known, the charge / discharge characteristics at a high rate of 200 C or higher are still not satisfactory.

JP 2012-169217 A

  Accordingly, an object of the present invention is to provide an electrode material that has improved high-speed charge / discharge characteristics by facilitating the movement of ions and electrons in an electrolytic solution, a power storage device including the electrode material, and a method for manufacturing the electrode material Is to provide.

  In order to achieve the above object, the present invention provides an electrode material obtained by combining a metal compound and a carbon material, wherein the carbon material includes an aggregate of fibrous carbon, and the electrode material includes fibrous carbon. And mesopores formed between the fibrous carbons by a metal compound lattice-bonded to each other, and macropores formed between the aggregates of the fibrous carbons.

  The carbon material has an average outer diameter of 50 nm or less.

  In addition, the average particle diameter of the metal oxide is 500 nm or less.

  The mesopores have at least a peak of pore volume in a range of 5 to 20 nm.

  The macropores have at least a peak of pore volume in a range of 50 to 100 nm.

  Further, an electricity storage device including an electrode using any of these electrode materials is also one embodiment of the present invention.

  Further, the manufacturing method of the present invention is a method of manufacturing an electrode material in which a metal compound and a carbon material are combined, and the precursor binding is performed to bond the precursor of the metal compound to the surface of fibrous carbon that is the carbon material. And heating the fibrous carbon and metal compound precursor, reacting and growing the precursor of the metal compound on the surface of the fibrous carbon, and integrating the fibrous carbon and the metal compound by lattice bonding And a metal compound forming step of forming mesopores by expanding between the fibrous carbons, and the obtained electrode material has mesopores and macropores.

  The precursor binding step is a process in which a mechanochemical reaction is performed by applying shear stress and centrifugal force to a solution containing fibrous carbon and a metal compound material source in a rotating reaction vessel. To do.

  According to the present invention, as the electrode material, mesopores are formed between the fibrous carbons by a metal compound lattice-bonded to the fibrous carbons, and macropores are formed in the electrode material. As a result, the electrolyte solution is impregnated to facilitate the movement of ions in the electrolyte solution within the electrode material, and because the fibrous carbon and the metal compound are lattice-bonded, the movement of electrons is accelerated. It becomes a resistance, and an electrode having excellent high-speed charge / discharge characteristics can be formed.

It is a HRTEM photograph of the electrode material which compounded the metallic compound and fibrous carbon of the present invention. The schematic diagram of the electrode material which compounded the metal compound of this invention and fibrous carbon is shown. It is a block diagram which shows the apparatus for the precursor coupling | bonding process of a metal compound. It is the graph which compared Example 1 and the approximate charging / discharging time of each technique published conventionally. It is a measurement result of the pore distribution of the electrode material which compounded the metal compound of this invention and fibrous carbon. It is the graph which compared Example 2 and the approximate charge / discharge time of each technique published conventionally.

  Hereinafter, embodiments for carrying out the present invention will be described. In addition, this invention is not limited to embodiment described below.

(1) Electrode material The metal compound contained in the electrode material according to the present invention may be any material that can operate as a positive electrode active material or a negative electrode active material of a power storage device such as a lithium ion secondary battery or a lithium ion capacitor.

For example, manganese oxide MnO, lithium iron phosphate LiFePO ₄ , lithium titanate Li ₄ Ti ₅ O ₁₂ , lithium cobaltate LiCoO ₂ , lithium vanadium phosphate Li ₃ V ₂ (PO ₄ ) ₃ , lithium iron manganese phosphate LiFe _x Mn _1-x PO ₄ [0 <x <1] can be used. As other oxides, metal oxides represented by MxOz, AxMyOz, Mx (DO4) y, AxMy (DO4) z (M: metal element A: alkali metal or lanthanoid element) can also be used. is there.

  In the case of manganese oxide MnO, for example, a manganese source such as sodium permanganate, manganese acetate, manganese nitrate, manganese sulfate and the like as a starting material, and a precursor of manganese oxide nanoparticles are dispersed by the mechanochemical reaction. A supported carbon composite is formed. By rapidly heating this composite in a nitrogen atmosphere, a composite of manganese oxide and carbon, which is the metal oxide of the present invention, is generated.

In the case of lithium iron phosphate LiFePO ₄ , for example, a precursor of lithium iron phosphate nanoparticles by the mechanochemical reaction using a manganese source such as sodium permanganate, manganese acetate, manganese nitrate, and manganese sulfate as a starting material and carbon. And a carbon composite in which this is dispersed and supported. By rapidly heating the composite in a nitrogen atmosphere, a composite of lithium iron phosphate, which is the metal oxide of the present invention, and carbon is produced.

In the case of lithium titanate Li ₄ Ti ₅ O ₁₂ , for example, a titanium source such as titanium alkoxide, a lithium source such as lithium acetate, lithium nitrate, lithium carbonate, lithium hydroxide is used as a starting material, and the mechanochemical reaction is performed. To produce a precursor of lithium titanate nanoparticles. By heating the precursor of the lithium titanate nanoparticles in a nitrogen atmosphere, the lithium titanate nanoparticles of the present invention in which nitrogen is doped at sites of oxygen defects are generated.

  As the carbon material contained in the electrode material, any fibrous carbon having conductivity can be used without any particular limitation. Examples include fibrous carbon such as carbon nanotubes (hereinafter referred to as CNT) and carbon nanofibers (hereinafter referred to as CNF).

  The carbon nanotubes used as the fibrous carbon may be single-walled carbon nanotubes having a single graphene sheet or multi-walled carbon nanotubes (MWCNTs) in which two or more graphene sheets are rounded coaxially and the tube wall forms a multilayer, They may be mixed. Moreover, since the capacity density of CNT itself is so high that there are few layers of the graphene sheet of CNT, CNT of the number of layers is 50 layers or less, Preferably the range of 10 layers or less is preferable from the point of capacity density.

  The average outer diameter (diameter) of the fibrous carbon is preferably 50 nm or less, more preferably 30 nm or less, and most preferably in the range of 1 to 20 nm. Fibrous carbons having such specific outer diameters tend to be closely bundled together and exist as an aggregate. Moreover, the average length of fibrous carbon is 1-1000 micrometers, Preferably it is 70-500 micrometers, Furthermore, what is in the range of 100-200 micrometers is preferable. The specific surface area of the fibrous carbon is 100 to 2600 m 2 / g, preferably 200 to 2000 m 2 / g. The outer diameter of the fibrous carbon is measured by ASTM D3849-04 (also referred to as ASTM particle diameter).

  The metal compound is lattice-bonded and integrated with the carbon material as nanoparticles. Here, the nanoparticle has nano-level primary particles. And a nanoparticle means the magnitude | size of 5-500 nm or less in the diameters in mass, such as circular, an ellipse, and a polygon. The particle size of the primary particles is a value obtained by observing the electrode material with an SEM, selecting randomly large particles and small particles, and measuring the particle size.

The state of lattice bonding between the metal compound and the carbon material will be described. FIG. 1 is an HRTEM photograph of a composite material of a metal compound and fibrous carbon. A composite material of LiFePO ₄ and CNF as a metal compound is shown. Here, the CNF 002 plane and the LiFePO ₄ 411 plane coincide with each other, and the CNF lattice and the LiFePO ₄ lattice can be seen simultaneously in the photograph. Therefore, the CNF and LiFePO ₄ are in close contact with each other. (Lattice coupling). Note that 70% or more, more preferably 90% or more of the metal compound is desirably lattice-bonded to the fibrous carbon.

  Thus, in the electrode material in which the metal compound and the carbon material of the present invention are composited, the metal compound is lattice-bonded to the carbon material, so that the movement of electrons is smooth, and the high-speed charge / discharge characteristics are good. Become. That is, it has a good electronic path.

  The electrode material of the present invention has mesopores and macropores. The mesopores are formed by expanding a metal compound between fibrous carbons. That is, in the aggregate of fibrous carbon, the metal compound is integrated by lattice bonding between the respective fibrous carbons, whereby a predetermined space (mesopore) is obtained. The mesopores formed between the fibrous carbons have at least a pore volume peak in the range of 5 to 20 nm. The macropores formed between the fibrous carbon aggregates have at least a peak of pore volume in the range of 50 to 100 nm. Through the mesopores and macropores in the electrode material, the ions in the electrolyte move smoothly, and the high-speed charge / discharge characteristics are improved. That is, it has a good ion path.

  Next, a schematic diagram of the electrode material of the present invention is shown in FIG. As shown in FIG. 2 (a), a plurality of fibrous carbon aggregates are folded to form an electrode material. On the surface of the fibrous carbon of the aggregate, the metal compound is integrated with the fibrous carbon by lattice bonding, and mesopores are formed between the fibrous carbon as gaps equivalent to the dimensions of the metal compound. Macropores are formed between the fibrous carbon aggregates. These mesopores and macropores become ion migration spaces when impregnated with the electrolytic solution. As shown in FIG. 2 (b), ions move through macropores that are large spaces, and can easily move through mesopores that are small spaces formed in an aggregate of fibrous carbon. Thus, the movement of ions in the electrolytic solution becomes smooth, and the movement of electrons due to the lattice bonding between the metal compound and the fibrous carbon becomes smooth, so that there is no conventional synergistic action of both the ion path and the electron path. The resistance of the electrode can be reduced, and high-speed charge / discharge characteristics are improved. It is desirable that at least about 60% of the theoretical capacity is obtained for the capacity value required for the fast charge / discharge characteristics.

  In the electrode material of the present embodiment, the carbon material is desirably contained in an amount of 25 wt% or more in the electrode material. In particular, an electrode material having good high-speed charge / discharge characteristics can be obtained by blending the carbon material at a ratio of 30 wt% or more. Further, the electrode material may be mixed with a spherical (for example, KB) carbon material or the like.

  The electrode material in which the metal compound and the carbon material are combined is obtained as a powder, and the electrode material powder is kneaded with a predetermined solvent and a binder to form an electrode that stores electrical energy. This electrode can be used for an electrochemical capacitor or a lithium ion secondary battery using an electrolytic solution containing lithium.

(2) Manufacturing method As an example of the manufacturing process of the electrode material which compounded the metal compound and carbon material of this embodiment, the process of following a) -c) is provided.
a) a preparation step of introducing a reaction liquid in which fibrous carbon is added as a carbon material into a solution in which at least one compound containing a metal serving as a material source of the metal compound is dissolved, into a swirlable reactor; and
b) a precursor binding step of binding a metal compound precursor to the surface of the fibrous carbon by swirling the reactor and applying shear stress and centrifugal force to the reaction solution; and
c) A metal compound forming step in which fibrous carbon and a precursor of the metal compound are heated and the fibrous carbon and the metal compound are integrated by lattice bonding.
Through the above steps a) to c), the metal compound and the carbon material are lattice-bonded and integrated, and mesopores are formed between the fibrous carbons of the aggregate, and the aggregate of fibrous carbon An electrode material having macropores formed therebetween is obtained. And the high-speed charge / discharge characteristic of the obtained electrode material is favorable.

(A) Adjustment process In the adjustment process, at least one compound containing a metal that is a material source of the metal compound (hereinafter referred to as “material source”) and fibrous carbon are added to the solvent, and the material source is changed. A reaction solution is obtained by dissolving in a solvent.

  As the solvent, any solvent that does not adversely influence the reaction can be used without particular limitation, and water, methanol, ethanol, isopropyl alcohol, and the like can be suitably used. Two or more solvents may be mixed and used.

  When the metal compound precursor reaction is a hydrolysis reaction, the material source includes a metal alkoxide M (OR) x. In the case where the reaction of the metal compound precursor is a complex formation reaction, examples of the material source include metal acetates, sulfates, nitrates, halogen compounds, and chelating agents. For example, when the metal compound is lithium iron phosphate, the material source of the metal compound precursor is Fe source such as iron (II) acetate, iron nitrate (II), iron chloride (II), iron (II) sulfate and phosphorus. A phosphoric acid source such as acid, ammonium dihydrogen phosphate, and diammonium hydrogen phosphate; and carboxylic acids such as citric acid, malic acid, and malonic acid.

  In addition, the main material source that binds to the carbon material by the mechanochemical reaction is a titanium source or a phosphoric acid source that is a material source having positively charged ions that easily bind to oxygen ions having unpaired electrons present in the functional group. Such as phosphorus.

  Moreover, a reaction inhibitor can be added to the reaction solution as necessary. By adding a predetermined compound that forms a complex with the metal alkoxide as a reaction inhibitor, it is possible to suppress the chemical reaction from being accelerated too much. The reaction is suppressed and controlled by adding 1 to 3 mol of a predetermined compound such as acetic acid that forms a complex with the metal alkoxide to 1 mol of the metal alkoxide to form a complex. It is to be noted that a metal-oxide composite nanoparticle, for example, a lithium-titanium oxide composite nanoparticle, which is a precursor of lithium titanate, is produced by this reaction, and is fired. Thus, a crystal of lithium titanate is obtained.

  Examples of substances that can form a complex with a metal alkoxide include acetic acid, citric acid, succinic acid, formic acid, lactic acid, tartaric acid, fumaric acid, succinic acid, propionic acid, carboxylic acid such as propionic acid, and EDTA. Examples include complexing agents represented by amino alcohols such as aminopolycarboxylic acid and triethanolamine.

(B) Precursor binding step The precursor binding step is a step of binding a precursor of a metal compound to the surface of the carbon material. As a method for bonding the precursor to the carbon material, the reactor shown in FIG. 3 is swirled to apply a shear stress and a centrifugal force to the reaction solution (hereinafter referred to as “UC treatment”). A material source is supported.

  As shown in FIG. 3, the reaction vessel includes an outer cylinder 1 having a cough plate 1-2 at an opening, and an inner cylinder 2 having a through hole 2-1 and turning. The reaction liquid is introduced into the inner cylinder 2 of the reactor, and the inner cylinder 2 is turned so that the material source and the fibrous carbon which are the reactants in the inner cylinder 2 by the centrifugal force are passed through the inner cylinder through-hole 2- 1 moves to the inner wall 1-3 of the outer cylinder. At this time, the reaction product collides with the inner wall 1-3 of the outer cylinder by the centrifugal force of the inner cylinder 2, and forms a thin film and slides up to the upper part of the inner wall 1-3. In this state, both the shear stress between the inner wall 1-3 and the centrifugal force from the inner cylinder are simultaneously applied to the reactant, and a large mechanical energy is applied to the thin-film reactant. This mechanical energy seems to be converted into chemical energy required for the reaction, so-called activation energy, but the reaction proceeds in a short time. In this way, shear stress and centrifugal force are applied to the material source and the fibrous carbon to bond at least a part of the material source to the fibrous carbon. In addition, the aggregates of fibrous carbon are dispersed by the UC treatment.

In this reaction, since the mechanical energy applied to the reaction product is large when it is in the form of a thin film, the thickness of the thin film is 5 mm or less, preferably 2.5 mm or less, more preferably 1.0 mm or less. The thickness of the thin film can be set according to the width of the dam plate and the amount of the reaction solution. For example, the centrifugal force required to produce on the thin film is 1500 N (kgms ^-2) or more, preferably 70000N (kgms ^-2) or more.

  Thus, the precursor of the metal compound combined with fibrous carbon can be generated by applying shear stress and centrifugal force to the reaction solution containing the metal compound material source through the precursor formation step. .

  Although fibrous carbon exists as an aggregate, a precursor of a metal compound enters between the fibrous carbons by UC treatment, and is bonded to the surface of the fibrous carbon. That is, in this UC process, the growth seed | species of a metal compound will be planted between fibrous carbon. In addition, macropores are formed between the fibrous carbon aggregates by this UC treatment.

(C) Metal compound formation process In this metal compound formation process, the precursor of a metal compound is converted into nanoparticles, such as an oxide.

  The heating atmosphere is not strictly limited as long as the target metal compound is obtained. Heat treatment in a vacuum, heat treatment in an inert atmosphere such as nitrogen or argon, or heat treatment in an oxygen-containing atmosphere such as oxygen or air may be used. Hydrothermal treatment may also be used. There is no strict limitation on the heating temperature and time, and it varies depending on the composition of the target metal compound and the amount of treatment, but in general, the heat treatment in an oxygen-containing atmosphere is performed at a temperature of 200 to 300 ° C. for 10 minutes to Heat treatment in an inert atmosphere for 10 hours is performed at a temperature of 250 to 900 ° C. for 10 minutes to 10 hours, and heat treatment in vacuum is performed at a temperature of room temperature to 200 ° C. for 10 minutes to 10 hours. In particular, heat treatment in a nitrogen atmosphere is preferred, and the metal compound is doped with nitrogen to increase the conductivity of the metal compound. As a result, rapid charge / discharge characteristics are improved.

  In this metal compound forming step, the precursor of the metal compound bonded to the surface of the fibrous carbon is heated. During this heating, the precursor of the metal compound reacts to the surface of the fibrous carbon. By growing it above, lattice bonding is performed, and the fibrous carbon and the metal compound are integrated. Furthermore, the precursor of the metal compound that has entered between the fibrous carbons of the fibrous carbon aggregates expands between the fibrous carbons in the process of growing by this reaction, resulting in a fibrous carbon aggregate. A mesopore serving as a space is formed.

  As described above, in the present invention, in the electrode material in which the metal compound and the carbon material are combined, the metal compound and the fibrous carbon are lattice-bonded, so that the movement of electrons becomes smooth and the metal By providing mesopores formed between the fibrous carbons of the aggregate by the lattice bonding of the compounds and macropores formed between the aggregates of the fibrous carbon, the movement of the ions of the electrolyte is smoothed. The resistance becomes low and the high-speed charge / discharge characteristics can be improved.

  Next, the characteristics of the electrode material of the present invention are confirmed.

(Example 1)
First, a reaction liquid prepared by mixing CNTs having an average outer diameter of 10 nm and an average length of 100 μm as fibrous carbon, and a lithium source and a titanium source as a material source is prepared (adjustment step). The UC treatment was performed for 5 minutes at a rotation speed of s. In this UC process, a centrifugal force of 75000 N (kgms ⁻² ) is applied. This UC process corresponds to a precursor bonding step of bonding a lithium titanate precursor to a carbon material.

  The obtained solution is filtered and dried, further rapidly heated to 800 ° C. in a nitrogen atmosphere, and held for 1 hour to obtain an electrode material in which lithium titanate nanoparticles and fibrous carbon are lattice-bonded. Obtained. At this time, the lithium titanate in the electrode material is adjusted to 70 wt% and the CNT is adjusted to 30 wt%.

  Next, the obtained electrode material and acetylene black as a conductive agent are mixed at a mass ratio of 90:10, and 5% by mass of the total polyvinylidene fluoride and an appropriate amount of N-methylpyrrolidone are added to sufficiently Kneaded to form a slurry, which was applied onto an aluminum foil and dried to obtain an electrode.

  Further, using the obtained electrode, a coin cell was prepared in which a 1M LiPF6 ethylene carbonate / diethyl carbonate 1: 1 solution was used as an electrolyte and the counter electrode was lithium.

(Example 2)
As the coin cell of Example 2, instead of the fibrous carbon used in Example 1, except that CNT which is fibrous carbon having an average outer diameter of 20 nm and an average length of 5 μm was used, the same as in Example 1, A coin cell was created.

  For the obtained coin cells of Example 1 and Example 2, the charge / discharge time was measured, and the result is shown in FIG.

  Moreover, in FIG. 4, the coin cell of Example 1 and Example 2 was compared with the approximate charging / discharging time of each technique conventionally disclosed as a conventional example. S. HUANG (2004), Y.A. Bai (2008), J.A. Kim (2007), H.C. Yu (2008), J.M. Huang (2008), G.H. Compared with Amatocci (2006) and conventional activated carbon, the charge / discharge time of the coin cell using the electrode material of Example 1 is extremely short (3 seconds: capacity is 85 mAh / g), and the electrode material of Example 2 is used. It can be seen that the charge / discharge time of the coin cell is extremely short (12 seconds) and the high-speed charge / discharge characteristics are good.

  Here, in the electrode material in which the metal compound of Example 1 and the carbon material were combined, the state of mesopores and macropores was verified. The result of measuring the pore distribution of the electrode material of Example 1 is shown in FIG. The electrode material of Example 1 has pore volume peaks at least in mesopores and micropores. In particular, the mesopores have at least a peak of pore volume in the range of 5 to 20 nm. It can also be seen that the macropores formed between the fibrous carbon aggregates have at least a peak of pore volume in the range of 50 to 100 nm. As for the pore volume of the mesopores in the electrode material of Example 1, it was found that the pore volume was remarkably increased (about 3 times) as compared with the case of using only fibrous carbon without using a metal compound.

Example 3
A reaction liquid in which CNF having an average outer diameter of 10 nm and an average length of 100 μm as fibrous carbon, and an iron source and a phosphoric acid source as a material source are mixed (adjustment process) is prepared, and 50 m / s is applied to the reaction liquid. The UC process was performed for 5 minutes at a rotational speed of. In this UC process, a centrifugal force of 75000 N (kgms ⁻² ) is applied. This UC process corresponds to a precursor binding step in which a precursor of olivine-type lithium iron phosphate by the UC process is bonded to a carbon material.

  Then, the obtained solution is filtered and dried, further rapidly heated to 700 ° C. in a nitrogen atmosphere, and held for 1 hour so that the lithium iron phosphate nanoparticles and the fibrous carbon are lattice-bonded. Got. At this time, adjustment is made so that lithium iron phosphate in the electrode material is 70 wt% and CNT is 30 wt%.

  Next, the obtained electrode material and acetylene black as a conductive agent are mixed at a mass ratio of 90:10, and 5% by mass of the total polyvinylidene fluoride and an appropriate amount of N-methylpyrrolidone are added to sufficiently Kneaded to form a slurry, which was applied onto an aluminum foil and dried to obtain an electrode.

  Further, using the obtained electrode, a coin cell was prepared in which a 1M LiPF6 ethylene carbonate / diethyl carbonate 1: 1 solution was used as an electrolyte and the counter electrode was lithium. About the obtained coin cell, charging / discharging time was measured and the result is shown in FIG.

  Moreover, in FIG. 6, the coin cell of Example 3 was compared with the approximate charging / discharging time of each technique conventionally disclosed as a conventional example. S. Franger (2003), D.C. R. Wheeler (2006), Y.M. H. Huang (2008), H.C. Zhou (2008), Taniguchi (2010), G.M. Compared with Ceder (2009), it can be seen that the charge / discharge time of the coin cell using the electrode material of Example 3 is extremely short (7 seconds: capacity is 95 mAh / g), and the high-speed charge / discharge characteristics are good.

DESCRIPTION OF SYMBOLS 1 ... Outer cylinder 1-2 ... Baffle 1-3 ... Inner wall 2 ... Inner cylinder 2-1 ... Through-hole

Claims (8)

An electrode material in which a metal compound and a carbon material are combined,
The carbon material includes an aggregate of fibrous carbon;
The electrode material includes mesopores formed between fibrous carbons by a metal compound lattice-bonded to the fibrous carbons,
Macropores formed between aggregates of fibrous carbon;
An electrode material comprising:   The electrode material according to claim 1, wherein the carbon material has an average outer diameter of 50 nm or less.   The electrode material according to claim 1 or 2, wherein an average particle diameter of the metal oxide is 500 nm or less.   The electrode material according to claim 1, wherein the mesopores have at least a peak of pore volume in a range of 5 to 20 nm.   The electrode material according to claim 1, wherein the macropore has at least a peak of pore volume in a range of 50 to 100 nm.   The electrical storage device provided with the electrode using the electrode material in any one of Claims 1-5. A method for producing an electrode material in which a metal compound and a carbon material are combined,
A precursor bonding step of bonding the precursor of the metal compound to the surface of fibrous carbon that is a carbon material;
Heating the fibrous carbon and metal compound precursor;
Reacting and growing metal compound precursors on the surface of fibrous carbon;
While integrating fibrous carbon and metal compound by lattice bonding,
A metal compound forming step of forming mesopores by expanding between the fibrous carbons,
The obtained electrode material has mesopores and macropores. The precursor binding step is a process in which a mechanochemical reaction is performed by applying shear stress and centrifugal force to a solution containing fibrous carbon and a metal compound material source in a rotating reaction vessel. Item 8. A method for producing an electrode material according to Item 7.