JP3369589B2 - Electrode material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrode material,
Related to electrode materials useful as electrodes for secondary batteries
It is. More specifically, the present invention relates to
Metal, especially preferred for secondary batteries that are lithium metal.
High capacity and long-term charge / discharge cycle characteristics suitable for use
Excellent electrode material that enables highly safe secondary batteries
It is about. [0002] 2. Description of the Related Art In recent years, to improve the performance of batteries
R & D activity is intense. One of them is a carbon material electrode
As rechargeable using electrochemical doping
There is research on secondary batteries. Graphite as a negative electrode as a carbon electrode
When used with Li⁺Cations such as ions are added between layers.
But can be very unstable in the electrolyte.
Is not suitable as an electrode material because it reacts with the electrolyte.
(J. Electrochem. Society. 125, 687 (1978),). one
On the other hand, using a conductive polymer such as polyacetylene as an electrode,
Rechargeable secondary battery using electrochemical doping
There is also a great deal of interest in the study of. For example,
No. 57-121168 discloses a battery using an acetylene polymer.
Has been proposed. But polyacetylene is acid in the air
Trace amount of water contained in the solvent
Deteriorated by reacting with oxygen and oxygen, resulting in poor electrode stability
You. In particular, the polyacetylene used as the negative electrode is
Degradation inside is severe. Therefore, both polyacetylene
The battery used for the pole has a strong self-discharge,
Inefficient and difficult to obtain high performance and high reliability batteries
No. [0003] Li metal is used as a negative electrode and a positive electrode is used.
For batteries using polyacetylene as the electrode,
Issues such as charge efficiency in
It is improved compared to the battery used, but in this case
As a result, the charge / discharge cycle characteristics become extremely poor. sand
That is, when the battery is discharged, Li is converted to Li ions from the negative electrode body.
And move into the electrolyte, and during charging, this Li ion
It becomes metal Li and is deposited again on the negative electrode body.
Metal Li deposited along with repeated cycles
Means dendrite-like. This dendrite
Li is an extremely active substance,
As a result, the charge / discharge cycle characteristics of the battery deteriorate
This causes the inconvenience. As this grows further,
Finally, this dendritic metal Li deposit is separated
Penetrates the generator and reaches the cathode body, causing a short circuit phenomenon
Problems arise. In other words, the charge / discharge cycle life is
The problem of shortness arises. The conductive polymer is lithium
Ion doping amount, that is, electrode capacity and stable charge
There is a disadvantage that the discharge characteristics are lacking. Such a problem
To avoid this, the organic compound was fired as the negative electrode
Using a carbonaceous material as a support, and Li or Li as a main component
Attempts to support and configure alkali metals
Have been. By using such a negative electrode body, secondary
Although the charge / discharge cycle characteristics of batteries have been dramatically improved,
However, the capacity of this rechargeable battery is satisfactorily large.
It wasn't good. Under such circumstances, the present invention
Secondary battery with large battery capacity and excellent charge / discharge cycle characteristics
It is intended to provide an electrode material for a pond.
You. [0004] Means for Solving the Problems The present inventor has solved the above problem.
As a result of intensive research on electrode materials,
A specific carbonaceous material described below and a specific metal or alloy
Is bound or covered by a specific carbonaceous material.
Polar materials are extremely effective for the above purpose.
The present invention has been made. That is, the electrode material of the present invention
Is the plane distance d of the (002) plane by X-ray wide-angle diffraction.₀₀₂
Is less than 3.45 ° and an alkali metal
Metals and / or alkalis capable of forming alloys
The metal material (B) made of a remetal alloy is combined with the following (A)
Do not bond or cover with a carbonaceous material (C) that satisfies the conditions.
ToFor secondary batteriesThe electrode material is: (B) Argon ion laser light with a wavelength of 5145 °
In the Raman spectrum used; 1580-1620
cm^-1Peak P in the range_A, 1350-1370cm
^-1Peak P in the range_BAnd the above P_AStrength I_ATo
P for_BStrength I_BRatio R = I_B/ I_AIs 0.4 or more
That. Hereinafter, the present invention will be described in more detail.
You. The electrode material of the present invention is, for example, as shown in FIG.
In addition, the metallic substance (B) and the carbonaceous material dispersed around it
(A) is bonded or covered with carbonaceous material (C).
I make it. [Carbonaceous matter (A)] The carbonaceous matter (A) of the present invention is an X-ray
Surface spacing d of (002) plane by angular diffraction₀₀₂Is not 3.45Å
Full, preferably less than 3.43 °, more preferably 3.35
３3.41Å, more preferably 3.35３3.40Å,
Particularly preferably 3.35-3.39 °, most preferably
3.35 to 3.37 °, the size of the crystallite in the C-axis direction
(Lc) is preferably 100 ° or more, more preferably 1 ° or more.
51 ° or more, more preferably 180 ° or more, particularly preferred
Preferably at least 200 mm, most preferably at least 250 mm1
000Å or less. This carbonaceous material (A) is in the form of particles,
It has any shape such as fibrous, but particles and fibrous are preferred.
Good. When the carbonaceous material (A) is in the form of particles, the particles
Preferably has a volume average particle size of 0.1 to 50 μm,
Preferably from 0.2 to 30 μm, more preferably from 0.3 to 30 μm.
20 μm, particularly preferably 0.4 to 10 μm, most preferably
More preferably, it is 0.5 to 8 μm. In addition, carbonaceous material (A)
When fibrous, the average diameter of the fibers is preferably
0.1 to 20 μm, more preferably 0.3 to 10 μm,
More preferably, it is 0.5 to 8 μm. The fiber length is
Preferably 3 mm or less, more preferably 2 mm or less,
More preferably 1 mm or less, particularly preferably 0.8 m
m, most preferably 0.5 mm or less. Carbonaceous
The true density of the product (A) is preferably 2.10 g / cm^ThreeLess than
Above, more preferably 2.12 g / cm^ThreeAbove, even more preferred
Or 2.15 g / cm^ThreeAs described above, particularly preferred is 2.1.
8 to 2.26 g / cm^Three, Most preferably 2.20 to 2.2
6g / cm^ThreeIt is. [Metallic Material (B)] The electrode material of the present invention is
In addition, metals that can form alloys with alkali metals
And / or metallic objects consisting of alkali metal alloys
(B). Can form alloys with alkali metals
Alloys with functional metals, preferably lithium metal.
As a metal that can be used, for example, aluminum (A
l), lead (Pb), zinc (Zn), tin (Sn), bis
Mass (Bi), indium (In), magnesium (M
g), gallium (Ga), cadmium (Cd), silver (A
g), silicon (Si), boron (B), gold (Au), white
Gold (Pt), palladium (Pd), antimony (Sb)
And the like, preferably Al, Pb, In, Bi and
And Cd, more preferably Al, Pb, In.
Al and Pb are particularly preferable, and most preferable are Al and Pb.
Is Al. Alloys with alkali metals, preferably lithium
The alloy (molar composition) of the metal alloy is L
When expressed as i x M (x is a molar ratio to metal M),
As M, the above-mentioned metals are used. Some of the above alloys
In addition to metals, other elements are contained in a range of 50 mol% or less.
You may have. In Li x M, x is 0 <x ≦ 9
And more preferably 0.1 ≦ x ≦
5, more preferably 0.5 ≦ x ≦ 3, and
More preferably, 0.7 ≦ x ≦ 2. With lithium metal
Alloys (Li x M) as one kind or two with different x
More than one alloy can be used. The above metal M
One or two or more can be used. Metal objects
(B) has an arbitrary form such as a particle form or a fibrous form.
More preferably, it is in the form of particles or fibers. Metallic material (B) is particles
, The volume average particle size is preferably from 0.3 to 10.
0 μm, more preferably 0.5 to 70 μm, even more preferably
0.8 to 50 μm, particularly preferably 1 to 30 μm
m, most preferably 2 to 20 μm. Metal objects
When (B) is a fiber, the average diameter is preferably 0.
1 to 100 μm, more preferably 0.5 to 70 μm,
More preferably 1 to 50 μm, particularly preferably 2 to 3 μm
0 μm, most preferably 3 to 20 μm. Also fiber
The length is preferably 3 mm or less, more preferably 2 mm or less.
Below, more preferably 1 mm or less, particularly preferably
0.8 mm or less, most preferably 500 μm or less
You. [Carbonaceous matter (C)] The carbonaceous matter of the present invention
(C) is the above-mentioned carbonaceous material (A) and metallic material (B)
Is bonded or coated. This carbonaceous material (C)
Uses argon ion laser light with a wavelength of 5145 °
In Raman spectrum analysis,
It has the characteristics of Torr. Below, unless otherwise noted,
The vector and peak are Raman spectra under the above conditions.
It is. That is, 1580-1620cm^-1In the range
Ark P_A, 1350-1370cm^-1Peak P in the range_B
Having. P_AGrows by laminating the spread of the aromatic ring network,
The peaks observed corresponding to the formed crystal structure
, P_BIs a peak corresponding to the disordered amorphous structure. Both
Peak intensity I_BAnd I_ARatio R (= I_B/ I_A)
Surface layer of carbonaceous material, that is, carbonaceous particles, carbonaceous fiber, etc.
The larger the ratio of the specific crystal structure part in
Show. In the present invention, R is at least 0.4, preferably at least 0.4.
6 or more, more preferably 0.9 or more, particularly preferably
0.90-1.5, most preferably 0.90-1.3.
You. That is, P_AIs the completeness of the crystal part
Varies depending on the degree of Carbonaceous material used in the present invention
P of object (C)_AIs between 1580 and 16
20cm^-1But preferably 1585 to 1620c
m^-1, More preferably 1590 to 1620 cm^-1And more
Preferably 1595 to 1615 cm^-1, Especially preferred
1600 ~ 1610cm^-1Range. Peaked
The half width at half maximum is narrower as the higher order structure of the carbonaceous material is more uniform.
No. P of the carbonaceous material (C) used in the present invention_AHalf value of half
The width is preferably 25 cm^-1Above, more preferably 27
cm^-1Above, more preferably 30 to 60 cm^-1Especially
Preferably 35 to 55 cm^-1It is. P_BIs usually 1
360cm^-1Has a peak. P_BHalf width at half
Preferably 20cm^-1Above, more preferably 20 to 150
cm^-1, More preferably 25-125 cm^-1Especially
Preferably 30 to 115 cm^-1, Most preferably 40-
110cm^-1It is. The carbonaceous material (C) is obtained by X-ray wide-angle diffraction.
(002) Surface distance d₀₀₂But preferably 3.45 mm or less
Above, more preferably 3.47 ° or more, even more preferably
3.48 to 3.75 °, particularly preferably 3.49 to 3.7
0 °, most preferably 3.50 to 3.65 °. C axis
The crystallite size Lc of the method is preferably 100 ° or less.
Below, more preferably 70 ° or less, even more preferably 50 °
Åor less, particularly preferably 10 to 30Å, most preferably
Is 15 to 30 °. True density of carbonaceous material (C) is preferred
Or 2.10 g / cm^ThreeLess than, more preferably 2.05
g / cm^ThreeHereinafter, more preferably, 1.30 to 2.05 g
/ Cm^ThreeAnd particularly preferably 1.40 to 2.05 g / c.
m^Three, Most preferably 1.80 to 2.03 g / cm^ThreeIn
You. [Composite structure of electrode material] Carbonaceous material (A)
And metals and alloys that can form alloys with alkali metals
And / or metallic objects consisting of alkali metal alloys
(B) is bonded or coated with a carbonaceous material (C)
As the state, for example, (a), (b), (c) of FIG.
Or (d), particles or fibers of the carbonaceous material (A)
And the particles or fibers of the metallic substance (B)
(C) bonded form or particles of carbonaceous material (A)
Or fibers and particles or fibers of the metallic substance (B)
(A), (b), (c) of FIG. 2 coated with the substance (C)
Or, there is the form of (d). Especially, as shown in Fig. 2,
The substance (A) and the metal substance (B) are combined with the carbonaceous substance (C).
Coated forms are preferred. Most preferably, FIG.
Surround the metal material (B) with the carbon material (A) like
And the carbonaceous material (C) further coats it.
In this case, the carbonaceous material (C) is the same as the carbonaceous material (A)
On the surface of the object (B), preferably 100 to 5 μm,
Preferably 200 ° -4 μm, more preferably 300
Å to 3 μm, particularly preferably 500 to 2 μm, most preferably
Preferably, it is formed to a thickness of 800-1 μm. The carbonaceous material (A) in the electrode material of the present invention
Weight ratio W_AIs preferably 20-94% by weight, more
Preferably 30 to 90% by weight, more preferably 35 to 90% by weight.
80% by weight, particularly preferably 40-70% by weight, most
Preferably it is 50 to 60% by weight. Electrode material of the present invention
Of the metallic substance (B) in the steel W_BIs preferably 3
~ 70% by weight, more preferably 5 ~ 60% by weight, furthermore
Preferably 7 to 50% by weight, particularly preferably 10 to 10% by weight.
45% by weight, most preferably 15 to 35% by weight.
You. Ratio of carbonaceous material (C) in electrode material of the present invention
W_CIs preferably 3 to 60% by weight, more preferably 5 to 60% by weight.
-50% by weight, more preferably 7-40% by weight, especially
Preferably from 8 to 35% by weight, most preferably from 10 to 3% by weight.
0% by weight. In addition, the electrode material of the present invention is shown in FIG.
(A), (b), (c) or (d) or FIG.
(A), (b), (c) or (d)
Can take any form, but a mixture of some of these forms
It may be a compound. [Other preferred properties]
The electrode material also complies with the above-mentioned structure in differential thermal analysis.
Preferably exhibit at least two exothermic peaks
No. That is, the peak corresponding to the carbonaceous material (A) is favorable.
Preferably 840 ° C or higher, more preferably 860 ° C or higher,
More preferably 880 ° C. or higher, particularly preferably 90 ° C.
0 ° C or higher, most preferably 920 ° C or higher and 1200 ° C or lower
It is. The peak corresponding to the carbonaceous material (C) is more preferable.
Or less than 880 ° C., more preferably less than 860 ° C.
More preferably below 840 ° C., particularly preferably 500
To 820 ° C, most preferably 600 to 810 ° C.
Further, it has a peak corresponding to the melting of the metal substance (B). The electrode material used in the present invention is an electrode material.
In the first derivative absorption spectrum of the child spin resonance,
Has two signal peaks corresponding to the structure of
Is preferred. Electron spin corresponding to carbonaceous material (A)
Line width between peaks of the first derivative absorption spectrum of resonance (ΔH
pp: Gauss), preferably less than 100 Gauss, more
Preferably less than 50 gauss, more preferably 30 gauss
Less than 20 gauss, especially preferably less than 20 gauss
Or less than 10 Gauss is used in the present invention.
Carbonaceous material that In addition, corresponding to carbonaceous material (C)
Between the peaks of the first derivative absorption spectrum of electron spin resonance
Has a line width (ΔHpp) of preferably 10 gauss or more.
More preferably 20 gauss or more, more preferably 30 gauss
Mouse or more, particularly preferably 50 gauss or more, most preferably
Or more than 100 gauss signal is used in the present invention.
Carbon material. The true density of the electrode material of the present invention is preferably
2.10 g / cm^ThreeMore preferably, 2.15 g /
cm^ThreeAbove, particularly preferably 2.20 to 2.60 g / c
m^Three, Most preferably 2.22 to 2.50 g / cm^ThreeIn
You. The electrode material of the present invention may be in any form, such as particulate, fibrous, etc.
Can be in the form of particles, particles, fibers, especially particles
This is particularly preferred. As the particulate form, preferably a body
The volume average particle size is 1 to 100 μm, more preferably 2 to 5 μm.
0 μm, more preferably 3 to 30 μm, particularly preferred
4 to 20 μm, most preferably 5 to 15 μm.
You. As the fibrous shape, the diameter is 0.5 to 25 μm, more preferably.
Preferably 1 to 20 μm, more preferably 2 to 10 μm
m, most preferably 3-5 μm, the length is preferably
Is less than 10 mm, more preferably less than 5 mm, even more preferred
Is 3 mm or less. The carbonaceous material of the present invention has a specific surface area.
(BET method), preferably 0.1 m^Two/ G or more and 100m
^Two/ G or less, more preferably 0.5 to 50 m^Two/ G, further
Preferably 1 to 25 m^Two/ G. Further, this electrode material has pores inside.
And the total pore volume is 1.5 × 10^-3ml / g or more
Preferably. More preferably, the total pore volume is 2.0.
× 10^-3ml / g or more, more preferably 3.0 × 10
^-3~ 8 × 10^-2ml / g, particularly preferably 4.0 × 1
0^-3~ 3 × 10^-2ml / g. Total pore volume and after
The average pore radius described above is calculated using the
Measure the amount of gas adsorbed or desorbed on the sample under force,
Determined from the amount of gas adsorbed on the sample. Total pore volume
Assumes that the pores are filled with liquid nitrogen,
Relative pressure P / P_O= From the total amount of gas adsorbed at 0.995
Ask. here, P: Vapor pressure of adsorption gas (mmHg) P_O ： Saturated vapor pressure of adsorption gas at cooling temperature (mmHg) It is. Furthermore, the amount of nitrogen gas adsorbed (Vads)
The amount of liquid nitrogen filled in the pores using the expression (1)
(Vliq) to determine the total pore volume. Vliq = (Patm · Vads · Vm) / RT (1) Here, Patm and T are respectively the atmospheric pressure (kgf / c
m^Two) And absolute temperature (K), and R is a gas constant.
Vm is the molecular volume of the adsorbed gas (34.7 cm for nitrogen)^Three
/ Mol). The average pore radius (γp) is
It is preferably 8 to 100 °. More preferably 1
0 to 80 °, more preferably 12 to 60 °, particularly preferred
Preferably it is 14 to 40 degrees. Average pore radius (γp)
Is obtained from Vliq obtained from the above equation (1) and the BET method.
From the determined specific surface area S, it is calculated using the following equation (2).
Ask by that. Here, the pores are assumed to be cylindrical.
Set. γp = 2Vliq / S (2) Further, the electrode material used in the present invention is a mercury porosimeter.
The pore volume of the filter is preferably 0.05 ml / g.
Or more, more preferably 0.10 ml / g or more, and still more preferably
0.15 to 2 ml / g, particularly preferably 0.2 to 2 ml / g
0-1.5 ml / g. [Synthesis of Carbonaceous Material (A)] Electrode Material of the Present Invention
The material can be synthesized, for example, by the following method. Charcoal
The substance (A) converts the organic compound under an inert gas flow,
Is preferably 1000 ° C. or higher in vacuum, more preferably
Preferably 1800 ° C. or higher, more preferably 2000 ° C.
Or more, particularly preferably 2500 ° C. or more, most preferably
By heating at a temperature of 2600-3000 ° C.
Can be decomposed, carbonized and graphitized, and synthesized.
You. Starting materials for obtaining the carbonaceous material used in the present invention
Naphthalene, phenanthrene, anthracene
, Triphenylene, pyrene, chrysene, naphthacene,
Like picene, perylene, pentaphene, pentacene
Two or more monocyclic hydrocarbon compounds having three or more rings
A condensed polycyclic hydrocarbon compound obtained by condensation;
Carboxylic acids, carboxylic anhydrides, carboxylic imides
Derivatives such as the above; a mixture of the above compounds as a main component
Various pitches; indole, isoindole, kinori
, Isoquinoline, quinoxaline, phthalazine, carba
Sol, acridine, phenazine, phenanthridine
At least three or more heterocyclic monocyclic compounds
Or two or more three-membered rings or more
A condensed heterocyclic compound bonded to a monocyclic hydrocarbon compound;
Carboxylic acid, carboxylic anhydride, carbohydrate of each of the above compounds
Derivatives such as acid imides;
And aromatic monocyclic hydrocarbons such as xylene,
Of carboxylic acids, carboxylic anhydrides, carboxylic imides
Such derivatives, for example, 1,2,4,5-tetracarboxylic
Derivatives such as acids, dianhydrides or diimides thereof
Can be The above-mentioned pitch will be described in more detail.
Ethylene heavy end pits generated during the decomposition of naphtha
H, Crude oil pitch generated during the cracking of crude oil, heat content of coal
For dissolving coal pitch and asphalt generated during solution
So, for example, the asphalt decomposition pitch generated
Can be mentioned. Also, adjust these various pitches.
In addition, heating under an inert gas flow, etc.
Preferably at least 80%, more preferably at least 90%,
Preferably with a mesophase pitch of 95% or more
Can be. And propane and propylene.
Such aliphatic saturated or unsaturated hydrocarbons are also used.
Further, cellulose; phenolic resin; polyacrylonitrile
Tolyl, poly (α-halogenated acrylonitrile), etc.
Acrylic resin; polyvinyl chloride, polyvinylidene chloride
Halogenated trees such as chlorinated polyvinyl chloride
Fat; polyamide imide resin; polyamide resin; polyacetate
Conjugated resins such as styrene and poly (p-phenylene)
Such organic polymer compounds can be exemplified. Ah
Or carbon black or coke as a starting material.
Which carbonaceous material is further heated to promote carbonization appropriately,
The carbonaceous material (A) used in the present invention can also be used. carbon
Use natural graphite or artificial graphite as the substance (A).
Can also be. [Synthesis of Carbonaceous Material (C) and Electrode Material]
A carbonaceous material (A) synthesized as described above, and a metallic material
(B) and then combined or coated with an organic compound
After that, it is heated, decomposed and carbonized to produce carbonaceous material (C).
Once formed, the electrode material of the present invention can be synthesized
You. Alternatively, the carbonaceous material synthesized as described above
An organic compound on a mixture of (A) and a metallic substance (B)
Is heated, decomposed and carbonized to form a carbonaceous material (C)
Thus, the electrode material of the present invention can be synthesized. Illustrating a specific synthesis method, the first
The method comprises mixing a carbonaceous material (A) with a metallic material (B),
Add the organic compound and heat to bring the organic compound into a liquid phase
To form carbonaceous material (C)
Bond or coat the substrate (A) and metal substrate (B)
Is the way. The organic compound used at this time is naphtha.
Len, phenanthrene, anthracene, triphenylene
, Pyrene, chrysene, naphthacene, picene, perile
, Pentaphene, and pentacene
Condensed ring formed by condensing two or more cyclic hydrocarbon compounds with each other
Formula hydrocarbon compounds, mainly containing a mixture of the above compounds
There are various pitches. As the pitch, the carbon
Crude oil pitches and nuts listed as raw materials for synthesizing the substance (A)
Husa pitch, asphalt pitch, coal tar pitch
, Polyvinyl chloride, polyvinylidene chloride, etc.
Is raised. Also, indole, isoindole
, Quinoline, isoquinoline, quinoxaline, phthalazine
, Carbazole, acridine, phenazine, phenato
Three or more membered heteromonocyclic compounds such as lysine
At least two bonds or at least one three-membered ring
Condensed heterocyclization formed by bonding with the above monocyclic hydrocarbon compounds
Compounds are given. In the second method, a carbonaceous material (A) and a metal
The mixture with the compound (B) is bound with an organic polymer compound or
After coating, it is heated, decomposed and carbonized in the solid phase.
To form the carbonaceous material (C), and the carbonaceous material (A) and the metal
The electrode material of the present invention bonded or coated with the substance (B)
How to get. Organic polymers used for this purpose include
Lulose resin, phenolic resin, furfuryl alcohol
Resin, polyacrylonitrile, poly (α-halogenated
Acrylic resin such as acrylonitrile), polyamide tree
Fat, polyimide resin, polyacetylene, poly- (p-f
Enylene), poly (p-phenylenevinylene), etc.
Role resins can be given. In the third method, a carbonaceous material (A) and a metal
The organic compound is thermally decomposed in a gas phase on the mixture of the product (B).
To form the carbonaceous material (C), and the carbonaceous material (A) and the metal
For bonding or coating the carbonaceous material (C) with the carbonaceous material (B)
Is the law. The organic compound used at this time is, for example, propane.
Aliphatic hydrocarbons, unsaturated hydrocarbon compounds, benzene,
Aromatic compounds such as ruene and xylene, benzene, naphtha
Aromatic compounds such as len and perylene, condensed cyclic hydrocarbons
Compound carboxylic acid, carboxylic anhydride, carboxylic acid
And derivatives such as [Electrode Forming] The electrode formed as described above
Carbonaceous matter (A), metallic matter (B) and carbonaceous matter
The carbonaceous electrode material of the present invention comprising (C) is preferably
Is mixed with the following polymer binder and molded into the shape of an electrode.
It is. As a polymer binder,   Polyethylene, polypropylene, cellulose, poly
Resins such as ethylene terephthalate and aromatic polyamide.   Styrene-butadiene rubber, isoprene rubber, pig
Diene rubber, ethylene / propylene rubber, butyl rubber
Which rubber.   Styrene / butadiene / styrene block copolymer
Ishi, this is hydrogenated, styrene, isoprene,
Styrene block copolymer or its hydrogenated
Such as thermoplastic elastomers.   Syndiotactic 1,2-polybutadiene, ethyl
Len / vinyl acetate copolymer, propylene / carbon number 2 or
Soft trees such as copolymers with 4 to 12 α-olefins
Fat.   Alkali metal ions, especially lithium ion conduction
And the like. The above-mentioned alkali metal ions, especially lithium ion
As a conductive polymer composition, ion-
Conductivity is preferably 10^-8scm^-1Above, more preferred
Or 10^-6scm^-1Above, more preferably 10^-Five
scm^-1Above, particularly preferably 10^-Fourscm^-1Less than
Above, most preferably 10^-3scm^-1Higher polymers
A composition is used. Specifically, polyethylene oxalate
, Polypropylene oxide, polyepoxychloride
, Polyphosphazene, polyvinylidene fluoride, poly
Polymer compounds such as acrylonitrile can be
Or complexed with an alkali metal salt mainly composed of lithium
Propylene carbonate, ethylene carbonate
And high-dielectric organic compounds such as γ-butyrolactone.
An added system or the like can be used. The polymer binder and the carbonaceous electrode material of the present invention
As a mixed form of the above, the binder particles and the carbonaceous electrode material
In the form of a mixture with the filler particles or in the form of fibers (preferably
Is 10 μm or less in diameter, more preferably 5 μm or less in diameter.
Microfibers (fibrils), particularly preferably fibrils
-Shaped (powder having tentacle-shaped ultra-fine fibrils)
The binder is entangled with the particles of the carbonaceous electrode material of the present invention.
Mixed form, or the above rubber, thermoplastic elastomer
-, Soft resins, binders such as ion-conductive polymer compositions
Are mixed on the surface of the particles of the carbonaceous electrode material of the present invention.
There is a form. The above-mentioned carbonaceous electrode material of the present invention
The mixing ratio of the binder and the binder is 100% by weight of the carbonaceous electrode material.
Parts by weight of a binder, preferably 0.1 to 30 parts by weight,
More preferably 0.5 to 20 parts by weight, more preferably 1 to 20 parts by weight.
10 to 10 parts by weight, particularly preferably 2 to 7 parts by weight. Book
The carbonaceous electrode material of the invention is a mixture with the above-mentioned binder and the like.
Or roll molding, compression molding, or
Is to dissolve or disperse the binder in the solvent,
Pellets, sheets, etc.
Etc. into various shapes of electrodes. As a metal current collector
Is a thin layer of metal such as Ni, Cu, Sus, a wire mesh, etc.
Used. The electrode compact is in the form of a sheet or pellet.
Any shape can be used. [Support of active material]
In the electrode molded body, an alkali metal as an active material, preferably
Lithium metal may be used prior to or during battery assembly.
It can be carried on. The active material is supported on the carrier
Methods include chemical, electrochemical, and physical
There are methods. For example, a certain concentration of alkali metal
The electrode is formed in an electrolyte containing thione, preferably Li ion.
By immersing the feature and using lithium as the counter electrode, this electrode
Method of impregnating an electrode with a molded body as an anode, obtaining an electrode molded body
Alkali metal powder, preferably lithium powder
Can be applied. There
Is the method that makes the lithium metal and the electrode
The method can also be used. In this case, lithium metal and
Lithium ion conduction with the carbonaceous electrode material in the electrode compact
It is preferable that the contact is made via a conductive polymer plastic. This
Lithium previously supported on the electrode compact as in
The amount of the rubber is preferably 0.03 per part by weight of the carrier.
0 to 0.250 parts by weight, more preferably 0.060 to 0.25 parts by weight.
200 parts by weight, more preferably 0.070 to 0.150
Parts by weight, particularly preferably 0.075 to 0.120 weight
Parts, most preferably 0.080-0.100 parts by weight.
You. Electrode of the present invention using such a carbonaceous electrode material
Is usually used as a negative electrode of a secondary battery, and a separator is
To face the positive electrode through. [Positive electrode] The material of the positive electrode body is not particularly limited.
No, for example, alkali metal clicks such as Li ions
Metallic metal that emits or obtains on in accordance with the charge / discharge reaction
It is preferred that it be composed of a lucogen compound. Such gold
As chalcogen compounds of the genus, oxides of vanadium,
Nadium sulfide, molybdenum oxide, molybdenum
Of sulfide, manganese oxide, chromium oxide, titanium
Oxides, sulfides of titanium and their composite oxides, composites
Sulfide and the like. Preferably Cr_ThreeO₈, V
_TwoO_Five, V₆O₁₃, VO_Two, Cr_TwoO_Five, MnO_Two, TiO_Two,
MoV_TwoO₈; TiS_Two, V_TwoS_Five, MoS_Two, MoS_Three, V
S_Two, Cr_0.25V_0.75S_Two, Cr_0.5V_0.5S_TwoEtc.
You. Also, LiCoO_Two, WO_ThreeOxides such as; CuS;
Fe_0.25V_0.75S_Two, Na_0.1CrS_TwoSuch as sulfide; N
iPS_Three, FePS_ThreeSuch as phosphorus and sulfur compounds; VSe
_Two, NbSe_ThreeSelenium compounds such as
Wear. In addition, conductive materials such as polyaniline and polypyrrole
Polymers can be used. In addition, the specific surface area is 10
m^Two/ G or more, preferably 100 m^Two/ G or more, even better
Preferably 500m^Two/ G or more, particularly preferably 100
0m^Two/ G or more, most preferably 2000 m^Two/ G or more
A carbonaceous material can be used for the positive electrode. [Electrolyte] LiCl is used as an electrolyte.
O_Four, LiPF₆, LiAsF₆, LiBF_Four, LiSO_Three
CF_Three, LiN (SO_TwoCF_Three)_TwoAlkali metal salts, such as
Electrolyte salts such as tetraalkylammonium salts
Lencarbonate, ethylene carbonate, butyleneca
-Carbonate, 1,3-dioxolan, 1,2-dimethoxy
Ethane, tetrahydrofuran, diethyl carbonate, etc.
Can be used. Lithium as electrolyte
Solid electrolyte with ionic conductivity can also be used
You. The separator that holds the electrolyte is generally
Excellent materials such as polyethylene, polypropylene, etc.
Polyolefin nonwovens can be used. [Assembly of secondary battery]
For example, a metal net for current collection is placed on the positive electrode can, and the positive electrode
Material, separator containing electrolyte, negative electrode material, current collector gold
Metal net, and further stacked on it in the order of negative electrode can,
Assembled by sealing the ends with gaskets
You. A battery constructed in this way, for example, a positive electrode
Using a metal chalcogen compound, the carbonaceous
In a battery using an electrode material, the negative electrode
Active material ions (preferably lithium ions)
And discharges active material ions during discharge.
Thus, the electrode reaction of charge and discharge proceeds. Charging at positive electrode
The active material ions are released from the positive electrode body during discharge,
Ions are doped and the electrode reaction of charge and discharge proceeds
You. In addition, the above-mentioned conductive polymer or specific surface area
Electrode material of the present invention using a carbonaceous material
In a battery using a charge, the negative electrode is charged when charging.
The cation in the lysate is doped, and during discharge,
The cations are released, and the electrode reaction of charge and discharge proceeds.
On the other hand, in the positive electrode, the anion
Doping, and anions in the cathode body are released during discharge.
Then, the electrode reaction of charge and discharge proceeds. [Measurement method] In the present invention, (a) X-ray
Wide-angle diffraction, (b) Raman spectrum, (c) true density,
(D) The following methods are used to measure the line width of electron spin resonance.
Was carried out by (B) X-ray wide-angle diffraction: spacing between (002) planes (d₀₀₂) If the carbonaceous material is in powder form,
Powder in an agate mortar and add about 15% by weight of X to the sample.
High purity silicon powder for wire standard mixed as internal standard
And fill the sample cell with a graphite monochromator
Monochromatic CuKα ray as a source, reflection type diffract
A wide-angle X-ray diffraction curve is measured by a meter method. curve
The correction of so-called Lorentz, polarization factor, absorption factor
The following simple method is used without correcting for
Used. That is, the baseline of the curve corresponding to the (002) diffraction
And plot the real intensity from the baseline
In this way, a correction curve for the (002) plane is obtained. The peak of this curve
A line parallel to the angle axis drawn at two-thirds of the height
Find the midpoint of the line segment that intersects the bent curve,
And the diffraction angle is set to twice the diffraction angle.
From the length λ, d₀₀₂Ask for. [0029] (Equation 1) (2) Size of crystallite in c-axis direction: Lc In the corrected diffraction curve obtained in the previous section, half the peak height
Crystal in the c-axis direction using the so-called half width β at the position
The size of the child is obtained from the following equation. [0031] (Equation 2) As the shape factor K, 0.90 was used. λ, θ
Has the same meaning as in the previous section. (B) Raman spectrum Using an argon laser beam as a light source, Japan spectrometer
The measurement was performed using a Kogyo Kogyo NR1000. (C) True density Multi-pycnometer (made by Yuasa Ionics)
The measurement was performed using a gas replacement method with helium gas. (D) Line width of electron spin resonance: ΔHpp The first derivative absorption spectrum of electron spin resonance is JEOL JES
-Measured in X band using FF IX ESR spectrometer
Set. The powdery sample remains as it is,
C. Powderize in a mortar, put into a 2 mm outer diameter capillary,
First, a capillary tube is placed in an ESR tube having an outer diameter of 5 mm. High frequency magnetic field
Is 6.3 Gauss. Above all, air atmosphere
Perform at 23 ° C. under ambient air. Peak of the first derivative absorption spectrum
The line width between the holes (ΔHpp) is Mn²⁺/ MgO standard sample
Determine using [0035] 【Example】 (Example 1) (1) Synthesis of electrode material and preparation of electrode compact Naphthalene-1,4,5,8-tetracarboxylic dianhydride
About 200 mg of the powder was heated at a rate of 10 ° C./min.
The temperature was raised to 380 ° C. and maintained at 380 ° C. for 30 minutes. this
Is further heated to 2400 ° C. at a rate of 20 ° C./min,
It was kept at 2400 ° C. for 1 hour. Crush this, average particle size
The carbonaceous material was 2 μm. Charcoal formed in this way
Substrate (A) has d in X-ray wide-angle diffraction.₀₀₂Is 3.39
Ｌ and Lc were 300 °. True density is 2.21 g / c
m^ThreeMet. 70 parts by weight of particles of the carbonaceous material (A)
And 30 particles of aluminum (volume average particle diameter 6 μm)
The parts were mixed mechanically. This mixture is pitch (condensed)
Polycyclic hydrocarbon compound) in toluene
Heat and pitch the carbonaceous material (A) and aluminum
The mixture was bonded and coated. This mixture is placed under a stream of nitrogen for 2 hours.
The temperature was raised to 750 ° C. at a rate of 0 ° C./min.
After holding for another 1 minute, the temperature is further increased to 950 ° C at a rate of 25 ° C / minute.
The temperature rose. Thus, the carbonaceous material (A) and aluminum
A mixture bonded and coated with the carbonaceous material (C) was prepared. This
Is lightly pulverized to an average particle size of 13.2 μm.
Was. The true density of this mixture is 2.27 g / cm^ThreeMet.
This mixture was prepared using argon ion laser light.
Raman spectrum analysis revealed that carbonaceous material (C)
1600cm^-1And 1360cm^-1Has a peak at
The peak intensity ratio R between the two was 0.92. In addition,
The proportion of the carbonaceous material (A) in the mixture was 56% by weight,
The ratio of aluminum is 24% by weight and the percentage of carbonaceous material (C)
The total was 20% by weight. 95 parts by weight of particles of this mixture
Was mixed with 5 parts by weight of polyethylene powder.
Crimping on a Ni wire mesh to form a pellet electrode with a diameter of 20 mm
Formed. This is dried by heating to 130 ° C under vacuum.
Was. (2) Electrode evaluation 1 mol / l concentration of LiClO_FourPropyle
The carbonate solution was added and the above cell was charged from the top of the cell.
The pole compact was suspended to form one electrode. In opposition to this
An electrode obtained by pressing lithium metal onto a Ni wire mesh is referred to as one electrode.
did. 0.5 mA / cm between both electrodes^TwoAt a constant current of
The operation of charging to 0 V and discharging to 1.5 V was repeated.
Table 1 shows the characteristics of the second cycle and the 40th cycle. (Comparative Example 1) (1) Synthesis of electrode material and preparation of electrode compact Only the carbonaceous material (A) in Example 1 was used as the electrode material.
In the same manner as in Example 1, an electrode molded body was synthesized. (2) Electrode evaluation Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1. (Comparative Example 2) (1) Synthesis of electrode material and preparation of electrode compact 75 parts by weight of the carbonaceous material (A) of Example 1 and aluminum
A material obtained by mechanically mixing 25 parts by weight of particles of
And a molded product was prepared in the same manner as in Example 1.
did. (2) Electrode evaluation The electrode was evaluated in the same manner as in Example 1, and the results are shown in Table 1.
Was. [0038] [Table 1] [0039] As described above, the electrode material of the present invention has the following features.
A carbonaceous material (A) and a metallic material (B) having certain properties
Is bonded or coated with a carbonaceous material (C).
The charge / discharge capacity is large,
As an electrode material for secondary batteries with extremely low load efficiency
It is suitable and its industrial value is extremely large.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 schematically shows a, b, c and d as examples of the structure of an electrode material used as a negative electrode of the present invention. FIG. 2 schematically shows a, b, c and d as examples of another structure of the electrode material used as the negative electrode of the present invention. [Description of Signs] 1 Carbonaceous matter (A) 2 Metallic matter (B) 3 Carbonaceous matter (C)

Claims (1)

(57) [Claims 1] It is possible to form an alloy with a carbonaceous material (A) having a (002) plane spacing d ₀₀₂ of less than 3.45 ° by X-ray wide-angle diffraction and an alkali metal. An electrode material for a secondary battery obtained by bonding or coating a metal material (B) made of a possible metal and / or an alkali metal alloy with a carbon material (C) satisfying the following condition (A): In a Raman spectrum using an argon ion laser beam having a wavelength of 5145 °, 1580 to 1620
cm- ^{1 in} the range of P _A , 1350-1370 cm
It has a peak _{P B} in the range of ^-1, the ratio _{R =} I B / _{I A} of the intensity _{I B} of _{P B} with respect to the intensity _{I A} of the _{P A} is 0.4 or more.