JP5439701B2 - Negative electrode material for lithium ion secondary battery, negative electrode for lithium ion secondary battery using the negative electrode material, and lithium ion secondary battery - Google Patents

Negative electrode material for lithium ion secondary battery, negative electrode for lithium ion secondary battery using the negative electrode material, and lithium ion secondary battery Download PDF

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JP5439701B2
JP5439701B2 JP2006118303A JP2006118303A JP5439701B2 JP 5439701 B2 JP5439701 B2 JP 5439701B2 JP 2006118303 A JP2006118303 A JP 2006118303A JP 2006118303 A JP2006118303 A JP 2006118303A JP 5439701 B2 JP5439701 B2 JP 5439701B2
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negative electrode
lithium ion
ion secondary
carbon
secondary battery
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圭児 岡部
義人 石井
達也 西田
清志 鈴木
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日立化成株式会社
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage
    • Y02E60/12Battery technologies with an indirect contribution to GHG emissions mitigation
    • Y02E60/122Lithium-ion batteries

Description

  The present invention relates to a negative electrode material for a lithium ion secondary battery, a manufacturing method thereof, a negative electrode for a lithium ion secondary battery using the negative electrode material, and a lithium ion secondary battery. More specifically, the lithium ion secondary is excellent in charge / discharge efficiency, input / output characteristics, and life (storage / cycle) characteristics, suitable for applications such as electric vehicles and power tools that require secondary batteries having high input / output characteristics. The present invention relates to a negative electrode material for a battery and a lithium ion secondary battery for obtaining the battery, a method for producing the negative electrode material, and a negative electrode for a lithium ion secondary battery using the negative electrode material.

  Lithium ion secondary batteries are lighter and have higher input / output characteristics than other secondary batteries such as nickel cadmium batteries, nickel metal hydride batteries, and lead storage batteries. It is expected as a power supply for high input / output such as a power supply. As a power source for a hybrid electric vehicle, a lithium ion secondary battery having an excellent balance of input / output characteristics and excellent life characteristics such as cycle characteristics and storage characteristics is required.

  In general, negative electrode active materials used for lithium ion secondary batteries are roughly classified into graphite and amorphous materials. Graphite has a structure in which hexagonal network surfaces of carbon atoms are regularly stacked, and insertion / extraction reaction of lithium ions proceeds from the end portions of the stacked network surfaces to perform charge / discharge. However, since the insertion / elimination reaction proceeds only at the end, the input / output performance is low. Further, since the crystallinity is high and there are few surface defects, there is a problem that the affinity with the electrolytic solution is poor and the life characteristics of the lithium ion secondary battery are deteriorated.

  On the other hand, amorphous carbon typified by hard carbon has irregular hexagonal network stacks or no network structure, so the lithium insertion / extraction reaction proceeds on the entire surface of the particles, It is easy to obtain a lithium ion secondary battery with excellent input / output characteristics. In general, amorphous carbon is roughly classified into two types, hard carbon and soft carbon. Hard carbon is carbon in which crystals do not easily develop even when heat-treated to a high temperature of 2500 ° C. or higher, and soft carbon is carbon that is easily changed to a highly crystalline graphite structure by high-temperature treatment.

  Hard carbon, in contrast to graphite, has low crystallinity on the particle surface and excellent affinity with the electrolyte. Therefore, lithium ion secondary batteries using this as a negative electrode material use graphite. Compared to, it has characteristics such as superior life characteristics. On the other hand, since the structure is irregular, the irreversible capacity is large and the specific gravity is small, so that it is difficult to increase the electrode density and the energy density is low.

Therefore, a lithium ion secondary battery having a small irreversible capacity, a large energy density, and excellent input / output characteristics and life characteristics and a negative electrode material for obtaining the lithium ion secondary battery are required.
Japanese Patent Laid-Open No. 04-370662 Japanese Patent Laid-Open No. 05-307956

  The present invention relates to a lithium ion secondary battery having a small irreversible capacity, a large energy density, and excellent input / output characteristics and life characteristics as compared with a conventional lithium ion secondary battery, and lithium ion for obtaining the same. An object of the present invention is to provide a negative electrode material for a secondary battery, a method for producing the same, and a negative electrode for a lithium ion secondary battery using the negative electrode material.

  The present invention relates to [1] carbon particles having a carbon 002 plane spacing d002 of 3.40-3.70 mm determined by X-ray diffractometer (XRD) measurement, and carbon formed on the surface of the carbon particles. And a ratio of the carbon layer to the carbon particles (weight ratio) is 0.001 to 0.1.

Further, the present invention is [2] in a profile obtained by laser Raman spectroscopy of the excitation wavelength 532 nm, the intensity of the peak appearing in the vicinity of 1360 cm -1 Id, the intensity of the peak appearing in the vicinity of 1580 cm -1 and Ig, It is related with the negative electrode material for lithium ion secondary batteries as described in said [1] whose R value is 0.5 or more and 1.5 or less when intensity ratio Id / Ig of both the peaks is made into R value.

The present invention also [3] The average particle diameter (50% D) is 5μm or more 30μm or less, the true specific gravity of 1.80 g / cm 3 or more 2.20 g / cm 3 or less, determined from nitrogen adsorption measurements at 77K Ratio obtained from carbon dioxide adsorption at a specific surface area of 0.5 m 2 / g to 25 m 2 / g and an adsorption amount up to a relative pressure of 1 to 5 cm 3 / g to 30 cm 3 / g at 273 K The surface area is 0.2 m 2 / g or more and 7.5 m 2 / g or less, and the amount of adsorption up to a relative pressure of 0.03 is 0.2 cm 3 / g or more and 5 cm 3 / g or less. The present invention relates to the negative electrode material for a lithium ion secondary battery according to the above [1] or [2].

  The present invention also provides [4] carbon particles having a carbon 002 plane spacing d002 of 3.40-3.70 mm determined by X-ray diffractometer (XRD) measurement, an organic compound in which carbonaceous matter remains by heat treatment. Mixing it in a mixed solution with a solvent for dissolving it, removing the solvent to produce carbon particles coated with the organic compound, and firing the carbon particles coated with the organic compound, It is related with the manufacturing method of the negative electrode material for lithium ion secondary batteries characterized by including.

  [5] The negative electrode material for a lithium ion secondary battery according to any one of [1] to [3], or the lithium produced by the production method according to [4]. The present invention relates to a negative electrode for a lithium ion secondary battery using a negative electrode material for an ion secondary battery.

  [6] The present invention also relates to a lithium ion secondary battery using the negative electrode for a lithium ion secondary battery according to [6] above [5].

  According to the present invention, compared to a conventional lithium ion secondary battery, a lithium ion secondary battery having a small irreversible capacity, a large energy density, excellent input / output characteristics and life characteristics, and lithium for obtaining the same An ion secondary battery negative electrode material, a method for producing the same, and a negative electrode for a lithium ion secondary battery using the negative electrode material can be provided.

  The negative electrode material for a lithium ion secondary battery according to the present invention includes carbon particles serving as a nucleus whose interplanar spacing d002 of the carbon 002 surface determined by X-ray diffractometer (XRD) measurement is 3.40 to 3.70 mm, and the carbon And a carbon layer formed on the surface of the particle, wherein a ratio (weight ratio) of the carbon layer to the carbon particle is 0.001 to 0.10.

  The carbon particles serving as the nucleus are not particularly limited as long as the carbon particles having a carbon 002 plane spacing d002 of 3.40 to 3.70 mm determined by XRD measurement are irreversible capacity, life characteristics, charge / discharge capacity. From the viewpoint of increasing the hardness, it is more preferable that the material obtained by baking (calcining) and pulverizing a material exhibiting graphitizable properties. Specifically, a material exhibiting graphitizability is calcined in an inert atmosphere of, for example, 800 ° C. or higher, and then pulverized by a known method such as a jet mill, a vibration mill, a pin mill, or a hammer mill. And the carbon particle used as a nucleus can be obtained by adjusting a particle size to 5-30 micrometers. The material exhibiting graphitizability is not particularly limited, and examples thereof include thermoplastic resins, naphthalene, anthracene, phenanthrolene, coal tar, tar pitch, and the like, preferably coal-based coal tar. And petroleum tar. In addition, heat treatment may be performed in advance before firing (calcining) the material exhibiting graphitizable properties. In this case, the material exhibiting graphitizable properties may be heat treated beforehand by an apparatus such as an autoclave. After coarse pulverization, carbon particles serving as nuclei can be obtained by calcining in an inert atmosphere at 800 ° C. or higher and pulverizing to adjust the particle size. The temperature of the heat treatment is preferably determined as appropriate depending on the material exhibiting graphitizable properties, and is not particularly limited. However, when the material exhibiting graphitizable properties is coal-based coal tar or petroleum-based tar. It is preferable that it is 400-450 degreeC.

  Further, the interplanar spacing d002 of the carbon 002 plane of the carbon particles serving as the nucleus may be 3.40 to 3.70 mm, but is preferably 3.40 to 3.60 mm. When the inter-surface distance d002 is less than 3.40 mm, the life characteristics / input / output characteristics of the lithium ion secondary battery are inferior, and when it exceeds 3.70 mm, the initial charge / discharge efficiency of the lithium ion secondary battery tends to decrease. In addition, the interplanar spacing d002 of the carbon 002 plane is a diffraction angle of 2θ = 24 to 26 ° based on a diffraction profile obtained by irradiating a carbon particle powder sample with X-rays (CuKα rays) and measuring diffraction lines with a goniometer. It can be calculated from the diffraction peak corresponding to the appearing carbon 002 plane using the Bragg equation.

  The carbon layer can be formed, for example, by attaching an organic compound (carbon precursor) that leaves a carbonaceous material to the surface of the carbon particles by heat treatment, followed by firing. A negative electrode material for a secondary battery can be obtained.

  The method for attaching the organic compound to the surface of the carbon particles is not particularly limited. For example, after the carbon particles (powder) serving as a nucleus are dispersed and mixed in a mixed solution in which the organic compound is dissolved or dispersed in a solvent. Examples thereof include a wet method for removing a solvent, a dry method in which carbon particles and an organic compound are mixed with each other, and mechanical energy is added to the mixture to adhere, and a vapor phase method such as a CVD method. From the viewpoint of uniformly covering the surface of the carbon particles with the carbon layer, the above wet method is preferable.

  Therefore, the negative electrode material for a lithium ion secondary battery of the present invention is a process in which the carbon particles are mixed with a mixed solution of an organic compound that leaves carbonaceous matter and a solvent that dissolves and disperses the carbonaceous material by heat treatment, and the solvent is removed to form an organic It is preferable to produce by a production method including a step of producing carbon particles coated with a compound and a step of firing carbon particles coated with an organic compound and carbonizing the organic compound.

  The organic compound may be a polymer compound such as a thermoplastic resin or a thermosetting resin, and is not particularly limited, but the thermoplastic polymer compound is carbonized via a liquid phase and has a specific surface area. In order to produce small carbon, it is preferable to cover the surface of the carbon particles because the specific surface area of the negative electrode material is also reduced, and as a result, the initial irreversible capacity of the lithium ion secondary battery can be reduced.

  The thermoplastic polymer compound is not particularly limited. For example, the thermoplastic polymer compound includes ethylene heavy end pitch, crude oil pitch, coal tar pitch, asphalt decomposition pitch, pitch generated by pyrolyzing polyvinyl chloride, naphthalene, etc. A synthetic pitch produced by polymerization in the presence of a strong acid can be used. In addition, thermoplastic synthetic resins such as polyvinyl chloride, polyvinyl alcohol, polyvinyl acetate, and polyvinyl butyral can also be used as the thermoplastic polymer compound. Natural products such as starch and cellulose can also be used.

  Further, the solvent for dissolving and dispersing the organic compound is not particularly limited. For example, when the organic compound is pitches, it is generated during tetrahydrofuran, toluene, xylene, benzene, quinoline, pyridine, or coal dry distillation. A liquid mixture (creosote oil) having a relatively low boiling point can be used. When the organic compound is polyvinyl chloride, for example, tetrahydrofuran, cyclohexanone, nitrobenzene, etc., and when the organic compound is polyvinyl acetate, polyvinyl butyral, etc., for example, alcohols, esters, ketones, etc. When the organic compound is polyvinyl alcohol, for example, water can be used. When water is used as a solvent, it is desirable to add a surfactant in order to promote the mixing / dispersion of carbon particles in the solution and improve the adhesion between the organic compound and the carbon particles.

  The solvent can be removed by heating in a normal pressure or reduced pressure atmosphere. The temperature at the time of solvent removal is preferably 200 ° C. or lower when the atmosphere is air. When the removal temperature exceeds 200 ° C., oxygen in the atmosphere reacts with an organic compound and a solvent (especially when creosote oil is used), and the amount of carbon produced by firing fluctuates and becomes more porous. As a result, the desired range of characteristics may not be achieved.

  Moreover, the firing conditions of the carbon particles coated with the organic compound may be appropriately determined in consideration of the carbonization rate of the organic compound, and are not particularly limited, but are preferably 700 to 1400 ° C. in a non-oxidizing atmosphere. More preferably, it is in the range of 800 to 1300 ° C. When the firing temperature is less than 700 ° C., when used as a negative electrode material, the initial irreversible capacity of the lithium ion secondary battery tends to increase. On the other hand, even if heated above 1400 ° C., the performance as the negative electrode material There is little change and it only causes an increase in production costs. Examples of the non-oxidizing atmosphere include an inert gas atmosphere such as nitrogen, argon, and helium, a vacuum atmosphere, and a circulated combustion exhaust gas atmosphere.

  Prior to firing, the organic compound-coated carbon particles may be heat-treated at a temperature of 150 to 300 ° C. For example, when polyvinyl alcohol is used as the organic compound, the carbonization rate can be increased by such heat treatment.

  Moreover, the negative electrode material for lithium ion secondary batteries of this invention can be obtained by performing the crushing process, a classification process, and a sieving process as needed for the carbon layer covering carbon particle after baking.

  In the negative electrode material for a lithium ion secondary battery of the present invention obtained as described above, the ratio of the surface carbon layer to the core carbon particles (weight ratio, hereinafter referred to as surface carbon ratio) is 0.001 to 0.10. However, it is preferably 0.001 to 0.05, more preferably 0.002 to 0.05, still more preferably 0.005 to 0.03, and particularly preferably 0.008 to 0.02. When the surface carbon ratio is less than 0.001, the life characteristics / input / output characteristics tend to decrease. When the surface carbon ratio exceeds 0.10, the initial charge / discharge efficiency decreases, and the lithium ion secondary battery to be manufactured The energy density tends to decrease. The surface layer carbon ratio can be calculated from the weight of carbon particles serving as a nucleus, the weight of a carbon precursor serving as a carbon layer, and the carbonization ratio of the carbon precursor.

  Moreover, it is preferable that the negative electrode material for lithium ion secondary batteries of this invention has the crystallinity of a surface layer carbon layer lower than the carbon particle used as a nucleus. By making the crystallinity of the surface carbon layer lower than the core carbon particles, the familiarity between the negative electrode material for a lithium ion secondary battery and the electrolytic solution is improved, and as a result, the cycle characteristics are improved.

The negative electrode material for a lithium ion secondary battery of the present invention, in a profile obtained by laser Raman spectroscopy of the excitation wavelength 532 nm, peaks appearing the intensity of the peak appearing in the vicinity of 1360 cm -1 Id, around 1580 cm -1 When the intensity ratio is Ig and the intensity ratio Id / Ig between the two peaks is the R value, the R value is preferably 0.5 or more and 1.5 or less, and 0.7 or more and 1.3 or less. It is more preferable. When the R value is less than 0.5, the life characteristics / input / output characteristics of the lithium ion secondary battery tend to be inferior. When the R value exceeds 1.5, the irreversible capacity of the lithium ion secondary battery tends to increase. . Laser Raman spectroscopic measurement can be performed using NSR-1000 manufactured by JASCO Corporation with settings of an excitation wavelength of 532 nm, a laser output of 3.9 mW, and an incident slit of 150 μm. The obtained data was corrected using a calibration curve obtained from the spectrum of indene (manufactured by Wako Pure Chemical Industries).

  In the negative electrode material for a lithium ion secondary battery of the present invention, the average particle size (50% D) is preferably 5 μm or more and 30 μm or less, and more preferably 5 μm or more and 25 μm or less. When the average particle diameter is less than 5 μm, the specific surface area is increased, the initial charge / discharge efficiency of the lithium ion secondary battery is lowered, and the contact between the particles is deteriorated and the input / output characteristics tend to be lowered. On the other hand, when the average particle diameter exceeds 30 μm, irregularities are likely to occur on the electrode surface, causing a short circuit of the battery and increasing the diffusion distance of Li from the particle surface to the inside. There is a tendency for output characteristics to deteriorate. The particle size distribution can be measured by dispersing a sample in purified water containing a surfactant and measuring with a laser diffraction particle size distribution measuring device (SALD-3000J, manufactured by Shimadzu Corporation), and the average particle size is 50% D Is calculated as

The negative electrode material for a lithium ion secondary battery of the present invention preferably has a true specific gravity of less 1.80 g / cm 3 or more 2.20 g / cm 3. When the true specific gravity is less than 1.80 g / cm 3 , the charge / discharge capacity per volume of the lithium ion secondary battery tends to decrease, and the initial charge / discharge efficiency tends to decrease. On the other hand, when the true specific gravity exceeds 2.20 g / cm 3 , the life characteristics of the lithium ion secondary battery tend to deteriorate. The true specific gravity can be determined by a pycnometer method using butanol.

The negative electrode material for a lithium ion secondary battery of the present invention preferably has a specific surface area determined from nitrogen adsorption measurements at 77K is less than 0.5 m 2 / g or more 25m 2 / g, 1.0m 2 / It is more preferable that they are g or more and 15 m < 2 > / g or less. In addition, the amount of adsorption up to a relative pressure of 1 is preferably 5 cm 3 / g or more and 30 cm 3 / g or less, and more preferably 10 cm 3 / g or more and 20 cm 3 / g or less. When this specific surface area is less than 0.5 m 2 / g, the input characteristics tend to deteriorate. On the other hand, when the specific surface area exceeds 25 m 2 / g, it is considered that the coated carbon is made porous for some reason, and the initial irreversible capacity of the lithium ion secondary battery tends to increase. Further, when the amount of adsorption up to a relative pressure of 1 is less than 5 cm 3 / g , the input characteristics tend to decrease, and when it exceeds 30 cm 3 / g , the initial irreversible capacity of the lithium ion secondary battery increases. Tend. In addition, the specific surface area by nitrogen adsorption can be calculated | required using the BET method from the adsorption isotherm obtained from the nitrogen adsorption measurement in 77K.

The negative electrode material for a lithium ion secondary battery of the present invention preferably has a specific surface area of 0.2 m 2 / g or more and 7.5 m 2 / g or less determined by carbon dioxide adsorption at 273 K, 0.3 m more preferably not more than 2 / g or more 5 m 2 / g. Further, the amount of adsorption up to a relative pressure of 0.03 is preferably 0.2 cm 3 / g or more and 5 cm 3 / g or less, and preferably 0.5 cm 3 / g or more and 3 cm 3 / g or less. More preferred. When this specific surface area is less than 0.2 m 2 / g, the input characteristics tend to deteriorate. On the other hand, when the specific surface area exceeds 7.5 m 2 / g, it is considered that the coated carbon is made porous for some reason, and the initial irreversible capacity of the lithium ion secondary battery tends to increase. Moreover, when the amount of adsorption up to a relative pressure of 0.03 is less than 0.2 cm 3 / g , the input characteristics tend to deteriorate, and when it exceeds 5 cm 3 / g , the initial irreversible capacity of the lithium ion secondary battery Tend to increase. In addition, the specific surface area by carbon dioxide adsorption can be calculated | required using a BET method from the adsorption isotherm obtained from the carbon dioxide adsorption measurement at 273K.

  The negative electrode for a lithium ion secondary battery of the present invention is prepared by, for example, kneading the negative electrode material for lithium ion secondary battery and the organic binder of the present invention together with a solvent using a dispersing device such as a stirrer, ball mill, super sand mill, pressure kneader or the like. The negative electrode material slurry is prepared and applied to a current collector to form a negative electrode layer, or the paste-like negative electrode material slurry is formed into a sheet shape, a pellet shape, etc. It can be obtained by integrating with.

  Although it does not specifically limit as said organic type binder, For example, a styrene-butadiene copolymer, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylonitrile, hydroxyethyl (meth) ) Ethylenically unsaturated carboxylic acid esters such as acrylates, ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid and maleic acid, polyvinylidene fluoride, polyethylene oxide, polyepichlorohydrin, polyphosphoric acid Examples thereof include polymer compounds having a large ion conductivity such as sphazene and polyacrylonitrile. The content of the organic binder is preferably 1 to 20 parts by weight with respect to 100 parts by weight in total of the negative electrode material for a lithium ion secondary battery and the organic binder of the present invention.

  Moreover, you may add the thickener for adjusting a viscosity to the said negative electrode material slurry. As the thickener, for example, carboxymethylcellulose, methylcellulose, hydroxymethylcellulose, ethylcellulose, polyvinyl alcohol, polyacrylic acid (salt), oxidized starch, phosphorylated starch, casein and the like can be used.

  Moreover, you may mix a conductive support material with the said negative electrode material slurry. Examples of the conductive auxiliary material include carbon black, graphite, acetylene black, or an oxide or nitride that exhibits conductivity. The usage-amount of a conductive support agent should just be about 1-15 weight% of the negative electrode material of this invention.

  Further, the material and shape of the current collector are not particularly limited. For example, a strip-shaped one made of aluminum, copper, nickel, titanium, stainless steel or the like in a foil shape, a punched foil shape, a mesh shape, or the like. Use it. A porous material such as porous metal (foamed metal) or carbon paper can also be used.

  The method of applying the negative electrode material slurry to the current collector is not particularly limited. For example, metal mask printing method, electrostatic coating method, dip coating method, spray coating method, roll coating method, doctor blade method, gravure coating And publicly known methods such as screen printing and the like. After the application, a rolling process using a flat plate press, a calendar roll or the like is performed as necessary. Further, the integration of the negative electrode material slurry formed into a sheet shape, a pellet shape, and the like with the current collector can be performed by a known method such as a roll, a press, or a combination thereof.

  The lithium ion secondary battery of the present invention can be obtained, for example, by arranging the negative electrode for a lithium ion secondary battery of the present invention and a positive electrode facing each other with a separator interposed therebetween and injecting an electrolytic solution.

  The positive electrode can be obtained by forming a positive electrode layer on the current collector surface in the same manner as the negative electrode. In this case, the current collector may be a band-shaped material made of a metal or an alloy such as aluminum, titanium, or stainless steel in a foil shape, a punched foil shape, a mesh shape, or the like.

The positive electrode material used for the positive electrode layer is not particularly limited. For example, a metal compound, metal oxide, metal sulfide, or conductive polymer material that can be doped or intercalated with lithium ions may be used. Without limitation, for example, lithium cobaltate (LiCoO 2 ), lithium nickelate (LiNiO 2 ), lithium manganate (LiMnO 2 ), and double oxides thereof (LiCoxNiyMnzO 2 , X + Y + X = 1), lithium manganese spinel (LiMn) 2 O 4), lithium vanadium compounds, V 2 O 5, V 6 O 13, VO 2, MnO 2, TiO 2, MoV 2 O 8, TiS 2, V 2 S 5, VS 2, MoS 2, MoS 3, Cr 3 O 8 , Cr 2 O 5 , olivine type LiMPO 4 (M: Co, Ni, Mn, Fe), conductive polymers such as polyacetylene, polyaniline, polypyrrole, polythiophene, and polyacene, porous carbon, and the like can be used alone or in combination.

  As the separator, for example, a nonwoven fabric mainly composed of polyolefin such as polyethylene and polypropylene, cloth, microporous film, or a combination thereof can be used. In addition, when it is set as the structure where the positive electrode and negative electrode of the lithium ion secondary battery to produce are not in direct contact, it is not necessary to use a separator.

Examples of the electrolyte include lithium salts such as LiClO 4 , LiPF 6 , LiAsF 6 , LiBF 4 , LiSO 3 CF 3 , ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, cyclopentanone, sulfolane, 3- Methyl sulfolane, 2,4-dimethyl sulfolane, 3-methyl-1,3-oxazolidine-2-one, γ-butyrolactone, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, butyl methyl carbonate, ethyl propyl carbonate, Butyl ethyl carbonate, dipropyl carbonate, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, methyl acetate A so-called organic electrolyte solution dissolved in a non-aqueous solvent of a simple substance such as ethyl acetate or a mixture of two or more components can be used.

  Although the structure of the lithium ion secondary battery of the present invention is not particularly limited, usually, a positive electrode and a negative electrode, and a separator provided as necessary, are wound into a flat spiral to form a wound electrode group, In general, these are laminated as a flat plate to form a laminated electrode plate group, and the electrode plate group is enclosed in an exterior body.

  The lithium ion secondary battery of the present invention is not particularly limited, but is used as a paper-type battery, a button-type battery, a coin-type battery, a laminated battery, a cylindrical battery, or the like.

  The lithium ion secondary battery of the present invention described above is superior in rapid charge / discharge characteristics, cycle characteristics, small irreversible capacity, and safety compared to a lithium ion secondary battery using a conventional carbon material as a negative electrode. Excellent.

  Hereinafter, the present invention will be described more specifically with reference to examples.

(Examples 1-4)
The coal-based coal tar was heat-treated at 400 ° C. using an autoclave to obtain raw coke. After pulverizing this raw coke, it was calcined in an inert atmosphere at 1200 ° C. to obtain a coke mass. The coke mass was pulverized using an impact pulverizer equipped with a classifier, and then coarse powder was removed with a 300-mesh sieve and subjected to experiments as carbon particles.

  15 g (Example 1), 154 g (Example 2), and 770 g (Example 3) of polyvinyl alcohol (polymerization degree 1700, complete saponification type) in ion exchange water in which 1 g of sodium dodecylbenzenesulfonate was dissolved as a surfactant. 1390 g (Example 4) were dissolved, and mixed solutions of four concentrations were prepared. Each of the obtained mixed solutions and 2000 g of the carbon particles produced above are put into a double-arm kneader having a heating mechanism, mixed at room temperature (25 ° C.) for 1 hour, then heated to 120 ° C., and water is added. Evaporation and removal were performed to obtain polyvinyl alcohol-coated carbon particles. The obtained polyvinyl alcohol-coated carbon particles are heat-treated in air at 200 ° C. for 5 hours to infusible polyvinyl alcohol, and then heated to 900 ° C. at a temperature increase rate of 20 ° C./hour under a nitrogen flow. The carbon layer-coated carbon particles were held for 1 hour. The obtained carbon-coated carbon particles were crushed with a cutter mill and passed through a 300-mesh standard sieve to obtain a negative electrode material sample. Polyvinyl alcohol was heat-treated at 200 ° C. for 5 hours alone, then heated to 900 ° C. at a rate of temperature increase of 20 ° C./hour under nitrogen flow, and the carbonization rate when held for 1 hour was 13%. When the surface layer carbon ratio in each example was calculated from this value and the carbon coating amount, 0.001 (Example 1), 0.01 (Example 2), 0.05 (Example 3),. 09 (Example 4). The physical properties and electrical characteristics of the carbon particles and the negative electrode material samples of each example were measured as follows. The measurement results are shown in Table 1.

  Interplanar spacing d002 of carbon 002 plane: Using a wide-angle X-ray diffractometer manufactured by Rigaku Corporation, Cu-Kα rays were monochromatized with a monochromator and measured using high-purity silicon as a standard substance.

  Raman spectrum peak intensity ratio (R value): measured using NRS-2100 manufactured by JASCO Corporation, laser output 10 mW, spectrometer F single, incident slit width 800 μm, number of integrations twice, exposure time 120 seconds. .

  Average particle size: A solution in which a negative electrode material sample is dispersed in purified water together with a surfactant is placed in a sample water tank of a laser diffraction type particle size distribution measuring apparatus (SALD-3000J, manufactured by Shimadzu Corporation) while applying ultrasonic waves. While circulating with a pump, measurement was performed by a laser diffraction method. The 50% cumulative particle size (50% D) of the obtained particle size distribution was taken as the average particle size.

  True specific gravity (true density): Measured by a butanol replacement method (JIS R 7212) using a specific gravity bottle.

  Specific surface area: The obtained negative electrode material sample was vacuum-dried at 200 ° C. for 1 hour, and then subjected to nitrogen adsorption at a liquid nitrogen temperature (77 K) or carbon dioxide adsorption at 273 K using a Quantochrome AUTOSORB-1. And calculated according to the BET method.

  Adsorption amount: After the obtained negative electrode material sample was vacuum-dried at 200 ° C. for 1 hour, using AUTASORB-1 manufactured by Quantachrome, nitrogen adsorption up to a relative pressure of 1 at a liquid nitrogen temperature (77 K), and relative at 273 K Carbon dioxide adsorption up to a pressure of 0.03 was measured and calculated by a multipoint method.

<Measurement of initial charge / discharge efficiency>
Polyvinylidene fluoride (PVDF) dissolved in N-methyl-2pyrrolidone was added to a solid content of 10% by weight with respect to 90% by weight of the negative electrode material sample of each example, and kneaded to obtain a paste-like negative electrode material slurry. Produced. The slurry was applied to an electrolytic copper foil having a thickness of 40 μm so as to have a diameter of 9.5 mm using a mask having a thickness of 200 μm, and further dried at 105 ° C. to remove N-methyl-2pyrrolidone, thereby obtaining a sample electrode (negative electrode) ) Was produced.

Next, after laminating the sample electrode, the separator, and the counter electrode (positive electrode) in this order, LiPF 6 is added to a mixed solvent of ethylene carbonate (EC) and methyl ethyl carbonate (MEC) (EC and MEC are in a volume ratio of 1: 3). A coin battery was manufactured by injecting an electrolyte solution dissolved to a concentration of 5 mol / liter. Metal lithium was used for the counter electrode, and a polyethylene microporous film having a thickness of 20 μm was used for the separator.

Between the sample electrode and the counter electrode of the obtained coin battery, it is charged to 0 V (Vvs. Li / Li + ) with a constant current of 0.2 mA / cm 2 , and then the current becomes 0.02 mA with a constant voltage of 0 V. Charged up to. Next, after a 30-minute rest period, a one-cycle test was conducted to discharge to 2.5 V (Vvs. Li / Li + ) at a constant current of 0.2 mA / cm 2 to measure the initial charge / discharge efficiency. The initial charge / discharge efficiency was calculated as (discharge capacity) / (charge capacity) × 100. The results are shown in Table 1.

<Evaluation of input / output characteristics>
A coin battery fabricated in the same manner as described above was charged at a constant current of 0.2 mA / cm 2 until 0V (Vvs.Li/Li +), after 30 minutes of dwell time, 0.2 mA / cm 2 constant current The cycle of discharging to 1 V (Vvs. Li / Li + ) was repeated three times, and the charge / discharge capacity per electrode volume at a low current was measured. Then, 4 cycle, charged at a constant current of 2 mA / cm 2 until 0V (Vvs.Li/Li +), after 30 minutes of dwell time, 2 mA / cm 2 constant current at 1V (Vvs.Li/Li +) to the discharge, it was measured charge-discharge capacity per electrode volume at a large current. The charge / discharge capacity per electrode volume (mAh / cm 3 ) was calculated by multiplying the measured value of the charge / discharge capacity per mAb material weight (mAh / g) by the electrode density (g / cm 3 ). Input / output characteristics are evaluated by the value obtained by dividing the charge / discharge capacity per electrode volume at the large current ( 2 mA / cm 2 ) by the charge / discharge capacity per electrode volume at the low current (0.2 mA / cm 2 ). did. It can be determined that the larger this value, the better the input / output characteristics. The results are shown in Table 1.

<Evaluation of life characteristics>
To 87% by weight of the negative electrode material sample of each example, 5% by weight of carbon black was added as a conductive auxiliary material, and polyvinylidene fluoride (PVDF) dissolved in N-methyl-2pyrrolidone was added to a solid content of 8% by weight. It knead | mixed and produced the paste-form negative electrode material slurry. This slurry was applied to an electrolytic copper foil having a thickness of 40 μm using a coating machine so that the coating amount per unit area was 4.5 mg / cm 2, and then dried at 130 ° C. to obtain N-methyl-2pyrrolidone. Was further compressed and molded by a roll press so that the composite material density was 1.0 g / cm 3 to prepare a sample electrode (negative electrode).

Further, 94% by weight of lithium cobaltate having a particle diameter of 5 μm as a positive electrode active material, 3% by weight of carbon black as a conductive auxiliary material, and 3% by weight of polyvinylidene fluoride (PVDF) dissolved in N-methyl-2pyrrolidone in solid content % And kneaded to prepare a paste-like positive electrode material slurry. This slurry was applied to an electrolytic aluminum foil having a thickness of 20 μm using a coating machine so that the coating amount per unit area was 8.0 mg / cm 2, and then dried at 130 ° C. to be N-methyl-2-pyrrolidone. Was further compression-molded with a roll press so that the mixture density was 2.5 g / cm 3 to produce a positive electrode.

Subsequently, the sample electrode (negative electrode) produced above was cut out into a 54 × 360 mm square, and the positive electrode was cut out into a 50 mm × 300 mm square to obtain a test electrode. A current collector (copper foil), a negative electrode, a separator, a positive electrode, and a current collector (aluminum foil) were stacked in this order and wound, and then the diameter was adjusted by winding a PTFE plate having a thickness of 1 mm. As the separator, two polyethylene microporous membranes having a thickness of 20 μm were stacked and used. The electrode plate group is put in a steel can, and LiPF 6 is added to a mixed solvent of ethylene carbonate (EC) and methyl ethyl carbonate (MEC) (EC and MEC are 1: 3 in a volume ratio) of 1.5 mol / 3 ml of the electrolyte solution dissolved to a concentration of 1 liter was poured and sealed to produce a wound cylindrical battery.

  Next, the battery was charged to 4.15 V at a constant current of 100 mA in a constant temperature bath at 25 ° C., further charged to a current of 10 mA at a constant voltage of 4.15 V, and after a pause of 30 minutes, a constant current of 100 mA Was discharged to 2.5V. Subsequently, the battery was transferred to a constant temperature bath at 50 ° C., charged to 4.15 V with a constant current of 100 mA, further charged to a current of 10 mA with a constant voltage of 4.15 V, and after a pause of 30 minutes, a constant current of 100 mA 1 cycle was discharged to 2.75V. The discharge capacity retention ratio from the first cycle when this cycle was repeated 500 times was measured, and the life characteristics were evaluated. The results are shown in Table 1.

(Comparative Example 1)
A lithium ion secondary battery for evaluation was prepared and evaluated in the same manner as in the example except that the surface of the carbon particle in the example was used as it was as a negative electrode material sample without being covered with a carbon layer. The results are shown in Table 1.

(Comparative Examples 2 and 3)
A negative electrode material sample and a lithium ion secondary battery for evaluation were prepared in the same manner as in the example except that the amount of polyvinyl alcohol dissolved in the example was changed to 7.5 g and 1850 g and the carbon particles were coated. Similar evaluations were made. The results are shown in Table 1. The surface layer carbon ratios of the negative electrode material samples of Comparative Examples 2 and 3 were 0.0005 (Comparative Example 2) and 0.12 (Comparative Example 3), respectively.

(Comparative Example 4)
Hexamine was added as a curing agent to the straight novolac resin, and curing was performed while mixing on a hot plate heated to 180 ° C. This cured resin was heat-treated in an oven at 200 ° C. for 5 hours to complete the curing process. Subsequently, the resin was roughly crushed with a hammer and then pulverized using an impact pulverizer equipped with a classifier. The pulverized resin was heated to 1000 ° C. at a temperature rising rate of 20 ° C./hour in a nitrogen atmosphere, and then kept at 1000 ° C. for 1 hour to obtain carbon powder.

  This carbon powder was used as carbon particles in the examples, and a carbon layer coating treatment was performed in the same manner as in Example 2, and coarse powder was removed using a 300-mesh sieve to obtain a negative electrode material sample. Furthermore, using this negative electrode material sample, a lithium ion secondary battery was produced in the same manner as in the example, and the same evaluation was performed. The results are shown in Table 1.

(Comparative Example 5)
Coal coal tar was heat-treated at 400 ° C. using an autoclave to obtain raw coke. After pulverizing this raw coke, it was calcined in an inert atmosphere at 1200 ° C. to obtain a coke mass. The coke mass is pulverized using an impact pulverizer equipped with a classifier, placed in a graphite case, heated to 3000 ° C. at 100 ° C./min in a nitrogen atmosphere, held for 30 minutes, and a 300 mesh standard sieve. The graphite particles were obtained by sieving and removing the coarse powder.

The graphite particles were used as carbon particles in the examples, and a carbon layer coating treatment was performed in the same manner as in Example 2 to obtain a negative electrode material sample. Furthermore, using this negative electrode material sample, a lithium ion secondary battery was produced in the same manner as in the example, and the same evaluation was performed. The results are shown in Table 1.

  As is clear from Table 1, the lithium ion secondary batteries using the negative electrode materials for lithium ion secondary batteries of Examples 1 to 4 are excellent in life characteristics and input / output characteristics while maintaining high charge / discharge efficiency.

As mentioned above, the lithium ion secondary battery which has a negative electrode to which the negative electrode material for lithium ion secondary batteries of this invention is applied is excellent in charging / discharging efficiency, a lifetime characteristic, input / output characteristics, and these balance.

Claims (5)

  1. A carbon particle having a surface spacing d002 of the carbon 002 plane of 3.40 to 3.70 回 折 determined by X-ray diffractometer (XRD) measurement, and a carbon layer formed on the surface of the carbon particle, the carbon The particles are amorphous carbon, the ratio (weight ratio) of the carbon layer to the carbon particles is 0.001 to 0.05, and the specific surface area determined by carbon dioxide adsorption at 273 K is 0.2 m 2 / The negative electrode material for lithium ion secondary batteries which is not less than g and not more than 7.5 m 2 / g.
  2. In the profile determined by laser Raman spectroscopy of the excitation wavelength 532 nm, 1360 cm -1 to the intensity of the peak appearing in the vicinity of Id, and Ig the intensity of a peak appearing near 1580 cm -1, at both peak intensity ratio Id / Ig of The negative electrode material for a lithium ion secondary battery according to claim 1, wherein the R value is from 0.5 to 1.5.
  3. The average particle diameter (50% D) is 5μm or more 30μm or less, the true specific gravity of 1.80 g / cm 3 or more 2.20 g / cm 3 or less and a specific surface area determined from nitrogen adsorption measurements at 77K is 0.5 m 2 / g above 25 m 2 / g or less, and, the adsorption amount until the relative pressure of 1 is 5 cm 3 / g or more 30 cm 3 / g or less, and carbon dioxide adsorption at 273K up to a relative pressure of 0.03 is 0.2 cm 3 / The negative electrode material for a lithium ion secondary battery according to claim 1, wherein the negative electrode material is at least g and at most 5 cm 3 / g.
  4.   The negative electrode for lithium ion secondary batteries which uses the negative electrode material for lithium ion secondary batteries of any one of Claims 1-3.
  5.   The lithium ion secondary battery which uses the negative electrode for lithium ion secondary batteries of Claim 4.
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JP5219422B2 (en) * 2007-07-31 2013-06-26 三洋電機株式会社 Nonaqueous electrolyte secondary battery
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JP2010009948A (en) * 2008-06-27 2010-01-14 Gs Yuasa Corporation Nonaqueous electrolyte secondary battery
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CN107528053A (en) * 2010-07-30 2017-12-29 日立化成株式会社 Anode material for lithium-ion secondary battery, lithium ion secondary battery cathode and lithium rechargeable battery
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