WO2009133807A1 - リチウム二次電池負極用炭素材、その製造方法、リチウム二次電池負極およびリチウム二次電池 - Google Patents
リチウム二次電池負極用炭素材、その製造方法、リチウム二次電池負極およびリチウム二次電池 Download PDFInfo
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- WO2009133807A1 WO2009133807A1 PCT/JP2009/058101 JP2009058101W WO2009133807A1 WO 2009133807 A1 WO2009133807 A1 WO 2009133807A1 JP 2009058101 W JP2009058101 W JP 2009058101W WO 2009133807 A1 WO2009133807 A1 WO 2009133807A1
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- secondary battery
- negative electrode
- lithium secondary
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a carbon material for a lithium secondary battery negative electrode, a manufacturing method thereof, a lithium secondary battery negative electrode, and a lithium secondary battery.
- lithium secondary batteries are required to be smaller and lighter or have higher energy density.
- tin, silicon, germanium, aluminum, or an oxide or alloy thereof, which is alloyed with lithium as a negative electrode material.
- the negative electrode material as described above expands in volume during charging to occlude lithium ions, and conversely shrinks in volume during discharge to release lithium ions. For this reason, it is known that the volume of the negative electrode material changes according to the repetition of the charge / discharge cycle, and as a result, the negative electrode material is pulverized and the negative electrode collapses.
- a catalyst is attached to the surface of an active material nucleus containing a metal or a metalloid capable of forming a lithium alloy, and then subjected to chemical vapor deposition treatment to thereby obtain the active material.
- a negative electrode material is known in which a plurality of carbon fibers are bonded at one end to the surface of a material nucleus (for example, Patent Document 1). According to the negative electrode material described in Patent Document 1, the conductivity between the active material nuclei is ensured by the entanglement of innumerable carbon fibers. No.
- the carbon fiber described in Patent Document 1 is formed by chemical vapor deposition, and is distinguished from that formed by carbonization of a carbon precursor.
- a current collector at least silicon-containing particles capable of occluding and releasing lithium ions, and carbon nano particles attached to the surface of the silicon-containing particles
- a composite negative electrode active material comprising a fiber and a catalyst element that promotes the growth of the carbon nanofiber, and further binding a first binder to the silicon-containing particles and the current collector;
- a negative electrode for a non-aqueous electrolyte secondary battery in which a carbon nanofiber is bound to each other is known (Patent Document 2).
- Patent Document 2 a non-aqueous electrolyte secondary battery having a high capacity and excellent cycle characteristics is provided.
- the carbon nanofiber described in Patent Document 2 is formed by a vapor phase growth method, and is distinguished from that formed by carbonization treatment of a carbon precursor.
- the negative electrode material of the lithium secondary battery includes carbon particles and fibrous carbon in which a carbonaceous material containing Si and / or Si compound is attached to at least a part of the surface of carbon particles having a graphite structure, and the carbonaceous material is A carbon material obtained by heat-treating a composition containing a polymer is known (Patent Document 3). According to the carbon material provided with fibrous carbon described in Patent Document 3, contact between the particles is sufficiently maintained even after repeated charge and discharge, and the cycle characteristics of the secondary battery are improved.
- the fibrous carbon described in Patent Document 3 is formed by a vapor phase growth method, and is distinguished from that formed by carbonization treatment of a carbon precursor.
- the negative electrodes for lithium secondary batteries described in Patent Documents 1 to 3 contain carbon nanofibers to suppress to some extent the decrease in conductivity caused by the volume expansion / contraction of the negative electrode active material due to the charge / discharge cycle.
- the inventions described in Patent Documents 1 and 2 cannot prevent the negative electrode collapse due to the pulverization of the negative electrode active material due to the charge / discharge cycle.
- the adhesion between the negative electrode active material and the fibrous carbon is reduced by the volume expansion / contraction of the negative electrode active material due to the charge / discharge cycle, and as a result, the conductivity is lowered.
- the negative electrodes for lithium secondary batteries described in Patent Documents 1 to 3 cannot be said to have sufficient charge / discharge cycle characteristics. Accordingly, an object of the present invention is to further improve the charge / discharge cycle characteristics of the carbon material for a lithium secondary battery negative electrode.
- Carbon or metal or metalloid which can occlude / release lithium ions, or a particle containing an alloy, oxide, nitride or carbide, A resin carbon material surrounding the particles;
- a carbon material for a negative electrode of a lithium secondary battery comprising a network structure composed of carbon nanofibers and / or carbon nanotubes which are bonded to the surfaces of the particles and surround the particles.
- the carbon precursor comprises a graphitizable material and / or a non-graphitizable material selected from the group consisting of petroleum pitch, coal pitch, phenol resin, furan resin, epoxy resin and polyacrylonitrile. Or carbon material for a lithium secondary battery negative electrode according to (3).
- a lithium secondary battery negative electrode comprising the carbon material for a lithium secondary battery negative electrode according to any one of (1) to (5) above.
- the pulverization of the carbon material for the negative electrode due to the charge / discharge cycle is suppressed, and the decrease in the conductivity of the carbon material is suppressed by maintaining the adhesion with the carbon nanofiber and / or the carbon nanotube. Therefore, a carbon material for a lithium secondary battery negative electrode that exhibits unprecedented excellent charge / discharge cycle characteristics is provided.
- the carbon material for a negative electrode of a lithium secondary battery according to the present invention includes a resin carbon material and carbon nanofibers and / or carbon nanotubes formed from the same carbon precursor at the time of carbonization treatment. It is not necessary to prepare carbon nanotubes by a vapor phase method, and the manufacturing process is simple.
- the carbon material for a negative electrode of a lithium secondary battery according to the present invention surrounds carbon, metal or metalloid, or an alloy, oxide, nitride, or carbide containing particles capable of occluding and releasing lithium ions, and the particles.
- a resin carbon material and a network structure composed of carbon nanofibers and / or carbon nanotubes (hereinafter referred to as “carbon nanofibers”) that bind to and surround the surface of the particles. .
- the network structure made of carbon nanofibers and the like is formed by carbonizing a carbon precursor starting from the surface of the particles.
- a network structure composed of carbon nanofibers or the like that bind to and surround the surface of particles capable of occluding and releasing lithium ions It is thought that it is entangled with the network structure caused by the particles. For this reason, the adhesion between the carbon nanofibers and the particles becomes high, and the carbon nanofibers and the like are hardly separated from the particles when the particle volume expands and contracts due to charge and discharge.
- the network structure of a plurality of adjacent particles is entangled with each other to form a stretchable network structure as a whole, the conductivity of the entire negative electrode is maintained when the particle volume expands and contracts due to charge and discharge. .
- Such a network structure peculiar to the present invention cannot be formed only by adding carbon nanofibers or the like separately formed by a vapor phase method as in the prior art.
- Examples of carbon that can occlude and release lithium ions include carbon black, acetylene black, graphite, heat-fired carbon, and charcoal.
- Examples of metals or metalloids capable of inserting and extracting lithium ions include silicon (Si), tin (Sn), germanium (Ge), and aluminum (Al).
- examples of these metal or metalloid alloys, oxides, nitrides or carbides include silicon monoxide (SiO), silicon nitride (Si 3 N 4 ), silicon carbide (SiC), tin oxide (SnO), nitriding Tin (SnN), tin carbide (SnC), germanium monoxide (GeO), germanium nitride (Ge 3 N 4 ), germanium carbide (GeC), aluminum oxide (Al 2 O 3 ), aluminum nitride (AlN), aluminum carbide (Al 4 C 3 ), aluminum lithium alloy (Al—Li system), titanium silicon alloy (Ti—Si system), and the like can be given.
- Si and Sn are preferable in terms of high energy density, and oxides thereof are more preferable because they have a smaller expansion coefficient during charging than the corresponding Si and Sn.
- the carbon or metal or metalloid particles capable of occluding and releasing lithium ions are not particularly limited in shape, and can have any particle shape such as a lump shape, a scale shape, a spherical shape, and a fiber shape.
- the lower limit of the particle size of these particles is set to 0.
- the thickness is 1 ⁇ m or more, preferably 1.0 ⁇ m or more.
- the particle size is increased, the gap between the particles is increased, the particle packing density is decreased, the thickness of the negative electrode is excessively increased, and the adhesion with the current collector is decreased.
- the upper limit of the diameter D50 is 100 ⁇ m or less, preferably 50 ⁇ m or less.
- the particle size distribution may be adjusted using a known pulverization method or classification method.
- the pulverizer include a hammer mill, a jaw crusher, and a collision pulverizer.
- the classification method air classification and classification with a sieve are possible.
- the air classification apparatus include a turbo classifier and a turboplex.
- Such a network structure unique to the present invention includes the above-described carbon or metal or metalloid capable of occluding and releasing lithium ions, particles containing an alloy, oxide, nitride or carbide, a carbon precursor, By mixing with a catalyst, the catalyst adheres to the surface of the particles, and a mixture in which the particles are dispersed in the carbon precursor is formed, and then the mixture is carbonized. be able to.
- the carbon precursor examples include an easily graphitizable material or a hardly graphitized material selected from the group consisting of petroleum pitch, coal pitch, phenol resin, furan resin, epoxy resin, and polyacrylonitrile.
- a mixture of an easily graphitizable material and a hardly graphitized material may be used.
- the catalyst examples include at least one element selected from the group consisting of copper (Cu), iron (Fe), cobalt (Co), nickel (Ni), molybdenum (Mo) and manganese (Mn) Is mentioned.
- the catalytic element may be contained as an impurity in the carbon precursor. In that case, it may not be necessary to intentionally prepare and mix a separate catalyst.
- These catalytic elements are preferably mixed with the particles as a solution in order to adhere to the surface of the particles. In order to provide such a solution, the catalyst element is preferably prepared as a metal salt compound.
- metal salt compounds examples include copper nitrate, iron nitrate, cobalt nitrate, nickel nitrate, molybdenum nitrate, manganese nitrate. Etc.
- the solvent used in such a solution may be appropriately selected from water, an organic solvent, and a mixture of water and an organic solvent.
- the organic solvent include ethanol, isopropyl alcohol, toluene, benzene, hexane. , Tetrahydrofuran and the like.
- the carbon precursor is converted into a resin carbon material, and the catalyst attached to the surface of the particle is used as a starting point.
- a nanofiber or the like grows, and a network structure entangled with carbon nanofiber or the like grown from another adjacent particle is formed.
- the particles may be blended so as to occupy preferably 5 to 95% by mass, more preferably 10 to 80% by mass in the carbon material after carbonization.
- the carbon precursor may be blended so that the carbonized resin carbon material occupies preferably 5 to 95% by mass, more preferably 20 to 90% by mass in the carbon material.
- the catalyst may be blended in an amount of preferably 0.001 to 20% by mass, more preferably 0.01 to 5% by mass with respect to the above particles.
- the mixture is preferably added in an amount of 70% by mass or less, more preferably 50% by mass or less.
- the method of mixing the particles, the carbon precursor, and the catalyst there are no particular restrictions on the method of mixing the particles, the carbon precursor, and the catalyst. Melting or solution mixing with a stirrer such as a homodisper or homogenizer; pulverizing and mixing with a pulverizer such as a centrifugal pulverizer, free mill, or jet mill Kneading and mixing with a mortar and pestle can be employed.
- a stirrer such as a homodisper or homogenizer
- pulverizing and mixing with a pulverizer such as a centrifugal pulverizer, free mill, or jet mill Kneading and mixing with a mortar and pestle
- the order in which the particles, the carbon precursor, and the catalyst are mixed is not particularly limited, but may be added to the solvent (when used) in the order of the carbon precursor and the particles (supported in advance with the catalyst).
- a normal pulverizer such as a free mill, a jet mill, a vibration mill, or a ball
- the heating temperature for the carbonization treatment may be suitably set within a range of preferably 600 to 1400 ° C, more preferably 800 to 1300 ° C. There is no particular limitation on the rate of temperature rise until the heating temperature is reached, and it may be set appropriately within a range of preferably 0.5 to 600 ° C./hour, more preferably 20 to 300 ° C./hour.
- the holding time at the heating temperature is suitably set within 48 hours, more preferably within a range of 1 to 12 hours.
- reducing atmosphere such as argon, nitrogen, a carbon dioxide, and hydrogen.
- the carbon material for a negative electrode of the lithium secondary battery according to the present invention is formed by combining the resin carbon material and carbon nanofibers from the same carbon precursor at the time of carbonization treatment. There is no need to prepare by the phase method, and the manufacturing process is simple.
- the negative electrode of the lithium secondary battery according to the present invention can be produced.
- the lithium secondary battery negative electrode according to the present invention can be produced by a conventionally known method.
- a carbon material according to the present invention as a negative electrode active material is added with a binder, a conductive agent, etc. to prepare a slurry having a predetermined viscosity with an appropriate solvent or dispersion medium, and this is applied to a current collector such as a metal foil. Then, a coating having a thickness of several ⁇ m to several hundred ⁇ m is formed.
- the negative electrode according to the present invention can be obtained.
- the binder used for preparing the negative electrode according to the present invention may be any conventionally known material, such as polyvinylidene fluoride resin, polytetrafluoroethylene, styrene / butadiene copolymer, polyimide resin, polyamide resin, polyvinyl alcohol, polyvinyl Butyral or the like can be used.
- the conductive agent used in the production of the negative electrode according to the present invention may be any material that is usually used as a conductive auxiliary material, and examples thereof include graphite, acetylene black, and ketjen black.
- the solvent or dispersion medium used for the preparation of the negative electrode according to the present invention may be any material that can uniformly mix the negative electrode active material, the binder, the conductive agent, and the like. Examples thereof include N-methyl-2-pyrrolidone, methanol, And acetanilide.
- the lithium secondary battery according to the present invention can be fabricated by using the lithium secondary battery negative electrode according to the present invention.
- the lithium secondary battery according to the present invention can be produced by a conventionally known method.
- the lithium secondary battery includes a negative electrode according to the present invention, a positive electrode, and an electrolyte, and further includes a separator that prevents the negative electrode and the positive electrode from being short-circuited. Including.
- the electrolyte is a solid electrolyte combined with a polymer and has the function of a separator, an independent separator is not necessary.
- the positive electrode used for the production of the lithium secondary battery according to the present invention can be produced by a conventionally known method.
- a slurry having a predetermined viscosity is prepared with a suitable solvent or dispersion medium by adding a binder, a conductive agent, etc. to the positive electrode active material, and this is applied to a current collector such as a metal foil, and a thickness of several ⁇ m to A solvent or dispersion medium may be removed by forming a coating of several hundred ⁇ m and heat-treating the coating at about 50 to 200 ° C.
- the positive electrode active material may be a conventionally known material, for example, a cobalt composite oxide such as LiCoO 2 , a manganese composite oxide such as LiMn 2 O 4 , a nickel composite oxide such as LiNiO 2 , and a mixture of these oxides. , LiNiO 2 in which part of nickel is replaced with cobalt or manganese, iron composite oxides such as LiFeVO 4 and LiFePO 4 , and the like can be used.
- a conventionally known electrolyte may be used, and lithium salt as an essential component, a room temperature molten salt, a polymer, a flame retardant electrolyte solubilizer, a plasticizer and other What contains an additive can be used.
- Such an electrolyte can be prepared by a conventionally known method. For example, it can be prepared by dissolving a lithium salt in the plasticizer or the room temperature molten salt.
- an electrolyte can be prepared by preparing a solution in which the above components are dissolved in an organic solvent such as alcohol or acetonitrile, and then removing the organic solvent by heating or the like.
- an electrolyte containing a room temperature molten salt In order to improve the charge / discharge characteristics of the lithium secondary battery, it is preferable to use an electrolyte containing a room temperature molten salt, and it is more preferable to use an anion component of the room temperature molten salt having a fluorosulfonyl group.
- lithium salt examples include LiPF 6 , LiClO 4 , LiCF 3 SO 3 , LiBF 4 , LiAsF 6 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 and LiC (CF 3 SO 2 ) 3 , room temperature molten salts containing Li ions as a cation component, such as lithium salts described in JP-A No. 2004-307481.
- the lithium salts may be used alone or in combination of two or more.
- the lithium salt is generally used in a content of 0.1% by mass to 89.9% by mass, preferably 1.0% by mass to 79.0% by mass, based on the entire electrolyte. Components other than the lithium salt of the electrolyte can be added in an appropriate amount on condition that the content of the lithium salt is within the above range.
- the ambient temperature molten salt is composed of a cation component and an anion component.
- a cation component a compound containing an element having a lone electron pair such as nitrogen, sulfur, phosphorus, oxygen, selenium, tin, iodine, antimony, or the like is used. Examples thereof include a cation having at least one group generated by coordination of an ionic type atomic group.
- the polymer used in the electrolyte is not particularly limited as long as it is electrochemically stable and has high ionic conductivity.
- an acrylate polymer, polyvinylidene fluoride, or the like can be used.
- polymers synthesized from those containing a salt monomer composed of an onium cation having a polymerizable functional group and an organic anion having a polymerizable functional group have particularly high ionic conductivity, which further improves charge / discharge characteristics. It is more preferable at the point which can contribute.
- the polymer content in the electrolyte is preferably in the range of 0.1% to 50% by weight, more preferably 1% to 40% by weight.
- the flame retardant electrolyte solubilizer is not particularly limited as long as it is a compound that exhibits self-extinguishing properties and can dissolve the electrolyte salt in the presence of the electrolyte salt.
- phosphate ester, halogen compound Phosphazene etc. can be used.
- plasticizer examples include cyclic carbonates such as ethylene carbonate and propylene carbonate, and chain carbonates such as ethyl methyl carbonate and diethyl carbonate.
- cyclic carbonates such as ethylene carbonate and propylene carbonate
- chain carbonates such as ethyl methyl carbonate and diethyl carbonate.
- the above plasticizers may be used alone or in combination of two or more.
- a separator When a separator is used in the lithium secondary battery according to the present invention, a conventionally known material that can prevent a short circuit between the positive electrode and the negative electrode and is electrochemically stable may be used.
- the separator include a polyethylene separator, a polypropylene separator, a cellulose separator, a nonwoven fabric, an inorganic separator, a glass filter, and the like.
- the electrolyte When a polymer is included in the electrolyte, the electrolyte may also have a separator function, and in that case, an independent separator is unnecessary.
- the lithium secondary battery according to the present invention can be produced by a conventionally known method.
- the positive electrode and the negative electrode are prepared by cutting into a predetermined shape and size, and then the positive electrode and the negative electrode are bonded together via a separator to produce a single-layer cell.
- An electrolyte can then be injected between the electrodes of the single layer cell.
- a single-layer cell may be produced by previously impregnating an electrode, a separator, or the like with an electrolyte, and then superimposing the electrode and the separator.
- a lithium secondary battery can be obtained by inserting and enclosing the thus obtained cell in an outer package made of, for example, a three-layer laminate film of polyester film / aluminum film / modified polyolefin film. .
- the polymer When using a polymer synthesized from a material containing the above-mentioned salt monomer as the separator, it is possible to use a mixture of a polymer, a lithium salt and a room temperature molten salt.
- the polymer can be diluted with a low boiling point solvent such as tetrahydrofuran, methanol and acetonitrile.
- the diluted solvent may be removed, and a single layer cell is produced by sandwiching an electrolyte containing this polymer between the positive electrode and the negative electrode, and a lithium secondary battery can be obtained in the same manner.
- Example 1 135 parts by weight of novolak type phenolic resin (PR-50237 manufactured by Sumitomo Bakelite Co., Ltd.) and 25 parts by weight of hexamethylenetetramine (manufactured by Mitsubishi Gas Chemical Co., Ltd.) as a carbon precursor were mixed with 86 mL of ethanol, and the novolak type phenolic resin and hexagonal resin were mixed. An ethanol solution in which the total amount with methylenetetramine accounted for 70% by mass of the whole was obtained.
- novolak type phenolic resin PR-50237 manufactured by Sumitomo Bakelite Co., Ltd.
- hexamethylenetetramine manufactured by Mitsubishi Gas Chemical Co., Ltd.
- the 300 g of the above compounded resin was transferred to a container (mullite mortar) and placed in a carbonization furnace (manufactured by Sankei Vacuum Co., Ltd.). First, in order to remove volatile components from the compounded resin, heating was started by setting the temperature rising rate of the carbonization furnace to 100 ° C./hour, and when the temperature reached 600 ° C., the temperature rising was stopped and held at that temperature for 1 hour. Then, after standing to cool to room temperature, the container was taken out from the carbonization furnace.
- the compounded resin was transferred to a pulverizer (manufactured by Chuo Kako Co., Ltd.) and pulverized until the center particle size D50 by the laser diffraction particle size distribution measurement method was 10 ⁇ m or less.
- the obtained pulverized product was transferred again to the vessel and placed in the carbonization furnace.
- heating was started at a temperature increase rate of the carbonization furnace of 100 ° C./hour, and when the temperature reached 1100 ° C., the temperature increase was stopped and held at that temperature for 6 hours.
- the container was taken out from the carbonization furnace and allowed to cool to room temperature to obtain a composite carbon material.
- Example 2 The procedure of Example 1 was repeated, except that the 1100 ° C. holding time of the compounded resin pulverized product in the carbonization step was changed from 6 hours to 1 hour.
- the result (electron micrograph) of observing the obtained composite carbon material with a scanning electron microscope is shown in FIG. As can be seen from FIG. 3, it was confirmed that carbon nanofibers and the like were generated from the particle surface of the composite carbon material and surrounded these particles.
- Example 3 100 parts by mass of silicon monoxide powder (average particle size 6 ⁇ m) and Fe 110 ppm (0.07 parts by mass of iron nitrate) were added to 228 parts by mass of the 70% by mass ethanol solution obtained in the same manner as in Example 1. In the high-speed stirrer, mixing was performed in the same manner as in Example 1 to obtain 328 g of a compounded resin. A composite carbon material was obtained from 300 g of the compounded resin in the same manner as in Example 1.
- Example 4 1 part by mass of iron nitrate is added to 100 parts by mass of silicon powder (average particle size 50 ⁇ m), and then kneaded with a mortar and pestle. 55249) 535 parts by mass were added, and pulverized and mixed simultaneously using a coffee mill to obtain a compounded resin.
- a composite carbon material was obtained from 500 g of the compounded resin in the same manner as in Example 1.
- Example 5 300 parts by weight of a novolak-type modified phenolic resin (PR-55249, manufactured by Sumitomo Bakelite Co., Ltd.) is placed in a container (mullite mortar) and placed in a carbonization furnace (manufactured by Sankei Vacuum Co., Ltd.). Setting was started and heating was started. When the temperature reached 600 ° C., the temperature increase was stopped and the temperature was maintained for 1 hour. Then, after standing to cool to room temperature, the container was taken out from the carbonization furnace.
- a novolak-type modified phenolic resin PR-55249, manufactured by Sumitomo Bakelite Co., Ltd.
- the heat-treated product was transferred to a pulverizer (manufactured by Chuo Kako Co., Ltd.), and pulverized until the center particle size D50 by the laser diffraction particle size distribution measurement method was 10 ⁇ m or less.
- 1 part by mass of iron nitrate was added to 100 parts by mass of silicon monoxide powder (average particle size 6 ⁇ m), and then kneaded with a mortar and pestle.
- This kneaded product was mixed with 83 parts by mass of the pulverized product obtained as a carbon precursor, transferred again to the vessel and placed in the carbonization furnace, and a composite carbon material was obtained in the same manner as in Example 1. .
- Example 4 Except not adding iron nitrate, the procedure of Example 4 was repeated to obtain a composite carbon material.
- FIG. 4 shows the result of observation of the obtained composite carbon material with a scanning electron microscope (electron micrograph). As can be seen from FIG. 4, it was confirmed that the composite carbon material particles were not surrounded by carbon nanofibers.
- Example 5 Except not adding iron nitrate, the procedure of Example 5 was repeated to obtain a composite carbon material.
- Initial charge / discharge efficiency (%) initial discharge capacity (mAh / g) / initial charge capacity (mAh / g) ⁇ 100 Further, the percentage obtained by dividing the discharge capacity after repeating 30 cycles with the set of the charging step and the discharging step as one cycle divided by the initial discharge capacity was calculated as the discharge capacity maintenance rate after 30 cycles. The evaluation results are shown in Table 1.
- the lithium ion secondary batteries of Examples 1 to 5 have a discharge capacity maintenance rate of 80% or more after 30 cycles, and charge / discharge compared to Comparative Examples 1 and 2 of 10% or less.
- the cycle characteristics were significantly improved.
- FIGS. 1 to 3 in the examples, carbon nanofibers and the like are generated from the particle surface of the composite carbon material, and as a result of surrounding these particles, the carbon for the negative electrode by the charge / discharge cycle is used. This is considered to be because the pulverization accompanying the expansion and contraction of the material was suppressed.
- FIG. 4 since there is no carbon nanofiber or the like surrounding the particle, pulverization accompanying the expansion and contraction of the carbon material for the negative electrode due to the charge / discharge cycle proceeds, and the electrode substantially Collapsed.
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Abstract
Description
該粒子を包囲する樹脂炭素材と、
該粒子の表面に結合し、かつ、該粒子を包囲するカーボンナノファイバーおよび/またはカーボンナノチューブからなる網状構造体と
を含んでなる、リチウム二次電池負極用炭素材。
実施例1
炭素前駆体としてのノボラック型フェノール樹脂(住友ベークライト株式会社製PR-50237)135質量部およびヘキサメチレンテトラミン(三菱ガス化学株式会社製)25質量部をエタノール86mLと混合し、ノボラック型フェノール樹脂とヘキサメチレンテトラミンとの合計が全体の70質量%を占めるエタノール溶液を得た。
このエタノール溶液228質量部に、一酸化ケイ素粉末(平均粒径6μm)100質量部、硝酸鉄0.0043質量部、硝酸銅0.00076質量部、硝酸モリブデン0.00104質量部およびアルミニウム粉末0.0011質量部(以上、関東化学株式会社製)を添加し、これらを室温下、高速撹拌機(プライミクス株式会社製ホモディスパー)において回転数3000rpmで3分間混合し、配合樹脂325gを得た。
実施例1の手順を繰り返したが、但し、炭化工程における配合樹脂粉砕物の1100℃保持時間を6時間から1時間に変更した。
得られた複合炭素材を走査型電子顕微鏡で観察した結果(電子顕微鏡写真)を図3に示す。図3からわかるように、カーボンナノファイバー等が複合炭素材の粒子表面から発生し、これらの粒子を包囲していることが確認された。
実施例1と同様にして得られた70質量%エタノール溶液228質量部に、一酸化ケイ素粉末(平均粒径6μm)100質量部、Fe110ppm(硝酸鉄0.07質量部)を添加し、これらを上記高速撹拌機において実施例1と同様に混合して配合樹脂328gを得た。上記配合樹脂300gから、実施例1と同様にして、複合炭素材を得た。
ケイ素粉末(平均粒径50μm)100質量部に、硝酸鉄1質量部を添加した後、乳鉢と乳棒にて混練し、さらに炭素前駆体であるノボラック型変性フェノール樹脂(住友ベークライト株式会社製PR-55249)535質量部を添加し、コーヒーミルを用いて、同時に粉砕混合し、配合樹脂を得た。
上記配合樹脂500gから、実施例1と同様にして、複合炭素材を得た。
ノボラック型変性フェノール樹脂(住友ベークライト株式会社製PR-55249)300質量部を容器(ムライトこう鉢)に入れ、これを炭化炉(サンケイ真空株式会社製)に配置し、昇温速度100℃/時に設定し加熱を始め、600℃に達したところで昇温を止めて、その温度で1時間保持した。その後、室温まで放冷後、容器を炭化炉から取り出した。次いで、熱処理品を粉砕機(中央化工機株式会社製)に移し、レーザー回折式粒度分布測定法による中心粒径D50が10μm以下になるまで粉砕処理をした。
一酸化ケイ素粉末(平均粒径6μm)100質量部に硝酸鉄1質量部を添加した後、乳鉢と乳棒にて混練した。この混練物を、炭素前駆体として得られた上記粉砕物83質量部に混合し、再度、上記容器に移して上記炭化炉に配置し、実施例1と同様にして、複合炭素材を得た。
硝酸鉄を添加しないことを除き、実施例4の手順を繰り返して複合炭素材を得た。
得られた複合炭素材を走査型電子顕微鏡で観察した結果(電子顕微鏡写真)を図4に示す。図4からわかるように、複合炭素材の粒子はカーボンナノファイバー等で包囲されていないことが確認された。
硝酸鉄を添加しないことを除き、実施例5の手順を繰り返して複合炭素材を得た。
(1)負極の作製
上記で得られた複合炭素材を用い、これに対してバインダーとしてポリフッ化ビニリデン10質量%、導電剤としてアセチレンブラック3質量%の割合でそれぞれ配合し、さらに、溶媒としてN-メチル-2-ピロリドンを適量加えて混合し、負極用スラリーを調製した。この負極用スラリーを、集電体として厚み10μmの銅箔の両面に塗布して塗膜を形成し、その後、塗膜を110℃で1時間真空乾燥した。真空乾燥後、ロールプレスで加圧成形することにより厚み100μmの電極を得た。これを幅40mm、長さ290mmの大きさに切り出し負極を作製した。この負極から、リチウムイオン二次電池用電極としてφ13mmの径で打ち抜き負極とした。
上記負極、セパレータ(ポリプロピレン製多孔質フィルム:幅45mm、厚さ25μm)、作用極としてリチウム金属(厚さ1mm)の順で、充放電試験用二極セル(宝泉株式会社製)内の所定の位置に配置した。さらに、エチレンカーボネートとジエチレンカーボネートの混合液(体積比1:1)に過塩素酸リチウムを1モル/リットルの濃度で溶解させた電解液をセルに注入し、リチウムイオン二次電池を作製した。
充電容量については、充電時の電流密度を25mA/gとして定電流充電を行い、電位が0Vに達した時点から、0Vで定電圧充電を行い、電流密度が1.25mA/gになるまでに充電した電気量を充電容量とした。
一方、放電容量については、放電時の電流密度も25mA/gとして定電流放電を行い、電位が2.5Vになるまでに放電した電気量を放電容量とした。
また、以下の式により初回の充放電効率を定義した。
初回充放電効率(%)=初回放電容量(mAh/g)/初回充電容量(mAh/g)×100
さらに、上記充電工程と上記放電工程のセットを1サイクルとして30サイクル繰り返した後の放電容量を、上記初回放電容量で除した百分率を、30サイクル後の放電容量維持率として算出した。
評価結果を表1に示す。
Claims (8)
- リチウムイオンの吸蔵・放出が可能な炭素または金属もしくは半金属もしくはこれらの合金、酸化物、窒化物もしくは炭化物を含む粒子と、
該粒子を包囲する樹脂炭素材と、
該粒子の表面に結合し、かつ、該粒子を包囲するカーボンナノファイバーおよび/またはカーボンナノチューブからなる網状構造体と
を含んでなる、リチウム二次電池負極用炭素材。 - 該樹脂炭素材および該網状構造体が、触媒を含有する炭素前駆体の炭化処理により生成したものである、請求項1に記載のリチウム二次電池負極用炭素材。
- 該触媒が、銅、鉄、コバルト、ニッケル、モリブデンおよびマンガンからなる群より選ばれた少なくとも1種の元素を含む、請求項2に記載のリチウム二次電池負極用炭素材。
- 該炭素前駆体が、石油ピッチ、石炭ピッチ、フェノール樹脂、フラン樹脂、エポキシ樹脂およびポリアクリロニトリルからなる群より選択された易黒鉛化材料および/または難黒鉛化材料を含む、請求項2または3に記載のリチウム二次電池負極用炭素材。
- 該金属もしくは半金属が、ケイ素、スズ、ゲルマニウムおよびアルミニウムからなる群より選ばれた少なくとも1種の元素を含む、請求項1~4のいずれか1項に記載のリチウム二次電池負極用炭素材。
- リチウムイオンの吸蔵・放出が可能な炭素または金属もしくは半金属もしくはこれらの合金、酸化物、窒化物もしくは炭化物を含む粒子と、炭素前駆体と、触媒とを混合することにより、該粒子の表面に該触媒が付着し、かつ、該粒子が該炭素前駆体に分散された混合物を形成し、次いで該混合物に炭化処理を施すことを特徴とする、リチウム二次電池負極用炭素材の製造方法。
- 請求項1~5のいずれか1項に記載のリチウム二次電池負極用炭素材を含むリチウム二次電池負極。
- 請求項7に記載のリチウム二次電池負極を含むリチウム二次電池。
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WO2011075489A1 (en) | 2009-12-18 | 2011-06-23 | Designed Nanotubes, LLC | High performance energy storage and collection devices containing exfoliated microtubules and spatially controlled attached nanoscale particles and layers |
KR101085048B1 (ko) | 2010-03-31 | 2011-11-21 | 한국화학연구원 | 개선된 핏치의 제조방법, 및 이를 이용한 석유화학 부산물로부터 고용량 금속-탄소 음극재료의 제조 방법 |
KR101162588B1 (ko) | 2010-05-14 | 2012-07-04 | 삼화콘덴서공업주식회사 | 음극활물질 및 그 제조방법과 그 음극활물질을 포함하는 2차 전지 및 슈퍼 커패시터 |
JP2014203828A (ja) * | 2013-04-03 | 2014-10-27 | 深▲セン▼市貝特瑞新能源材料股▲ふん▼有限公司 | リチウムイオン電池用黒鉛負極材及びその製造方法 |
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JP2018170250A (ja) * | 2017-03-30 | 2018-11-01 | Tdk株式会社 | リチウムイオン二次電池用負極活物質、負極及びリチウムイオン二次電池 |
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