WO2006129415A1 - 非水電解質二次電池およびその負極の製造方法 - Google Patents
非水電解質二次電池およびその負極の製造方法 Download PDFInfo
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- WO2006129415A1 WO2006129415A1 PCT/JP2006/306418 JP2006306418W WO2006129415A1 WO 2006129415 A1 WO2006129415 A1 WO 2006129415A1 JP 2006306418 W JP2006306418 W JP 2006306418W WO 2006129415 A1 WO2006129415 A1 WO 2006129415A1
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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 nonaqueous electrolyte secondary battery, and more specifically, the present invention relates to a nonaqueous electrolyte secondary battery having high energy density and excellent long-term cycle characteristics by improving the negative electrode. It relates to batteries.
- Non-aqueous electrolyte batteries can reduce the size and weight of devices with high energy density, and demand for main power sources and memory backup power sources for various electronic devices has been increasing year by year. ing. In recent years, with the remarkable development of portable electronic devices, there is a demand for further downsizing and higher performance of the devices, and there is a strong demand for non-aqueous electrolyte secondary batteries with high energy density from the viewpoint of maintenance-free. Te!
- the positive electrode mixture and the negative electrode mixture may also be composed of an active material responsible for the electron transfer reaction, a conductive agent that contributes to the electron conductivity in the electrode, and a binder that joins them together.
- Si as a negative electrode active material can generate an intermetallic compound with Li and reversibly store and release Li.
- the charge and discharge capacity when Si is used as the active material for non-aqueous electrolyte secondary batteries is about 4200 mAhZg in theoretical capacity, which is extremely high compared to about 370 mAhZg for carbon materials and about 970 mAhZg for aluminum. large. Therefore, since the battery can be downsized and have a high capacity, many improvements for using Si as the active material of the nonaqueous electrolyte secondary battery have been studied.
- Patent Document 1 has at least two-phase force of the A phase mainly composed of Si and the B phase containing a transition metal and a silicide of Si.
- One or both forces Amorphous state and low crystalline state force We propose a negative electrode active material in at least one state selected.
- Patent Documents 2 to 5 propose the use of Si powder having a reduced average particle size.
- average particle size 1 to: LOOnm (Patent Document 2), average particle size 0.1 ⁇ m to 2.5 ⁇ m (Patent Document 3), particle size 1 nm to 200 nm (Patent Document 4) ), And an average particle size of 0.01-50 ⁇ m (Patent Document 5) is proposed.
- Patent Document 1 JP 2004-335272 A
- Patent Document 2 Japanese Patent Laid-Open No. 2003-109590
- Patent Document 3 Japanese Patent Application Laid-Open No. 2004-185810
- Patent Document 4 Japanese Patent Laid-Open No. 2004-214055
- Patent Document 5 JP 2000-36323 A
- the negative electrode active material containing Si has an extremely large expansion and contraction during charge / discharge compared to the carbonaceous negative electrode active material used in the lithium ion secondary battery. For this reason, making the negative electrode active material containing Si into fine particles is effective in improving the cycle life of the battery.
- a pellet-shaped electrode is produced by pressure-molding a mixture that has power, such as an active material, a conductive agent, and a binder.
- the average particle size of the active material is small! / ⁇ , and when the pellet is molded, the density of the pellet is reduced, and the energy per unit volume is reduced. Density also decreases. Therefore, there exists a fault that battery capacity becomes small. Further, since the amount of irreversible reaction of the battery increases, there is a disadvantage that the battery capacity is reduced. Furthermore, when the particle size of the active material is small, the reactivity with moisture contained in the electrolyte solution is increased, gas is easily generated, and defects such as poor cycle characteristics and storage characteristics occur.
- Patent Documents 2 to 5 studies on the problems peculiar to the above-described pellet-shaped electrode are not completely cut.
- an object of the present invention is to provide a non-aqueous electrolyte secondary battery having a negative electrode pellet having a high capacity and excellent cycle life.
- the nonaqueous electrolyte secondary battery of the present invention includes a negative electrode made of a molded pellet containing a negative electrode active material, a conductive agent and a binder, a positive electrode capable of inserting and extracting lithium ions, and a lithium ion conductive nonaqueous solution.
- a non-aqueous electrolyte secondary battery comprising an electrolyte, wherein the negative electrode active material is
- the average particle size (median diameter of volume cumulative particle size distribution: D50) of the negative electrode active material is 0.50-20 ⁇ m, and the 10% diameter (D10) and 90% diameter ( D90) is 0.10 to 5. and 5.0 to 80 m, respectively.
- the negative electrode according to the present invention has a uniform distribution of the active material in the pellet of the negative electrode, the expansion and contraction in the pellet during charge and discharge can be made uniform, and the cycle life is excellent.
- a water electrolyte secondary battery can be provided.
- the negative electrode pellet having a sufficient density can be obtained, a high-capacity nonaqueous electrolyte secondary battery can be provided.
- FIG. 1 is a longitudinal sectional view of a coin-type battery in an example of the present invention.
- the active material contained in the negative electrode pellet of the present invention includes a first phase mainly composed of Si and a second phase containing a transition metal halide, and the first phase and the second phase At least one of the phases is amorphous or low-crystalline, the average particle diameter (D50) of the negative electrode active material is 0.50-20 / ⁇ ⁇ , and the 10% diameter (D10) of the volume cumulative particle size distribution And 90% diameter (D90) are 0.10 to 5. O / zm and 5.0 to 80 ⁇ , respectively.
- the negative electrode active material is composed of a first phase mainly composed of Si (A phase) and a second phase (B phase) containing a transition metal halide, and the first phase and the second phase If at least one of the phases is in an amorphous state or a low crystalline state, a non-aqueous electrolyte secondary battery having a high capacity and an excellent cycle life can be provided.
- the first phase comprises a first phase mainly composed of Si (A phase) and a second phase (B phase) containing a transition metal halide.
- the negative electrode active material in which at least one of the second phase and the second phase is amorphous and in a low crystalline state means a Si alloy.
- the A phase is a phase mainly composed of Si, particularly preferably a Si single phase.
- the A phase is a phase that occludes and releases Li, and is a phase that can electrochemically react with Li.
- a single Si phase a large amount of Li can be absorbed and released per weight and per volume.
- Si since Si has poor electron conductivity, it may contain a small amount of additive elements such as phosphorus and boron, or transition metals.
- the B phase can have a high affinity with the A phase by including a halide, and can particularly suppress cracks at the crystal interface due to volume expansion during charging.
- phase B is superior to Si in terms of electron conductivity and hardness, so phase B improves the low electron conductivity of phase A, and its shape against expansion stress. Has a role to maintain.
- a plurality of phases may exist in the B phase.
- two or more phases having different composition ratios of the transition metal element M and Si, for example, MSi and MSi may exist.
- different transition metals Two or more phases may be present by including a cation with an element.
- the transition metal element is at least one selected from the group consisting of Ti, Zr, Ni, Cu, and Fe.
- T is Zr, more preferably Ti. These elements have a higher electron conductivity and higher strength than those of other elements when they are formed.
- the B phase containing the transition metal silicide contains TiSi having high electron conductivity.
- the density of the negative electrode pellet contains TiSi, the density of the negative electrode pellet
- the density of the pellet is related to the porosity of the pellet, and the porosity is preferably 20 to 49%. If the porosity exceeds 49%, the battery capacity decreases, and if it is less than 20%, the capacity retention rate decreases.
- the negative electrode for a non-aqueous electrolyte secondary battery according to the present invention is preferably produced by a first phase and transition mainly composed of Si by a mechano-caloring method using a mixture of Si powder and transition metal powder.
- Producing a negative electrode active material comprising a second phase containing a metal halide, wherein at least one of the first phase and the second phase is amorphous or low crystalline;
- the negative electrode active material has an average diameter (median diameter: D50) of 0.50 to 20 / ⁇ ⁇ , and 10% diameter (D10) and 90% diameter of the volume cumulative particle size distribution.
- D50 median diameter
- D10 10% diameter
- D90 wet pulverizing to have a value of 0.10 to 5 and 5.0 to 80 m
- the method includes the step of pressure-molding the pulverized negative electrode active material, the conductive agent and the binder material to obtain a negative electrode pellet.
- the first phase mainly composed of Si (A phase) and the second phase (B phase) containing a transition metal halide, and either or both of the A phase and the B phase Compatibility
- the mechano-caloring method is preferable as a method for preparing the negative electrode active material in an amorphous V and low crystalline state.
- other methods may be used as long as the negative electrode active material in the above-described state can be realized.
- a forging method a gas atomizing method, a liquid quenching method, an ion beam sputtering method, a vacuum deposition method, a plating method, and a gas phase chemical reaction method.
- the phase state can be easily controlled. This is a preferred method. Further, before the step of performing the mechano-caloring treatment, there may be a step of melting the raw material and a step of rapidly cooling and solidifying the molten material.
- the form of the negative electrode active material is not particularly limited as long as the ratio of elements necessary as the negative electrode active material can be realized.
- a mixture of elemental elements constituting the negative electrode active material in a target ratio, an alloy having a target element ratio, a solid solution, or an intermetallic compound can be used.
- the method for producing a negative electrode active material by the mechano-caloring treatment described above is a synthesis method in a dry atmosphere, but has a drawback that the particle size distribution after synthesis is very large. Therefore, after the synthesis, it is preferable to perform a classification process for adjusting the particle size.
- classification methods for example, a sieve that classifies particles according to the size of sieves through which particles do not pass, a classification method, a sedimentation classification method that utilizes the fact that the sedimentation speed of solid particles in the fluid medium varies depending on the particle size, etc. There is.
- these classification methods are disadvantageous in terms of material cost because particles outside the predetermined particle size cannot be used as the active material. Therefore, it is preferable to adjust the particles to the required particle size.
- the pulverization technique has been used in various industries for a long time. It is important to select an efficient grinding method according to the purpose of the object. By pulverization, it is possible to simultaneously perform (1) pulverization and particle size adjustment of aggregated particles, (2) mixing and dispersion of several kinds of powders, and (3) surface modification of particles “activity”.
- the pulverization methods are roughly classified into dry pulverization and wet pulverization.
- the dry method has several times the capacity of the pulverization effect due to the large friction coefficient between the particles and the ball compared to the wet method.
- the particles to be crushed adhere to the ball (media) or the wall of the container.
- the width of the particle size distribution is widened.
- a dispersion medium such as water is added to the particles to be pulverized and pulverized into a slurry. Therefore, it is difficult for particles to adhere to the balls and container walls, and the particles are dispersed in the dispersion medium. Therefore, it is easy to make the particle size uniform compared to dry pulverization.
- wet pulverization is very common because the ball mill type pulverizer that can be wet pulverized has a simple structure, the balls of the pulverization media are easily available in various materials, and pulverization occurs at the contact points between the balls. There are merits such as that the pulverization progresses uniformly at the location.
- active material particles are prepared by a dry mechano-caloring method, and then the average particle diameter (D50) is 0.5 0 to 20 by a wet milling method such as ball milling. Adjust the particle size to 111, the 10% diameter (010) of the volume cumulative particle size distribution is 0.10 to 5. O / zm, and the 90% diameter (D90) of the volume cumulative particle size distribution is 5.0 to 80 ⁇ m. The method is preferred.
- wet pulverization when wet pulverization is used, it is easy to form a thin oxide film that functions as an anti-oxidation film of the negative electrode active material on the particle surface. Therefore, a wet pulverization method is used for pulverization of the negative electrode active material of the present invention. Is preferably adopted. In addition, when wet pulverization is used, a surface oxide film is gently formed on the surface of the material, and this functions as an antioxidant, so there is no need to strictly control the oxygen concentration in the atmosphere during pulverization.
- Dispersion media used for wet pulverization include non-proton solvents such as hexane, acetone, and n-butyl acetate, and water, methyl alcohol, ethyl alcohol, 1-propyl alcohol, 2-propyl alcohol, One-protic solvents such as 1-butyl alcohol and 2-butyl alcohol can be used.
- non-proton solvents such as hexane, acetone, and n-butyl acetate
- water methyl alcohol, ethyl alcohol, 1-propyl alcohol, 2-propyl alcohol
- One-protic solvents such as 1-butyl alcohol and 2-butyl alcohol can be used.
- a protic solvent when wet pulverization is performed in a closed system, it is not preferable to use a protic solvent because gas is generated during pulverization and the container swells or leaks. This is because the Si powder reacts with the protic solvent to generate hydrogen gas. Therefore, it is preferable to use an aprotic solvent as a dispersion medium used for wet grinding. If a protic solvent is used, it is preferable to perform pulverization with an open pulverizer.
- the surface of the finely pulverized negative electrode active material particles can be coated with the carbon material by adding a carbon material.
- the oxidation of the active material particles containing Si can be suppressed.
- the effect of reducing the contact resistance between the particles and reducing the electrode resistance can be obtained.
- the carbon material used here is graphite, it is hard and poor in malleability and ductility. Therefore, the effect of preventing the material from adhering to the pulverization container can be obtained.
- the carbon material as an additive is preferably mixed with the raw material before pulverization, but may be added during the pulverization.
- a pulverizing apparatus As a pulverizing apparatus, a general apparatus may be used, but an apparatus capable of wet powder such as an attritor, a vibration mill, a ball mill, a planetary ball mill, and a bead mill can be used.
- an electron conducting aid such as carbon black and graphite, a binder, and a dispersion medium are added to and mixed with the negative electrode active material. To do.
- the amount of the carbon material added is not particularly limited, but is preferably 1 to 50% by weight of the negative electrode active material, and more preferably 1 to 40% by weight.
- the non-aqueous electrolyte used in the non-aqueous electrolyte secondary battery of the present invention includes a non-aqueous solvent and a lithium salt power that dissolves in the non-aqueous solvent.
- Non-aqueous solvents include, for example, cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, chain carbonates such as dimethyl carbonate, jetyl carbonate, ethylmethyl carbonate, and dipropyl carbonate, methyl formate, and acetic acid.
- Aliphatic carboxylic esters such as methyl, methyl propionate, ethyl propionate, etc., ⁇ / —latatones such as petit-mouth ratataton, 1,2-dimethoxyethane, 1,2-jetoxy peun, ethoxymethoxyethane
- Chain ethers such as tetrahydrofuran, cyclic ethers such as 2-methyltetrahydrofuran, dimethyl sulfoxide, 1,3-dioxolane, formamide, acetoamide, dimethylformamide, dioxolane, aceto Nitrile, propylnitrile, nitromethane, ethyl monoglyme, phosphoric acid triester, trimethoxymethane, dioxolane derivatives, sulfolane, methylsulfolane, 1,3-dimethyl-2-imidazolidinone, 3-methyl-2-oxazolidinone, propylene carbonate
- lithium salts dissolved in these solvents include LiCIO, LiBF, LiPF, and LiAl.
- the negative electrode includes a graphite material, and a binder that holds the negative electrode active material, the conductive agent, and the like in a certain shape.
- the binder may be any material as long as it is electrochemically inactive to Li in the working potential range of the negative electrode and does not affect other substances.
- styrene-butylene copolymer rubber polyacrylic acid, polyethylene, polyurethane, polymethyl methacrylate, polyvinylidene fluoride, polytetrafluoroethylene, carboxymethylcellulose, methylcellulose, polyimide, and the like are suitable.
- the negative electrode active material containing Si has a large volume change
- styrene-butylene copolymer rubber that can respond to the volume change relatively flexibly, and can maintain a strong binding state even when the volume changes
- polyacrylic Preference is given to acids and polyimides.
- Binder can be used in combination,
- an insulating microporous thin film having a large ion permeability and a predetermined mechanical strength is used. Because of its resistance to organic solvents and hydrophobicity, it is possible to use a sheet of nonwoven fabric or woven fabric made of polypropylene, polyethylene, polyphenylene sulfide, polyethylene terephthalate, polyamide, polyimide or the like or a glass fiber.
- the thickness of the separator is generally 10 to 300 m.
- the porosity of the separator is determined according to the permeability of electrons and ions and the membrane pressure of the material, but generally 30 to 80% is desirable. Usually, inexpensive polypropylene is used.
- polypropylene sulfide When used on an electronic component that is mounted on a circuit board and soldered by reflow soldering, it is preferable to use polypropylene sulfide, polyethylene terephthalate, polyamide, polyimide, etc. with a heat distortion temperature of 230 ° C or higher. Good.
- a lithium-containing or non-containing compound can be used as the positive electrode material used in the nonaqueous electrolyte secondary battery of the present invention.
- a lithium-containing or non-containing compound can be used as the positive electrode material used in the nonaqueous electrolyte secondary battery of the present invention.
- the above X value is the value before the start of charge / discharge, and increases and decreases with charge / discharge.
- positive electrode materials such as transition metal chalcogenides, vanadate and its lithium compounds, niobate and its lithium compounds, conjugated polymers using organic conductive materials, chevrel phase compounds, etc. It is also possible to use. It is also possible to use a mixture of a plurality of different positive electrode materials.
- the non-aqueous electrolyte secondary battery of the present invention is suitably in the shape of a flat type or a coin type.
- the present invention is not limited to this.
- a negative electrode active material was produced by a mechanical alloying method of a dry method such as a vibration ball mill, and the negative electrode active material was wet pulverized by a ball mill.
- the particle size of the pulverized negative electrode active material particles was measured with a particle size distribution meter using a laser scattering method.
- the particle size represents the typical size of irregular particles, and there is an expression method such as the equivalent circle diameter or Feret diameter.
- the particle size distribution can be measured by the microtrack method or particle image analysis.
- the powder dispersed in a dispersion medium such as water is irradiated with laser light and its diffraction is examined. This is the distribution of the secondary particle size, and it is possible to know the average particle size (D50: particle size at the center of the particle size distribution) and the 10% diameter (D10) and 90% diameter (D90) of the volume cumulative particle size distribution. You can.
- the particle size distribution can also be obtained by image processing of images observed with a scanning electron microscope (SEM).
- a negative electrode active material was produced by the following method.
- raw materials for transition metals powders of metal Ti, metal Zr, metal Ni, metal Cu, and metal Fe (both 99.99% purity, manufactured by High Purity Chemical Co., Ltd., 20 m under) are used.
- raw materials for Si powders of under 99 m of Kanto Igaku Co., Ltd. and under 20 m were used.
- the weight ratio of S ⁇ that is A phase in the negative electrode active material to be synthesized was 30%, each raw material was weighed and mixed so as to have the following weight ratio.
- (6) and (7) are comparative examples.
- the negative electrode active material obtained from the above mixed powder (1) contains Ti-Si alloy and Si single phase and TiSi phase, which are estimated as a result of X-ray diffraction. did.
- the negative electrode active material obtained from the mixed powders (2), (3), (4) and (5) is the same.
- the presence of Zr-Si alloy, Ni-Si alloy, Cu-Si alloy, and Fe-Si alloy was confirmed. From the X-ray diffraction results, in addition to Si single phase, ZrSi phase, NiSi phase, CuSi respectively
- Batteries were prepared by adjusting the particle size of the negative electrode active material particles having a wide range of particle sizes obtained as described above, and various evaluations were performed.
- a particle size distribution measuring device called HRA MODEL No. 9320—X100 manufactured by Microtrac was used.
- ultrasonic dispersion as pre-processing before measurement 1
- the particles were dispersed in water by running for 80 seconds.
- transition metals were Co and Mn
- the raw materials were metal Co and metal Mn (both 99.99% purity, high purity chemical, 20 m under), and the mixing weight ratio of the raw materials was as follows. Mixed powder was prepared. A negative electrode active material was prepared in the same manner as described above except for this weight ratio.
- the negative electrode active material obtained above, graphite as a conductive agent (manufactured by Nippon Graphite Co., Ltd., SP-5030), and binder as polyacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd., average molecular weight 15) 10) were mixed at a weight ratio of 100: 20: 10.
- This mixture was pressure-molded into a disk shape having a diameter of 4 mm at a molding pressure of 30 MPa, and then dried at 150 ° C. for 12 hours to obtain a negative electrode pellet.
- Lithium manganese oxide and lithium hydroxide were mixed at a molar ratio of 2: 1, and the mixture was calcined in air at 400 ° C for 12 hours to obtain lithium manganate.
- the lithium manganate, carbon black as a conductive agent, and an aqueous disperse water of fluorine resin as a binder were mixed in a weight ratio of 88: 6: 6.
- This mixture was pressure-molded into a disk shape having a diameter of 4 mm at a molding pressure of 3 OMPa, and then dried at 250 ° C. for 12 hours.
- the positive electrode pellet thus obtained had a porosity of 30%.
- the structure shown in FIG. 1 has a diameter of 6.8 mm and a thickness of 2.1 mm.
- a coin-type battery was manufactured.
- the positive electrode can 1 also serves as a positive electrode terminal and is made of stainless steel having excellent corrosion resistance.
- the negative electrode can 2 also serves as a negative electrode terminal, and has the same stainless steel strength as the positive electrode can 1.
- the gasket 3 insulates the positive electrode can 1 and the negative electrode can 2 and seals them, and is made of polypropylene. A pitch is applied to the surface of the gasket 3 in contact with the positive electrode can 1 and the negative electrode can 2.
- the electrolyte was prepared by mixing 1 mol Z1 of LiN (CF 2 SO 4) into a mixed solvent in which propylene carbonate, ethylene carbonate, and 1,2-dimethoxyethane were mixed at a volume ratio of 1: 1: 1.
- the coin-type battery was set in a thermostat set to 20 ° C, and a charge / discharge cycle test was conducted under the following conditions.
- the negative electrode active material obtained from the mixed powder (1) was used, and the average particle size was examined.
- the weight ratio of the Si phase as the A phase in the negative electrode active material was 30% by weight.
- This negative electrode active material is classified by sieving to adjust the particle size distribution shown in Table 1, and then A negative electrode pellet was formed using a negative electrode active material having a particle size distribution, and a battery was evaluated using this negative electrode pellet.
- the negative electrode active material of batteries 1-8 was classified by a sieve. Table 1 shows the evaluation results.
- the average particle diameter (D50) of the negative electrode active material is 0.50 to 20 / zm, and the 10% diameter (D10) of the volume cumulative particle size distribution is 0.10 to 5. O / zm. It can be seen that when the 90% diameter (D90) of the particle size distribution is 5.0 to 80 / ⁇ ⁇ , the capacity is high and the capacity retention after 50 cycles is high. The reason is considered as follows. That is, as the average particle size increases, the battery capacity increases, but the distribution of the active material in the pellet becomes non-uniform, so that the expansion / contraction during charge / discharge also becomes non-uniform in the pellet. As a result, current collection is not performed well, and the cycle life is adversely affected.
- the negative electrode active material of the present invention has an average particle diameter (D50) of 0.50 to 20 ⁇ and a 10% diameter (D10) of volume cumulative particle size distribution of 0.10 to 5. It is suitable that the 90% diameter (D90) of the volume cumulative particle size distribution is 5.0 to 80 ⁇ m.
- the negative electrode active material obtained from the mixed powders (2) to (5) was used.
- the weight ratio of the Si phase, which is the A phase in the negative electrode active material was 30% by weight.
- the types of transition metals contained in the second phase (B phase) were examined for Ti, Zr, Ni, Cu, and Fe.
- the case where the transition metals were Co and Mn was also examined.
- the manufacturing method of the negative electrode active material was as described above, and the weight ratio of S ⁇ which is the A phase in the negative electrode active material was 30% by weight.
- the average particle size (D50) obtained after sieving was 1. ⁇ ⁇ ⁇ as shown in Table 2.
- the main cause of cycle deterioration which is a problem with negative electrodes using materials such as silicon, is the deterioration of current collection due to charge and discharge.
- the expansion and contraction of the negative electrode active material that occurs when lithium is occluded / released destroys the electrode structure and increases the overall resistance of the negative electrode.
- the cycle characteristics there exists a more appropriate phase state, and the cycle characteristics are further improved by selecting an appropriate transition metal.
- This is thought to be related to a more appropriate strength of the material against expansion during charging. That is, including transition metals
- the phase that contains Ti, Zr, Ni, Cu, or Fe is considered to be a suitable state with fewer cracks during charging.
- T is preferably Zr, more preferably Ti. Even when the phase containing the transition metal contains Co or Mn, there is a possibility that it can be used by improving the conductivity of the material and improving the type and amount of the conductive material used in the electrode.
- phase B a method of wet-grinding a negative electrode active material prepared by mecha-caloring using a ball medium was examined.
- the ball (media) used was a 5 mm diameter zircon ball
- the container was a polyethylene 500 ml container
- the dispersion medium was 120 ml of n-butyl acetate.
- the rotation speed of the ball mill was 120 rpm, and then the dispersion medium was removed to recover the negative electrode active material.
- the predetermined particle size adjustment was performed by adjusting the grinding time.
- the method for synthesizing the negative electrode active material, the method for producing the battery, and the evaluation method are the same as in the above examples.
- Table 3 shows the material yield when the particle size was adjusted by wet pulverization in this example. In addition, for comparison, the results are as shown in Example 1 and the material yield when classified is also shown.
- wet pulverization using a ball medium is preferred as a method for adjusting the particle size of the negative electrode active material of the present invention.
- the yield of the sieve material is expressed as a percentage of the weight of the active material recovered after the classification treatment (sieving classification or wet grinding) with respect to the charged weight of the active material classification treatment (sieving, classification or wet grinding). did. The closer this value is to 100%, the better the material yield. Furthermore, wet pulverization has a smaller value of (D50-D10) and (D90-50) and a narrower particle size distribution than sieve classification. Therefore, wet pulverization is suitable for adjusting the width of the particle size distribution of the negative electrode active material more narrowly!
- the dispersion medium in the wet pulverization step of the negative electrode active material was examined.
- the pulverization time is 24 hours in the same manner as in Example 3. Went.
- Table 4 shows the results of observation of the polyethylene container after wet grinding.
- the dispersion medium is an aprotic solvent
- the container was swollen during pulverization, and a part of the solvent was found to leak outside the container. This is presumably because the negative electrode active material reacts with the protic solvent during pulverization to generate gas.
- the aprotic solvent is preferable as the dispersion medium for the wet pulverization when the pulverization is performed with a closed system.
- gas is generated in the pulverization step, so it is preferable to perform pulverization with an open pulverizer.
- Example 5 In this example, a study was made to diffuse graphite with mechanical stress on the surface of the negative electrode active material by adding a carbonaceous material to the negative electrode active material during wet pulverization.
- the negative electrode active material produced by mechanical alloying was wet-ground by the same method as in Example 3. During this wet pulverization, graphite (SP-5030, manufactured by Nippon Graphite Co., Ltd.) was added at a weight ratio of 20% with respect to the negative electrode active material to coat the surface of the negative electrode active material with graphite.
- graphite SP-5030, manufactured by Nippon Graphite Co., Ltd.
- the cycle life and capacity of a non-aqueous electrolyte secondary battery including a negative electrode containing Si can be improved. Therefore, the nonaqueous electrolyte secondary battery according to the present invention is particularly useful as a main power source and a memory backup power source for various electronic devices such as mobile phones and digital cameras.
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
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Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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CNB200680002961XA CN100533821C (zh) | 2005-06-03 | 2006-03-29 | 非水电解质二次电池及其负极的制备方法 |
EP06730366A EP1833109A1 (en) | 2005-06-03 | 2006-03-29 | Rechargeable battery with nonaqueous electrolyte and process for producing negative electrode |
JP2006545838A JP5079334B2 (ja) | 2005-06-03 | 2006-03-29 | リチウムイオン二次電池およびその負極の製造方法 |
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JP2005-163891 | 2005-06-03 | ||
JP2005163891 | 2005-06-03 |
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WO2006129415A1 true WO2006129415A1 (ja) | 2006-12-07 |
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PCT/JP2006/306418 WO2006129415A1 (ja) | 2005-06-03 | 2006-03-29 | 非水電解質二次電池およびその負極の製造方法 |
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US (1) | US20080113271A1 (ja) |
EP (1) | EP1833109A1 (ja) |
JP (1) | JP5079334B2 (ja) |
KR (1) | KR100911799B1 (ja) |
CN (1) | CN100533821C (ja) |
WO (1) | WO2006129415A1 (ja) |
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JP5079334B2 (ja) | 2012-11-21 |
CN100533821C (zh) | 2009-08-26 |
US20080113271A1 (en) | 2008-05-15 |
CN101107734A (zh) | 2008-01-16 |
JPWO2006129415A1 (ja) | 2008-12-25 |
KR100911799B1 (ko) | 2009-08-12 |
KR20070098924A (ko) | 2007-10-05 |
EP1833109A1 (en) | 2007-09-12 |
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