WO2011135713A1 - 電極体およびそれを用いた二次電池 - Google Patents
電極体およびそれを用いた二次電池 Download PDFInfo
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- WO2011135713A1 WO2011135713A1 PCT/JP2010/057677 JP2010057677W WO2011135713A1 WO 2011135713 A1 WO2011135713 A1 WO 2011135713A1 JP 2010057677 W JP2010057677 W JP 2010057677W WO 2011135713 A1 WO2011135713 A1 WO 2011135713A1
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- metal oxide
- electrode body
- active material
- conductive
- secondary battery
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
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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 an electrode body from which a high-capacity secondary battery can be obtained.
- Patent Document 1 discloses a material in which TiO 2 is heat-treated in NH 3 and oxygen atoms are substituted with nitrogen as an active material of a Li ion battery. In this Li ion battery, the internal resistance of the active material can be reduced.
- Patent Document 2 discloses an active material having improved electron conductivity by introducing oxygen atom deficiency by heat-treating TiO 2 in an Ar atmosphere containing hydrogen, ammonia and carbon monoxide. Yes.
- the electrode body is composed only of an active material, sufficient electron conductivity cannot be obtained. Therefore, the addition of a carbon-based material having electron conductivity as a conductive additive improves the electron conductivity. It has been.
- the capacity of the secondary battery cannot be increased because the introduction of nitrogen improves the electronic conductivity but decreases the capacity.
- the active material disclosed in Patent Document 2 may cause a decrease in capacity even though the electron conductivity is improved only to about 10 ⁇ 6 S / cm by introducing only oxygen deficiency. Is expensive.
- the carbon-based material has electronic conductivity but not lithium ion conductivity, when the carbon-based material is used as a conductive additive, the lithium ion conduction path in the electrode body is cut, and the capacity is reduced. There is a risk of inviting.
- a carbonaceous material does not contribute to the capacity
- the present invention has been made in view of the above circumstances, and has as its main object to provide an electrode body that can provide a high-capacity secondary battery.
- an active material composed of a metal oxide and a conductive material in which a part of oxygen atoms in the metal oxide is lost and a nitrogen atom is introduced into the metal oxide.
- An electrode body comprising an auxiliary agent is provided.
- the conductive auxiliary agent is formed by losing some oxygen atoms in the metal oxide constituting the active material and introducing nitrogen atoms into the metal oxide. It has ionic conductivity and electronic conductivity. Thereby, high capacity
- the present invention also provides an electrode body comprising an active material and a conductive additive made of a conductive metal oxide having an electron conductivity of 10 ⁇ 4 S / cm or more.
- the conductive additive has lithium ion conductivity and high electronic conductivity as described above. Thereby, high capacity
- the active material is made of a metal oxide
- the conductive metal oxide is formed by losing a part of oxygen atoms in the metal oxide and introducing nitrogen atoms into the metal oxide. It is preferable. This is because a secondary battery using the electrode body can effectively achieve a high capacity.
- the metal oxide is preferably a Li 4 Ti 5 O 12. This is because, in a secondary battery using the electrode body, a higher capacity can be realized more effectively.
- a part of oxygen atoms of Li 4 Ti 5 O 12 is missing and nitrogen atoms are introduced, and the electron conductivity is 10 ⁇ 4 S / cm or more.
- a conductive additive for a secondary battery is provided.
- the secondary battery conductive additive has lithium ion conductivity and high electron conductivity as described above.
- capacitance is realizable in the secondary battery which used the said conductive support agent for secondary batteries for the electrode body.
- the present invention also provides a secondary battery characterized in that the electrode body is used for at least one of a positive electrode layer and a negative electrode layer.
- the capacity can be increased.
- the electrode body of the present invention the conductive additive for secondary battery, and the secondary battery using the electrode body will be described in detail.
- the electrode body of the present invention includes an active material made of a metal oxide, and a conductive auxiliary agent in which a part of oxygen atoms in the metal oxide is lost and a nitrogen atom is introduced into the metal oxide. Categorized into two modes: a material (first embodiment) and a material having an active material and a conductive assistant composed of a conductive metal oxide having an electron conductivity of 10 ⁇ 4 S / cm or more (second embodiment) can do.
- first embodiment a material having an active material and a conductive assistant composed of a conductive metal oxide having an electron conductivity of 10 ⁇ 4 S / cm or more
- the electrode body of this aspect includes an active material composed of a metal oxide, a conductive auxiliary agent in which a part of oxygen atoms in the metal oxide is deficient, and a nitrogen atom is introduced into the metal oxide. , Characterized by having.
- the conductive assistant is formed by losing a part of oxygen atoms in the metal oxide constituting the active material and introducing nitrogen atoms into the metal oxide.
- the conductive auxiliary agent has electronic conductivity, lithium ion conductivity, and capacity.
- the charge / discharge potentials of the conductive aid and the active material are the same, the charge / discharge capacity of the conductive aid can be effectively used in the electrode body. Thereby, in the secondary battery using the said electrode body, the improvement of a volume energy density is realizable.
- the electrode body of this embodiment will be described in detail.
- the active material in this embodiment is made of a metal oxide.
- the metal oxide used as the active material in this embodiment will be described.
- the metal oxide is not particularly limited as long as it has electron conductivity as well as lithium ion conductivity and a capacity when a part of oxygen atoms is lost and a nitrogen atom is introduced. It is not something.
- M is preferably one or more selected from the group consisting of Co, Mn, Ni, V, Fe, and the like.
- Li 4 Ti 5 O 12 Li (Ni 0.5 Mn 1.5 ) O 4 , LiCoO 2 , LiMnO 2 , LiNiO 2 , LiVO 2 , LiNi 1/3 Co 1/3 Mn 1/3 O 2 , LiMn 2 O 4 , Li 2 FeSiO 4 , Li 2 MnSiO 4 and the like.
- Li 4 Ti 5 O 12 Li (Ni 0.5 Mn 1.5 ) O 4, and the like are preferable, and Li 4 Ti 5 O 12 is particularly preferable. This is because a part of the oxygen atom of Li 4 Ti 5 O 12 is deficient and a conductive additive in which a nitrogen atom is introduced can have high electronic conductivity.
- the metal oxide in the present embodiment it is also possible to use other metal oxides such as Li 2 FeSiO 4.
- the conductive auxiliary agent in this embodiment is one in which a part of oxygen atoms in the metal oxide constituting the active material is lost and a nitrogen atom is introduced into the metal oxide.
- the conductive additive and the production method thereof in this embodiment will be described.
- the conductive auxiliary agent is obtained by modifying a metal oxide constituting the active material.
- the description regarding the metal oxide is the same as that described in the section of “A. Electrode body 1. First embodiment 1-1. Active material (1) Metal oxide”, and thus the description thereof is omitted here.
- the conductive auxiliary agent is one in which part of the oxygen atoms in the metal oxide is deficient and nitrogen atoms are introduced into the metal oxide. .
- the conductive auxiliary agent is one in which a part of oxygen atom is lost in the metal oxide and a nitrogen atom is partially arranged at a position where a part of oxygen atom is lost.
- the amount of oxygen atoms missing and the amount of nitrogen atoms introduced are determined as appropriate on the condition that the conductive additive has electronic conductivity, lithium ion conductivity, and capacity. be able to.
- the range of oxygen atom deficiency a is a range in which the electronic conductivity of the conductive auxiliary agent is dramatically improved, so that the crystal structure of the metal oxide does not break down. As long as it is within this range, it can be determined as appropriate.
- the range of the introduction amount b of nitrogen atoms is a range in which the electronic conductivity of the conductive auxiliary agent is dramatically improved and there is no possibility that the crystal structure of the metal oxide is destroyed. Can be determined as appropriate.
- the range of the oxygen atom deficiency c is a range in which the electronic conductivity of the conductive auxiliary agent is drastically improved, so that the crystal structure of the metal oxide does not break down. As long as it is within this range, it can be determined as appropriate.
- the range of the introduction amount d of nitrogen atoms is a range in which the electronic conductivity of the conductive auxiliary agent is dramatically improved and there is no possibility that the crystal structure of the metal oxide is destroyed. Can be determined as appropriate.
- the conductive aid preferably has a high electronic conductivity of 10 ⁇ 4 S / cm or more. This is because the electronic conductivity of the electrode body can be improved without degrading the performance of a secondary battery using such a conductive additive for the electrode body.
- the conductive auxiliary agent has lithium ion conductivity and charge / discharge capacity. For this reason, when the above-mentioned conductive aid is used for the electrode body, the lithium ion conduction path is cut as compared with the case where the conductive aid made of a general carbon-based material is used for the electrode body. Can be prevented, and the charge / discharge capacity of the electrode body can be improved.
- the charge / discharge potential of the conductive auxiliary agent is as described above. It becomes the same as the charge / discharge potential of the active material. Therefore, by using the conductive additive together with the active material in the electrode body, the charge / discharge capacity of the conductive auxiliary agent can be effectively used in the electrode body.
- the conductive aid is preferably one in which some of the oxygen atoms of Li 4 Ti 5 O 12 are deficient and nitrogen atoms are introduced.
- a conductive additive in which some of the oxygen atoms of Li 4 Ti 5 O 12 are missing and nitrogen atoms are introduced has an electron conductivity of 10 ⁇ 4 S / cm or more at room temperature (25 ° C.). Among them, it is preferable to have an electron conductivity of 10 ⁇ 2 S / cm or more, particularly 10 ⁇ 1 S / cm or more.
- the electron conductivity is obtained by causing some of the oxygen atoms in the metal oxide to be deficient and introducing nitrogen atoms into the metal oxide. It is not particularly limited as long as it is a method capable of producing the above-mentioned conductive additive having a lithium ion conductivity and a capacity.
- a method for producing the conductive assistant a method of heating the metal oxide in an atmosphere of a mixed gas of ammonia and nitrogen can be mentioned.
- the said conductive support agent can be manufactured also by the method of heating the said metal oxide in the atmosphere of ammonia alone.
- a method for introducing nitrogen atoms into the metal oxide a method in which the metal oxide and urea are mixed and heated may be employed.
- the metal oxide is Li 4 Ti 5 O 12 and a method of heating the Li 4 Ti 5 O 12 in a mixed gas atmosphere of ammonia and nitrogen is used as a method for producing the conductive additive
- the temperature for heating Li 4 Ti 5 O 12 is preferably in the range of 500 ° C. to 900 ° C., more preferably in the range of 600 ° C. to 800 ° C., particularly in the range of 700 ° C. to 800 ° C. Is preferred. This is because by setting the temperature within these ranges, in the metal oxide, a part of oxygen atoms is lost, and a reaction in which a nitrogen atom is introduced at a position where the oxygen atom is lost easily proceeds.
- the heating temperature is within a range of 500 ° C. to 900 ° C. In particular, it is preferably in the range of 600 ° C. to 800 ° C., more preferably in the range of 700 ° C. to 800 ° C. This is because by setting the temperature within these ranges, in the metal oxide, a part of oxygen atoms is lost, and a reaction in which a nitrogen atom is introduced at a position where the oxygen atom is lost easily proceeds.
- the time for heating the metal oxide is such that a part of oxygen atoms in the metal oxide is lost and a nitrogen atom is introduced into the metal oxide, so that high electron conductivity is obtained.
- the conductive additive having lithium ion conductivity and capacity it is not particularly limited, but is preferably in the range of 0.5 hours to 20 hours, In particular, it is preferably within the range of 0.5 hours to 10 hours. This is because if the heating time is less than the above range, the reaction is insufficient, and if the heating time is longer than the above range, the crystal structure of the metal oxide may be destroyed. .
- the pretreatment for heating the metal oxide in the nitrogen gas atmosphere is performed before the metal oxide is heated in the mixed gas atmosphere of the reducing gas and the nitrogen introduction gas. Good. Thereby, impurities can be removed from the metal oxide.
- the electrode body of this embodiment contains the said active material and the said conductive support agent.
- the electrode body of this aspect contains the above active material and the above conductive auxiliary agent
- an aspect in which the above active material particles and the above conductive auxiliary particle are mixed (A aspect)
- the surface of the above active material particles There are three possible modes: an embodiment in which the conductive assistant is coated (B embodiment), and an embodiment in which the surface of the active material particles is altered to form the conductive assistant (C embodiment).
- B embodiment an embodiment in which the conductive assistant is coated
- C embodiment an embodiment in which the surface of the active material particles is altered to form the conductive assistant
- FIG. 1 shows the electrode body 10 which has the mode (A mode) which mixes the particle 1 of the said active material, and the particle
- the particle size of the active material particles is not particularly limited.
- the particle diameter of the conductive auxiliary agent particles is not particularly limited, but is preferably in the range of 0.1 ⁇ m to 5 ⁇ m, and more preferably in the range of 0.1 ⁇ m to 3 ⁇ m. Preferably there is.
- the electrode body of this embodiment it is preferable to use a particle having a smaller particle size than that of the active material particles. This is because the contact area between the active material and the conductive additive is increased, an electron path is easily secured, and the electron conductivity of the electrode body is increased. Further, the gap between the active material and the conductive additive is reduced, and the capacity per unit volume of the electrode body can be increased.
- FIG. 2 is a schematic cross-sectional view showing an electrode body 10 having a mode (B mode) in which the conductive assistant film 3 is formed on the surface of the active material particles 1.
- the conductive auxiliary agent film 3 may be formed on a part of the surface of the active material particles 1 as shown in FIG. 3, and as shown in FIG.
- the conductive assistant film 3 may be formed on the entire surface of the particle 1. Since the conductive auxiliary agent has lithium ion conductivity, even if the conductive auxiliary agent film is formed on the entire surface of the active material particles, the lithium ion conductive path is not cut off. This is because the battery performance is not deteriorated.
- the particle diameter of the active material particles can be determined in the same manner as the particle diameter of the active material particles in the aforementioned embodiment A.
- the thickness of the conductive aid film is not particularly limited.
- FIGS. 5 and 6 show an electrode body having a mode (C mode) in which the surface of the active material particles 1 is transformed into the conductive auxiliary agent to form the altered layer 4 of the conductive auxiliary agent. It is the schematic sectional drawing which showed. Since the conductive auxiliary agent has lithium ion conductivity, the lithium ion conductive path is cut even if the altered layer 4 of the conductive auxiliary agent is formed on the entire surface of the active material particles 1. There is no deterioration in battery performance.
- the particle diameter of the active material particles 1 containing the altered layer 4 can be determined in the same manner as the particle diameter of the active material particles in the above-described A embodiment. Moreover, in the electrode body of this aspect, the thickness of the altered layer 4 is not particularly limited.
- the electrode body of the present aspect is characterized by having an active material and a conductive assistant made of a conductive metal oxide having an electron conductivity of 10 ⁇ 4 S / cm or more.
- the conductive additive is made of a conductive metal oxide having a high electronic conductivity of 10 ⁇ 4 S / cm or more, the conductive additive is used in the electrode body. In the secondary battery, high performance can be realized.
- the electrode body of this embodiment will be described.
- the active material in this embodiment is not particularly limited regardless of whether it is a positive electrode active material or a negative electrode active material.
- the active material is a positive electrode active material, the same active material as the metal oxide described in the item “A. Electrode body 1.
- Active material may be used as the active material. it can.
- an olivine-type positive electrode active material such as LiFePO 4 or LiMnPO 4 can be used.
- examples of the active material include a metal active material and a carbon active material.
- the metal active material include In, Al, Si, and Sn.
- examples of the carbon active material include mesocarbon microbeads (MCMB), highly oriented graphite (HOPG), hard carbon, and soft carbon.
- the conductive aid in this embodiment is characterized by comprising a conductive metal oxide having an electron conductivity of 10 ⁇ 4 S / cm or more at room temperature (25 ° C.).
- the conductive metal oxide constituting the conductive assistant will be described.
- the conductive metal oxide is not particularly limited as long as the electron conductivity is 10 ⁇ 4 S / cm or more at room temperature (25 ° C.).
- Examples of the conductive metal oxide include a part of oxygen atoms in the metal oxide represented by the general formula (1) described in the item “A. Electrode body 1. First embodiment 1-1. Active material”. In which a nitrogen atom is introduced into the metal oxide. Since such a modified metal oxide is as described above, description thereof is omitted here.
- Electrode Body has the above active material and the above conductive additive.
- the conductive material is composed of a metal oxide
- the conductive assistant is a conductive metal in which some of the oxygen atoms in the metal oxide are deficient, and nitrogen atoms are introduced into the metal oxide. It is preferably made of an oxide. This is because the charge / discharge potentials of the conductive auxiliary agent and the active material are the same, and the charge / discharge capacity of the electrode body is increased.
- the active material is composed of Li 4 Ti 5 O 12
- the conductive assistant is deficient in a part of oxygen atoms in Li 4 Ti 5 O 12 , and nitrogen atoms are present in the metal oxide. It is preferable that the conductive metal oxide is introduced. This is because the charge / discharge potential of the conductive auxiliary agent and the active material becomes higher.
- the electrode body of the present invention is preferably used in a lithium secondary battery. And the electrode body of this invention can be used for both a positive electrode and a negative electrode in a lithium secondary battery.
- the conductive additive for secondary batteries of the present invention has a part of the oxygen atom of Li 4 Ti 5 O 12 deficient and a nitrogen atom introduced into Li 4 Ti 5 O 12 , and has an electron conductivity of 10 ⁇ . 4 S / cm or more.
- the conductive additive for secondary batteries of the present invention and the production method thereof will be described.
- Li 4 Ti 5 O 12 that is a raw material for the conductive additive for secondary batteries is usually used as an active material in an electrode body and has lithium ion conductivity and capacity. Therefore, Li 4 Ti 5 part of oxygen atoms O 12 is missing, and Li 4 Ti 5 O 12 is a nitrogen atom has been introduced into the secondary battery conductive additive, at room temperature (25 ° C.) It has high electron conductivity of 10 ⁇ 4 S / cm or more, and also has lithium ion conductivity and capacity.
- the secondary battery according to the present invention is characterized in that at least one of the positive electrode layer and the negative electrode layer is composed of the electrode body described in the item “A. Electrode body”.
- FIG. 7 is a schematic cross-sectional view showing an example of the secondary battery of the present invention.
- the secondary battery 40 shown in FIG. 7 has a positive electrode layer 41, a negative electrode layer 42, and an electrolyte layer 43 formed between the positive electrode layer and the negative electrode layer. .
- the secondary battery 40 further includes a positive electrode layer current collector 44 that collects current from the positive electrode layer 41 and a negative electrode layer current collector 45 that collects current from the negative electrode layer 42.
- the positive electrode layer 41 has positive electrode active material particles 1 a and conductive aid particles 2.
- the negative electrode layer 42 has negative electrode active material particles 1 b and conductive aid particles 2.
- the electrolyte layer 43 has electrolyte particles 5.
- the secondary battery will be described.
- the negative electrode layer and the positive electrode layer in the present invention will be described.
- at least one of the negative electrode layer and the positive electrode layer is composed of the electrode body described in the item “A. Electrode body”.
- both the said negative electrode layer and the said positive electrode layer may consist of an electrode body demonstrated by the item of "A. Electrode body.”
- Electrode body When only one of the negative electrode layer and the positive electrode layer is composed of the electrode body described in the above item “A. Electrode body”, a commonly used negative electrode layer or positive electrode layer can be used as the other electrode body.
- the negative electrode layer and the electrode body constituting the positive electrode layer may further contain a solid electrolyte.
- a solid electrolyte is not particularly limited as long as it has lithium ion conductivity, and examples thereof include an oxide solid electrolyte and a sulfide solid electrolyte.
- the solid electrolyte is a sulfide solid electrolyte. This is because the sulfide solid electrolyte has high lithium ion conductivity and can improve the lithium ion conductivity of the negative electrode layer and the positive electrode layer.
- the sulfide solid electrolyte include Li 7 P 3 S 11 .
- the negative electrode layer and the positive electrode layer may contain a binder.
- a binder used by this invention, a fluorine-containing binder etc. can be mentioned, for example.
- the thickness of the negative electrode layer and the positive electrode layer is preferably in the range of 0.1 ⁇ m to 1000 ⁇ m, for example.
- the electrolyte layer used in the present invention is formed between the positive electrode layer and the negative electrode layer.
- the electrolyte layer is not particularly limited as long as it is a layer capable of conducting lithium ion conduction, but is preferably a solid electrolyte layer. This is because a highly safe all-solid secondary battery can be obtained.
- the thickness of the solid electrolyte layer is, for example, preferably in the range of 0.1 ⁇ m to 1000 ⁇ m, and more preferably in the range of 0.1 ⁇ m to 300 ⁇ m.
- a formation method of a solid electrolyte layer the method of compression-molding a solid electrolyte material etc. can be mentioned, for example.
- As such a solid electrolyte used for the solid electrolyte layer the same one as described in “C. Secondary battery 1. Negative electrode layer and positive electrode layer” can be used.
- the secondary battery includes at least the positive electrode layer, the electrolyte layer, and the negative electrode layer.
- the secondary battery further includes a positive electrode layer current collector for collecting the positive electrode layer and a negative electrode layer current collector for collecting the negative electrode layer.
- the material for the positive electrode current collector include SUS, aluminum, nickel, iron, titanium, and carbon. Among them, SUS is preferable.
- examples of the material for the negative electrode layer current collector include SUS, copper, nickel, and carbon. Among them, SUS is preferable.
- it is preferable that the thickness and shape of the positive electrode layer current collector and the negative electrode layer current collector are appropriately selected according to the use of the secondary battery.
- the battery case of a general secondary battery can be used for the battery case used for this invention.
- the battery case include a SUS battery case.
- the secondary battery of the present invention is an all-solid battery, the secondary battery may be formed inside the insulating ring.
- Secondary battery is useful as, for example, a vehicle-mounted battery.
- Examples of the shape of the secondary battery of the present invention include a coin type, a laminate type, a cylindrical type, and a square type.
- the manufacturing method of the secondary battery of this invention will not be specifically limited if it is a method which can obtain the secondary battery mentioned above, The method similar to the manufacturing method of a general secondary battery is used. be able to.
- the secondary battery of the present invention is an all-solid battery, as an example of a manufacturing method thereof, a material constituting the positive electrode layer, a material constituting the solid electrolyte layer, and a material constituting the negative electrode layer are sequentially pressed.
- a method of producing a secondary battery, housing the secondary battery in the battery case, and caulking the battery case can be exemplified.
- Li 4 Ti 5 O 12 (8.2 mg) as an active material, Li 4 Ti 5 O 12-x N y (3.28 mg) as a conductive aid, and 75Li 2 S-25P 2 S 5 (electrolyte)
- a positive electrode layer manufactured by mixing (4.92 mg)
- an electrolyte layer manufactured from 75Li 2 S-25P 2 S 5
- a negative electrode layer manufactured from In—Li. .
- Li 4 Ti 5 O 12-x N y which is a raw material of the positive electrode layer is heated in a mixed gas of N 2 gas and NH 3 gas after heating Li 4 Ti 5 O 12 in N 2 gas.
- x and y indicate the amount of oxygen atom deficiency and the amount of nitrogen atom introduced, respectively.
- Example 2 The positive electrode layer was formed by using Li 4 Ti 5 O 12 (6.56 mg), Li 4 Ti 5 O 12-x N y (4.92 mg) as a conductive auxiliary agent, and 75Li 2 S-25P 2 S 5 (4.92 mg). ) Were mixed in the same manner as in Example 1 except that the all-solid-state secondary battery was manufactured. The particle sizes of Li 4 Ti 5 O 12 , Li 4 Ti 5 O 12-x N y , and 75Li 2 S-25P 2 S 5 are the same as those used in Example 1, respectively.
- Example 1 All solids were prepared in the same manner as in Example 1 except that the positive electrode layer was produced by mixing Li 4 Ti 5 O 12 (11.48 mg) and 75Li 2 S-25P 2 S 5 (4.92 mg). A secondary battery was manufactured. The particle sizes of Li 4 Ti 5 O 12 and 75Li 2 S-25P 2 S 5 are the same as those used in Example 1, respectively.
- Example 3 (Raw material pretreatment) Li 4 Ti 5 O 12 (30 g) was kept in N 2 gas (1 L / min) at 800 ° C. for 10 hours. Thereafter, heating was terminated and natural cooling was performed.
- the particle size of Li 4 Ti 5 O 12 is the same as that used in Example 1.
- Example 4 A sample was obtained in the same manner as in Example 3 except that the raw material pretreatment was not performed.
- Li 4 Ti 5 O 12 (30 g) was used as a sample as it was.
- the particle size of Li 4 Ti 5 O 12 is the same as that used in Example 1.
- Example 3 (X-ray photoelectron spectroscopy measurement) The sample obtained in Example 3 was subjected to X-ray photoelectron spectroscopy measurement.
- the X-ray photoelectron spectroscopy measurement results for the sample obtained in Example 3 are shown in FIG.
- FIG. 10 in Ti2p spectrum measurement, Ti 4+ derived from Li 4 Ti 5 O 12 and Ti 3+ derived from oxygen atom deficiency were detected. Further, as shown in FIG. 10, in the N1s spectrum measurement, since the peak appears at 400 eV or less, it was found that nitrogen was not adsorbed on the surface but contained in the structure.
- Example 3 (Electron conductivity evaluation) About 1 g of the sample obtained in Example 3 and Example 4 was put in a cylinder having four probes on the bottom, and a pressure of 20 kN was applied to measure resistance at room temperature (25 ° C.). The electrical conductivity at room temperature (25 ° C.) was calculated from the obtained resistance value. Table 1 shows the results of the electronic conductivity evaluation for the samples obtained in Example 3 and Example 4.
- Li 4 Ti 5 O 12 that is an active material Li 4 Ti 5 O 12 that is an active material, the sample obtained in Example 3, carbon (HS100) that is a conductive additive, and a binder (PTFE), a positive electrode layer, an electrolyte layer (PST3), And the all-solid-state secondary battery was created from the negative electrode layer (Pt foil).
- Li 4 Ti 5 O 12 as an active material, the sample obtained in Example 4, carbon (HS100) as a conductive additive, and a binder (PTFE) were mixed to form a positive electrode layer and an electrolyte layer ( An all-solid secondary battery was prepared from DST3) and the negative electrode layer (Pt foil).
- FIG. 11 and FIG. 12 show the results of charge and discharge characteristics evaluation for the all-solid-state secondary battery prepared from the sample of Example 3 and the all-solid-state secondary battery prepared from the sample of Example 4, respectively.
- the discharge capacity of the all-solid-state secondary battery prepared from the sample of Example 3 was 80 mAh compared to the theoretical discharge capacity of 175 mAh / g of the all-solid-state secondary battery prepared from Li 4 Ti 5 O 12 of Comparative Example 2. / G or less. Moreover, the discharge capacity of the all-solid-state secondary battery prepared from the sample of Example 4 was compared with the theoretical discharge capacity of 175 mAh / g of the all-solid-state secondary battery prepared from Li 4 Ti 5 O 12 of Comparative Example 2. , And decreased to 60 mAh / g or less.
- Example 3 lacked oxygen atoms in Li 4 Ti 5 O 12 and contained nitrogen atoms in the structure. It was.
- Example 3 and Example 4 have higher electron conductivity than Li 4 Ti 5 O 12 in Comparative Example 2. . It was confirmed that the electron conductivity in the samples obtained in Example 3 and Example 4 was 10 ⁇ 4 S / cm or more at room temperature (25 ° C.). From the results of the charge / discharge characteristics, it was confirmed that in the samples obtained in Example 3 and Example 4, the charge / discharge capacity was reduced as compared with Li 4 Ti 5 O 12 in Comparative Example 2.
- Li 4 Ti 5 O 12 a conductive additive having electronic conductivity and charge / discharge capacity can be obtained by depleting oxygen atoms and incorporating nitrogen in the structure. confirmed.
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Abstract
Description
まず、本発明の電極体について説明する。本発明の電極体は、金属酸化物からなる活物質と、上記金属酸化物における酸素原子の一部が欠損され、かつ上記金属酸化物に窒素原子が導入されてなる導電助剤と、を有するもの(第1態様)および、活物質と、電子伝導性が10-4S/cm以上の導電性金属酸化物からなる導電助剤と、を有するもの(第2態様)の二つの態様に分類することができる。以下、各態様にわけて、本発明の電極体について詳細に説明する。
本態様の電極体は、金属酸化物からなる活物質と、上記金属酸化物における酸素原子の一部が欠損され、かつ上記金属酸化物に窒素原子が導入されてなる導電助剤と、を有することを特徴とするものである。
本態様における活物質は金属酸化物からなることを特徴とするものである。以下、本態様において活物質として用いられる金属酸化物について説明する。
本態様における導電助剤は、上記活物質を構成する金属酸化物における酸素原子の一部が欠損され、かつ上記金属酸化物に窒素原子が導入されてなるものである。以下、本態様における導電助剤およびその製造方法について説明する。
上記導電助剤は、上記活物質を構成する金属酸化物が変性されてなるものである。上記金属酸化物に関する説明は、「A.電極体 1.第1態様 1-1.活物質 (1)金属酸化物」の項目で説明した内容と重複するのでここでの説明は省略する。
上記導電助剤は、上記金属酸化物における酸素原子の一部が欠損され、かつ上記金属酸化物に窒素原子が導入されてなるものである。具体的には、上記導電助剤は、上記金属酸化物において酸素原子の一部が欠損され、かつ酸素原子の一部が欠損された位置に部分的に窒素原子が配置されたものである。そして、酸素原子の一部が欠損する量および窒素原子が導入される量は、上記導電助剤が電子伝導性を有するとともにリチウムイオン伝導性も有し、容量を有することを条件として、適宜定めることができる。上記金属酸化物が上述した一般式(1)で表すことができるものである場合、上記導電助剤は、一般式(2)LixMyOz-aNb(Mは遷移金属元素であり、x=0.02~2.2、y=1~2、z=1.4~4、a=酸素原子の欠損量、b=窒素原子の導入量)で表すことができる。上記一般式(2)において、酸素原子の欠損量aの範囲は、上記導電助剤の電子伝導が劇的に向上するような範囲であって上記金属酸化物の結晶構造が崩れる恐れがないような範囲であることを条件として、適宜定めることができる。同様に、窒素原子の導入量bの範囲は、上記導電助剤の電子伝導が劇的に向上するような範囲であって上記金属酸化物の結晶構造が崩れる恐れがないような範囲であることを条件として、適宜定めることができる。
上記導電助剤は、上記活物質を構成する金属酸化物における酸素原子の一部が欠損され、かつ上記金属酸化物に窒素原子が導入されてなるものである。そして、上記金属酸化物において、酸素原子の一部が欠損し、窒素原子が導入されていることは、例えば、X線光電子分光(XPS)により確認することができる。
上記導電助剤は、10-4S/cm以上の高い電子伝導性を有することが好ましい。このような上記導電助剤を電極体に用いる二次電池の性能を低下させることなく、電極体の電子伝導性を向上させることができるからである。また、上記導電助剤はリチウムイオン伝導性を有し充放電容量を有する。このため、上記導電助剤を電極体に用いた場合には、一般的な炭素系材料からなる導電助剤を電極体に用いた場合と比較して、リチウムイオン伝導パスが切断されることを防止することができ、電極体の充放電容量を向上することができる。
上記導電助剤の製造方法としては、上記金属酸化物における酸素原子の一部を欠損させ、かつ上記金属酸化物に窒素原子を導入させることにより、電子伝導性を有するとともにリチウムイオン伝導性も有し、容量を有する上記導電助剤を製造できる方法であれば、特に限定されるものではない。具体的に、上記導電助剤を製造する方法としては、アンモニアおよび窒素の混合ガスの雰囲気において、上記金属酸化物を加熱する方法が挙げられる。また、アンモニア単独の雰囲気において上記金属酸化物を加熱する方法でも、上記導電助剤を製造できる。また、上記金属酸化物に窒素原子を導入する方法としては、上記金属酸化物および尿素を混合して加熱する方法を取ってもよい。
次に、本態様の電極体について説明する。本態様の電極体は、上記活物質および上記導電助剤を含有するものである。本態様の電極体が、上記活物質および上記導電助剤を含有する態様としては、上記活物質の粒子および上記導電助剤の粒子を混合する態様(A態様)、上記活物質の粒子の表面に上記導電助剤を被覆する態様(B態様)、および上記活物質の粒子の表面を変質させて、上記導電助剤を形成する態様(C態様)の三つが考えられる。以下、A態様、B態様およびC態様のそれぞれについて説明する、
図1は、上記活物質の粒子1および上記導電助剤の粒子2を混合する態様(A態様)を有する電極体10を示すものである。本態様の電極体において、上記活物質の粒子の粒径は、特に限定されるものではない。本態様の電極体において、上記導電助剤の粒子の粒径は、特に限定されるものではないが、0.1μm~5μmの範囲内あることが好ましく、中でも0.1μm~3μmの範囲内であることが好ましい。
図2は、上記活物質の粒子1の表面に上記導電助剤の皮膜3を形成する態様(B態様)を有する電極体10を示した概略断面図である。本態様の電極体においては、図3に示すように上記活物質の粒子1の表面の一部に上記導電助剤の皮膜3を形成してもよく、図4に示すように上記活物質の粒子1の表面の全体に上記導電助剤の皮膜3を形成してもよい。上記導電助剤はリチウムイオン伝導性を有しているため、上記活物質の粒子の表面の全体に上記導電助剤の皮膜を形成しても、リチウムイオン伝導のパス切れが発生することはなく、電池性能の低下を招くことはないからである。
図5および図6は、上記活物質の粒子1の表面を上記導電助剤に変質させて、上記導電助剤の変質層4を形成する態様(C態様)を有する電極体を示した概略断面図である。上記導電助剤はリチウムイオン伝導性を有しているため、上記活物質の粒子1の表面の全体に上記導電助剤の変質層4を形成したとしても、リチウムイオン伝導パスが切断されることはなく、電池性能の低下を招くことはない。
本態様の電極体は、活物質と、電子伝導性が10-4S/cm以上の導電性金属酸化物からなる導電助剤と、を有することを特徴とするものである。
本態様における活物質は、正極活物質および負極活物質であるかどうかを問わず、特に限定されるものではない。上記活物質としては、上記活物質が正極活物質である場合、「A.電極体 1.第1態様 1-1.活物質」の項目で説明した金属酸化物と同一のものを用いることができる。さらに、上記金属酸化物以外にも、LiFePO4、LiMnPO4等のオリビン型正極活物質を用いることができる。また、上記活物質が負極活物質である場合には、上記活物質としては、例えば金属活物質およびカーボン活物質を挙げることができる。上記金属活物質としては、例えばIn、Al、SiおよびSn等を挙げることができる。一方、上記カーボン活物質としては、例えばメソカーボンマイクロビーズ(MCMB)、高配向性グラファイト(HOPG)、ハードカーボン、ソフトカーボン等を挙げることができる。
本態様における導電助剤は、電子伝導性が室温(25℃)において10-4S/cm以上の導電性金属酸化物からなることを特徴とするものである。以下、上記導電助剤を構成する上記導電性金属酸化物について説明する。
本態様における電極体は、上記活物質と、上記導電助剤とを有することを特徴とするものである。本態様においては、上記活物質が金属酸化物からなり、上記導電助剤が上記金属酸化物における酸素原子の一部が欠損され、かつ上記金属酸化物に窒素原子が導入された上記導電性金属酸化物からなることが好ましい。上記導電助剤および上記活物質の充放電電位が同一となり、上記電極体の充放電容量が大きくなるからである。さらに、本態様においては、上記活物質がLi4Ti5O12からなり、上記導電助剤がLi4Ti5O12における酸素原子の一部が欠損され、かつ上記金属酸化物に窒素原子が導入された上記導電性金属酸化物からなることが好ましい。上記導電助剤および上記活物質の充放電電位がより高くなるからである。
本発明の電極体は、リチウム二次電池において用いられるものであることが好ましい。そして、本発明の電極体は、リチウム二次電池において、正極および負極のどちらにも用いることができるものである。
次に、本発明の二次電池用導電助剤について説明する。本発明の二次電池用導電助剤は、Li4Ti5O12の酸素原子の一部が欠損され、かつLi4Ti5O12に窒素原子が導入されてなり、電子伝導性が10-4S/cm以上であることを特徴とするものである。以下、本発明の二次電池用導電助剤およびその製造方法について説明する。
次に、本発明の二次電池について説明する。本発明における二次電池は、正極層および負極層の少なくとも一方が、「A.電極体」の項目で説明した電極体からなることを特徴とするものである。
まず、本発明における負極層および正極層について説明する。本発明においては、上記負極層および上記正極層の少なくとも一方が、「A.電極体」の項目で説明した電極体からなるものである。そして、上記負極層および上記正極層の両方が、「A.電極体」の項目で説明した電極体からなるものであってもよい。なお、負極層および正極層の一方のみが上記「A.電極体」の項目で説明した電極体からなる場合、他方の電極体は一般に用いられている負極層もしくは正極層を用いることができる。
次に、上記電解質層について説明する。本発明に用いられる電解質層は上記正極層および上記負極層の間に形成される。上記電解質層は、リチウムイオン伝導を行うことができる層であれば特に限定されるものではないが、固体電解質層であることが好ましい。安全性の高い全固体二次電池を得ることができるからである。固体電解質層の厚さは、例えば0.1μm~1000μmの範囲内、中でも0.1μm~300μmの範囲内であることが好ましい。また、固体電解質層の形成方法としては、例えば、固体電解質材料を圧縮成形する方法等を挙げることができる。このような、固体電解質層に用いられる固体電解質としては、「C.二次電池 1.負極層および正極層」で説明したものと同じものを用いることができる。
上記二次電池は、上記正極層、上記電解質層および上記負極層を少なくとも有するものである。通常、上記二次電池は、上記正極層の集電を行う正極層集電体、および上記負極層の集電を行う負極層集電体をさらに有する。正極層集電体の材料としては、例えばSUS、アルミニウム、ニッケル、鉄、チタンおよびカーボン等を挙げることができ、中でもSUSが好ましい。一方、負極層集電体の材料としては、例えばSUS、銅、ニッケルおよびカーボン等を挙げることができ、中でもSUSが好ましい。また、正極層集電体および負極層集電体の厚さや形状等については、二次電池の用途等に応じて適宜選択することが好ましい。また、本発明に用いられる電池ケースには、一般的な二次電池の電池ケースを用いることができる。電池ケースとしては、例えばSUS製電池ケース等を挙げることができる。また、本発明の二次電池が全固体電池である場合、二次電池を絶縁リングの内部に形成しても良い。
本発明の二次電池は、例えば車載用電池として有用である。本発明の二次電池の形状としては、例えば、コイン型、ラミネート型、円筒型および角型等を挙げることができる。
活物質であるLi4Ti5O12(8.2mg)、導電助剤であるLi4Ti5O12-xNy(3.28mg)、および電解質である75Li2S-25P2S5(4.92mg)を混合することにより製造した正極層と、75Li2S-25P2S5から製造した電解質層と、In-Liから製造した負極層と、からなる全固体二次電池を製造する。ここで、正極層の原材料であるLi4Ti5O12-xNyは、Li4Ti5O12をN2ガス中において加熱した後に、N2ガスおよびNH3ガスの混合ガス中において加熱することにより得られたものであり、Li4Ti5O12-xNyにおけるxおよびyは酸素原子の欠損量および窒素原子の導入量をそれぞれ示したものである。
正極層を、Li4Ti5O12(6.56mg)、導電助剤であるLi4Ti5O12-xNy(4.92mg)、および75Li2S-25P2S5(4.92mg)を混合することにより製造すること以外は実施例1と全て同様にして、全固体二次電池を製造した。なお、Li4Ti5O12、Li4Ti5O12-xNy、および75Li2S-25P2S5の粒径は、実施例1に用いたものの粒径とそれぞれ同じである。
正極層を、Li4Ti5O12(11.48mg)および75Li2S-25P2S5(4.92mg)を混合することにより製造すること以外は実施例1と全て同様にして、全固体二次電池を製造した。なお、Li4Ti5O12および75Li2S-25P2S5の粒径は、実施例1に用いたものの粒径とそれぞれ同じである。
(充放電特性評価)
電流密度0.1Cにおいて充放電(電位領域0.5V~2.5V)を実施して充放電特性を評価した。実施例1、実施例2、および比較例1において製造した全固体二次電池についての充放電特性評価の結果を図8にそれぞれに示す。
(原料前処理)
Li4Ti5O12(30g)を、N2ガス(1L/min)中において800℃で10時間保持した。その後、加熱を終了して自然冷却した。なお、Li4Ti5O12の粒径は、実施例1に用いたものの粒径と同じである。
前処理を実施したLi4Ti5O12(30g)を、N2ガス(1L/min)およびNH3ガス(1L/min)をフローしながら、再び800℃で10時間保持した。その後、加熱を終了して自然冷却した。これにより、目的の試料を得た。
原料前処理を行わなかったこと以外は実施例3と同様にして試料を得た。
Li4Ti5O12(30g)をそのまま試料とした。なお、Li4Ti5O12の粒径は、実施例1に用いたものの粒径と同じである。
(X線回折測定)
実施例3で得た試料についてX線回折測定を行った。実施例3で得た試料についてX線回折測定をおこなった結果を図9に示す。実施例3で得た試料のX線回折スペクトルは、比較例2で得たLi4Ti5O12のX線回折スペクトルと同一であった。
実施例3で得た試料について、X線光電子分光測定を行った。実施例3で得た試料についてのX線光電子分光測定結果を図10に示す。図10に示すように、Ti2pスペクトル測定において、Li4Ti5O12由来のTi4+および酸素原子欠損由来のTi3+が検出された。また、図10に示すように、N1sスペクトル測定において、ピークが400eV以下に表れていることから、窒素が表面吸着しているのではなく構造中に含有されていることが分かった。
底面に4探針が設置された筒体に、実施例3および実施例4で得た試料を1g程度入れ、20kNの圧力をかけて、室温(25℃)において抵抗測定を行った。得られた抵抗値から室温(25℃)における導電率の算出を行った。実施例3および実施例4で得た試料についての電子伝導性評価の結果を表1に示す。
活物質であるLi4Ti5O12、実施例3で得た試料、導電助剤であるカーボン(HS100)、およびバインダ(PTFE)を混合することにより作成した正極層、電解質層(PST3)、および負極層(Pt箔)から全固体二次電池を作成した。同様に、活物質であるLi4Ti5O12、実施例4で得た試料、導電助剤であるカーボン(HS100)、およびバインダ(PTFE)を混合することにより作成した正極層、電解質層(DST3)および負極層(Pt箔)から全固体二次電池を作成した。そして、これらの全固体二次電地について、電流密度0.2mA/cm2において充放電(電位領域0.5V~2.5V)を実施して、充放電特性を評価した。実施例3の試料から作成した全固体二次電池および実施例4の試料から作成した全固体二次電池についての充放電特性評価の結果を、図11および図12にそれぞれに示す。
1a … 正極活物質の粒子
1b … 負極活物質の粒子
2 … 導電助剤の粒子
3 … 導電助剤の皮膜
4 … 導電助剤の変質層
5 … 電解質の粒子
10 …電極体
40 …二次電池
41 …正極層
42 …負極層
43 …電解質層
44 …正極層集電体
45 …負極層集電体
Claims (6)
- 金属酸化物からなる活物質と、前記金属酸化物における酸素原子の一部が欠損され、かつ前記金属酸化物に窒素原子が導入されてなる導電助剤と、を有することを特徴とする電極体。
- 活物質と、電子伝導性が10-4S/cm以上の導電性金属酸化物からなる導電助剤と、を有することを特徴とする電極体。
- 前記活物質が金属酸化物からなり、前記導電性金属酸化物が、前記金属酸化物における酸素原子の一部が欠損され、かつ前記金属酸化物に窒素原子が導入されてなるものであることを特徴とする請求の範囲第2項に記載の電極体。
- 前記金属酸化物が、Li4Ti5O12であることを特徴とする請求の範囲第1項または第3項に記載の電極体。
- Li4Ti5O12の酸素原子の一部が欠損され、かつ窒素原子が導入されてなり、電子伝導性が10-4S/cm以上であることを特徴とする二次電池用導電助剤。
- 請求の範囲第1項から第4項までのいずれかに記載の電極体を、正極層および負極層の少なくとも一方に用いたことを特徴とする二次電池。
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PCT/JP2010/057677 WO2011135713A1 (ja) | 2010-04-30 | 2010-04-30 | 電極体およびそれを用いた二次電池 |
US13/520,447 US20130071754A1 (en) | 2010-04-30 | 2010-04-30 | Electrode body and secondary battery using same |
CN2010800656222A CN102870255A (zh) | 2010-04-30 | 2010-04-30 | 电极体以及使用电极体的二次电池 |
JP2012512601A JP5440695B2 (ja) | 2010-04-30 | 2010-04-30 | 電極体およびそれを用いた二次電池 |
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Cited By (2)
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JP2021057317A (ja) * | 2019-10-02 | 2021-04-08 | 三菱マテリアル株式会社 | 薄膜リチウム二次電池、およびその製造方法 |
JP2023528708A (ja) * | 2021-05-13 | 2023-07-06 | 蜂巣能源科技股▲ふん▼有限公司 | 複合負極材料およびその製造方法、負極材料およびリチウムイオン電池 |
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JPH06223831A (ja) * | 1993-01-22 | 1994-08-12 | Fuji Photo Film Co Ltd | リチウム二次電池 |
JPH11283626A (ja) * | 1998-03-31 | 1999-10-15 | Sanyo Electric Co Ltd | リチウム二次電池用負極材料及びそれを用いたリチウム二次電池 |
JP2005078985A (ja) * | 2003-09-02 | 2005-03-24 | Toshiba Battery Co Ltd | 非水系二次電池用電極及びこれを用いたリチウム二次電池。 |
WO2006043470A1 (ja) * | 2004-10-21 | 2006-04-27 | Matsushita Electric Industrial Co., Ltd. | 電池用負極とこれを用いた電池 |
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CN100344019C (zh) * | 2004-06-16 | 2007-10-17 | 松下电器产业株式会社 | 活性物质材料、其制造方法及含该材料的非水电解质二次电池 |
JP5116303B2 (ja) * | 2006-01-24 | 2013-01-09 | 三洋電機株式会社 | 非水電解質二次電池 |
JP5438299B2 (ja) * | 2008-10-14 | 2014-03-12 | 株式会社東芝 | 非水電解質電池および電池パック |
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2010
- 2010-04-30 US US13/520,447 patent/US20130071754A1/en not_active Abandoned
- 2010-04-30 WO PCT/JP2010/057677 patent/WO2011135713A1/ja active Application Filing
- 2010-04-30 JP JP2012512601A patent/JP5440695B2/ja not_active Expired - Fee Related
- 2010-04-30 CN CN2010800656222A patent/CN102870255A/zh active Pending
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JPH06223831A (ja) * | 1993-01-22 | 1994-08-12 | Fuji Photo Film Co Ltd | リチウム二次電池 |
JPH11283626A (ja) * | 1998-03-31 | 1999-10-15 | Sanyo Electric Co Ltd | リチウム二次電池用負極材料及びそれを用いたリチウム二次電池 |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2021057317A (ja) * | 2019-10-02 | 2021-04-08 | 三菱マテリアル株式会社 | 薄膜リチウム二次電池、およびその製造方法 |
JP2023528708A (ja) * | 2021-05-13 | 2023-07-06 | 蜂巣能源科技股▲ふん▼有限公司 | 複合負極材料およびその製造方法、負極材料およびリチウムイオン電池 |
JP7416965B2 (ja) | 2021-05-13 | 2024-01-17 | 蜂巣能源科技股▲ふん▼有限公司 | 複合負極材料およびその製造方法、負極材料およびリチウムイオン電池 |
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US20130071754A1 (en) | 2013-03-21 |
JP5440695B2 (ja) | 2014-03-12 |
CN102870255A (zh) | 2013-01-09 |
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