WO2004042852A1 - 非水電解質電池 - Google Patents
非水電解質電池 Download PDFInfo
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- WO2004042852A1 WO2004042852A1 PCT/JP2003/014093 JP0314093W WO2004042852A1 WO 2004042852 A1 WO2004042852 A1 WO 2004042852A1 JP 0314093 W JP0314093 W JP 0314093W WO 2004042852 A1 WO2004042852 A1 WO 2004042852A1
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- current collector
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- electrolyte battery
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- aqueous electrolyte
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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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
-
- 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
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
-
- 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
-
- 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 non-aqueous electrolyte battery, and more particularly to a non-aqueous electrolyte battery having a current collector.
- A1 is known as a metal material that satisfies the basic properties required for this current collector.
- a non-aqueous electrolyte battery in which an A1 foil is used as a current collector and an electrode active material layer is formed on the A1 foil is known.
- Such a non-aqueous electrolyte battery is disclosed, for example, in Japanese Patent Publication No. 7-73027.
- the current collector made of the conventional A1 foil described above has good current collection performance, but has the disadvantage that its characteristics change depending on the type of electrolyte used. For example, in the case of using an organic electrolytic solution L i PF 6 is dissolved, it is possible to use a high potential of 6 V. However, when an organic electrolyte solute other than L i PF 6 was dissolved, 3. To at 5 V before and after the elution of the current collector occurs, in the high-potential was difficult to use. In particular, in the organic electrolyte in which L i N (CF 3 SO 2 ) 2 and L i N (C 2 F 5 S 0 2 ) 2 are dissolved, the elution of A 1, a constituent element of the current collector, increases. However, power collection itself was difficult. As a result, when A1 foil is used as the current collector, There was a problem in that it was difficult to expand the range of electrolyte selection because of the large number of degradations. Disclosure of the invention
- One object of the present invention is to provide a non-aqueous electrolyte battery capable of expanding the range of electrolyte selection.
- Another object of the present invention is to easily obtain a chemically stable current collector in the above nonaqueous electrolyte battery.
- the inventors of the present invention have conducted intensive studies and have found that as a current collector of a non-aqueous electrolyte battery, a transition metal element and at least one of Group 3, Group 4, and Group 5 elements are used. It has been found that by using the compound contained, excellent current collecting performance can be obtained in a plurality of types of electrolytes.
- a non-aqueous electrolyte battery includes a positive electrode, a negative electrode, and a non-aqueous electrolyte, and at least one of the positive electrode and the negative electrode has a transition metal element; Includes compounds containing at least one element from Group 4, 4 and 5 elements.
- the current collector of at least one of the positive electrode and the negative electrode is formed of a transition metal element and at least one element of Group 3, Group 4, and Group 5 And a compound containing a transition metal element and at least one of Group 3, Group 4, and Group 5 elements. Since it is inert, it is possible to obtain a current collector having excellent current collecting performance that is stable over a wide potential range in a plurality of types of electrolytes.
- the transition metal element contained in the compound is preferably titanium (T i).
- TiN is a material used as a barrier metal, it is a very preferable material for obtaining a chemically stable current collector.
- the non-aqueous electrolyte solution it is favorable preferable that L i N (CF 3 SO 2 ) 2 and L i N least one solute of (C 2 F 5 SO 2) 2 is dissolved .
- a current collector made of TiN can provide particularly chemically stable performance, and can be used as a more chemically stable current collector.
- the transition metal element contained in the compound is preferably zirconium (Zr).
- Zr zirconium
- the non-aqueous electrolyte solution L i N (C 2 F 5 SO 2) 2, L i PF 6 and then it is better good that at least one of i BF 4 one solute is dissolved No.
- the current collector made of ZrN can be used as a more chemically stable current collector because particularly stable performance is obtained. .
- the transition metal element contained in the compound is preferably tantalum (Ta).
- Ta tantalum
- T a N is the material used as the noble metal Therefore, it is a very preferable material for obtaining a chemically stable current collector.
- the non-aqueous electrolyte includes a non-aqueous electrolyte solution L i PF 6 as a solute was dissolve.
- a current collector made of TaN can provide particularly chemically stable performance, and thus can be used as a more chemically stable current collector.
- the non-aqueous electrolytic solution may contain a mixed solvent of ethylene carbonate and diethyl carbonate as a solvent.
- the compound containing the transition metal element and at least one of Group 3, Group 4, and Group 5 elements is formed in a film shape.
- a conventionally used collection metal can be obtained. Since it can be formed to the same thickness as the metal foil as an electrical conductor, it is easy to collect a compound containing a transition metal element and at least one of the elements from Group 3, 4 and 5 Can be used as a body.
- the compound containing the transition metal element and at least one of the group 3, 4 and 5 elements is formed into a film by the sputtering method. According to this structure, the compound containing the transition metal element and at least one of Group 3, 4 and 5 elements can be easily formed into a film.
- the compound containing a transition metal element and at least one element of Groups 3, 4, and 5 is formed on a film-shaped substrate.
- the film-shaped substrate is rich in flexibility, so that the current collector formed on the film-shaped substrate is also flexible.
- a battery electrode that can be easily deformed can be formed.
- the film-like substrate is preferably made of polyimide.
- the film is excellent not only in flexibility but also in heat resistance. Substrate can be obtained.
- the current collector may be a positive electrode current collector.
- the compound containing a transition metal element and at least one element of Group 3, Group 4, and Group 5 is T i N, Z r N and Any one selected from the group consisting of T a N.
- a chemically stable current collector made of TIN, ZrN, or TAN, which is an interstitial nitride.
- TiN, ZrN, or TaN is a material used as a noble metal, and is therefore a very preferable material for obtaining a chemically stable current collector.
- FIG. 1 is a schematic diagram showing a sputtering device used for producing a positive electrode current collector commonly used in nonaqueous electrolyte batteries according to Examples 11 to 15 of the present invention.
- FIG. 2 is a cyclic voltammogram showing the relationship between the scanning potential and the oxidation current according to Example 11 of the present invention.
- FIG. 3 is a cyclic voltammogram showing the relationship between the scanning potential and the oxidation current according to Embodiments 1-2 of the present invention.
- FIG. 4 is a cyclic voltammogram showing the relationship between the scanning potential and the oxidation current according to Examples 13 to 13 of the present invention.
- FIG. 5 is a cyclic portogram showing the relationship between the scanning potential and the oxidation current according to Examples 14 to 14 of the present invention.
- FIG. 6 is a cyclic voltammogram showing the relationship between the scanning potential and the oxidation current according to Embodiments 15 of the present invention.
- FIG. 7 is a cyclic voltammogram showing the relationship between the scanning potential and the oxidation current according to Comparative Example 1-1.
- FIG. 8 is a graph showing the relationship between the scanning potential and the oxidation current according to Comparative Examples 1-2. This is an Ikpol Pol evening gram.
- FIG. 9 is a cyclic voltammogram showing the relationship between the scanning potential and the oxidation current in Comparative Examples 13 to 13.
- FIG. 10 is a cyclic voltammogram showing the relationship between the scanning potential and the oxidation current according to Example 2-1 of the present invention.
- FIG. 11 is a cyclic pollogram showing the relationship between the scanning potential and the oxidation current according to Example 2-2 of the present invention.
- FIG. 12 is a cyclic pollogram showing the relationship between the scanning potential and the oxidation current according to Example 2-3 of the present invention.
- FIG. 13 is a cyclic pollogram showing the relationship between the scanning potential and the oxidation current according to Example 2-4 of the present invention.
- FIG. 14 is a cyclic pollogram showing the relationship between the scanning potential and the oxidation current according to Example 2-5 of the present invention.
- FIG. 15 is a cyclic pollogram showing the relationship between the scanning potential and the oxidation current according to the third embodiment of the present invention.
- This sputtering apparatus includes a vacuum vessel 1, a water-cooled rotary drum 2 rotatably supported in the vacuum vessel 1, a target 3 installed opposite the water-cooled rotary drum 2, and a high-frequency power supply to the target 3.
- High-frequency power supply 4 for supplying air, Ar gas introduction valve 5a for introducing Ar gas into vacuum vessel 1, and N 2 gas introduction valve for introducing N 2 gas into vacuum vessel 1. 5 b, and a vacuum exhaust valve 6 for controlling the degree of vacuum of the vacuum vessel 1.
- the current collector commonly used for the non-aqueous electrolyte batteries of Examples 1-1 to 115 When manufacturing the body, as shown in Fig. 1, a substrate 7 made of polyimide film (Kapton 70 V, manufactured by Toray DuPont) was placed on the water-cooled rotating drum 2, and Under the conditions shown, a TiN film was formed on the substrate 7. table 1
- the conditions for forming the TiN film commonly used in Examples 1—1 to 1—5 are as follows: operating gas (atmosphere gas) flow rate: Ar gas (50 sccm) and group 5 element N 2 gas (5 sccm) consisting of N (nitrogen), operating gas pressure: 0.18 Pa, high frequency power input to the evening gate: 200 W, formation time: 180 min.
- N (nitrogen) is an example of “at least one element of Group 3, Group 4, and Group 5” of the present invention.
- T i titanium
- the thickness of the substrate 7 made of a polyimide film was set to 17.5 / zm, and the thickness of the TiN film formed on the substrate 7 was set to 0.3 m.
- the inside of the vacuum vessel 1 shown in FIG. 1 is evacuated by opening the evacuating valve 6.
- Ar gas (50 sccm) and N 2 gas (5 sccm) are introduced from the Ar gas introduction valve 5 a and the N 2 gas introduction valve 5 b, and further vacuum is applied.
- the opening of the exhaust valve 6 was adjusted to obtain a pressure of 0.18 Pa. Soshi
- high-frequency power (200 W) from the high-frequency power supply 4 to the target 3 (Ti metal) plasma 8 was generated.
- ions in the plasma 8 collide with the surface of the target 3, and the atoms (T i) constituting the target 3 are repelled.
- Example 1 A positive electrode current collector commonly used for nonaqueous electrolyte batteries according to 1 to 1-5 was prepared.
- Example 11-1 to Example 1-5 Comparative Example 11-1 to Comparative Example 1-3
- Examples 1-1 to 1-5 and Comparative Example 11 produced as described above: !
- the following cyclic polling measurement was performed.
- Example 11 and Comparative Example 11 as an electrolyte an equal volume mixed solvent of ethylene carbonate (EC) and getyl carbonate (DEC) (E CZD EC (1/1)) was used. Dissolves Li N (CF 3 S ⁇ 2 ) 2 A solution prepared so as to have a concentration of 1 molar Z liter was used. In Examples 1-2 and Comparative Examples 1-2, LiN (C 2 F 5 S 0 2 ) 2 was dissolved in E CZD EC (11) as an electrolytic solution to reduce the concentration of 1 mol Those prepared to have were used.
- E CZD EC (11) LiN (C 2 F 5 S 0 2 ) 2 was dissolved in E CZD EC (11) as an electrolytic solution to reduce the concentration of 1 mol Those prepared to have were used.
- Example 1 - In 5 as the electrolytic solution, the EC / DEC (1 Z 1), by dissolving L i BF 4, use was prepared to have a concentration of 1 mole / liter.
- the potential scanning range was set to a natural potential of ⁇ 6 V vs. L i ZL i + in Examples 1-1, 1-2, 114, 1-5 and Comparative Example 1-2.
- the natural potential was set to V5 V vs. L i ZL i +.
- the natural potential was set to 4.4.7 V vs. Li ZLi +.
- FIGS. 2 to 6 show cyclic voltammograms showing the relationship between the scanning potential and the oxidation current according to Examples 11 to 1-5 of the present invention, respectively.
- 9 show cyclic voltammograms showing the relationship between the scanning potential and the oxidation current in Comparative Examples 1_1 to 1_3, respectively. Lamb is shown.
- L i N (CF a SO 2) 2 is made from lysed EC ZD EC electrolyte and T i N combinations in an exemplary of a current collector made of a film 1 one In Example 1 and Example 1, which are a combination of an electrolytic solution composed of EC ZD EC in which L i N (C 2 F 5 SO 2 ) 2 is dissolved and a current collector composed of a T i N film, It was found that the oxidation current value decreased with each cycle. This is considered to be because the surface of the current collector was covered with an inactive substance in the first cycle, and it became difficult for the oxidation current to flow in the measurements after the second cycle.
- the T i N film constituting the current collector was composed of EC / DEC in which L i N (CF a S 0 2 ) 2 or L i N (C 2 F 5 S ⁇ 2 ) 2 was dissolved It can be said that it hardly elutes in the electrolytic solution.
- a T iN film as a current collector and E CZD EC in which L i N (CF 3 S 0 2 ) 2 or L i N (C 2 F 5 S ⁇ 2 ) 2 are dissolved It has been found that a combination with an electrolyte can be used at a high potential of 6 V.
- Examples 11 to 13 which are a combination of an electrolytic solution composed of E CZD EC in which LiPF 6 is dissolved and a current collector composed of a TiN film, the cycle is repeated. It was found that the value of the oxidation current increased each time. This is thought to be because the elution of the current collector into the electrolytic solution increases the surface area of the current collector that is oxidized with each cycle, so that the oxidizing current that flows increases accordingly. .
- T i N film to configure the current collector can be said to be L i PF 6 is eluted into the electrolytic solution comprising a dissolved EC / ⁇ ⁇ C.
- the scanning potential is 4 VV s.
- the T i N film as a current collector in combination with the electrolytic solution L i PF 6 consists dissolved EC / DEC, when it can be used in 4 V or less considered Erareru. '
- the oxidation current value decreases with each cycle, It was found that the value of the oxidation current in the direction (direction of decreasing the potential) exceeded the value of the oxidation current in the direction of oxidation (the direction of increasing the potential). This is because the current collector is eluted into the electrolytic solution, so that the surface area where the current collector is oxidized is larger when scanning the potential in the reduction direction than when scanning the potential in the oxidation direction. Therefore, it is considered that the oxidation current became easier to flow.
- T i N film constituting the collector can be said to be eluted in the electrolyte solution consisting of L i CF 3 S_ ⁇ 3 is dissolved E CZD EC.
- the scanning potential is 4 V vs. L i ZL i + or less, almost no oxidation current flows.
- the combination of the T i N film as a current collector, and L i CF 3 S_ ⁇ 3 is from lysed E CZ DEC electrolyte is believed that can be used in the 4 V or less.
- Example 1-15 in which the electrolytic solution composed of E CZD EC in which L i BF 4 was dissolved and the current collector composed of the T i N film, the cycle was repeated.
- the oxidation current value decreases every time, but when the scanning potential exceeds 4.5 VV s .L i ZL i +, the oxidation current value will be on the order of mA and will be as large as 3.4 mA at maximum. There was found. From this result, when the potential exceeds 4.5 V V s. Li / L i + , the T i N film constituting the current collector has an electrolyte of EC / DEC in which Li BF 4 is dissolved.
- FIG. 7 a comparative example in which a combination of an electrolytic solution composed of EQ, / DEC in which LiN (CF 3 S 0 2 ) 2 is dissolved and a current collector composed of A1 foil is shown.
- the oxidation current value increases with each cycle, the oxidation current value in the reduction direction exceeds the oxidation current value in the oxidation direction, and
- a comparative example is a combination of an electrolyte solution composed of EC / DEC in which LiN (C 2 F 5 S ⁇ 2 ) 2 is dissolved and a current collector composed of A1 foil.
- a 1 foil constituting the collector is said to L i N (C 2 F 5 SO 2) very easily eluted in 2 consists dissolved EC / ⁇ ⁇ C electrolyte.
- the elution of the current collector increases the surface area on which the current collector is oxidized, and it is considered that the elution of the current collector further increases with each cycle. Therefore, A as a current collector
- TiN containing Group 5 element N nitrogen
- the L i N (CF 3 S 0 2) 2 and L i N (C 2 F 5 S_ ⁇ 2) 2 hard electrolyte used in the conventional current collector made A 1 foil such as a high potential Therefore, the selection range of the electrolyte can be expanded. Since TiN is a chemically stable interstitial nitride, a chemically stable current collector can be easily obtained.
- a powdery transition metal element is usually formed using a sputtering device.
- a compound containing Ti (titanium) and N (nitrogen), which is a Group 5 element in the form of a film, the same thickness as the metal foil as a current collector conventionally used can be obtained. Since it can be formed, a compound containing Ti as a transition metal element and N as a Group 5 element can be easily used as a current collector.
- the amount of impurities contained in the current collector can be reduced as compared with the case where the current collector is formed on the substrate by the coating method, and the substrate 7 and the Adhesion with the current collector can be improved.
- the polyimide film is rich in flexibility, so that the current collector formed on the substrate 7 made of the polyimide film is also very flexible. I get stuck. This makes it possible to form a positive electrode for a non-aqueous electrolyte battery that is easily deformed.
- the polyimide film has excellent heat resistance, even if the substrate temperature increases during the formation of the TiN film, it is possible to suppress the deterioration of the substrate 7 made of the polyimide film.
- Example 2— In 2-5, the current collection of the positive electrode commonly used in the non-aqueous electrolyte batteries according to Examples 2_1 to 2_5 was performed using the same spattering method as in Examples 1-1_1 to 15-5. The body was made. However, in Examples 2-1 to 215, the substrate 7 made of polyimide film (see FIG. 1) Under the conditions shown in Table 2, a ZrN film having a thickness of 0.3 m was formed. ZrN is an example of the “compound” and the “interstitial nitride” of the present invention. Table 2
- the conditions for forming the ZrN film commonly used in Examples 2_1 to 2_5 are as follows: operating gas (atmosphere gas) flow rate: Ar gas (50 sccm) and group 5 element N 2 gas (3 sccm) composed of N (nitrogen), operating gas pressure: 0.18 Pa, high frequency power input to the evening gate: 200 W, formation time: 120 min.
- operating gas (atmosphere gas) flow rate Ar gas (50 sccm) and group 5 element N 2 gas (3 sccm) composed of N (nitrogen)
- operating gas pressure 0.18 Pa
- high frequency power input to the evening gate 200 W
- formation time 120 min.
- Example 2 produced as described above; In order to examine the difference in performance due to the combination of the current collector according to ⁇ 2-5 and the electrolyte, the following cyclic polling measurement was performed.
- Example 2— In Examples 2 to 5, the same cyclic voltammetric measurement as in Example 11-1 to 1-5 was performed. That is, the current collector (positive electrode) produced in Example 2-1 to 2-5 above was used as a working electrode, and a molded Li metal was used as a counter electrode (negative electrode) and a reference electrode.
- Example 2-1 As an electrolyte, ethylene carbonate (EC) and getyl carbonate (DEC) were used in the same manner as in Example 1-1.
- E CZD EC (1/1 ) was dissolved L i N (CF 3 S 0 2) 2, use was prepared to have a concentration of 1 mole Z liter.
- the potential scanning range was set to the natural potential to 6 Vvs.LiZLi +, and the oxidation current flowing between the working electrode composed of ZrN and the counter electrode composed of Li was measured.
- the results of this cyclic voltammetry measurement are shown in FIGS. 10 to 14.
- FIGS. 10 to 14 show Example 2 of the present invention, respectively. 2 to 5 show cyclic polarograms showing the relationship between the scanning potential and the oxidation current.
- Example 2—1 in which a combination of an electrolytic solution composed of EC / DEC in which LiN (CF 3 SO 2 ) 2 was dissolved and a current collector composed of a ZrN film was used.
- Example 1-1 in which a current collector made of a TiN film was used, it was found that it could be used only at a low potential. That is, in Example 2-1, while the value of the oxidation current decreases each time the cycle is repeated, the value of the oxidation current in the reduction direction decreases when the scan potential is 4.8 VVs.Lii + or more. It can exceed the value of the oxidation current in the oxidation direction found.
- Z r N film constituting the collector may have a L i N (CF 3 S 0 2) 2 is eluted into the electrolytic solution comprising a dissolved E CZD EC.
- L i N (CF 3 S_ ⁇ 2) 2 consists of dissolved EC / DEC electrolyte as a collector, it is used in 3. 4 V or less It is thought that it is possible.
- Example 2 in which Li N (C 2 F 5 S ⁇ 2 ) 2 is a combination of an electrolytic solution composed of EC / DEC and a current collector composed of a ZrN film is dissolved.
- Li N (C 2 F 5 S ⁇ 2 ) 2 is a combination of an electrolytic solution composed of EC / DEC and a current collector composed of a ZrN film is dissolved.
- _2 it was found that it can be used at a high potential of 6 V, as in the case of Example 1-2 (see FIG. 3) using the current collector made of a TiN film. That is, in Example 2-2, it was found that the value of the oxidation current decreased every time the cycle was repeated.
- Z r N film constituting the collector can be said to be L i N (C 2 F 5 S 0 2) 2 is hardly eluted in an electrolyte solution consisting of dissolved EC / ⁇ ⁇ C.
- Example 2-3 which is a combination of an electrolytic solution composed of E CZD EC in which L i PF 6 was dissolved and a current collector composed of a ZrN film, a TiN film was used.
- a current collector made of
- Z r N film constituting the collector may have a hardly eluted into an electrolytic solution L i PF 6 consists lysed E CZD EC.
- Example 2 _ 4 which is a combination of an electrolyte composed of ECNO DEC in which L i CF 3 SO 3 is dissolved and a current collector composed of a ZrN film, T i
- Example 2-4 the value of the oxidation current decreases with each cycle, but when the scanning potential exceeds 4.2 VVs.LiZLi +, the value of the oxidation current decreases by m. It became clear that the current became A order and the maximum became 1.2 mA. The results, Z r N film constituting the current collector, the scanning potential 4.
- Example 2-5 which is a combination of an electrolyte composed of E CZD EC in which L i BF 4 was dissolved and a current collector composed of a ZrN film
- the T i N film was used.
- a current collector consisting of That is, in Examples 2-5, it was found that the value of the oxidation current decreased with each cycle. From these results, it can be said that the ZrN film constituting the current collector hardly elutes in the electrolytic solution composed of E CZD EC in which Li BF 4 is dissolved, Example 2— :!
- Example 1 Same as 1-1 to 5. That is, by forming the ZrN film by the sputtering method, it is possible to form the ZrN film with the same thickness as that of a metal foil as a current collector conventionally used. Can be used as a current collector. Further, the amount of impurities contained in the current collector can be reduced, and the adhesion between the substrate 7 and the current collector can be improved. In addition, by forming the current collector on the substrate 7 made of a polyimide film, the polyimide film is rich in flexibility and excellent in heat resistance, so that the positive electrode for a nonaqueous electrolyte battery which is easily deformed is formed. Can be formed, and deterioration of the substrate 7 due to an increase in the substrate temperature during the formation of the ZrN film can be suppressed.
- Example 3 a current collector of a positive electrode used in the nonaqueous electrolyte battery according to Example 3 was produced by using the same sputtering method as in Examples 11 to 1-5. However, in Example 3, the substrate 7 made of polyimide film was used.
- T aN represents the “compound” of the present invention
- the conditions for forming the TaN film used in Example 3 were as follows: operating gas (atmospheric gas) flow rate: Ar gas (50 sccm) and N (nitrogen) which is a Group 5 element N 2 gas (5 0 sccm), working gas pressure: 2. 6 X 1 0 _ 1 P a, the target turned frequency power: 2 0 0 W, formation time: a 1 2 0 m in.
- As target 3 see Fig. 1), a molded Ta metal containing 99.9% of Ta (tantalum), a transition metal element, was used. Note that Ta (internal) is an example of the “transition metal element” of the present invention.
- Example 3 the same cyclic porometry measurement was performed as in Examples 11 to 11 described above. That is, the current collector (positive electrode) manufactured in Example 3 was used as a working electrode, and a molded Li metal was used as a counter electrode (negative electrode) and a reference electrode.
- Example 3 ethylene carbonate (EC) and getyl carbonate were used as the electrolyte in the same manner as in Examples 13 to 13 and Examples 2 to 3 described above.
- the potential scanning range was set to a natural potential of 6 V vs. Li / Li +, and the oxidation current flowing between the working electrode composed of TaN and the counter electrode composed of Li was measured.
- the results of this cyclic voltammetry measurement are shown in Figure 15.
- Example 3 which is a combination of an electrolytic solution composed of E CZD EC in which L i PF 6 is dissolved and a current collector composed of a T a N film
- the electrode is composed of a T i N film. It was found that, unlike the above-mentioned Examples 13 to 13 using a current collector (see FIG. 4), it could be used at a high potential of 6 V. That is, in Example 3, as in Example 2-3 (see FIG. 12) using a current collector made of a ZrN film, it was found that the value of the oxidation current decreased with each cycle. did.
- the T aN film constituting the current collector hardly elutes in the electrolyte composed of EC ZD EC in which Li PF 6 is dissolved.
- the current collector of the positive electrode is configured by a TaN film.
- T a N containing the transition metal element T a (tantalum) and the group V element N (nitrogen) has conductivity and is chemically inert. in no event of using the electrolyte PF 6 is dissolved, it is possible to obtain a current collector having a stable high current collecting performance over a wide potential range.
- the effects of the fabrication process of the third embodiment are the same as those of the above-described embodiments 11 to 11 and 2-1 to 2-5.
- the TaN film by sputtering, it is possible to form the same thickness as the metal foil as a current collector that has been conventionally used. Can be used as a body. Further, the amount of impurities contained in the current collector can be reduced, and the adhesion between the substrate 7 and the current collector can be improved.
- the current collector on the substrate 7 made of a polyimide film the polyimide film is rich in flexibility and excellent in heat resistance, so that it can be easily deformed for non-aqueous electrolyte batteries. A positive electrode can be formed, and deterioration of the substrate 7 due to an increase in substrate temperature during the formation of the TaN film can be suppressed.
- Examples 11-1 to 1-5, Examples 2_1 to 2-5, and Example 3 the transition metal elements Ti (titanium), Zr (zirconium), or Ta (tantalum) And a TiN film, a ZrN film, or a TaN film containing Group 5 element N (nitrogen) are used as the current collector, but the present invention is not limited to this.
- Elements and of group 3, 4 and 5 Any compound containing at least one element of Further, in Examples 11 to 1-5, Examples 2-1 to 2-5, and Example 3, a TiN film, a ZrN film, or a TaN film, which is an interstitial nitride, is collected.
- the present invention is used as a current collector, the present invention is not limited to this, and a current collector made of another interstitial nitride other than TiN, ZrN, and Ta a may be used.
- T i N, Z r The interstitial nitrides other than N and T a N, or a nitride containing a rare earth element, H f N, VN, N b N, C r N, UN, T h N 2 , WN 2 , Mo 2 N, W 2 N, Fe 2 N, Mn 3 N 2 , Co 3 1 ⁇ 2 and i 3 N 2 .
- Examples 1-1 to 1-5, Examples 2-1 to 2-5, and Example 3 current was collected on a film-like substrate made of polyimide as an example of a film-like substrate.
- the present invention is not limited to this, and the current collector may be formed on a film-shaped substrate other than polyimide.
- a film-like substrate made of polyethylene, polypropylene, polyethylene terephthalate, polyvinylidene chloride, polyvinyl chloride, polycarbonate and the like can be mentioned.
- a film-like substrate made of polyimide is particularly preferable because it is a substrate having excellent flexibility and heat resistance.
- the current collector of the present invention is used as a current collector of a positive electrode.
- the present invention is not limited to this, and may be used as a current collector of a negative electrode. . Further, the current collector of the present invention may be used for both the positive electrode and the negative electrode.
- the current collector was formed on the substrate by using the sputtering method.
- the method is not limited to this, and other methods may be used as long as the method supplies the raw material from the gas phase.
- the current collector may be formed on the substrate by using a PVD method such as an evaporation method or a CVD method such as a plasma CVD method.
- the present invention is not limited to this. It is preferable to form a positive electrode active material layer thereon.
- a material capable of inserting and extracting lithium can be used as the positive electrode active material.
- Materials that can be used as the positive electrode active material include, for example, oxides having tunnel-like vacancies such as inorganic compounds Li 2 Fe 3 , Ti 2 and V 2 5 , metal chalcogen compound having a layered structure, such as T i S 2 and M o S 2, and the like.
- As the positive electrode active material and more to use L i x M0 2 (0 ⁇ x ⁇ 1) or L i y M 2 ⁇ 4 (0 ⁇ y ⁇ 2) composite oxide having a composition formula represented by preferable. Note that M in the composition formula is a transition element.
- L i C O_ ⁇ 2 L i M n O 2 , L i N i ⁇ 2, L i C R_ ⁇ 2 and L i Mn 2 0 4 is No.
- a partially substituted Li site and a partially substituted transition metal may be used.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Primary Cells (AREA)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2003277547A AU2003277547A1 (en) | 2002-11-08 | 2003-11-05 | Nonaqueous electrolyte battery |
US10/962,401 US7381499B2 (en) | 2002-11-08 | 2004-10-13 | Nonaqueous electrolyte battery |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
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JP2002325507 | 2002-11-08 | ||
JP2002-325507 | 2002-11-08 | ||
JP2003-131138 | 2003-05-09 | ||
JP2003131138 | 2003-05-09 | ||
JP2003365386A JP4508601B2 (ja) | 2002-11-08 | 2003-10-27 | 非水電解質電池 |
JP2003-365386 | 2003-10-27 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US10/962,401 Continuation US7381499B2 (en) | 2002-11-08 | 2004-10-13 | Nonaqueous electrolyte battery |
Publications (1)
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WO2004042852A1 true WO2004042852A1 (ja) | 2004-05-21 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/JP2003/014093 WO2004042852A1 (ja) | 2002-11-08 | 2003-11-05 | 非水電解質電池 |
Country Status (5)
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US (1) | US7381499B2 (ja) |
JP (1) | JP4508601B2 (ja) |
KR (1) | KR100588027B1 (ja) |
AU (1) | AU2003277547A1 (ja) |
WO (1) | WO2004042852A1 (ja) |
Families Citing this family (1)
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JP2011049125A (ja) * | 2009-08-28 | 2011-03-10 | Equos Research Co Ltd | リチウムイオン電池用正極及びLi2NiPO4F系正極活物質の電気化学特性の測定方法 |
Citations (4)
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JPH0680588B2 (ja) * | 1986-02-10 | 1994-10-12 | 松下電器産業株式会社 | 円筒形リチウム電池 |
JPH06333569A (ja) * | 1993-05-20 | 1994-12-02 | Fuji Photo Film Co Ltd | 非水二次電池 |
JP2000357517A (ja) * | 1999-06-14 | 2000-12-26 | Matsushita Electric Ind Co Ltd | 電極とこれを用いた電池及び非水電解質二次電池 |
JP2002231224A (ja) * | 2001-01-30 | 2002-08-16 | Sanyo Electric Co Ltd | リチウム二次電池用電極及びその製造方法並びにリチウム二次電池 |
Family Cites Families (11)
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---|---|---|---|---|
JPS59175555A (ja) * | 1983-03-24 | 1984-10-04 | Toshiba Battery Co Ltd | 有機溶媒電池 |
JPS62295350A (ja) * | 1986-06-13 | 1987-12-22 | Matsushita Electric Ind Co Ltd | 円筒形リチウム電池 |
JPH0770327B2 (ja) | 1986-11-08 | 1995-07-31 | 旭化成工業株式会社 | 二次電池 |
JPS63266774A (ja) * | 1987-04-24 | 1988-11-02 | Mitsubishi Petrochem Co Ltd | 扁平型有機電解質電池 |
JP3019326B2 (ja) * | 1989-06-30 | 2000-03-13 | 松下電器産業株式会社 | リチウム二次電池 |
JP3441141B2 (ja) * | 1993-12-29 | 2003-08-25 | Tdk株式会社 | リチウム二次電池 |
US5464706A (en) * | 1994-03-02 | 1995-11-07 | Dasgupta; Sankar | Current collector for lithium ion battery |
JP3111945B2 (ja) * | 1997-10-23 | 2000-11-27 | 日本電気株式会社 | ポリマー二次電池 |
JP3615415B2 (ja) * | 1999-03-24 | 2005-02-02 | 三洋電機株式会社 | 非水系二次電池 |
AU4885601A (en) * | 2000-04-26 | 2001-11-12 | Sanyo Electric Co., Ltd. | Lithium secondary battery-use electrode and lithium secondary battery |
US20040048157A1 (en) * | 2002-09-11 | 2004-03-11 | Neudecker Bernd J. | Lithium vanadium oxide thin-film battery |
-
2003
- 2003-10-27 JP JP2003365386A patent/JP4508601B2/ja not_active Expired - Lifetime
- 2003-11-05 WO PCT/JP2003/014093 patent/WO2004042852A1/ja active IP Right Grant
- 2003-11-05 AU AU2003277547A patent/AU2003277547A1/en not_active Abandoned
- 2003-11-05 KR KR1020047014448A patent/KR100588027B1/ko not_active IP Right Cessation
-
2004
- 2004-10-13 US US10/962,401 patent/US7381499B2/en not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0680588B2 (ja) * | 1986-02-10 | 1994-10-12 | 松下電器産業株式会社 | 円筒形リチウム電池 |
JPH06333569A (ja) * | 1993-05-20 | 1994-12-02 | Fuji Photo Film Co Ltd | 非水二次電池 |
JP2000357517A (ja) * | 1999-06-14 | 2000-12-26 | Matsushita Electric Ind Co Ltd | 電極とこれを用いた電池及び非水電解質二次電池 |
JP2002231224A (ja) * | 2001-01-30 | 2002-08-16 | Sanyo Electric Co Ltd | リチウム二次電池用電極及びその製造方法並びにリチウム二次電池 |
Also Published As
Publication number | Publication date |
---|---|
JP4508601B2 (ja) | 2010-07-21 |
US20050048373A1 (en) | 2005-03-03 |
US7381499B2 (en) | 2008-06-03 |
KR100588027B1 (ko) | 2006-06-12 |
KR20050044755A (ko) | 2005-05-12 |
AU2003277547A1 (en) | 2004-06-07 |
JP2004363078A (ja) | 2004-12-24 |
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