WO2014157024A1 - 酸化チタン化合物並びにこれを用いた電極及びリチウムイオン二次電池 - Google Patents
酸化チタン化合物並びにこれを用いた電極及びリチウムイオン二次電池 Download PDFInfo
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Definitions
- the present invention relates to a titanium oxide compound, and further relates to an electrode using the titanium oxide compound as an electrode active material, and a lithium ion secondary battery using the electrode as a positive electrode or a negative electrode.
- thermal runaway abnormal heat generation and ignition (so-called thermal runaway) of such lithium ion secondary batteries have been frequently reported.
- the thermal runaway described above is considered as one of the causes due to an internal short circuit of the battery. This is because when an internal short circuit of the battery occurs, an excessive inrush current flows toward the negative electrode, which causes heat generation of the negative electrode and other members.
- the negative electrode of the lithium ion secondary battery it is also known to use spinel type lithium titanate (S-LTO) in addition to the carbon-based material.
- S-LTO spinel type lithium titanate
- the negative electrode potential is as high as 1.55 V (vs. Li)
- the theoretical capacity of the negative electrode was only about 175 mAh / g (the carbon-based material was 372 mAh / g).
- Patent Document 1 the initial charge / discharge efficiency is improved by producing an isotropic bronze-type titanium oxide compound using a mixture of a sodium compound and titanium oxide as a raw material.
- the electrode active material of Patent Document 1 has a capacity of about 170 mAh / g, and the initial charge capacity is reduced to the same level as S-LTO, resulting in a new problem that the advantage of using a bronze-type titanium oxide compound is impaired.
- the present invention has a high capacity and a titanium oxide that can be used as an electrode active material having a high initial charge and discharge efficiency with a specific surface area reduced by controlling the particle shape into a plate shape. It aims at providing a compound, an electrode using the same, and a lithium ion secondary battery.
- the titanium oxide compound according to one aspect of the present invention is bronze-type titanium oxide or titanium oxide mainly composed of bronze-type titanium oxide, and contains 0.005 mass% or more and 2.5 mass% of calcium. % Or less (first configuration).
- a titanium oxide compound according to another aspect of the present invention is bronze-type titanium oxide or titanium oxide mainly composed of bronze-type titanium oxide, and contains 0.15% by mass or more and 0.55% of silicon. It is set as the structure (2nd structure) containing below mass%.
- a titanium oxide compound according to still another aspect of the present invention is bronze-type titanium oxide or titanium oxide mainly composed of bronze-type titanium oxide, and contains calcium in an amount of 0.005% by mass or more. 2 mass% or less and silicon is contained in an amount of 0.15 mass% or more and 0.2 mass% or less, or calcium is contained in an amount of 0.005 mass% or more and 0.1 mass% or less, and silicon is 0 It is set as the structure (3rd structure) containing 15 mass% or more and 0.5 mass% or less.
- the titanium oxide compound according to the present invention in any one of the first to third configurations, at least a part of the calcium and / or at least a part of the silicon is dissolved in the titanium oxide crystal. It is preferable that the pore volume is 0.01 to 0.5 mL / g and the specific surface area is 1.0 to 20 m 2 / g. It is preferable to have a certain configuration (fifth configuration).
- the electrode according to the present invention has a configuration (sixth configuration) using the titanium oxide compound having any one of the first to fifth configurations as an electrode active material.
- the lithium ion secondary battery according to the present invention has a configuration (seventh configuration) in which the electrode having the sixth configuration is used as a positive electrode or a negative electrode.
- the present invention it is possible to reduce the specific surface area and to improve the initial charge / discharge efficiency without changing the conditions such as the firing conditions in which the raw materials used are produced in a specific chemical composition or the firing temperature is changed during the production process.
- a titanium oxide compound that can be used as a high electrode active material, an electrode using the same, and a lithium ion secondary battery can be provided.
- the specific surface area is small, the viscosity is hardly increased when the electrode slurry is produced, and an effect of improving the coating property can be expected.
- the flowchart which shows an example of the process of manufacturing the titanium oxide compound based on this invention.
- Schematic diagram showing the schematic configuration of a lithium ion secondary battery Schematic diagram of coin cell used for battery performance evaluation Table showing evaluation results of Examples 1-1 to 1-4 and Comparative Examples 1-1 to 1-2 Scanning electron micrograph of the titanium oxide compound of Example 1-3 Scanning electron micrograph of the titanium oxide compound of Comparative Example 1-1 Table showing evaluation results of Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-2 Scanning electron micrograph of the titanium oxide compound of Example 2-2 Table showing evaluation results of Examples 3-1 to 3-2 and Comparative Examples 3-1 to 3-3 Table showing X-ray diffraction measurement results of potassium tetratitanate
- the titanium oxide compound according to the first embodiment of the present invention is bronze-type titanium oxide or titanium oxide mainly composed of bronze-type titanium oxide, and contains 0.005% by mass to 2.5% by mass of calcium.
- the titanium oxide mainly composed of bronze type titanium oxide include titanium oxide mainly composed of bronze type titanium oxide and containing a trace amount of anatase type, rutile type or hydrated titanium oxide. If the bronze-type titanium oxide is 60% by mass or more, a titanium oxide compound having the same effect can be obtained. More preferably, the bronze-type titanium oxide is 80% by mass or more, and more preferably 90% by mass or more. .
- FIG. 1 is a flowchart showing an example of a schematic process for producing a titanium oxide compound according to the present invention.
- a mixed solution of titanium dioxide (TiO 2 ) and potassium carbonate (K 2 CO 3 ) mixed at a predetermined composition ratio is spray-dried (step S1) and baked (step S2).
- step S1 a mixed solution of titanium dioxide (TiO 2 ) and potassium carbonate (K 2 CO 3 ) mixed at a predetermined composition ratio
- step S2 a mixed solution of titanium dioxide (TiO 2 ) and potassium carbonate (K 2 CO 3 ) mixed at a predetermined composition ratio
- step S1 a mixed solution of titanium dioxide (TiO 2 ) and potassium carbonate (K 2 CO 3 ) mixed at a predetermined composition ratio
- the above-described potassium dititanate is subjected to a depotassification treatment (step S3) and a firing treatment (step S4) to convert the structure from a TiO 5 triangular pyramidal body to a TiO 6 octahedron, whereby four Potassium titanate (K 2 Ti 4 O 9 ) is synthesized. That is, this potassium tetratitanate was obtained by elution of a part of the potassium ion of potassium dititanate represented by the general formula K 2 Ti 2 O 5 to convert the composition, followed by firing treatment. is there.
- the above-mentioned potassium tetratitanate is subjected to a pulverization process (the pulverization process may be omitted) (step S5) and a proton exchange process (step S6) to obtain a hydrated tetratitanate compound (H 2 Ti 4 O 9 ⁇ nH 2 O). Then, the hydrated tetratitanate compound is subjected to a heat treatment (step S7) in the range of 200 ° C. to 550 ° C. to synthesize a titanium oxide compound.
- the manufacturing method shown in FIG. 1 is only an example of the manufacturing method of the titanium oxide compound according to the present invention, and the titanium oxide compound according to the present invention may be manufactured by a method other than the manufacturing method shown in FIG.
- a synthesis method of potassium dititanate (K 2 Ti 2 O 5 ) is performed using titanium dioxide (TiO 2 ) and potassium carbonate (K 2 CO 3 ) mixed at a predetermined composition ratio.
- the mixture may be subjected to a melting treatment and a solidification treatment to synthesize potassium dititanate (K 2 Ti 2 O 5 ).
- FIG. 2 is a schematic diagram showing a schematic configuration of the lithium ion secondary battery.
- the lithium ion secondary battery 10 of this configuration example includes a positive electrode 11, a negative electrode 12, a nonaqueous electrolyte 13, and a separator 14.
- the positive electrode 11 has, for example, a structure in which a positive electrode mixture layer is provided on one side or both sides of a positive electrode current collector.
- the positive electrode mixture layer includes, for example, a positive electrode material capable of inserting and extracting lithium as a positive electrode active material, and a conductive agent such as carbon black or graphite and a binder such as polyvinylidene fluoride as necessary. It is composed with an agent.
- the negative electrode 12 has, for example, a structure in which a negative electrode mixture layer is provided on one side or both sides of a negative electrode current collector.
- the negative electrode mixture layer may contain another negative electrode active material or a conductive agent in addition to the negative electrode material according to the present embodiment (that is, the titanium oxide compound according to the present embodiment described above).
- non-aqueous electrolyte 13 in addition to a liquid non-aqueous electrolyte prepared by dissolving an electrolyte (lithium salt) in an organic solvent, a gel-like non-aqueous electrolyte in which a liquid electrolyte and a polymer material are combined can be used.
- the electrolyte include LiClO 4 , LiPF 6 , and LiBF 4, and any one or two or more of these can be used in combination.
- organic solvent include propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, 1,2-dimethoxyethane, and any one or a mixture of two or more of these can be used. .
- the separator 14 separates the positive electrode 11 and the negative electrode 12 and allows lithium ions to pass through while preventing a short circuit of current due to contact between both electrodes.
- the separator 14 is made of, for example, a porous film made of a synthetic resin made of polytetrafluoroethane, polypropylene, or polyethylene, or a porous film made of an inorganic material such as a ceramic nonwoven fabric. It is good also as a structure which laminated
- the negative electrode 12 of the lithium ion secondary battery 10 is configured using the negative electrode material according to this embodiment (the titanium oxide compound according to this embodiment described above) instead of the carbon-based material, It becomes possible to improve the safety of the lithium ion secondary battery 10 by the triple mechanism shown in FIG.
- the titanium oxide compound changes to insulating properties when lithium ions are completely released. Therefore, the surface of the titanium oxide compound at the short-circuited portion is insulated to suppress the progress of the discharge reaction. That is, in a general lithium ion secondary battery using a carbon negative electrode, a rapid discharge (heat generation) occurs at the time of an internal short circuit, whereas in a lithium ion secondary battery using a titanium oxide compound negative electrode, a slow discharge occurs. Proceeds and does not heat up.
- Titanium oxide compounds are extremely unlikely to cause thermal runaway when triggered by an electrolyte solution.
- titanium oxide compounds do not burn unlike carbon, the risk of thermal runaway to ignition is very low.
- the lithium ion secondary The initial charge / discharge efficiency can be increased while maintaining the high capacity of the battery 10.
- Example 1-1 26.2 parts by weight of titanium oxide (TiO 2 ) containing 0.01% by mass of calcium (Ca) was mixed with 100 parts by weight of water and stirred for 30 minutes. Thereafter, 23.8 parts by weight of potassium carbonate (K 2 CO 3 ) was added and further stirred for 1 hour. The mixed solution was spray dried at 200 ° C. and heat treated at 800 ° C. for 3 hours to synthesize potassium dititanate (K 2 Ti 2 O 5 ).
- TiO 2 titanium oxide
- Ca calcium
- potassium dititanate obtained by the above synthesis was immersed in water, the mixture was stirred for 2 hours with a stirrer to perform potassium removal. After removing this supernatant, it was dehydrated with a suction filter, dried at 120 ° C. overnight, and then heat treated at 850 ° C. for 2 hours to synthesize potassium tetratitanate (K 2 Ti 4 O 9 ).
- the potassium tetratitanate obtained by the above synthesis was put into a 0.5 M sulfuric acid solution and stirred for 2 hours to perform potassium removal. After removing this supernatant, it was dehydrated with a suction filter and heat treated at 450 ° C. for 1 hour to synthesize a titanium oxide compound.
- the calcium content of the obtained titanium oxide compound was 0.006% by mass as a result of inductively coupled plasma optical emission spectrometry.
- the average aspect ratio of primary particles of the obtained titanium oxide compound (the average value of the aspect ratios of 100 arbitrary primary particles observed with a scanning electron microscope) is 5.74, and the average pore diameter is 54 ⁇ m.
- the BET specific surface area was 12.10 m 2 / g, and the pore volume was 0.163 cm 3 / g.
- the X-ray diffraction spectrum (X-ray source: Cu-K ⁇ ) of the obtained titanium oxide compound showed bronze type titanium oxide having a tunnel structure.
- Example 1-2 A titanium oxide compound was synthesized by the same process as Example 1-1 except that titanium oxide containing 0.15% by mass of calcium was used.
- the calcium content of the obtained titanium oxide compound was 0.11% by mass as a result of inductively coupled plasma emission spectrometry.
- the average aspect ratio of the primary particles of the obtained titanium oxide compound is 4.58, the average pore diameter is 43 ⁇ m, the BET specific surface area is 9.38 m 2 / g, and the pore volume is 0.100 cm. 3 / g. Further, the X-ray diffraction spectrum (X-ray source: Cu-K ⁇ ) of the obtained titanium oxide compound showed bronze type titanium oxide having a tunnel structure.
- Example 1-3 A titanium oxide compound was synthesized in the same process as Example 1-1, except that 26.2 parts by weight of titanium oxide and 3.94 parts by weight of calcium carbonate were mixed with 100 parts by weight of water and stirred for 30 minutes. .
- the calcium content of the obtained titanium oxide compound was 1.15% by mass as a result of inductively coupled plasma emission spectroscopy.
- the average aspect ratio of the primary particles of the obtained titanium oxide compound is 3.52, the average pore diameter is 34 ⁇ m, the BET specific surface area is 7.03 m 2 / g, and the pore volume is 0.059 cm. 3 / g. Further, the X-ray diffraction spectrum (X-ray source: Cu-K ⁇ ) of the obtained titanium oxide compound showed bronze type titanium oxide having a tunnel structure.
- Example 1-4 A titanium oxide compound was synthesized by the same process as Example 1-3, except that the amount of calcium carbonate mixed was 6.57 parts by weight.
- the calcium content of the obtained titanium oxide compound was 2.37% by mass as a result of inductively coupled plasma optical emission spectrometry.
- the average aspect ratio of the primary particles of the obtained titanium oxide compound is 3.28, the average pore diameter is 30 ⁇ m, the BET specific surface area is 4.52 m 2 / g, and the pore volume is 0.034 cm. 3 / g. Further, the X-ray diffraction spectrum (X-ray source: Cu—K ⁇ ) of the obtained titanium oxide compound showed bronze type titanium oxide having a tunnel structure.
- Example 1-1 A titanium oxide compound was synthesized in the same process as in Example 1-1 except that titanium oxide containing 0.003% by mass of calcium was used.
- the calcium content of the obtained titanium oxide compound was 0.003% by mass as a result of inductively coupled plasma emission spectral analysis.
- the average aspect ratio of the primary particles of the obtained titanium oxide compound is 7.41, the average pore diameter is 60 ⁇ m, the BET specific surface area is 15.40 m 2 / g, and the pore volume is 0.231 cm. 3 / g. Further, the X-ray diffraction spectrum (X-ray source: Cu-K ⁇ ) of the obtained titanium oxide compound showed bronze type titanium oxide having a tunnel structure.
- Example 1-2 A titanium oxide compound was synthesized in the same process as in Example 1-3, except that the amount of calcium carbonate mixed was 9.04 parts by weight.
- the calcium content of the obtained titanium oxide compound was 2.64% by mass as a result of inductively coupled plasma emission spectroscopy.
- the average aspect ratio of the primary particles of the obtained titanium oxide compound is 3.01, the average pore diameter is 25 ⁇ m, the BET specific surface area is 4.05 m 2 / g, and the pore volume is 0.025 cm. 3 / g. Further, the X-ray diffraction spectrum (X-ray source: Cu-K ⁇ ) of the obtained titanium oxide compound showed bronze type titanium oxide having a tunnel structure.
- each electrode was produced using the titanium oxide compounds synthesized in Examples 1-1 to 1-4 and Comparative Examples 1-1 to 1-2 as the active material. Specifically, first, 10 parts by weight of polyvinylidene fluoride is dissolved in N-methyl-2-pyrrolidone, and then 20 parts by weight of conductive carbon as a conductive auxiliary, Examples 1-1 to 1-4 and comparison A coating material was prepared by adding 70 parts by weight of the titanium oxide compound obtained in Examples 1-1 to 1-2 and kneading with a planetary stirrer. This paint was applied on an aluminum foil so as to have a density of about 40 g / m 2 , then vacuum-dried at 120 ° C. and pressed, and then punched into a circular shape having a diameter of 13 mm.
- a coin-type cell 20 shown in FIG. 3 was assembled using each of the electrodes prepared above.
- the coin cell 20 has an electrode 21, a counter electrode 22, a nonaqueous electrolyte 23, and a separator 24 sandwiched between an upper case 25a and a lower case 25b, and the periphery of the upper case 25a and the lower case 25b is sealed with a gasket 26. It was made.
- a metal lithium foil was used for the counter electrode 22.
- the non-aqueous electrolyte 23 a solution obtained by dissolving 1 mol / L of LiPF 6 in ethylene carbonate: dimethyl carbonate 1: 1 v / v% was used.
- a polypropylene porous membrane was used for the separator 24.
- FIG. 4A is a table showing a list of evaluation results of Examples 1-1 to 1-4 and Comparative Examples 1-1 to 1-2 of the present embodiment.
- the initial discharge capacity is set to about 185 mAh / g or more.
- the initial charge capacity can be about 203 mAh / g or more, and the initial discharge capacity and the initial charge capacity can be prevented from decreasing. The reason for this is that if the calcium content is more than 2.5% by mass, precipitation of by-products such as calcium titanate and adverse effects on the crystal phase increase, resulting in a decrease in initial discharge capacity and initial charge capacity. I think that.
- the calcium content is preferably 0.1% by mass or more and 1.2% by mass or less.
- the initial charge / discharge efficiency can be substantially 90%, and the decrease in the initial discharge capacity can be substantially suppressed.
- the titanium oxide compound according to the second embodiment of the present invention is bronze-type titanium oxide or titanium oxide mainly composed of bronze-type titanium oxide, and contains 0.15% by mass or more and 0.55% by mass or less of silicon.
- the titanium oxide mainly composed of bronze type titanium oxide include titanium oxide mainly composed of bronze type titanium oxide and containing a trace amount of anatase type, rutile type or hydrated titanium oxide. If the bronze-type titanium oxide is 60% by mass or more, a titanium oxide compound having the same effect can be obtained. More preferably, the bronze-type titanium oxide is 80% by mass or more, and more preferably 90% by mass or more. .
- Example 2-1 Except for mixing 26.2 parts by weight of titanium oxide with respect to 100 parts by weight of water and 1.58 parts by weight of silicon dioxide instead of calcium carbonate and stirring for 30 minutes, titanium oxide was subjected to the same process as in Example 1-3. The compound was synthesized.
- the silicon content of the obtained titanium oxide compound was 0.16% by mass as a result of inductively coupled plasma emission spectroscopy.
- the average aspect ratio of the primary particles of the obtained titanium oxide compound is 3.12, the average pore diameter is 42 ⁇ m, the BET specific surface area is 3.15 m 2 / g, and the pore volume is 0.035 cm. 3 / g. Further, the X-ray diffraction spectrum (X-ray source: Cu-K ⁇ ) of the obtained titanium oxide compound showed bronze type titanium oxide having a tunnel structure.
- Example 2-2 A titanium oxide compound was synthesized in the same process as in Example 2-1, except that the amount of silicon dioxide mixed was 1.99 parts by weight.
- the silicon content of the obtained titanium oxide compound was 0.20% by mass as a result of inductively coupled plasma emission spectroscopy.
- the average aspect ratio of the primary particles of the obtained titanium oxide compound is 2.89, the average pore diameter is 44 ⁇ m, the BET specific surface area is 2.64 m 2 / g, and the pore volume is 0.029 cm. 3 / g. Further, the X-ray diffraction spectrum (X-ray source: Cu-K ⁇ ) of the obtained titanium oxide compound showed bronze type titanium oxide having a tunnel structure.
- Example 2-3 A titanium oxide compound was synthesized in the same process as in Example 2-1, except that the amount of silicon dioxide mixed was 4.93 parts by weight.
- the silicon content of the obtained titanium oxide compound was 0.46% by mass as a result of inductively coupled plasma emission spectrometry.
- the average aspect ratio of the primary particles of the obtained titanium oxide compound is 2.64, the average pore diameter is 39 ⁇ m, the BET specific surface area is 2.25 m 2 / g, and the pore volume is 0.022 cm. 3 / g. Further, the X-ray diffraction spectrum (X-ray source: Cu-K ⁇ ) of the obtained titanium oxide compound showed bronze type titanium oxide having a tunnel structure.
- Example 2-4 A titanium oxide compound was synthesized in the same process as in Example 2-1, except that the amount of silicon dioxide mixed was 5.91 parts by weight.
- the silicon content of the obtained titanium oxide compound was 0.54% by mass as a result of inductively coupled plasma emission spectrometry.
- the average aspect ratio of the primary particles of the obtained titanium oxide compound is 2.55, the average pore diameter is 38 ⁇ m, the BET specific surface area is 2.04 m 2 / g, and the pore volume is 0.019 cm. 3 / g. Further, the X-ray diffraction spectrum (X-ray source: Cu-K ⁇ ) of the obtained titanium oxide compound showed bronze type titanium oxide having a tunnel structure.
- Example 2-1 A titanium oxide compound was synthesized in the same process as in Example 2-1, except that titanium oxide containing 0.1% by mass of silicon was used and silicon dioxide was not mixed.
- the silicon content of the obtained titanium oxide compound was 0.02% by mass as a result of inductively coupled plasma emission spectrometry.
- the average aspect ratio of the primary particles of the obtained titanium oxide compound is 7.41, the average pore diameter is 60 ⁇ m, the BET specific surface area is 15.40 m 2 / g, and the pore volume is 0.231 cm. 3 / g. Further, the X-ray diffraction spectrum (X-ray source: Cu-K ⁇ ) of the obtained titanium oxide compound showed bronze type titanium oxide having a tunnel structure.
- Example 2-2 A titanium oxide compound was synthesized in the same process as in Example 2-1, except that the amount of silicon dioxide mixed was 6.77 parts by weight.
- the silicon content of the obtained titanium oxide compound was 0.68% by mass as a result of inductively coupled plasma optical emission spectrometry.
- the average aspect ratio of the primary particles of the obtained titanium oxide compound is 2.15, the average pore diameter is 29 ⁇ m, the BET specific surface area is 2.05 m 2 / g, and the pore volume is 0.015 cm. 3 / g. Further, the X-ray diffraction spectrum (X-ray source: Cu-K ⁇ ) of the obtained titanium oxide compound showed bronze type titanium oxide having a tunnel structure.
- FIG. 5A is a table showing a list of evaluation results of Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-2 of the present embodiment.
- the initial discharge capacity is set to about 186 mAh / g or more.
- the initial charge capacity can be about 204 mAh / g or more, and the initial discharge capacity and the initial charge capacity can be prevented from decreasing. The reason for this is considered that when the silicon content is more than 0.55% by mass, the adverse effect on the crystal phase is increased, and as a result, the initial discharge capacity and the initial charge capacity are lowered.
- the silicon content is preferably 0.2% by mass or more and 0.5% by mass or less. Thereby, the initial charge / discharge efficiency can be increased to 90% or more, and the decrease in the initial discharge capacity can be substantially suppressed.
- the titanium oxide compound according to the third embodiment of the present invention is a titanium oxide mainly composed of bronze-type titanium oxide or bronze-type titanium oxide, and contains 0.005 mass% or more and 1.2 mass% or less of calcium, And it contains 0.15 mass% or more and 0.2 mass% or less of silicon, or 0.005 mass% or more and 0.1 mass% or less of calcium, and 0.15 mass% or more of silicon It contains 0.5 mass% or less.
- the titanium oxide mainly composed of bronze type titanium oxide include titanium oxide mainly composed of bronze type titanium oxide and containing a trace amount of anatase type, rutile type or hydrated titanium oxide. If the bronze-type titanium oxide is 60% by mass or more, a titanium oxide compound having the same effect can be obtained. More preferably, the bronze-type titanium oxide is 80% by mass or more, and more preferably 90% by mass or more. .
- Example 3-1 Example 1-3 and Example 1-3 except that 26.2 parts by weight of titanium oxide containing 0.1% by mass of silicon and 3.94 parts by weight of calcium carbonate were mixed with 100 parts by weight of water and stirred for 30 minutes. A titanium oxide compound was synthesized in the same process.
- the calcium concentration of the obtained titanium oxide compound is 1.15% by mass as a result of inductively coupled plasma emission spectroscopy, and the silicon content of the obtained titanium oxide compound is 0 as a result of inductively coupled plasma emission spectroscopy. 0.02% by mass.
- the average aspect ratio of the primary particles of the obtained titanium oxide compound is 3.52, the average pore diameter is 34 ⁇ m, the BET specific surface area is 7.03 m 2 / g, and the pore volume is 0.059 cm. 3 / g. Further, the X-ray diffraction spectrum (X-ray source: Cu-K ⁇ ) of the obtained titanium oxide compound showed bronze type titanium oxide having a tunnel structure.
- Example 3-1 Comparative Example 3-1 except that 26.2 parts by weight of titanium oxide, 3.94 parts by weight of calcium carbonate, and 1.58 parts by weight of silicon dioxide were mixed with 100 parts by weight of water and stirred for 30 minutes. A titanium oxide compound was synthesized in the same process.
- the calcium concentration of the obtained titanium oxide compound is 1.050% by mass as a result of inductively coupled plasma emission spectrometry, and the silicon content of the obtained titanium oxide compound is 0 as a result of inductively coupled plasma emission spectroscopy. 19% by mass.
- the average aspect ratio of the primary particles of the obtained titanium oxide compound is 2.85, the average pore diameter is 39 ⁇ m, the BET specific surface area is 2.05 m 2 / g, and the pore volume is 0.020 cm. 3 / g. Further, the X-ray diffraction spectrum (X-ray source: Cu-K ⁇ ) of the obtained titanium oxide compound showed bronze type titanium oxide having a tunnel structure.
- Comparative Example 3-2 Comparative Example 3-1 except that 26.2 parts by weight of titanium oxide containing 0.003% by mass of calcium and 4.93 parts by weight of silicon dioxide were mixed with 100 parts by weight of water and stirred for 30 minutes. A titanium oxide compound was synthesized in the same process.
- the calcium concentration of the obtained titanium oxide compound is 0.003% by mass as a result of inductively coupled plasma emission spectroscopy, and the silicon content of the obtained titanium oxide compound is 0 as a result of inductively coupled plasma emission spectroscopy. It was .46% by mass.
- the average aspect ratio of the primary particles of the obtained titanium oxide compound is 2.64, the average pore diameter is 39 ⁇ m, the BET specific surface area is 2.25 m 2 / g, and the pore volume is 0.022 cm. 3 / g. Further, the X-ray diffraction spectrum (X-ray source: Cu-K ⁇ ) of the obtained titanium oxide compound showed bronze type titanium oxide having a tunnel structure.
- Example 3-2 Comparative Example 3-1, except that 26.2 parts by weight of titanium oxide, 1.58 parts by weight of calcium carbonate, and 4.93 parts by weight of silicon dioxide were mixed with 100 parts by weight of water and stirred for 30 minutes. A titanium oxide compound was synthesized in the same process.
- the calcium concentration of the obtained titanium oxide compound is 0.045% by mass as a result of inductively coupled plasma emission spectroscopy, and the silicon content of the obtained titanium oxide compound is 0 as a result of inductively coupled plasma emission spectroscopy. It was .46% by mass.
- the average aspect ratio of the primary particles of the obtained titanium oxide compound is 2.34, the average pore diameter is 32 ⁇ m, the BET specific surface area is 2.03 m 2 / g, and the pore volume is 0.016 cm. 3 / g. Further, the X-ray diffraction spectrum (X-ray source: Cu-K ⁇ ) of the obtained titanium oxide compound showed bronze type titanium oxide having a tunnel structure.
- Comparative Example 3-3 Comparative Example 3-1 except that 26.2 parts by weight of titanium oxide, 3.94 parts by weight of calcium carbonate and 4.93 parts by weight of silicon dioxide were mixed with 100 parts by weight of water and stirred for 30 minutes. A titanium oxide compound was synthesized in the same process.
- the calcium concentration of the obtained titanium oxide compound is 0.910% by mass as a result of inductively coupled plasma emission spectroscopy, and the silicon content of the obtained titanium oxide compound is 0 as a result of inductively coupled plasma emission spectroscopy. It was .42% by mass.
- the average aspect ratio of the primary particles of the obtained titanium oxide compound is 2.04, the average pore diameter is 28 ⁇ m, the BET specific surface area is 1.98 m 2 / g, and the pore volume is 0.014 cm. 3 / g. Further, the X-ray diffraction spectrum (X-ray source: Cu-K ⁇ ) of the obtained titanium oxide compound showed bronze type titanium oxide having a tunnel structure.
- FIG. 6 is a table showing a list of evaluation results of Examples 3-1 to 3-2 and Comparative Examples 3-1 to 3-3 of the present embodiment.
- the calcium content is 0.005 mass% or more and 1.2 mass% or less. If the silicon content is 0.15 mass% or more and 0.2 mass% or less, the initial charge capacity and the initial charge capacity are maintained while maintaining the initial charge / discharge efficiency at about 91% or more due to the synergistic effect of calcium and silicon.
- the discharge capacities can be improved to about 191 mAh / g or more and 210 mAh / g or more, respectively.
- the calcium content is 0.005 mass% or more and 0.1 mass% or less. If the silicon content is 0.15 mass% or more and 0.5 mass% or less, the initial charge capacity and the initial charge capacity are maintained while maintaining the initial charge and discharge efficiency at about 91% or more due to the synergistic effect of calcium and silicon.
- the discharge capacities can be improved to about 192 mAh / g or more and about 211 mAh / g or more, respectively.
- Calcium and silicon contained in the titanium oxide compound according to the first to third embodiments of the present invention are not all present on the crystal surface of the titanium oxide compound, but are contained in the crystal of the titanium oxide compound. It is considered that at least a part is present in solid solution. The reason is as follows. X-ray diffractometer: Rigaku Corporation, Ultimate 4 for potassium tetratitanate, which is an intermediate synthesized in each of Comparative Example 1-1, Example 1-3, Example 2-2, and Example 3-1. As shown in FIG. 7, when the content of calcium or silicon increases, the change in the interplanar spacing of potassium tetratitanate is confirmed.
- the titanium oxide compound according to the present invention can be used, for example, as an electrode active material used for an electrode of a lithium ion secondary battery.
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Abstract
Description
(概要)
本発明の第1実施形態に係る酸化チタン化合物は、ブロンズ型酸化チタン又はブロンズ型酸化チタンを主体とする酸化チタンであって、カルシウムを0.005質量%以上2.5質量%以下含有している。ブロンズ型酸化チタンを主体とする酸化チタンとしては、例えば、ブロンズ型酸化チタンを主体としアナターゼ型、ルチル型若しくは水和酸化チタンが微量に含まれている酸化チタンを挙げることができる。ブロンズ型酸化チタンが60質量%以上であれば同様の効果を奏する酸化チタン化合物を得ることができるが、より好ましくはブロンズ型酸化チタンが80質量%以上、さらに90質量%以上であることが好ましい。
図1は、本発明に係る酸化チタン化合物を製造する概略工程の一例を示したフローチャートである。図1に示す製造方法では、まず、所定の組成比で混合された二酸化チタン(TiO2)と炭酸カリウム(K2CO3)の混合溶液をスプレードライ処理(ステップS1)及び焼成処理(ステップS2)に付して、二チタン酸カリウム(K2Ti2O5)を合成する。
図2は、リチウムイオン二次電池の概略構成を示す模式図である。本構成例のリチウムイオン二次電池10は、正極11と、負極12と、非水電解質13と、セパレータ14と、を有する。
水100重量部に対して、カルシウム(Ca)を0.01質量%含有する酸化チタン(TiO2)を26.2重量部混合し30分攪拌した。その後、23.8重量部の炭酸カリウム(K2CO3)を加えてさらに1時間攪拌した。混合した溶液を200℃で噴霧乾燥(スプレードライ)し、800℃で3時間熱処理し、二チタン酸カリウム(K2Ti2O5)を合成した。
カルシウムを0.15質量%を含有する酸化チタン使用したこと以外は、実施例1-1と同じ工程で酸化チタン化合物を合成した。
水100重量部に対して、酸化チタンを26.2重量部、炭酸カルシウムを3.94重量部混合し30分攪拌したこと以外は、実施例1-1と同じ工程で酸化チタン化合物を合成した。
炭酸カルシウムの混合量を6.57重量部にしたこと以外は、実施例1-3と同じ工程で酸化チタン化合物を合成した。
カルシウムを0.003質量%含有する酸化チタンを使用したこと以外は、実施例1-1と同じ工程で酸化チタン化合物を合成した。
炭酸カルシウムの混合量を9.04重量部にしたこと以外は、実施例1-3と同じ工程で酸化チタン化合物を合成した。
上記の実施例1-1~1-4および比較例1-1~1-2で使用した分析装置は、下記の通りである。
誘導結合プラズマ発光分光分析装置:株式会社島津製作所、ICPS-8100
平均細孔径/BET比表面積/細孔容積測定装置:日本ベル株式会社、BELSORP-miniII
X線回折装置:株式会社リガク、Ultima4、Cu-Kα線による測定
活物質として実施例1-1~1-4および比較例1-1~1-2で合成された酸化チタン化合物を用いて各電極を作製した。具体的には、まず、ポリフッ化ビニリデン10重量部をN-メチル-2-ピロリドンに溶解させ、次に導電助剤として導電性カーボンを20重量部、実施例1-1~1-4および比較例1-1~1-2で得られた酸化チタン化合物70重量部を加え、遊星式攪拌機にて混錬することにより塗料を作成した。この塗料をアルミ箔上に40g/m2程度になるように塗布し、その後120℃で真空乾燥しプレスした後、Φ13mmの円形状に打ち抜いた。
上記で作製した各電極を用い、図3に示すコイン型セル20を組み立てた。コイン型セル20は、上ケース25aと下ケース25bとの間に、電極21、対極22、非水電解質23、及びセパレータ24を挟み込み、上ケース25aと下ケース25bの周囲をガスケット26で封止して作製された。
ここで、上記のようなコイン型セルでは、対極に金属リチウムを使用しているため、各電極の電位は対極に対して貴となる。よって充放電によるリチウムイオンの挿入・脱離の方向は各電極をリチウムイオン二次電池の負極として用いたときと反対になる。しかし、以下において、便宜的にリチウムイオンが対象電極から脱離する方向を放電、各電極に挿入される方向を充電と表現する。
図4Aは、本実施形態の実施例1-1~1-4および比較例1-1~1-2の評価結果の一覧を示すテーブルである。
(概要)
本発明の第2実施形態に係る酸化チタン化合物は、ブロンズ型酸化チタン又はブロンズ型酸化チタンを主体とする酸化チタンであって、ケイ素を0.15質量%以上0.55質量%以下含有している。ブロンズ型酸化チタンを主体とする酸化チタンとしては、例えば、ブロンズ型酸化チタンを主体としアナターゼ型、ルチル型若しくは水和酸化チタンが微量に含まれている酸化チタンを挙げることができる。ブロンズ型酸化チタンが60質量%以上であれば同様の効果を奏する酸化チタン化合物を得ることができるが、より好ましくはブロンズ型酸化チタンが80質量%以上、さらに90質量%以上であることが好ましい。
第1実施形態と同様であるため説明を省略する。
第1実施形態と同様であるため説明を省略する。なお、リチウムイオン二次電池10の負極12として、カーボン系素材ではなく、本実施形態に係る負極材料(先述の本実施形態に係る酸化チタン化合物)を用いた構成であれば、第1実施形態に係る負極材料を用いた構成と同様の効果を奏する。
水100重量部に対して、酸化チタンを26.2重量部、炭酸カルシウムに代わり二酸化ケイ素を1.58重量部混合し30分攪拌したこと以外は、実施例1-3と同じ工程で酸化チタン化合物を合成した。
二酸化ケイ素の混合量を1.99重量部にしたこと以外は、実施例2-1と同じ工程で酸化チタン化合物を合成した。
二酸化ケイ素の混合量を4.93重量部にしたこと以外は、実施例2-1と同じ工程で酸化チタン化合物を合成した。
二酸化ケイ素の混合量を5.91重量部にしたこと以外は、実施例2-1と同じ工程で酸化チタン化合物を合成した。
ケイ素を0.1質量%含有する酸化チタンを使用し二酸化ケイ素を混合しなかったこと以外は、実施例2-1と同じ工程で酸化チタン化合物を合成した。
二酸化ケイ素の混合量を6.77重量部にしたこと以外は、実施例2-1と同じ工程で酸化チタン化合物を合成した。
上記の実施例2-1~2-4および比較例2-1~2-2で使用した分析装置は、第1実施形態と同様であるため説明を省略する。
第1実施形態と同様であるため説明を省略する。
第1実施形態と同様であるため説明を省略する。
図5Aは、本実施形態の実施例2-1~2-4および比較例2-1~2-2の評価結果の一覧を示すテーブルである。
(概要)
本発明の第3実施形態に係る酸化チタン化合物は、ブロンズ型酸化チタン又はブロンズ型酸化チタンを主体とする酸化チタンであって、カルシウムを0.005質量%以上1.2質量%以下含有し、且つ、ケイ素を0.15質量%以上0.2質量%以下含有している、又は、カルシウムを0.005質量%以上0.1質量%以下含有し、且つ、ケイ素を0.15質量%以上0.5質量%以下含有している。ブロンズ型酸化チタンを主体とする酸化チタンとしては、例えば、ブロンズ型酸化チタンを主体としアナターゼ型、ルチル型若しくは水和酸化チタンが微量に含まれている酸化チタンを挙げることができる。ブロンズ型酸化チタンが60質量%以上であれば同様の効果を奏する酸化チタン化合物を得ることができるが、より好ましくはブロンズ型酸化チタンが80質量%以上、さらに90質量%以上であることが好ましい。
第1実施形態および第2実施形態と同様であるため説明を省略する。
第1実施形態および第2実施形態と同様であるため説明を省略する。なお、リチウムイオン二次電池10の負極12として、カーボン系素材ではなく、本実施形態に係る負極材料(先述の本実施形態に係る酸化チタン化合物)を用いた構成であれば、第1実施形態および第2実施形態に係る負極材料を用いた構成と同様の効果を奏する。
水100重量部に対して、ケイ素を0.1質量%含有する酸化チタンを26.2重量部、炭酸カルシウムを3.94重量部混合し30分攪拌したこと以外は、実施例1-3と同じ工程で酸化チタン化合物を合成した。
水100重量部に対して、酸化チタンを26.2重量部、炭酸カルシウムを3.94重量部、二酸化ケイ素を1.58重量部混合し30分攪拌したこと以外は、比較例3-1と同じ工程で酸化チタン化合物を合成した。
水100重量部に対して、カルシウムを0.003質量%含有する酸化チタンを26.2重量部、二酸化ケイ素を4.93重量部混合し30分攪拌したこと以外は、比較例3-1と同じ工程で酸化チタン化合物を合成した。
水100重量部に対して、酸化チタンを26.2重量部、炭酸カルシウムを1.58重量部、二酸化ケイ素を4.93重量部混合し30分攪拌したこと以外は、比較例3-1と同じ工程で酸化チタン化合物を合成した。
水100重量部に対して、酸化チタンを26.2重量部、炭酸カルシウムを3.94重量部、二酸化ケイ素を4.93重量部混合し30分攪拌したこと以外は、比較例3-1と同じ工程で酸化チタン化合物を合成した。
上記の実施例3-1~3-2および比較例3-1~3-3で使用した分析装置は、第1実施形態および第2実施形態と同様であるため説明を省略する。
第1実施形態および第2実施形態と同様であるため説明を省略する。
第1実施形態および第2実施形態と同様であるため説明を省略する。
図6は、本実施形態の実施例3-1~3-2および比較例3-1~3-3の評価結果の一覧を示すテーブルである。
本発明の第1実施形態~第3実施形態に係る酸化チタン化合物に含有しているカルシウムおよびケイ素はそれぞれ、酸化チタン化合物の結晶表面に全てが存在するのではなく、酸化チタン化合物の結晶内に少なくとも一部が固溶して存在していると考えられる。その理由は、次の通りである。比較例1-1、実施例1-3、実施例2-2、実施例3-1それぞれにおいて合成された中間体である四チタン酸カリウムに対して、X線回折装置:株式会社リガク、Ultima4を使用しCu-Kα線源を用いたX線回折測定を行ったところ、図7に示すようにカルシウム又はケイ素の含有量が増えると、4チタン酸カリウムの面間隔の変化が確認される。例えば、四チタン酸カリウムの-313面の面間隔には違いが見られないが、200面の面間隔が短くなっていることが確認される。このことから、これらの元素が結晶中に存在し、結晶面間隔に影響を及ぼしていると推定される。
11 正極
12 負極
13、23 非水電解質
14、24 セパレータ
20 コイン型セル
21 電極
22 対極
25a、25b 上ケース、下ケース
26 ガスケット
Claims (7)
- ブロンズ型酸化チタン又はブロンズ型酸化チタンを主体とする酸化チタンであって、
カルシウムを0.005質量%以上2.5質量%以下含有している酸化チタン化合物。 - ブロンズ型酸化チタン又はブロンズ型酸化チタンを主体とする酸化チタンであって、
ケイ素を0.15質量%以上0.55質量%以下含有している酸化チタン化合物。 - ブロンズ型酸化チタン又はブロンズ型酸化チタンを主体とする酸化チタンであって、
カルシウムを0.005質量%以上1.2質量%以下含有し、且つ、ケイ素を0.15質量%以上0.2質量%以下含有する、又は、
カルシウムを0.005質量%以上0.1質量%以下含有し、且つ、ケイ素を0.15質量%以上0.5質量%以下含有する酸化チタン化合物。 - 前記カルシウムの少なくとも一部、及び/又は、前記ケイ素の少なくとも一部が酸化チタン結晶内に固溶して存在している請求項1~3に記載の酸化チタン化合物。
- 前記酸化チタン化合物の細孔容積が0.01~0.5mL/g、且つ、
比表面積が1.0~20m2/gである請求項1~4に記載の酸化チタン化合物。 - 請求項1~請求項5のいずれかに記載の酸化チタン化合物を電極活物質として用いた電極。
- 請求項6に記載の電極を正極又は負極に用いたリチウムイオン二次電池。
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US20180226645A1 (en) | 2018-08-09 |
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