WO2012077268A1 - リチウムイオン二次電池負極材用粉末、これを用いたリチウムイオン二次電池負極およびキャパシタ負極、ならびにリチウムイオン二次電池およびキャパシタ - Google Patents
リチウムイオン二次電池負極材用粉末、これを用いたリチウムイオン二次電池負極およびキャパシタ負極、ならびにリチウムイオン二次電池およびキャパシタ Download PDFInfo
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- WO2012077268A1 WO2012077268A1 PCT/JP2011/005647 JP2011005647W WO2012077268A1 WO 2012077268 A1 WO2012077268 A1 WO 2012077268A1 JP 2011005647 W JP2011005647 W JP 2011005647W WO 2012077268 A1 WO2012077268 A1 WO 2012077268A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- negative electrode
- ion secondary
- lithium ion
- secondary battery
- powder
- Prior art date
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- 239000000843 powder Substances 0.000 title claims abstract description 128
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 121
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 76
- 239000003990 capacitor Substances 0.000 title claims description 23
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 91
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 90
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 77
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 69
- 239000002245 particle Substances 0.000 claims abstract description 40
- 238000009826 distribution Methods 0.000 claims abstract description 24
- 238000004438 BET method Methods 0.000 claims abstract description 8
- 125000001475 halogen functional group Chemical group 0.000 claims abstract description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 19
- 230000005260 alpha ray Effects 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 abstract 3
- 238000000576 coating method Methods 0.000 abstract 3
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- 238000000151 deposition Methods 0.000 description 9
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
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- 229910052744 lithium Inorganic materials 0.000 description 8
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- -1 nickel metal hydride Chemical class 0.000 description 3
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- GBROPGWFBFCKAG-UHFFFAOYSA-N picene Chemical compound C1=CC2=C3C=CC=CC3=CC=C2C2=C1C1=CC=CC=C1C=C2 GBROPGWFBFCKAG-UHFFFAOYSA-N 0.000 description 2
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- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
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- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
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- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
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- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
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Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- 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
- H01M4/625—Carbon or graphite
-
- 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
-
- 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
- Y02E60/13—Energy storage using capacitors
Definitions
- the present invention relates to a powder for a negative electrode material that can be used for a lithium ion secondary battery, has a large discharge capacity, has good cycle characteristics, and can obtain a lithium ion secondary battery that can withstand use at a practical level.
- the present invention also relates to a lithium ion secondary battery negative electrode and capacitor negative electrode, and a lithium ion secondary battery and capacitor using the negative electrode material powder.
- high energy density secondary batteries include nickel cadmium batteries, nickel metal hydride batteries, lithium ion secondary batteries, and polymer batteries.
- lithium ion secondary batteries have a much longer lifespan and higher capacity than nickel cadmium batteries and nickel metal hydride batteries, and thus the demand thereof has shown high growth in the power supply market.
- FIG. 1 is a diagram showing a configuration example of a coin-shaped lithium ion secondary battery.
- the lithium ion secondary battery maintains the electrical insulation between the positive electrode 1, the negative electrode 2, the separator 3 impregnated with the electrolyte, and the positive electrode 1 and the negative electrode 2 and seals the battery contents. It consists of a gasket 4.
- lithium ions reciprocate between the positive electrode 1 and the negative electrode 2 through the electrolytic solution of the separator 3.
- the positive electrode 1 includes a counter electrode case 1a, a counter electrode current collector 1b, and a counter electrode 1c, and lithium cobaltate (LiCoO 2 ) and lithium manganate (LiMn 2 O 4 ) are mainly used for the counter electrode 1c.
- the negative electrode 2 is composed of a working electrode case 2a, a working electrode current collector 2b, and a working electrode 2c, and the negative electrode material used for the working electrode 2c is generally an active material capable of occluding and releasing lithium ions (negative electrode active material). And a conductive assistant and a binder.
- carbon-based materials have been used as negative electrode active materials for lithium ion secondary batteries.
- a new negative electrode active material having a higher capacity of a lithium ion secondary battery than conventional ones a composite oxide of lithium and boron, a composite oxide of lithium and a transition metal (V, Fe, Cr, Mo, Ni, etc.) Si, Ge, or a compound containing Sn and N and O, Si particles whose surface is coated with a carbon layer by chemical vapor deposition, and the like have been proposed.
- silicon oxide powder represented by SiO x (0 ⁇ x ⁇ 2) such as SiO As the negative electrode active material.
- Silicon oxide can be a negative electrode active material with a larger effective charge / discharge capacity because it has less degradation such as collapse of the crystal structure and generation of irreversible materials due to insertion and extraction of lithium ions during charge and discharge. Therefore, by using silicon oxide as a negative electrode active material, lithium has a higher capacity than when carbon is used, and has better cycle characteristics than when a high capacity negative electrode material such as Si or Sn alloy is used. An ion secondary battery has been obtained.
- silicon oxide powder is used as the negative electrode active material
- carbon powder or the like is generally mixed as a conductive aid in order to compensate for the low electrical conductivity of silicon oxide.
- the electrical conductivity of the contact part vicinity of a silicon oxide powder and a conductive support agent is securable.
- electrical conductivity cannot be ensured at a location away from the contact portion, and it is difficult to function as a negative electrode active material.
- Patent Document 1 a carbon film is formed by CVD (chemical vapor deposition) on the surface of particles (conductive silicon composite) having a structure in which silicon microcrystals are dispersed in silicon dioxide.
- CVD chemical vapor deposition
- Patent Document 1 According to the method proposed in Patent Document 1, a uniform carbon film is formed on the conductive silicon composite, and sufficient electrical conductivity can be imparted.
- the lithium ion secondary battery using the conductive silicon composite of Patent Document 1 uses silicon dioxide in which silicon microcrystals are dispersed as the negative electrode material. Lithium ion occlusion, expansion and contraction during release increase, and repeated charge / discharge causes problems such as a sudden drop in capacity at a certain point. Further, the discharge capacity and cycle characteristics were not sufficient.
- the present inventors have made various studies on silicon oxide, which is considered to be a negative electrode material powder (negative electrode active material) capable of increasing the capacity of a lithium ion secondary battery.
- the decrease in initial efficiency (the value of the ratio of the discharge capacity to the charge capacity at the time of the first charge / discharge (at the time of the first charge / discharge) after the manufacture of the lithium ion secondary battery) is Li 4 led to think to be due to the formation of SiO 4.
- Li 22 Si 5 in the first term on the right side of the equation (1) is a component responsible for reversible capacity, and Li 4 SiO 4 in the second term is responsible for irreversible capacity. Li 4 SiO 4 cannot release lithium ions.
- the theoretical characteristic of the lithium ion secondary battery when silicon oxide (SiO x ) is used as the negative electrode material powder and x 1 is a reversible capacity of 2007 mAh / g, The initial efficiency was found to be 76%.
- Conventional lithium ion secondary batteries using silicon oxide as a negative electrode material powder have a reversible capacity of about 1500 mAh / g, so a lithium ion secondary battery using silicon oxide as a negative electrode material powder. It was found that there is still room for improvement in the reversible capacity of the battery.
- the present invention has been made in view of this problem, and has a large discharge capacity, good cycle characteristics, and a negative electrode material powder for a lithium ion secondary battery that can withstand use at a practical level, and the negative electrode material. It is an object to provide a lithium ion secondary battery negative electrode and a capacitor negative electrode, and a lithium ion secondary battery and a capacitor using the powder for use.
- the present inventors have studied a method for suppressing the generation of bubbles during slurry preparation.
- the inventors presumed that among the SiO x powders, fine powder is a cause of easily generating bubbles. Then, to remove the fines by sedimentation, was using SiO x powder that suppresses the spread of the particle size distribution was found that air bubbles at the time of generation of the slurry as compared to those that do not remove fine powder is small.
- the slurry using the SiO x powder from which the fine powder has been removed has a higher density than that without removing the fine powder, and the lithium ion secondary battery using this slurry as the negative electrode material has a high initial discharge capacity. did. These are considered to be due to the reduction of bubbles inside the slurry.
- the present invention has been made on the basis of the above findings.
- the gist of the present invention is as follows. (1) to (6) Lithium ion secondary battery negative electrode powder, (7) Lithium ion secondary battery negative electrode And a capacitor negative electrode of the following (8), a lithium ion secondary battery of the following (9), and a capacitor of the following (10).
- the “lower silicon oxide powder” is an SiO x powder satisfying x ⁇ 0.4 ⁇ x ⁇ 1.2.
- x of SiOx, D50, D10, the thickness of the conductive carbon film, the specific surface area, the proportion of the conductive carbon film in the negative electrode material powder, and the tar component content will be described later.
- Lithium ion secondary battery negative electrode powder according to the present invention, and lithium ion secondary battery negative electrode or capacitor negative electrode are used to provide lithium having a large discharge capacity and good cycle characteristics, and can be used at a practical level. An ion secondary battery or a capacitor can be obtained. Moreover, the lithium ion secondary battery and capacitor of the present invention have a large discharge capacity and good cycle characteristics.
- FIG. 1 is a diagram illustrating a configuration example of a coin-shaped lithium ion secondary battery.
- FIG. 2 is a diagram showing a configuration example of a silicon oxide manufacturing apparatus.
- FIG. 3 is a graph showing the particle size distribution before and after the sedimentation separation of the SiO powder.
- FIG. 3 (a) shows the distribution before the sedimentation separation, and
- FIG. 3 (b) shows the distribution after the sedimentation separation.
- Powder for negative electrode material of lithium ion secondary battery of the present invention has a conductive carbon film on the surface of lower silicon oxide powder, and in the particle size distribution of this silicon oxide powder, 1 ⁇ m ⁇ D50 ⁇ 20 ⁇ m, and the relationship between D50 and D10 satisfies 1.4 ⁇ D50 / D10 ⁇ 2.4.
- the lower silicon oxide powder is a SiO x powder in which x satisfies 0.4 ⁇ x ⁇ 1.2.
- the reason why x is in this range is that when the value of x is less than 0.4, the lithium ion secondary battery using the negative electrode material powder of the present invention and the capacitor are severely deteriorated due to charge / discharge cycles, and 1.2. This is because the capacity of the battery is reduced when the value exceeds.
- x preferably satisfies 0.8 ⁇ x ⁇ 1.05.
- the discharge capacity of a lithium ion secondary battery using this lower silicon oxide powder as a negative electrode material powder can be improved.
- the thickness of the conductive carbon film is preferably 1.5 nm or more and 7.5 nm or less. If the conductive carbon film is less than 1.5 nm, the electrical conductivity may be insufficient, and if it is thicker than 7.5 nm, it is easy to peel off from the surface of the lower silicon oxide powder. In either case, the lithium ion secondary battery This is because the discharge capacity may be insufficient.
- the thickness of the conductive film is more preferably 2.0 nm or more and 5.0 nm or less.
- the powder for a negative electrode material for a lithium ion secondary battery of the present invention has a particle size distribution of 1 ⁇ m ⁇ D50 ⁇ 20 ⁇ m.
- Dn (0 ⁇ n ⁇ 100) is the particle size when the cumulative frequency from the smaller particle size reaches n%.
- D50 ⁇ 1 ⁇ m bubbles are likely to be generated during the production of the slurry, and thus the adhesion between the electrode substrate and the negative electrode is weakened.
- D50 preferably satisfies 3 ⁇ m ⁇ D50 ⁇ 12 ⁇ m.
- the relationship between D50 and D10 in the particle size distribution satisfies 1.4 ⁇ D50 / D10 ⁇ 2.4.
- 1.4 ⁇ D50 / D10 ⁇ 2.4 indicates that the particle size distribution is moderately sharp.
- the particle size distribution is excessively sharp, and the bulk density of the slurry prepared by mixing the powder for negative electrode material with a binder or a conductive auxiliary agent is increased. In this case, the slurry also contains bubbles. In the same manner as in the above case, the discharge capacity of the lithium ion secondary battery decreases because it is easily peeled off from the applied working electrode current collector. Further, when D50 / D10> 2.4, the particle size distribution is broad, the amount of bubbles generated is large at the time of slurry production, and it is difficult to mix uniformly, and when used as an electrode, a lithium ion secondary battery The discharge capacity is reduced.
- the relationship between D50 and D10 preferably satisfies 1.6 ⁇ D50 / D10 ⁇ 2.1.
- Lithium-ion secondary battery negative electrode material powder of this invention the specific surface area measured by the BET method, 0.3 m 2 / g or more, preferably not more than 7.0 m 2 / g.
- the specific surface area of the negative electrode material powder is small, generation of an SEI film (Solid Electrolyte Interface, irreversible capacity component) on the electrode surface during the first charge / discharge can be suppressed.
- SEI film Solid Electrolyte Interface, irreversible capacity component
- the specific surface area is larger than 7.0 m 2 / g, the surface area becomes considerably wide, so that the ratio of the SEI film formed on the particle surface is increased, and the capacity of the lithium ion secondary battery may be decreased.
- the specific surface area measured by the BET method is more preferably 0.5 m 2 / g or more and 6.0 m 2 / g or less.
- the powder for the negative electrode material of the lithium ion secondary battery preferably has a ratio of the conductive carbon film (hereinafter referred to as “carbon film ratio”) of 0.5 mass% or more and 10 mass% or less. This is due to the following reason.
- the carbon film also contributes to the charge / discharge capacity of the lithium ion secondary battery as in the case of lower silicon oxide, but its charge / discharge capacity per unit mass is smaller than that of lower silicon oxide. Therefore, the carbon film rate of the powder for a lithium ion secondary battery negative electrode material is preferably 10% by mass or less from the viewpoint of securing the charge / discharge capacity of the lithium ion secondary battery. On the other hand, if the carbon film ratio is less than 0.5% by mass, the effect of imparting conductivity by the conductive carbon film cannot be obtained, and the lithium ion secondary battery using the negative electrode material powder is difficult to function as a battery. .
- the carbon film rate is more preferably 0.5% by mass or more and 2.5% by mass or less.
- the total content of tar components is preferably 1 mass ppm or more and 4000 mass ppm or less.
- the tar component is generated when the conductive carbon film is formed, as will be described later.
- the total content of the tar components is more than 4000 ppm by mass, resistance to expansion and contraction of the negative electrode accompanying charging / discharging of the lithium ion secondary battery is poor, and the cycle characteristics are inferior.
- it is 4000 mass ppm or less, a lithium ion secondary battery having good initial efficiency and cycle characteristics can be obtained, and in particular, cycle characteristics are improved. If it is 1500 ppm by mass or less, initial efficiency and cycle characteristics are further improved.
- the total content of the tar component is more preferably 40 mass ppm or more and 1500 mass ppm or less.
- O content in powder for lithium ion secondary battery negative electrode material was analyzed by 10% of sample by inert gas melting / infrared absorption method using oxygen concentration analyzer (Leco, TC436). It is calculated from the O content in the sample quantitatively evaluated.
- Si content in the negative electrode powder for lithium ion secondary batteries was determined by adding nitric acid and hydrofluoric acid to the sample to dissolve the sample, and then adding the resulting solution to an ICP emission spectrometer (Shimadzu Corporation). And the Si content in the sample under quantitative evaluation.
- the Si / C is preferably 0.05 or less, and more preferably 0.02 or less. “Si / C is 0.02 or less” is a state in which most of the surface of the lower silicon oxide powder is covered with C and Si is hardly exposed.
- D50 and D10 can be measured using a laser diffraction particle size distribution measuring device.
- the measurement conditions are as shown in Table 2.
- a 2 g sample is placed in the apparatus, and 2 g / L sodium hexametaphosphate is added as a dispersant.
- the measurement range is 0.02 ⁇ m to 2000 ⁇ m, and the weight distribution is measured.
- D10 is the particle size when the cumulative frequency from the smaller particle size reaches 10%
- D50 is the particle size when the cumulative frequency from the smaller particle size reaches 10%.
- the thickness of the conductive carbon film is calculated from the specific surface area of the lower silicon oxide powder and the carbon film ratio measured by the BET method described later, when the thickness is uniform. can do.
- the density of both lower silicon oxide and carbon is about 2.2 g / cm 3 , although it varies somewhat depending on the composition and degree of graphitization. Assuming that these densities are equal, when the thickness of the conductive carbon film is as small as nanometer order, the film thickness A [nm] is equal to the specific surface area B [m 2 / g] and the carbon coverage C From [wt%], it can be calculated using the following equation (1).
- A 4.55 ⁇ C ⁇ B (1)
- the specific surface area of lower silicon oxide powder formed with a conductive carbon film can be measured by the following BET method. 0.5 g of sample is put in a glass cell and dried under reduced pressure at 200 ° C. for about 5 hours. Then, the specific surface area is calculated from the nitrogen gas adsorption isotherm at the liquid nitrogen temperature ( ⁇ 196 ° C.) measured for this sample. The measurement conditions are as shown in Table 3.
- Carbon film ratio measurement method The carbon film ratio is determined by measuring the mass of the powder for the negative electrode material of the lithium ion secondary battery and the CO 2 gas by an oxygen gas flow combustion-infrared absorption method using a carbon concentration analyzer (Leco, CS400). It is calculated from the result of carbon amount quantitatively evaluated by analysis.
- the crucible is a ceramic crucible, the auxiliary combustor is copper, and the analysis time is 40 seconds.
- TPD-MS Temporal Programmed Desorption-Mass Spectroscopy
- the tar component is a high molecular weight component such as an aromatic hydrocarbon generated when a hydrocarbon or organic gas is thermally decomposed.
- the total amount of components having molecular weights of 57, 106, 178, 202, 252 and 276 is defined as the residual tar component amount (see Table 5 described later).
- Representative chemical species of each molecular weight are 106 for xylene, 178 for phenanthrene and anthracene, 202 for pyrene, 252 for perylene and benzopyrene, and 276 for pentacene and picene.
- FIG. 2 is a diagram showing a configuration example of a silicon oxide manufacturing apparatus.
- This apparatus includes a vacuum chamber 5, a raw material chamber 6 disposed in the vacuum chamber 5, and a deposition chamber 7 disposed on the upper portion of the raw material chamber 6.
- the raw material chamber 6 is formed of a cylindrical body, and a cylindrical raw material container 8 and a heating source 10 surrounding the raw material container 8 are disposed at the center thereof.
- a heating source 10 for example, an electric heater can be used.
- the deposition chamber 7 is composed of a cylindrical body arranged so that its axis coincides with the raw material container 8.
- a deposition base 11 made of stainless steel is provided on the inner peripheral surface of the deposition chamber 7 for vapor deposition of gaseous silicon oxide generated by sublimation in the raw material chamber 6.
- a vacuum device (not shown) for discharging the atmospheric gas is connected to the vacuum chamber 5 that accommodates the raw material chamber 6 and the deposition chamber 7, and the gas is discharged in the direction of arrow A.
- a mixed granulated raw material 9 in which silicon powder and silicon dioxide powder are blended at a predetermined ratio as a raw material, mixed, granulated and dried is used.
- the mixed granulated raw material 9 is filled in the raw material container 8 and heated (heated by a heating source 10) in an inert gas atmosphere or vacuum to generate (sublimate) SiO.
- Gaseous SiO generated by the sublimation rises from the raw material chamber 6 and enters the deposition chamber 7, is vapor-deposited on the surrounding deposition base 11, and is deposited as lower silicon oxide 12. Thereafter, the lower silicon oxide 12 deposited from the deposition base 11 is removed and pulverized using a ball mill or the like to obtain a lower silicon oxide powder.
- the lower silicon oxide powder obtained in this way contains fine powder, and thus, for example, the fine powder is removed by the following method.
- Lower silicon oxide powder is immersed in a beaker containing water so that the water depth becomes 10 cm, and ultrasonic vibration is applied by an ultrasonic cleaner. Thereafter, natural sedimentation is performed, the fine water remaining in the aqueous layer is removed by discarding the supernatant water, and only the settled powder is recovered.
- the particle size of the lower silicon oxide powder can be adjusted, and the value of D50 / D10 can be set within a predetermined range. When the sedimentation time is long, not only the particles having a large particle size but also fine powder remaining in the aqueous layer sinks, and the value of D50 / D10 increases.
- FIG. 3 is a diagram showing the particle size distribution before and after sedimentation separation.
- FIG. 3 (a) shows the distribution before sedimentation separation
- FIG. 3 (b) shows the distribution after sedimentation separation.
- the figure (a) is a particle size distribution about the test number 4 which is a comparative example in the below-mentioned Example
- the figure (b) is the particle size distribution about the test number 1 which is an example of this invention. From these figures, it can be seen that fine powder having a particle size of about 1 ⁇ m has been removed by sedimentation separation.
- the recovered lower silicon oxide powder is dried in an oven at 130 ° C. for 24 hours or more under atmospheric pressure. Then, it is crushed in an agate mortar and further dried under the same conditions.
- the method of adjusting the particle size of the lower silicon oxide powder is not limited to sedimentation separation, and can be performed by air classification or the like.
- the conductive carbon film is formed on the surface of the lower silicon oxide powder having the adjusted particle size by CVD or the like. Specifically, a rotary kiln is used as the apparatus, and a mixed gas of a hydrocarbon gas or an organic substance-containing gas that is a carbon source and an inert gas is used as a gas.
- hydrocarbon gas consisting only of C and H is preferable as the carbon source.
- a hydrocarbon gas is used as a carbon source, an aromatic substance composed of only C and H is generated as a tar component, and components having molecular weights of 57, 106, 178, 202, 252 and 276 are the main components.
- the forming temperature of the conductive carbon film is 700 ° C. or higher and 750 ° C. or lower.
- the treatment time is 20 minutes or more and 120 minutes or less, and is set according to the thickness of the conductive carbon film to be formed.
- This treatment condition is a range in which a conductive carbon film having low crystallinity can be obtained. Moreover, it is also the range in which the production
- the conductive carbon film has better cycle characteristics of the lithium ion secondary battery when the crystallinity is lower. This is considered to be due to the fact that the higher the crystallinity of the conductive carbon film, the lower the lithium ion acceptance rate and the lower the ability to relax the expansion and contraction of silicon oxide. Further, SiC is generated near the interface between the surface of the lower silicon oxide powder and the carbon film when the heating temperature is excessively high. Since generation of SiC reduces the amount of Si that can contribute to the capacity of the battery, it is preferable to suppress generation of SiC.
- Vacuum treatment method of lower silicon oxide powder with conductive carbon film formed The lower silicon oxide powder with conductive carbon film formed under vacuum at a temperature of 600 ° C. or higher and 750 ° C. or lower for 10 minutes or longer and 1 hour or shorter Apply vacuum treatment to hold.
- the vacuum treatment is performed in a state where the lower silicon oxide powder is housed in a vacuum chamber, and the internal pressure of the vacuum chamber is maintained at 1 Pa or less using an oil diffusion pump. This internal pressure is measured using a Pirani gauge.
- the tar component generated during the formation of the carbon film can be volatilized and removed from the carbon film by vacuum treatment. Moreover, when the heating holding temperature is in the above range, the generation of SiC in the vicinity of the interface between the silicon oxide and the carbon film is suppressed.
- the negative electrode material used for the negative electrode 2, that is, the working electrode 2c constituting the negative electrode of the lithium ion secondary battery of the present invention is configured using the powder for negative electrode material of the lithium ion secondary battery of the present invention. Specifically, it can be comprised with the powder for lithium ion secondary battery negative electrode materials of this invention which is an active material, another active material, a conductive support agent, and a binder. Of the constituent materials in the negative electrode material, the ratio of the powder for the negative electrode material of the lithium ion secondary battery of the present invention to the total of the constituent materials excluding the binder is 20% by mass or more. It is not always necessary to add an active material other than the powder for a negative electrode material of the lithium ion secondary battery of the present invention.
- the conductive assistant for example, acetylene black or carbon black can be used
- the binder for example, polyacrylic acid (PAA) or polyvinylidene fluoride can be used.
- the lithium ion secondary battery of the present invention uses the above-described powder for a lithium ion secondary battery negative electrode material and a lithium ion secondary battery negative electrode of the present invention, the discharge capacity is large, the cycle characteristics are good, and the practical level. Can withstand use in
- the powder for negative electrode material of the present invention and the negative electrode using the same can also be applied to capacitors.
- Test conditions 1-1 Configuration of Lithium Ion Secondary Battery
- the configuration of the lithium ion secondary battery was the coin shape shown in FIG.
- the negative electrode 2 will be described. Silicon powder and silicon dioxide powder are blended at a predetermined ratio, and mixed, granulated and dried mixed granulated raw materials are used as raw materials, and lower silicon oxide is deposited on the deposition substrate using the apparatus shown in FIG. .
- the deposited lower silicon oxide was pulverized for 24 hours using an alumina ball mill to obtain a powder having a D50 of 4.4 ⁇ m.
- This lower silicon oxide powder was subjected to particle size adjustment by natural sedimentation for a maximum of 168 hours by the method described above.
- the values of D50, D10 and D50 / D10 after adjusting the sedimentation time and particle size were as shown in Tables 4 to 6 below (test numbers 1 to 14).
- This lower silicon oxide (SiO x ) powder satisfied x 1.
- a conductive carbon film was formed on the surface of the lower silicon oxide powder to obtain a negative electrode material powder for a lithium ion secondary battery.
- a rotary kiln was used as the apparatus, a mixed gas of normal butane and Ar was used as the gas, and the treatment temperature was 700 ° C.
- the formation temperature of carbon film, the rate of carbon film, and the thickness of the carbon film were as shown in Tables 4-6.
- Test Nos. 1 to 6 shown in Table 4 the value of D50 / D10 was changed by changing the sedimentation time.
- Test numbers 1 to 3 are examples of the present invention, and the value of D50 / D10 satisfied the definition of the present invention.
- Test numbers 4 to 6 are comparative examples, and the value of D50 / D10 did not satisfy the definition of the present invention.
- Test Nos. 7 and 8 shown in Table 5 a vacuum treatment was performed after forming a conductive carbon film.
- the holding temperature was 700 ° C.
- the holding time was as shown in Table 4, and the internal pressure of the vacuum chamber was kept at 1 Pa or less using an oil diffusion pump.
- Test Nos. 9 to 14 shown in Table 6 the carbon film ratio was changed.
- Test numbers 7 to 14 are all examples of the present invention, and the value of D50 / D10 satisfied the definition of the present invention.
- the values of D50 / D10 are in the range of 1.70 or more and 1.80 or less.
- a slurry is prepared by adding n-methylpyrrolidone to a mixture of 65% by mass of the negative electrode material powder for lithium ion secondary battery, 10% by mass of acetylene black, and 25% by mass of PAA. This slurry was applied to a copper foil having a thickness of 20 ⁇ m, dried in an atmosphere at 120 ° C. for 30 minutes, and then punched out to a size with an area of 1 cm 2 on one side to obtain a negative electrode 2.
- the counter electrode 1c was a lithium foil.
- LiPF 6 lithium phosphorous hexafluoride
- EC ethylene carbonate
- DEC diethyl carbonate
- a polyethylene porous film having a thickness of 30 ⁇ m was used as the separator.
- Test results A lithium-ion secondary battery produced under the above conditions was subjected to a charge / discharge test and evaluated using the initial discharge capacity as an index. Moreover, about the powder for lithium ion secondary battery negative electrode materials, the specific surface area measured by BET method, the carbon film rate, and the thickness of the carbon film were also measured. For test numbers 1, 7 and 8, the total content of tar components was also measured. These values are shown in Tables 4 to 6 together with the test conditions.
- test numbers 9 to 14 had excellent initial discharge capacities of 1659 mAh / g or more.
- the thickness of the carbon film is 1.5 nm or more as in Test Nos. 9 to 12.
- the thickness was 7.5 nm or less, a further excellent value was obtained.
- Test No. 9 has a carbon coverage of 0.5% by mass or more and 2.5% by mass or less, a carbon film thickness of 2.0 nm or more and 5.0 nm or less, and an initial discharge capacity. It was the most excellent value of 1734 mAh / g.
- Lithium ion secondary battery negative electrode powder according to the present invention, and lithium ion secondary battery negative electrode or capacitor negative electrode are used to provide lithium having a large discharge capacity and good cycle characteristics, and can be used at a practical level. An ion secondary battery or a capacitor can be obtained. Moreover, the lithium ion secondary battery and capacitor of the present invention have a large discharge capacity and good cycle characteristics. Therefore, the present invention is a useful technique in the field of secondary batteries and capacitors.
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Abstract
Description
SiOx+(44-x)/10Li++(44-x)/10e-
→ (4-x)/20Li22Si5+x/4Li4SiO4 …(1)
本発明のリチウムイオン二次電池負極材用粉末は、低級酸化珪素粉末の表面に導電性炭素皮膜を有し、この酸化珪素粉末の粒度分布において、1μm≦D50≦20μmであり、D50とD10の関係が1.4≦D50/D10≦2.4を満足することを特徴とする。
2-1.SiOxのxの算出方法
SiOxのxは、リチウムイオン二次電池負極材用粉末中のO含有率とSi含有率のモル比(O/Si)であり、例えば下記測定方法で測定したO含有率およびSi含有率を用いて算出することができる。
リチウムイオン二次電池負極材用粉末中のO含有率は、酸素濃度分析装置(Leco社製、TC436)を用いて、試料10mgを不活性ガス融解・赤外線吸収法によって分析することで定量評価した試料中のO含有量から算出する。
リチウムイオン二次電池負極材用粉末中のSi含有率は、試料に硝酸およびフッ酸を加えて試料を溶解させ、得られた溶液をICP発光分光分析装置(株式会社島津製作所製)で分析することによって定量評価下試料中のSi含有量から算出する。
本発明のリチウムイオン二次電池負極材用粉末において、「低級酸化珪素粉末の表面に導電性炭素皮膜を有する」とは、AlKα線(1486.6eV)を用いたX線光電子分光分析装置(XPS)で、導電性炭素皮膜の形成処理を施した低級酸化珪素粉末の表面分析を行った場合に、SiとCとのモル比の値Si/Cが0.1以下であることをいう。XPSの測定条件は表1に示す通りとする。リチウムイオン二次電池負極材用粉末に十分に電気伝導性を付与するには、Si/Cは、0.05以下が好ましく、0.02以下がさらに好ましい。「Si/Cが0.02以下」とは、低級酸化珪素粉末の表面のほとんどがCに覆われており、Siがほとんど露出していない状態である。
D50およびD10は、レーザー回折式粒度分布測定装置を使用して測定することができる。測定条件は表2に示す条件とし、2gの試料を装置に入れて、分散剤として2g/Lのヘキサメタリン酸ナトリウムを添加する。測定範囲は0.02μmから2000μmまでとし、重量分布を測定する。D10は、粒径が小さい方からの積算頻度が10%に達する時の粒径であり、D50は、粒径が小さい方からの積算頻度が10%に達する時の粒径である。
導電性炭素皮膜の厚さは、厚さが均一である場合の値を、後述するBET法によって測定した低級酸化珪素粉末の比表面積と炭素被膜率から算出することができる。組成や黒鉛化度によって多少異なるが、低級酸化珪素および炭素の密度はともに約2.2g/cm3である。これらの密度が等しいとすると、導電性炭素皮膜の厚さがナノメートルのオーダーと小さい場合には、皮膜の厚さA[nm]は、比表面積B[m2/g]および炭素被覆率C[wt%]から、下記(1)式を用いて算出することができる。
A=4.55×C÷B …(1)
導電性炭素皮膜を形成した低級酸化珪素粉末の比表面積は、以下のBET法によって測定することができる。試料0.5gをガラスセルに入れて、200℃で約5時間、減圧乾燥する。そして、この試料について測定した液体窒素温度(-196℃)における窒素ガス吸着等温線から比表面積を算出する。測定条件は表3に示す通りとする。
炭素皮膜率は、リチウムイオン二次電池負極材用粉末の質量と、炭素濃度分析装置(Leco社製、CS400)を用いて酸素気流燃焼-赤外線吸収法によってCO2ガスを分析することで定量評価した炭素量の結果から算出する。ルツボはセラミックルツボを、助燃剤は銅を用い、分析時間は40秒とする。
リチウムイオン二次電池負極材用粉末の残留タール成分量は、以下のTPD-MS(Temperature Programmed Desorption‐Mass Spectroscopy;昇温熱脱離・質量分析法)によって測定することができる。試料50mgをシリカ製セルに入れ、50mL/minのヘリウムガスフロー中で、室温から1000℃まで10K/minの速度で昇温する。そして、発生したガスを質量分析計(株式会社島津製作所製、GC/MS QP5050A)で分析する。
図2は、酸化珪素の製造装置の構成例を示す図である。この装置は、真空室5と、真空室5内に配置された原料室6と、原料室6の上部に配置された析出室7とを備える。
このようにして得られた低級酸化珪素粉末は微粉を含有するため、例えば次の方法で微粉を除去する。水深10cmとなるように水を入れたビーカー内で低級酸化珪素粉末を浸漬させ、超音波洗浄機によって超音波振動を付与する。その後、自然沈降を行い、上澄みの水を捨てることによって水層に残った微粉を除去し、沈降した粉末のみを回収する。析出低級酸化珪素の粉砕時間および低級酸化珪素粉末の沈降時間を調整することにより、低級酸化珪素粉末の粒度を調整し、D50/D10の値を所定の範囲とすることができる。沈降時間が長いと、粒径の大きなもののみならず、水層に残った微粉も沈むため、D50/D10の値が大きくなる。
粒度を調整した低級酸化珪素粉末の表面への導電性炭素皮膜の形成は、CVD等により行う。具体的には、装置としてロータリーキルンを用い、ガスとして炭素源である炭化水素ガスまたは有機物含有ガスと、不活性ガスとの混合ガスを用いて行う。
導電性炭素皮膜を形成した低級酸化珪素粉末には、真空下で、600℃以上、750℃以下の温度に10分以上、1時間以下保持する真空処理を施す。真空処理は、低級酸化珪素粉末を真空槽に収容した状態で行い、真空槽の内圧は、油拡散ポンプを用いて1Pa以下に保つ。この内圧は、ピラニー真空計を用いて測定する。
本発明のリチウムイオン二次電池負極材用粉末およびリチウムイオン二次電池負極を用いた、コイン形状のリチウムイオン二次電池の構成例を、前記図1を参照して説明する。同図に示すリチウムイオン二次電池の基本的構成は、上述の通りである。
1-1.リチウムイオン二次電池の構成
リチウムイオン二次電池の構成は、前記図1に示すコイン形状とした。
充放電試験には、二次電池充放電試験装置(株式会社ナガノ製)を用いた。充電は、リチウムイオン二次電池の両極間の電圧が0Vに達するまでは1mAの定電流で行い、電圧が0Vに達した後は、0Vを維持したまま充電を行った。その後、電流値が20μAを下回った時点で充電を終了した。放電は、リチウムイオン二次電池の両極間の電圧が1.5Vに達するまでは1mAの定電流で行った。以上の充放電試験は10サイクル行った。
上記条件で作製したリチウムイオン二次電池について充放電試験を行い、初回放電容量を指標として評価を行った。また、リチウムイオン二次電池負極材用粉末について、BET法で測定した比表面積、炭素皮膜率、炭素皮膜の厚さも測定した。試験番号1、7および8についてはタール成分の合計含有率も測定した。これらの値を試験条件と併せて前記表4~6に示す。
前記表4に示す試験結果に基づいて、粒度分布、すなわちD50/D10の値の影響について説明する。試験番号1~6の全てにおいて、比表面積、炭素被覆率および炭素皮膜の厚さは、本発明で好ましいとする範囲内であった。
前記表5に示す試験結果に基づいて、タール成分の合計含有率の影響について説明する。試験番号7および8のいずれも、比表面積、炭素被覆率および炭素皮膜の厚さは、本発明で好ましいとする範囲内であった。表5には、比較対象として試験番号1も記載している。
前記表6に示す試験結果に基づいて、炭素被覆率および炭素皮膜の影響について説明する。表6に示す試験番号9~14のうち、試験番号9~12はいずれも、比表面積、炭素被覆率および炭素皮膜の厚さは、本発明で好ましいとする範囲内であった。試験番号13は炭素皮膜の厚さが、試験番号14は炭素被覆率および炭素皮膜の厚さが、それぞれ本発明で好ましいとする範囲外であった。
2:負極、 2a:作用極ケース、 2b:作用極集電体、
2c:作用極、 3:セパレーター、 4:ガスケット、 5:真空室、
6:原料室、 7:析出室、 8:原料容器、 9:混合造粒原料、
10:加熱源、 11:析出基体、 12:低級酸化珪素
Claims (10)
- 低級酸化珪素粉末の表面に導電性炭素皮膜を有し、この酸化珪素粉末の粒度分布において、1μm≦D50≦20μmであり、D50とD10の関係が1.4≦D50/D10≦2.4を満足することを特徴とするリチウムイオン二次電池負極材用粉末。
- 前記導電性炭素皮膜の厚さが、1.5nm以上、7.5nm以下であることを特徴とする請求項1に記載のリチウムイオン二次電池負極材用粉末。
- BET法で測定した比表面積が、0.3m2/g以上、7.0m2/g以下であることを特徴とする請求項1または2に記載のリチウムイオン二次電池負極材用粉末。
- 前記導電性炭素皮膜の占める割合が、0.5質量%以上、10質量%以下であることを特徴とする請求項1~3のいずれかに記載のリチウムイオン二次電池負極材用粉末。
- TPD-MSで測定したタール成分の合計含有率が、1質量ppm以上、4000質量ppm以下であることを特徴とする請求項1~4のいずれかに記載のリチウムイオン二次電池負極材用粉末。
- CuKα線を用いたX線回折装置で測定した場合に、2θ=10°~30°に現れるSiOxに由来するハローの最大値P1と、2θ=28.4±0.3°に現れるSi(111)の最強線ピークの値P2の関係が、P2/P1<0.01を満足することを特徴とする請求項1~5のいずれかに記載のリチウムイオン二次電池負極材用粉末。
- 請求項1~6のいずれかに記載のリチウムイオン二次電池負極材用粉末を用いたリチウムイオン二次電池負極。
- 請求項1~6のいずれかに記載のリチウムイオン二次電池負極材用粉末を用いたキャパシタ負極。
- 請求項7に記載のリチウムイオン二次電池負極を用いたリチウムイオン二次電池。
- 請求項8に記載のキャパシタ負極を用いたキャパシタ。
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002373653A (ja) * | 2001-06-15 | 2002-12-26 | Shin Etsu Chem Co Ltd | 非水電解質二次電池用負極材 |
JP3952180B2 (ja) * | 2002-05-17 | 2007-08-01 | 信越化学工業株式会社 | 導電性珪素複合体及びその製造方法並びに非水電解質二次電池用負極材 |
JP2011065934A (ja) * | 2009-09-18 | 2011-03-31 | Osaka Titanium Technologies Co Ltd | 珪素酸化物およびリチウムイオン二次電池用負極材 |
JP2011090869A (ja) * | 2009-10-22 | 2011-05-06 | Shin-Etsu Chemical Co Ltd | 非水電解質二次電池用負極材料、非水電解質二次電池用負極材の製造方法並びに非水電解質二次電池用負極及び非水電解質二次電池 |
JP2011192453A (ja) * | 2010-03-12 | 2011-09-29 | Shin-Etsu Chemical Co Ltd | 非水電解質二次電池用負極材及び非水電解質二次電池用負極材の製造方法並びにリチウムイオン二次電池及び電気化学キャパシタ |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004063433A (ja) * | 2001-12-26 | 2004-02-26 | Shin Etsu Chem Co Ltd | 導電性酸化珪素粉末、その製造方法及び該粉末を用いた非水電解質二次電池用負極材 |
JP4810794B2 (ja) * | 2004-03-31 | 2011-11-09 | 株式会社Gsユアサ | 非水電解質二次電池 |
CN1913200B (zh) * | 2006-08-22 | 2010-05-26 | 深圳市贝特瑞电子材料有限公司 | 锂离子电池硅碳复合负极材料及其制备方法 |
JP5131429B2 (ja) * | 2006-12-15 | 2013-01-30 | 信越化学工業株式会社 | 非水電解質二次電池用負極及びその製造方法 |
JP5555978B2 (ja) * | 2008-02-28 | 2014-07-23 | 信越化学工業株式会社 | 非水電解質二次電池用負極活物質、及びそれを用いた非水電解質二次電池 |
JP5245559B2 (ja) | 2008-06-16 | 2013-07-24 | 信越化学工業株式会社 | 非水電解質二次電池用負極材及びその製造方法、ならびにリチウムイオン二次電池及び電気化学キャパシタ |
-
2011
- 2011-10-07 CN CN2011800569500A patent/CN103229336A/zh active Pending
- 2011-10-07 KR KR1020137012843A patent/KR101513820B1/ko active IP Right Grant
- 2011-10-07 JP JP2012547676A patent/JP5648070B2/ja active Active
- 2011-10-07 WO PCT/JP2011/005647 patent/WO2012077268A1/ja active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002373653A (ja) * | 2001-06-15 | 2002-12-26 | Shin Etsu Chem Co Ltd | 非水電解質二次電池用負極材 |
JP3952180B2 (ja) * | 2002-05-17 | 2007-08-01 | 信越化学工業株式会社 | 導電性珪素複合体及びその製造方法並びに非水電解質二次電池用負極材 |
JP2011065934A (ja) * | 2009-09-18 | 2011-03-31 | Osaka Titanium Technologies Co Ltd | 珪素酸化物およびリチウムイオン二次電池用負極材 |
JP2011090869A (ja) * | 2009-10-22 | 2011-05-06 | Shin-Etsu Chemical Co Ltd | 非水電解質二次電池用負極材料、非水電解質二次電池用負極材の製造方法並びに非水電解質二次電池用負極及び非水電解質二次電池 |
JP2011192453A (ja) * | 2010-03-12 | 2011-09-29 | Shin-Etsu Chemical Co Ltd | 非水電解質二次電池用負極材及び非水電解質二次電池用負極材の製造方法並びにリチウムイオン二次電池及び電気化学キャパシタ |
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WO2013069197A1 (ja) * | 2011-11-11 | 2013-05-16 | 株式会社豊田自動織機 | リチウムイオン二次電池用の負極材及び負極、並びにリチウムイオン二次電池 |
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US9819008B2 (en) | 2011-11-11 | 2017-11-14 | Kabushiki Kaisha Toyota Jidoshokki | Negative-electrode stuff and negative electrode for use in lithium-ion secondary battery as well as lithium-ion secondary battery |
JPWO2013069197A1 (ja) * | 2011-11-11 | 2015-04-02 | 株式会社豊田自動織機 | リチウムイオン二次電池用の負極材及び負極、並びにリチウムイオン二次電池 |
US9819009B2 (en) | 2011-11-11 | 2017-11-14 | Kabushiki Kaisha Toyota Jidoshokki | Negative-electrode stuff and negative electrode for use in lithium-ion secondary battery as well as lithium-ion secondary battery |
JP5909552B2 (ja) * | 2012-06-25 | 2016-04-26 | 株式会社大阪チタニウムテクノロジーズ | リチウムイオン二次電池負極材用粉末、これを用いたリチウムイオン二次電池負極およびキャパシタ負極、ならびにリチウムイオン二次電池およびキャパシタ |
WO2014002356A1 (ja) * | 2012-06-25 | 2014-01-03 | 株式会社大阪チタニウムテクノロジーズ | リチウムイオン二次電池負極材用粉末、これを用いたリチウムイオン二次電池負極およびキャパシタ負極、ならびにリチウムイオン二次電池およびキャパシタ |
JPWO2014002356A1 (ja) * | 2012-06-25 | 2016-05-30 | 株式会社大阪チタニウムテクノロジーズ | リチウムイオン二次電池負極材用粉末、これを用いたリチウムイオン二次電池負極およびキャパシタ負極、ならびにリチウムイオン二次電池およびキャパシタ |
CN110010880A (zh) * | 2012-10-26 | 2019-07-12 | 日立化成株式会社 | 锂离子二次电池用负极材料、锂离子二次电池用负极和锂离子二次电池 |
US10693130B2 (en) | 2012-10-26 | 2020-06-23 | Hitachi Chemical Company, Ltd. | Negative electrode material for lithium ion secondary battery, negative electrode for lithium ion secondary battery, and lithium ion secondary battery |
JPWO2014065417A1 (ja) * | 2012-10-26 | 2016-09-08 | 日立化成株式会社 | リチウムイオン二次電池用負極材料、リチウムイオン二次電池用負極及びリチウムイオン二次電池 |
US11251421B2 (en) | 2012-10-26 | 2022-02-15 | Showa Denko Materials Co., Ltd. | Negative electrode material for lithium ion secondary battery, negative electrode for lithium ion secondary battery, and lithium ion secondary battery |
CN110635124A (zh) * | 2012-10-26 | 2019-12-31 | 日立化成株式会社 | 锂离子二次电池用负极材料、锂离子二次电池用负极和锂离子二次电池 |
CN104737337A (zh) * | 2012-10-26 | 2015-06-24 | 日立化成株式会社 | 锂离子二次电池用负极材料、锂离子二次电池用负极和锂离子二次电池 |
CN110635123A (zh) * | 2012-10-26 | 2019-12-31 | 日立化成株式会社 | 锂离子二次电池用负极材料、锂离子二次电池用负极和锂离子二次电池 |
CN110021735A (zh) * | 2012-10-26 | 2019-07-16 | 日立化成株式会社 | 锂离子二次电池用负极材料、锂离子二次电池用负极和锂离子二次电池 |
TWI624984B (zh) * | 2012-10-26 | 2018-05-21 | 日立化成股份有限公司 | 鋰離子二次電池用負極材料、鋰離子二次電池用負極及鋰離子二次電池 |
WO2014065417A1 (ja) * | 2012-10-26 | 2014-05-01 | 日立化成株式会社 | リチウムイオン二次電池用負極材料、リチウムイオン二次電池用負極及びリチウムイオン二次電池 |
JP2015530704A (ja) * | 2012-12-06 | 2015-10-15 | エルジー・ケム・リミテッド | リチウム二次電池用高容量負極活物質、その製造方法、及びそれを含むリチウム二次電池 |
JP2014175071A (ja) * | 2013-03-06 | 2014-09-22 | Sony Corp | 二次電池用活物質、二次電池用電極、二次電池、電池パック、電動車両、電力貯蔵システム、電動工具および電子機器 |
JP2015022964A (ja) * | 2013-07-22 | 2015-02-02 | 株式会社デンソー | リチウムイオン二次電池用負極材料,その製造方法及びリチウムイオン二次電池 |
US9742007B2 (en) | 2014-02-27 | 2017-08-22 | Sony Corporation | Active material, electrode, secondary battery, battery pack, electric vehicle, electric power storage system, electric power tool, and electronic apparatus |
JP2017199657A (ja) * | 2016-04-21 | 2017-11-02 | 信越化学工業株式会社 | 負極活物質、混合負極活物質材料、及び負極活物質の製造方法 |
JP6995488B2 (ja) | 2016-04-21 | 2022-02-04 | 信越化学工業株式会社 | 負極活物質、混合負極活物質材料、及び負極活物質の製造方法 |
JPWO2018198377A1 (ja) * | 2017-04-28 | 2020-03-12 | 日立化成株式会社 | リチウムイオン二次電池用負極材、リチウムイオン二次電池用負極、及びリチウムイオン二次電池 |
US10446846B2 (en) | 2017-08-24 | 2019-10-15 | Toyota Jidosha Kabushiki Kaisha | Negative electrode active material particle, negative electrode, lithium ion secondary battery, and method of producing negative electrode active material particle |
US20210028438A1 (en) * | 2018-06-12 | 2021-01-28 | Lg Chem, Ltd. | Negative electrode active material for lithium secondary battery and lithium secondary battery comprising the same |
JP7420836B2 (ja) | 2019-10-22 | 2024-01-23 | 博賽利斯(南京)有限公司 | 電極材料用のシリカ粒子及びその製造方法と適用 |
JP2022514713A (ja) * | 2019-11-14 | 2022-02-14 | 寧徳新能源科技有限公司 | 負極材料、並びにそれを含む電気化学装置及び電子装置 |
JP7349498B2 (ja) | 2019-11-14 | 2023-09-22 | 寧徳新能源科技有限公司 | 負極材料、並びに、それを含む電気化学装置及び電子装置 |
JP7350072B2 (ja) | 2019-11-14 | 2023-09-25 | 寧徳新能源科技有限公司 | 負極材料、並びにそれを含む電気化学装置及び電子装置 |
JP2022515216A (ja) * | 2019-11-14 | 2022-02-17 | 寧徳新能源科技有限公司 | 負極材料、並びにそれを含む電気化学装置及び電子装置 |
EP4080610A4 (en) * | 2019-12-20 | 2023-06-21 | Posco | METHOD OF MANUFACTURE OF ANODE MATERIAL FOR LITHIUM SECONDARY BATTERY, ACTIVE ANODE MATERIAL FOR LITHIUM SECONDARY BATTERY MANUFACTURED BY METHOD, AND LITHIUM SECONDARY BATTERY WITH THE ACTIVE ANODE MATERIAL |
WO2022259914A1 (ja) | 2021-06-08 | 2022-12-15 | 信越化学工業株式会社 | 負極活物質、負極及びリチウムイオン二次電池 |
WO2022259920A1 (ja) | 2021-06-08 | 2022-12-15 | 信越化学工業株式会社 | 負極活物質、負極及びリチウムイオン二次電池 |
KR20240019115A (ko) | 2021-06-08 | 2024-02-14 | 신에쓰 가가꾸 고교 가부시끼가이샤 | 부극 활물질, 부극 및 리튬 이온 이차 전지 |
KR20240019114A (ko) | 2021-06-08 | 2024-02-14 | 신에쓰 가가꾸 고교 가부시끼가이샤 | 부극 활물질, 부극 및 리튬 이온 이차 전지 |
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JP5648070B2 (ja) | 2015-01-07 |
JPWO2012077268A1 (ja) | 2014-05-19 |
KR20130101097A (ko) | 2013-09-12 |
CN103229336A (zh) | 2013-07-31 |
KR101513820B1 (ko) | 2015-04-20 |
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