WO2011077654A1 - 非水系二次電池用負極活物質およびその製造方法 - Google Patents
非水系二次電池用負極活物質およびその製造方法 Download PDFInfo
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- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a non-aqueous secondary battery such as a lithium ion secondary battery, and particularly relates to an active material for a non-aqueous secondary battery.
- a lithium ion secondary battery has an active material capable of inserting and removing lithium (Li) in each of a positive electrode and a negative electrode. And it operate
- the performance of the secondary battery depends on the materials of the positive electrode, the negative electrode, and the electrolyte constituting the secondary battery. Among them, active research and development of active material forming active material is being actively conducted.
- silicon oxide SiO x: x is about 0.5 ⁇ x ⁇ 1.5
- SiO x decomposes into Si and SiO 2 when heat-treated. This is called a disproportionation reaction, and if it is a homogeneous solid silicon monoxide SiO having a ratio of Si to O of approximately 1: 1, it is separated into two phases of Si phase and SiO 2 phase by solid internal reaction. .
- the Si phase obtained by separation is very fine.
- the SiO 2 phase covering the Si phase has a function of suppressing decomposition of the electrolytic solution. Therefore, the secondary battery using the negative electrode active material obtained by decomposing SiO x into Si and SiO 2 has excellent cycle characteristics.
- Patent Document 1 discloses a nanocomposite containing Si, SiO 2 and a metal oxide.
- Example 1 of Patent Document 2 SiO 2 , Si and B 2 O 3 were heat-treated at 800 ° C. under reduced pressure, and then rapidly cooled to obtain a composite in which SiO 1.48 was doped with B.
- JP 2009-70825 A Japanese Patent Laid-Open No. 2005-259697
- the negative electrode active material contains SiO 2 , the initial charge / discharge efficiency is deteriorated. This is because, for example, when SiO 2 occludes lithium ions, a stable compound (Li 4 SiO 4 ) is formed, and lithium ions are hardly released, resulting in an irreversible capacity.
- SiO 2 occludes lithium ions
- a stable compound Li 4 SiO 4
- lithium ions are hardly released, resulting in an irreversible capacity.
- the cycle characteristics deteriorate. Therefore, there is a demand for a novel silicon oxide-based negative electrode active material that replaces the conventional negative electrode active material mainly containing Si phase and SiO 2 phase, and a method for producing the same.
- an object of the present invention is to provide a novel negative electrode active material containing silicon and a method for producing the same.
- M-Si—O phase M—Si—O-based composite oxide phase
- M-Si—O phase M—Si—O phase
- M-Si—O phase M—Si—O phase
- the M-Si-O phase sufficiently exerts the effect of suppressing the decomposition of the electrolytic solution in a smaller amount than the SiO 2 phase.
- the inventors of the present invention have developed the results and completed various inventions described below.
- the negative electrode active material for a non-aqueous secondary battery of the present invention includes at least a silicon phase and a composite oxide phase containing silicon and at least one element selected from the group consisting of Group 2 (Group 2A) elements of the periodic table. It is characterized by that.
- the method for producing a negative electrode active material for a non-aqueous secondary battery according to the present invention is a method for producing the negative electrode active material for a non-aqueous secondary battery according to the present invention,
- the negative electrode active material for a non-aqueous secondary battery of the present invention mainly includes a silicon (Si) phase and the above composite oxide phase.
- a silicon (Si) phase can be easily obtained by reacting silicon oxide with the above silicon compound.
- the composite oxide phase sufficiently exhibits the effect of suppressing the decomposition of the electrolytic solution in a smaller amount than the SiO 2 phase. Therefore, even if the proportion of the negative electrode active material occupied by the Si phase is increased, the cycle characteristics are unlikely to deteriorate. Since the ratio of the Si phase can be increased and it is not necessary to include the SiO 2 phase, the initial charge / discharge efficiency is also improved.
- the negative electrode active material for a non-aqueous secondary battery of the present invention mainly includes a silicon phase and a composite oxide phase containing at least one element selected from the group consisting of Group 2 (Group 2A) elements of the periodic table and silicon.
- the SiO and CaSi 2 7 is an X-ray diffraction pattern of the reaction product obtained by heat treatment (CVD process) after milling 1 molar ratio.
- the charging / discharging curve of a lithium secondary battery provided with the negative electrode containing the negative electrode active material for non-aqueous secondary batteries of this invention is shown. It is a graph which shows the cycling characteristics of a lithium secondary battery provided with the negative electrode containing the negative electrode active material for non-aqueous secondary batteries of this invention, Comprising: The charge capacity in each cycle is shown.
- SiO silicon monoxide
- 3 is an X-ray diffraction pattern of a reaction product obtained by mixing and milling SiO and CaSi 2 at a molar ratio of 3: 1 and then heat-treating at 900 ° C. for 6 hours.
- 3 is an X-ray diffraction pattern of a reaction product obtained by mixing and milling SiO and CaSi 2 at a molar ratio of 4: 1 and then heat-treating at 900 ° C. for 6 hours.
- It is a graph which shows the cycle characteristic of a lithium secondary battery provided with the negative electrode containing the negative electrode active material for non-aqueous secondary batteries of this invention, Comprising: A discharge capacity maintenance factor is shown.
- It is a graph which shows the cycle characteristic of a lithium secondary battery provided with the negative electrode containing the negative electrode active material for non-aqueous secondary batteries of this invention, Comprising: Charging / discharging efficiency is shown.
- the numerical range “p to q” described in this specification includes the lower limit p and the upper limit q.
- the numerical range can be configured by arbitrarily combining the numerical values described in the present specification within the numerical range.
- the method for producing a negative electrode active material for a non-aqueous secondary battery according to the present invention includes a composite oxide phase containing at least a silicon phase and at least one element selected from the group consisting of Group 2 (Group 2A) elements of the periodic table and silicon. And a method for producing a negative electrode active material for a non-aqueous secondary battery.
- This production method mainly includes a raw material preparation step for preparing a mixed raw material and a reaction step for reacting the mixed raw material. Below, each process is demonstrated.
- the raw material preparation step is a step of preparing a mixed raw material containing at least silicon oxide and a silicon compound.
- Usable silicon oxide is preferably represented by the composition formula SiO n (0.1 ⁇ n ⁇ 2). Specifically, silicon monoxide (SiO), silicon dioxide (SiO 2 ), and silicon oxide having a composition slightly deviated from SiO or SiO 2 are also included. A single silicon may be included together with silicon oxide.
- the silicon compound contains at least one element selected from the group consisting of Group 2 (Group 2A) elements of the periodic table and silicon. Note that Group 2 of the periodic table belongs to the former Group 2A.
- a silicon compound containing at least one of group 2 elements can be used.
- group 2 elements that is, beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba) and radium (Ra)
- first principle calculation described below.
- an electronic state calculation program based on a density functional method using an ultrasoft pseudopotential was used as a calculation program.
- GGA generalized density gradient correction
- the calculation method to be used is not limited to the density functional method, and may be any method that can predict the electronic state of a substance with high accuracy by first-principles calculation.
- First-principles calculations can determine the crystal structure and electronic state of a substance without referring to experimental values.
- the reaction formula: xSiO 2 + M y Si z ⁇ aSi + b (M ⁇ Si—O) the generation energy ( ⁇ H) is obtained by first-principles calculation, but the obtained ⁇ H value is not significantly different from the experimental value. It is known.
- Table 1 shows the reaction formula obtained by the first principle calculation and the value of ⁇ H obtained by the first principle calculation.
- Si phase Si phase
- M-Si—O phase composite oxide phase
- a silicon compound containing at least one element selected from the group consisting of group 2 elements, preferably Mg and alkaline earth metal elements (Ca, Sr, Ba and Ra) and silicon can be used as a mixed raw material. It can be said that.
- the silicon oxide and the silicon compound described in the reaction formula of Table 1 are not limited to the silicon oxide and the silicon compound, and the silicon oxide and the silicon compound have a composition in which the generation energy ( ⁇ H) obtained by the first principle calculation is a negative value, and ⁇ H Can be used as a mixed raw material if they are mixed at a negative molar ratio.
- the silicon compound may be a binary compound containing Si and Ca, such as CaSi 2 , but may be a ternary or higher compound. Specifically, CaMgSi, CaNi 2 Si 2 , CaCu 2 Si 2 or the like can be used. However, calcium silicates such as CaSiO 3 are excluded.
- the raw material preparation step may be a step of preparing a mixed raw material powder containing a silicon oxide-based powder containing silicon oxide and a silicon compound-based powder containing a silicon compound.
- silicon oxide may be classified (screened) to 50 ⁇ m or less, further 35 ⁇ m or less, and silicon compounds may be classified to 500 ⁇ m or less, further 450 ⁇ m or less, and 50 ⁇ m or less.
- the silicon oxide powder is classified so as to include particles larger than the silicon compound powder so that the silicon oxide particles are covered.
- the silicon compound-based powder tends to adhere to the surface.
- the silicon oxide powder may be classified (sieved) to 50 ⁇ m or less, further 35 ⁇ m or less, and the silicon compound powder may be classified to 30 ⁇ m or less, further 20 ⁇ m or less.
- the powder containing silicon monoxide particles may be directly subjected to the reaction step, or the powder containing silicon monoxide particles may be used as the raw silicon oxide powder.
- the silicon oxide powder containing two phases of SiO 2 phase and Si phase may be used. That is, the negative electrode active material manufacturing method of the present invention is performed before the raw material preparation step, and is obtained by disproportionating the silicon monoxide raw material silicon oxide powder containing the silicon monoxide powder into a SiO 2 phase and a Si phase. A disproportionation step for obtaining a silicon-based powder may be included.
- the disproportionation step, Si and O and the atomic ratio of approximately 1: 1 homogeneous solid at a silicon monoxide is Si by the reaction of an internal solid
- the disproportionation reaction which separates into two phases of the phase and SiO 2 phase proceeds. That is, the silicon oxide-based powder obtained after the disproportionation step includes silicon oxide-based particles including a Si phase and a SiO 2 phase.
- the raw material silicon oxide powder containing amorphous silicon monoxide powder is subjected to heat treatment at 800 to 1200 ° C. for 1 to 5 hours in an inert atmosphere such as vacuum or in an inert gas.
- a silicon oxide-based powder containing two phases of an amorphous SiO 2 phase and a crystalline Si phase is obtained.
- the reaction step is a step of reacting the mixed raw materials.
- the reaction between silicon oxide and the silicon compound proceeds by applying energy.
- a method of heating a mixed raw material, milling a mixed raw material, or the like can be given.
- the heat treatment is the simplest because it only heats the mixed raw material. Milling is said not only to mix raw materials, but also to refine particles and cause chemical atomic diffusion at the solid phase interface. Therefore, the composite powder obtained by milling has a form different from a simple mixed powder.
- the method for producing a negative electrode active material of the present invention includes a milling step of milling a mixed raw material powder containing a silicon oxide powder and a silicon compound powder in an inert atmosphere as a reaction step. It is considered that the silicon oxide powder and the silicon compound powder are refined by adding mechanical energy by milling, and the silicon oxide and the silicon compound react at the solid phase interface. That is, part of the mechanical energy of milling contributes to chemical atomic diffusion at the solid phase interface between the silicon oxide powder and the silicon compound powder, and forms a silicon compound phase, a silicon phase, and the like.
- Milling is preferably performed in an inert atmosphere such as in argon gas in order to suppress oxidation of raw material powder and unexpected reaction. Moreover, although it is thought that diffusion is accelerated
- each powder may be mixed using a V-type mixer, ball mill, attritor, jet mill, vibration mill, high energy ball mill, or the like. It is desirable because the powders are uniformly mixed and the particles become finer. If a ball milling device is used, the balls introduced together with the raw material powder are preferably made of zirconia, and may be substantially spherical with a diameter of 3 to 20 mm. The milling conditions should be appropriately selected according to the amount and type of raw material powder to be milled.
- the degree of milling is daringly specified, at least crystalline Si is clearly observed when only X-ray diffraction measurement is performed after milling only a silicon oxide-based powder containing a crystalline silicon phase produced by a disproportionation reaction. It is desirable to perform milling until it becomes amorphous to such an extent that a large diffraction peak cannot be detected.
- the rotation speed of the container of the ball milling device is preferably 500 rpm or more, 700 rpm or more, more preferably 700 to 800 rpm, and the mixing time is 10 to 50 hours.
- the reaction between the silicon oxide powder and the silicon compound powder can be further promoted. That is, the complex oxide phase increases due to the heat treatment.
- the silicon phase may be disproportionated by heat treatment to increase the silicon phase.
- the reaction temperature should be equal to or higher than the decomposition temperature of silicon oxide, specifically 800 ° C. or higher, 800 to 1200 ° C. 850-1000 ° C.
- a negative active material for a non-aqueous secondary battery containing a finely structured silicon phase and composite oxide phase by holding for 1 hour or more, 1.5 hours or more, 3 hours or more, or 5 to 7 hours in a desired temperature range Is obtained. If it is less than 1 hour, silicon oxide and the silicon compound do not react sufficiently, and a large amount of unreacted substances are likely to remain. The longer the holding time, the finer silicon phase and complex oxide phase are produced, but 10 hours or less is practical.
- heat treatment for the purpose of disproportionation of silicon monoxide the same treatment as the disproportionation step described above may be performed, but heat treatment at 800 to 1100 ° C. for 1 to 5 hours is performed. This is desirable because a crystalline silicon phase is produced.
- the atmosphere of the reaction step it is preferable to carry out in an inert atmosphere such as vacuum or argon gas in order to suppress oxidation of the composite powder and an unexpected reaction.
- an inert atmosphere such as vacuum or argon gas
- the heat treatment step only needs to be performed mainly for the purpose of generating a composite oxide phase, but if it is within a predetermined temperature range, it is performed in parallel with other treatments such as surface treatment of the composite particle surface. May be.
- a CVD process for forming a carbon-based film on the surface of the composite particle may be performed after the milling step.
- the formation of the carbon film is expected to improve conductivity.
- the formation of the carbon-based film by the CVD process is performed in an atmosphere in which the oxygen concentration is reduced and the composite powder is heated to a certain high temperature during the process. Therefore, the above crystallization process or disproportionation process is performed simultaneously with the CVD process. It becomes possible.
- a non-aqueous secondary battery including at least a silicon phase and a composite oxide phase containing silicon and at least one element selected from the group consisting of Group 2 (Group 2A) elements of the periodic table
- a negative electrode active material is obtained.
- the silicon phase and the composite oxide phase can be confirmed by, for example, X-ray diffraction (XRD) measurement.
- XRD X-ray diffraction
- the obtained negative electrode active material for a non-aqueous secondary battery is obtained with a composition and structure according to the type of raw material powder and the preparation procedure.
- the silicon oxide powder contains silicon monoxide particles
- the SiO phase remains unless exposed to a high temperature that is disproportionated in the production process.
- the silicon monoxide is disproportionated, and a negative electrode active material containing a Si phase and a SiO 2 phase is obtained.
- a composite oxide phase is formed in the reaction step. In the milling process alone, the composite oxide is formed by concentrating on the surface layer of the secondary particles, but by further heat treatment after milling, the reaction proceeds to the vicinity of the center of the secondary particles and the composite oxide phase increases. I can guess.
- the reaction product obtained after the reaction step may be sintered and hardened, it may be pulverized after the reaction step.
- a V-type mixer, a ball mill, a vibration mill, a high energy ball mill or the like may be used.
- the particle size becomes suitable for producing a negative electrode for a non-aqueous secondary battery.
- the reaction product after pulverization may be classified to 20 ⁇ m or less, further 5 ⁇ m or less, and then used for production of a negative electrode.
- a negative electrode for a non-aqueous secondary battery is produced using the negative electrode active material for a non-aqueous secondary battery.
- the negative electrode for a non-aqueous secondary battery mainly includes a negative electrode active material, a conductive additive, and a binder that binds the negative electrode active material and the conductive additive.
- the negative electrode active material is the above-described negative electrode active material for non-aqueous secondary batteries.
- you may add and use another already known negative electrode active material for example, graphite, Sn, Si, etc.
- a material generally used for an electrode of a lithium secondary battery may be used.
- conductive carbon materials such as carbon black (carbonaceous fine particles) such as acetylene black and ketjen black, and carbon fibers.
- known conductive materials such as conductive organic compounds are also used.
- An auxiliary agent may be used. One of these may be used alone or in combination of two or more.
- the binder is not particularly limited, and a known one may be used.
- a resin that does not decompose even at a high potential such as a fluorine-containing resin such as polytetrafluoroethylene or polyvinylidene fluoride, can be used.
- the negative electrode active material is generally used in a state in which the negative electrode is pressed onto a current collector as an active material layer.
- a metal mesh or metal foil can be used for the current collector.
- a current collector made of copper or copper alloy may be used.
- the method for producing the negative electrode is not particularly limited, and may be performed in accordance with a generally practiced method for producing an electrode for a non-aqueous secondary battery.
- the conductive additive and the binder are mixed with the negative electrode active material, and an appropriate amount of an organic solvent is added as necessary to obtain a paste-like electrode mixture.
- the electrode mixture is applied to the surface of the current collector, dried, and then pressed and pressed as necessary. According to this manufacturing method, the produced electrode becomes a sheet-like electrode. This sheet-like electrode may be cut into dimensions according to the specifications of the non-aqueous secondary battery to be produced.
- Non-aqueous secondary battery A non-aqueous secondary battery is composed of the positive electrode, the negative electrode for a non-aqueous secondary battery, and a non-aqueous electrolyte solution in which an electrolyte material is dissolved in an organic solvent.
- This non-aqueous secondary battery includes a separator and a non-aqueous electrolyte sandwiched between a positive electrode and a negative electrode in addition to a positive electrode and a negative electrode, as in a general secondary battery.
- the separator separates the positive electrode and the negative electrode and holds the non-aqueous electrolyte, and a thin microporous film such as polyethylene or polypropylene can be used.
- the nonaqueous electrolytic solution is obtained by dissolving an alkali metal salt as an electrolyte in an organic solvent.
- an organic solvent there is no limitation in particular in the kind of nonaqueous electrolyte solution used with a nonaqueous secondary battery provided with said negative electrode for nonaqueous secondary batteries.
- aprotic organic solvents such as propylene carbonate (PC), ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC) and the like. Can be used.
- an alkali metal salt that is soluble in an organic solvent such as LiPF 6 , LiBF 4 , LiAsF 6 , LiI, LiClO 4 , NaPF 6 , NaBF 4 , NaAsF 6 , LiBOB can be used.
- the negative electrode is as described above.
- the positive electrode includes a positive electrode active material into which alkali metal ions can be inserted and removed, and a binder that binds the positive electrode active material. Further, a conductive aid may be included.
- the positive electrode active material, the conductive additive, and the binder are not particularly limited as long as they can be used in the nonaqueous secondary battery. Specifically, examples of the positive electrode active material include LiCoO 2 , LiNi 1/3 Co 1/3 Mn 1/3 O 2 , Li 2 MnO 2 , and S.
- the current collector may be any material that is generally used for the positive electrode of a non-aqueous secondary battery, such as aluminum, nickel, and stainless steel.
- the shape of the non-aqueous secondary battery is not particularly limited, and various shapes such as a cylindrical shape, a stacked shape, and a coin shape can be adopted. Regardless of the shape, a separator is sandwiched between the positive electrode and the negative electrode to form an electrode body, and the space between the positive electrode current collector and the negative electrode current collector to the positive electrode terminal and the negative electrode terminal is used for current collection. After connecting using a lead or the like, the electrode body is sealed in a battery case together with a non-aqueous electrolyte to form a battery.
- Example 1-1 Heat-treated SiO powder and CaSi 2 powder (High Purity Chemical Laboratory Co., Ltd.) were prepared.
- the heat-treated SiO powder was obtained by heat-treating amorphous SiO powder (Sigma Aldrich Japan Co., Ltd.) in a vacuum at 1100 ° C. for 5 hours. After classifying the heat-treated SiO powder to 31 ⁇ m or less and the CaSi 2 powder to 15 ⁇ m or less, 3.81 g of the heat-treated SiO powder and 1.19 g of CaSi 2 powder were weighed, and the heat-treated SiO powder and CaSi 2 powder were 7: 1 ( A raw material powder contained in a molar ratio) was obtained.
- Example 1-2 A composite powder (negative electrode active material # 12) was obtained in the same manner as in Example 1-1 except that untreated amorphous SiO powder not subjected to disproportionation treatment was used instead of the heat treated SiO powder.
- Table 2 shows the production conditions for each of the examples and comparative examples.
- X-ray diffraction measurement> XRD measurement using CuK ⁇ was performed on the powder obtained by subjecting the composite powder (negative electrode active material # 11) obtained in Example 1-1 to CVD. Moreover, in order to compare with the raw material powder before milling, the same measurement was performed on the heat-treated SiO powder # C1 used as the raw material. The results are shown in FIG. 1 and FIG. 1 and 2 indicate the peak positions of Si, CaSiO 3 , and SiO 2 calculated from the inter-surface distance d described in the ASTM card.
- An electrode (negative electrode) was prepared using any of the negative electrode active materials described above.
- a negative electrode active material composite powder
- ketjen black (KB) as a conductive additive were mixed to obtain a mixed powder.
- the compounding ratio of the negative electrode active material, KB, and binder (solid content) was 80.75: 4.25: 15 by mass ratio.
- the prepared slurry was applied to the surface of an electrolytic copper foil (current collector) having a thickness of 18 ⁇ m using a doctor blade, and a negative electrode active material layer was formed on the copper foil. Then, it dried at 80 degreeC for 20 minute (s), and NMP was volatilized and removed from the negative electrode active material layer. After drying, the current collector and the negative electrode active material layer were firmly and closely joined with a roll press. This was heated and cured at 200 ° C. for 2 hours to obtain an electrode having an active material layer thickness of about 15 ⁇ m.
- a lithium secondary battery (half cell) was produced using the electrode produced by the above procedure as an evaluation electrode.
- the counter electrode was a metal lithium foil (thickness 500 ⁇ m).
- the counter electrode was cut to ⁇ 13 mm, the evaluation electrode was cut to ⁇ 11 mm, and a separator (Hoechst Celanese glass filter and celgard 2400) was sandwiched between them to form an electrode body battery.
- This electrode body battery was accommodated in a battery case (CR2032 coin cell manufactured by Hosen Co., Ltd.).
- the initial charge / discharge efficiency is a value determined by a percentage ((initial charge capacity) / (initial discharge capacity) ⁇ 100) obtained by dividing the initial charge capacity by the initial discharge capacity.
- the cycle characteristics are from 1 to 5th cycle, under a temperature environment of 25 ° C., charged at a constant current of 0.05 mA to a discharge end voltage of 0.01 V on the basis of metallic Li, and then 0 to a discharge end voltage of 2 V.
- Charging / discharging for discharging and charging at a constant current of .05 mA was repeated. Subsequently, charging / discharging was repeated at 0.1 mA for the 6th to 10th cycles, 0.2 mA for the 11th to 15th cycles, and 0.05 mA for the 16th to 20th cycles.
- the final charge / discharge voltage was 0.01 to 2 V in all cycles.
- the charge capacity in each cycle is shown in FIG.
- the capacity retention rate is a value obtained by a percentage ((N-cycle discharge capacity) / (first-cycle discharge capacity) ⁇ 100) obtained by dividing the N-cycle charge capacity by the initial charge capacity. is there. N is an integer of 1 to 15.
- the lithium secondary batteries A1 and A2 were excellent in both initial charge / discharge efficiency and cycle characteristics. Moreover, the initial charge / discharge efficiency and cycle characteristics of the lithium secondary battery C1 were superior to the lithium secondary battery C2. In other words, it was found that when the heat-treated SiO powder was milled, the initial charge / discharge efficiency and cycle characteristics were lowered by the energy generated by milling affecting the structure of the Si phase related to the insertion and release of Li. However, the lithium secondary battery A1 using the negative electrode active material # 11 obtained by milling the heat-treated SiO powder (# C1) together with the CaSi 2 powder showed excellent initial charge / discharge efficiency and cycle characteristics. That is, in the preparation of # 11, the energy of milling is hardly act on the Si phase, could be inferred that it was consumed in the reaction with the CaSi 2 of SiO 2 and CaSi 2 powder heat treatment SiO powder.
- Example 2-1 SiO powder (Sigma Aldrich Japan Co., Ltd.) and CaSi 2 powder (High Purity Chemical Laboratory Co., Ltd.) were prepared. After the SiO powder was classified to 45 ⁇ m or less and the CaSi 2 powder was classified to 425 ⁇ m or less, 2.89 g (0.066 mol) of the SiO powder and 2.11 g (0.022 mol) of the CaSi 2 powder were weighed to obtain a planetary ball mill (Fritsch). -Using P-7) manufactured by Japan Co., Ltd., mixing was performed at 700 rpm for 50 hours to prepare a mixed raw material. In order to further react the SiO powder and the CaSi 2 powder, the obtained mixed raw material was kept at 900 ° C. for 2 hours in an argon gas atmosphere. Thereafter, the heated mixed raw material was allowed to cool to obtain a reaction product. This reaction product was designated as # 21.
- Example 2-2 Reaction product # 22 was obtained in the same manner as in Example 1 except that the mixing conditions were 700 rpm for 74 hours and the reaction conditions were 900 ° C. for 6 hours. This reaction product was pulverized using the above planetary ball mill at a rotation speed of 700 rpm for 10 hours.
- Example 2-3 Weigh 3.23 g (0.073 mol) of the SiO powder and 1.77 g (0.018 mol) of the CaSi 2 powder, and use a planetary ball mill (P-7 manufactured by Fritsch Japan Co., Ltd.) at 50 rpm at a rotation speed of 700 rpm. It mixed for time and the mixed raw material was prepared. In order to further react the SiO powder and the CaSi 2 powder, the obtained mixed raw material was kept at 900 ° C. for 6 hours in an argon gas atmosphere. Thereafter, the heated mixed raw material was allowed to cool to obtain a reaction product. This reaction product was designated as # 23. This reaction product was pulverized using the above planetary ball mill at a rotation speed of 700 rpm for 10 hours.
- P-7 manufactured by Fritsch Japan Co., Ltd.
- Example 2-4 The reaction product # 24 was prepared in the same manner as in Example 3 except that the mixing ratio of the mixed raw materials was changed (SiO powder: 2.39 g (0.054 mol), CaSi 2 powder: 2.61 g (0.027 mol)). Obtained. This reaction product was pulverized using the above planetary ball mill at a rotation speed of 700 rpm for 10 hours.
- Table 4 shows the production conditions for each of the examples and comparative examples.
- Example 2-4 2SiO + CaSi 2 ⁇ 2 / 3CaSiO 3 + 1 / 3CaSi 2 + 8 / 3Si
- a lithium secondary battery including an electrode (negative electrode) using any one of the reaction products # 21 to # 24 and # C3 as a negative electrode active material was produced. Any of the reaction products (negative electrode active material) and ketjen black (KB) as a conductive additive were mixed to obtain a mixed powder. Also, alkoxy-containing silane-modified polyamic acid resin as a binder (produced by Arakawa Chemical Industries, solvent composition: N, N-dimethylacetamide (DMAc), cure residue 15.1%, viscosity) to N-methylpyrrolidone (NMP) 5100 mmPa ⁇ s / 25 ° C., silica in the cured residue, 2 wt%) was dissolved.
- DMAc N-dimethylacetamide
- NMP N-methylpyrrolidone
- This solution and a mixed powder of the reaction product and KB were mixed to prepare a slurry.
- the compounding ratio of the negative electrode active material, KB, and binder (solid content) was 80: 5: 15 by mass ratio.
- the prepared slurry was applied to the surface of an electrolytic copper foil (current collector) having a thickness of 18 ⁇ m using a doctor blade, and a negative electrode active material layer was formed on the copper foil. Then, it dried at 80 degreeC for 20 minute (s), and NMP was volatilized and removed from the negative electrode active material layer. After drying, the current collector and the negative electrode active material layer were firmly and closely joined with a roll press. This was heated and cured at 350 ° C.
- the counter electrode was a metal lithium foil (thickness 500 ⁇ m).
- the counter electrode was cut to ⁇ 13 mm and the negative electrode was cut to ⁇ 11 mm, and a separator (Hoechst Celanese glass filter, celgard 2400) was sandwiched between them to form an electrode body battery.
- This electrode body battery was accommodated in a battery case (CR2032 coin cell manufactured by Hosen Co., Ltd.).
- a non-aqueous electrolyte in which LiPF 6 was dissolved at a concentration of 1 M was injected into the battery case in a mixed solvent in which ethylene carbonate and diethyl carbonate were mixed at a ratio of 1: 1 (volume ratio).
- the battery case was sealed to obtain lithium secondary batteries (battery C3 and batteries B1 to B4).
- the initial charge / discharge efficiency is a value obtained as a percentage of the value obtained by dividing the initial charge capacity by the initial discharge capacity ((initial charge capacity) / (initial discharge capacity) ⁇ 100).
- Table 5 shows the conditions of the charge / discharge test, the initial discharge capacity, the initial charge capacity, and the initial efficiency.
- the initial charge / discharge efficiency of battery C3 using # C3 as the negative electrode active material was the lowest. This is presumably because a part of Li ions is occluded due to the generation of the SiO 2 phase.
- the initial efficiency of the battery B1 using the negative electrode active material of # 21 manufactured using the raw material powder containing CaSi 2 was improved as compared with the battery C3.
- the batteries B2 to B4 were subjected to a charge / discharge test under the same conditions. Among these, the battery B2 using # 22 as the negative electrode active material had the highest initial efficiency. This is considered to be because there was no SiO 2 phase causing the irreversible capacity, and only the Si phase and the CaSiO 3 phase were present.
- the battery B4 using # 24 as the negative electrode active material had the same initial efficiency as the batteries B2 and B3. Therefore, the negative electrode active material of # 24 is also considered to contain a Si phase and a CaSiO 3 phase because the generation of SiO 2 phase is suppressed.
- the discharge capacity retention ratio is a value obtained by dividing the N-th cycle discharge capacity by the initial discharge capacity ((N-cycle discharge capacity) / (first-cycle discharge capacity) ⁇ 100). It is.
- the charge / discharge efficiency is obtained as a percentage of the charge capacity of the Nth cycle divided by the discharge capacity of the Nth cycle ((charge capacity of the Nth cycle) / (discharge capacity of the Nth cycle) ⁇ 100). Value.
- N is an integer of 1 to 20.
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Abstract
Description
少なくとも、酸化珪素と、周期表2族(2A族)元素からなる群から選択された少なくとも一種の元素および珪素を含む珪素化合物と、を含む混合原料を調製する原料調製工程と、
前記混合原料を反応させる反応工程と、
を含むことを特徴とする。
本発明の非水系二次電池用負極活物質の製造方法は、少なくとも珪素相と、周期表2族(2A族)元素からなる群から選択された少なくとも一種の元素および珪素を含む複合酸化物相と、を含む非水系二次電池用負極活物質の製造方法である。本製造方法は、混合原料を調製する原料調製工程と、その混合原料を反応させる反応工程と、を主として含む。以下に、それぞれの工程を説明する。
上記の非水系二次電池用負極活物質を用い、非水系二次電池用負極が作製される。非水系二次電池用負極は、主として、負極活物質と、導電助材と、負極活物質および導電助材を結着する結着剤と、を含む。
正極と、上記の非水系二次電池用負極と、電解質材料を有機溶媒に溶解した非水電解液と、で非水系二次電池が構成される。この非水系二次電池は、一般の二次電池と同様、正極および負極の他に、正極と負極の間に挟装されるセパレータおよび非水電解液を備える。
熱処理SiO粉末およびCaSi2粉末(株式会社高純度化学研究所)を準備した。なお、熱処理SiO粉末は、非晶質SiO粉末(シグマ・アルドリッチ・ジャパン株式会社)を1100℃×5時間真空中で熱処理して不均化させて得た。
熱処理SiO粉末を31μm以下、CaSi2粉末を15μm以下にそれぞれ分級した後、熱処理SiO粉末を3.81g、CaSi2粉末を1.19g秤量し、熱処理SiO粉末とCaSi2粉末とを7:1(モル比)で含む原料粉末を得た。
原料粉末5gをZrO2製でφ12mmのボールが100個入ったZrO2製容器(容量:45cc)に投入し、遊星型ボールミル(フリッチュ・ジャパン株式会社製P-7)を用いてミリングして、複合粉末(負極活物質#11)を得た。ミリングは、アルゴンガス雰囲気において容器の回転数700rpmで10時間行った。
熱処理SiO粉末のかわりに、不均化処理を施さない未処理の非晶質SiO粉末を用いたほかは実施例1-1と同様にして、複合粉末(負極活物質#12)を得た。
上記の熱処理SiO粉末を負極活物質#C1とした。
上記の熱処理SiO粉末(5g)のみを実施例1-1と同様のミリング条件でミリングして、負極活物質#C2を得た。
実施例1-1で得られた複合粉末(負極活物質#11)に対してCVD処理を行った粉末について、CuKαを使用したXRD測定を行った。また、ミリング前の原料粉末と比較するために、原料として用いた熱処理SiO粉末#C1についても、同様の測定を行った。結果を図1および図2に示した。なお、図1および図2に示した●、▲および△は、ASTMカードに記載の面間隔dから算出したSiおよびCaSiO3、SiO2のピーク位置を示す。
(実施例1-1)
3.5Si+3.5SiO2+CaSi2→5Si+CaSiO3+2SiO2
(実施例1-2)
7SiO+CaSi2→4Si+4SiO+CaSiO3
上記のいずれかの負極活物質を用いて電極(負極)を作製した。
負極活物質(複合粉末)と、導電助剤としてのケッチェンブラック(KB)とを混合して混合粉末を得た。また、N-メチルピロリドン(NMP)に結着剤としてのポリアミドイミド-シリカハイブリッド樹脂(荒川化学工業製、溶剤組成:NMP/キシレン=4/1、硬化残分30.0%、硬化残分中のシリカ:2%(割合は全て質量比)、粘度8700mPa・S/25℃)を溶解させた。この溶液と、複合粉末とKBとの混合粉末と、を混合してスラリーを調製した。負極活物質、KBおよび結着剤(固形分)の配合比は、質量比で80.75:4.25:15であった。調製したスラリーを、厚さ18μmの電解銅箔(集電体)の表面にドクターブレードを用いて塗布し、銅箔上に負極活物質層を形成した。その後、80℃で20分間乾燥し、負極活物質層からNMPを揮発させて除去した。乾燥後、ロールプレス機により、集電体と負極活物質層を強固に密着接合させた。
これを200℃で2時間加熱硬化させて、活物質層の厚さが15μm程度の電極とした。
上記の手順で作製した電極を評価極として用い、リチウム二次電池(ハーフセル)を作製した。対極は、金属リチウム箔(厚さ500μm)とした。対極をφ13mm、評価極をφ11mmに裁断し、セパレータ(ヘキストセラニーズ社製ガラスフィルターおよびcelgard2400)を両者の間に挟装して電極体電池とした。この電極体電池を電池ケース(宝泉株式会社製CR2032コインセル)に収容した。また、電池ケースには、エチレンカーボネートとジエチルカーボネートとを1:1(体積比)で混合した混合溶媒にLiPF6を1Mの濃度で溶解した非水電解質を注入した。電池ケースを密閉して、リチウム二次電池(C1、C2、A1およびA2)を得た。
作製した四種類のリチウム二次電池に対して充放電試験を行い、初期充放電効率およびサイクル特性を評価した。
充放電試験は、25℃の温度環境のもと、金属Li基準で放電終止電圧0.01Vまで0.05mAの定電流で充電を行った後、充電終止電圧2Vまで0.05mAの定電流で放電を行った。「充電」は評価極の活物質がLiを吸蔵する方向、「放電」は評価極の活物質がLiを放出する方向、である。
充放電曲線を図3に示した。図3より、初期充電容量、1Vでの初期放電容量および2Vでの初期放電容量を読み取り、初期充放電効率を算出した。なお、初期充放電効率は、初期充電容量を初期放電容量で除した値の百分率((初期充電容量)/(初期放電容量)×100)で求められる値である。
各サイクルにおける充電容量を図4に、各サイクルにおける放電容量維持率を図5に、それぞれ示した。なお、容量維持率は、Nサイクル目の充電容量を初回の充電容量で除した値の百分率((Nサイクル目の放電容量)/(1サイクル目の放電容量)×100)で求められる値である。Nは1~15の整数である。
SiO粉末(シグマ・アルドリッチ・ジャパン株式会社)およびCaSi2粉末(株式会社高純度化学研究所)を準備した。SiO粉末を45μm以下、CaSi2粉末を425μm以下にそれぞれ分級した後、SiO粉末を2.89g(0.066mol)、CaSi2粉末を2.11g(0.022mol)秤量し、遊星型ボールミル(フリッチュ・ジャパン株式会社製P-7)を用い回転数700rpmで50時間混合し、混合原料を調製した。
SiO粉末とCaSi2粉末とをさらに反応させるため、得られた混合原料をアルゴンガス雰囲気中で900℃に2時間保った。その後、加熱した混合原料を放冷し、反応生成物を得た。この反応生成物を#21とした。
混合条件を700rpm74時間、反応条件を900℃6時間とした他は、実施例1と同様にして反応生成物#22を得た。この反応生成物を上記の遊星型ボールミルを用い回転数700rpm10時間で粉砕した。
上記SiO粉末を3.23g(0.073mol)、上記CaSi2粉末を1.77g(0.018mol)秤量し、遊星型ボールミル(フリッチュ・ジャパン株式会社製P-7)を用い回転数700rpmで50時間混合し、混合原料を調製した。
SiO粉末とCaSi2粉末とをさらに反応させるため、得られた混合原料をアルゴンガス雰囲気中で900℃に6時間保った。その後、加熱した混合原料を放冷し、反応生成物を得た。この反応生成物を#23とした。この反応生成物を上記の遊星型ボールミルを用い回転数700rpm10時間で粉砕した。
混合原料の混合割合を変更(SiO粉末:2.39g(0.054mol)、CaSi2粉末:2.61g(0.027mol))した他は、実施例3と同様にして反応生成物#24を得た。この反応生成物を上記の遊星型ボールミルを用い回転数700rpm10時間で粉砕した。
上記SiO粉末のみを900℃で2時間熱処理し、#C3の反応生成物を得た。
上記の反応生成物#21~23および#C3について、CuKαを使用したXRD測定を行った。結果を図6~図9に示す。#C3からは、Si相の存在を示す回折ピークが確認できた(図6)。一方、#21~23からは、Si相の存在を示す回折ピークとともにCaSiO3相の存在を示す回折ピークが確認できた(図7~図9)。特に、反応条件のうち反応時間が異なる#21の回折ピーク(図7)と#23の回折ピーク(図9)とを比較すると、#23の回折ピークの方の幅が広かった。反応時間を長くしたことで、微細なSi相およびCaSiO3相が生成されたからであると考えられる。
(比較例3)2SiO→Si+SiO2
(実施例2-1および2-2)
3SiO+CaSi2→4Si+CaSiO3
(実施例2-3)
4SiO+CaSi2→4.5Si+CaSiO3+0.5SiO2
(実施例2-4)
2SiO+CaSi2→2/3CaSiO3+1/3CaSi2+8/3Si
上記の反応生成物#21~24および#C3のうちのいずれかを負極活物質として用いた電極(負極)を備えるリチウム二次電池を作製した。
いずれかの反応生成物(負極活物質)と、導電助剤としてのケッチェンブラック(KB)とを混合して混合粉末を得た。また、N-メチルピロリドン(NMP)に結着剤としてのアルコキシ含有シラン変性ポリアミック酸樹脂(荒川化学工業製、溶剤組成:N,N-ジメチルアセトアミド(DMAc)、硬化残分15.1%、粘度5100mmPa・s/25℃、硬化残分中のシリカ、2wt%)を溶解させた。この溶液と、反応生成物とKBとの混合粉末と、を混合してスラリーを調製した。負極活物質、KBおよび結着剤(固形分)の配合比は、質量比で80:5:15であった。調製したスラリーを、厚さ18μmの電解銅箔(集電体)の表面にドクターブレードを用いて塗布し、銅箔上に負極活物質層を形成した。その後、80℃で20分間乾燥し、負極活物質層からNMPを揮発させて除去した。乾燥後、ロールプレス機により、集電体と負極活物質層を強固に密着接合させた。
これを350℃で10分間加熱硬化させて、活物質層の厚さが15μm程度の電極とした。
上記の手順で作製した電極を、それぞれ評価極として用い、四種類のリチウム二次電池C3およびB1~B3を作製した。対極は、金属リチウム箔(厚さ500μm)とした。対極をφ13mm、負極をφ11mmに裁断し、セパレータ(ヘキストセラニーズ社製ガラスフィルター,celgard2400)を両者の間に挟装して電極体電池とした。この電極体電池を電池ケース(宝泉株式会社製CR2032コインセル)に収容した。また、電池ケースには、エチレンカーボネートとジエチルカーボネートとを1:1(体積比)で混合した混合溶媒にLiPF6を1Mの濃度で溶解した非水電解質を注入した。電池ケースを密閉して、リチウム二次電池(電池C3および電池B1~B4)を得た。
作製した五種類のリチウム二次電池に対して充放電試験を行い、充放電特性を評価した。はじめに、初期充放電特性を評価した。充放電試験は、25℃の温度環境のもと、電池C3およびB1については、金属Li基準で放電終止電圧0.01Vまで0.2mAの定電流で放電を行った後、充電終止電圧1.2Vまで0.2mAの定電流で放電を行い、初期充放電効率を求めた。電池B2~B4については、金属Li基準で放電終止電圧0.01Vまで0.05mAの定電流で放電を行った後、充電終止電圧2Vまで0.05mAの定電流で放電を行い、初期充放電効率を求めた。初期充放電効率は、初回の充電容量を初回の放電容量で除した値の百分率((初回の充電容量)/(初回の放電容量)×100)で求められる値である。なお、充放電試験の条件と、初回の放電容量、初回の充電容量および初期効率を表5に示す。
電池B2~B4は、同じ条件で充放電試験を行った。これらのうちで、初期効率が最も高かったのは、負極活物質として#22を用いた電池B2であった。これは、不可逆容量の原因であるSiO2相がなく、Si相およびCaSiO3相のみが存在したためであると考えられる。
また、負極活物質として#24を用いた電池B4は、電池B2およびB3と同程度の初期効率であった。そのため、#24の負極活物質も、SiO2相の生成が抑えられ、Si相およびCaSiO3相を含むと考えられる。
サイクル特性を評価するために、初期充放電効率が高かった電池B2およびB3に対してさらに充放電試験を行った。初回の充放電試験後の最初の充放電試験を1サイクル目とし、5サイクル目まで同様の充放電を繰り返し行った。引き続き、6~10サイクル目は0.1mA、11~15サイクル目までは0.2mA、16~20サイクル目までは0.05mA、として充放電を繰り返し行った。充放電の終止電圧は、いずれのサイクルも0.01~2Vであった。
各サイクルで、電圧に対する電極活物質単位質量当たりの放電容量および充電容量を測定した。そして、各サイクルにおける放電容量維持率および充放電効率を算出した。結果を図10および図11に示す。
なお、放電容量維持率は、Nサイクル目の放電容量を初回の放電容量で除した値の百分率((Nサイクル目の放電容量)/(1サイクル目の放電容量)×100)で求められる値である。また、充放電効率は、Nサイクル目の充電容量をNサイクル目の放電容量で除した値の百分率((Nサイクル目の充電容量)/(Nサイクル目の放電容量)×100)で求められる値である。Nは1~20の整数である。
Claims (13)
- 少なくとも珪素相ならびに周期表2族(2A族)元素からなる群から選択された少なくとも一種の元素および珪素を含む複合酸化物相を含むことを特徴とする非水系二次電池用負極活物質。
- 酸化珪素を含有する酸化珪素系粉末および周期表2族(2A族)元素からなる群から選択された少なくとも一種の元素と珪素とを含む珪素化合物系粉末をミリングして複合化した複合粉末を含み、該複合粉末は前記珪素相および前記複合酸化物相を含む請求項1記載の非水系二次電池用負極活物質。
- 前記珪素化合物系粉末は、珪素およびカルシウムを含み、
前記複合粉末は、前記酸化珪素系粉末および前記珪素化合物系粉末が反応してなる前記珪素相およびCaSiO3を含む前記複合酸化物相と、を含む請求項2記載の非水系二次電池用負極活物質。 - 請求項1~3のいずれかに記載の非水系二次電池用負極活物質の製造方法であって、
少なくとも、酸化珪素と、周期表2族(2A族)元素からなる群から選択された少なくとも一種の元素および珪素を含む珪素化合物と、を含む混合原料を調製する原料調製工程と、
前記混合原料を反応させる反応工程と、
を含むことを特徴とする非水系二次電池用負極活物質の製造方法。 - 前記原料調製工程は、前記酸化珪素を含有する酸化珪素系粉末と、前記珪素化合物を含む珪素化合物系粉末と、を含む混合原料粉末を調製する工程であって、
前記反応工程は、前記混合原料粉末に不活性雰囲気中でミリングを施して該酸化珪素系粉末および該珪素化合物系粉末を複合化するミリング工程を含む請求項4記載の非水系二次電池用負極活物質の製造方法。 - 前記反応工程は、ミリング工程後に行われる熱処理工程を含む請求項4または5記載の非水系二次電池用負極活物質の製造方法。
- 前記原料調製工程の前に行われ、一酸化珪素粉末を含む原料酸化珪素粉末の一酸化珪素を二酸化珪素相と珪素相とに不均化して前記酸化珪素系粉末を得る不均化工程を含む請求項4~6のいずれかに記載の非水系二次電池用負極活物質の製造方法。
- 前記混合原料は、前記珪素化合物よりも前記酸化珪素をモル比で多く含む請求項5~7のいずれかに記載の非水系二次電池用負極活物質の製造方法。
- 前記酸化珪素および前記珪素化合物は、第一原理計算により求めた生成エネルギー(ΔH)が負の値となる組成をもち、かつΔHが負の値となるモル比で混合される請求項5~8のいずれかに記載の非水二次電池用負極活物質の製造方法。
- 前記珪素化合物は、マグネシウム(Mg)、カルシウム(Ca)、ストロンチウム(Sr)およびバリウム(Ba)からなる群から選択された少なくとも一種の元素を含む請求項5~9のいずれかに記載の非水系二次電池用負極活物質の製造方法。
- 前記珪素化合物はCaとSiとからなり、前記酸化珪素と該珪素化合物とのモル比が、1.5:1~8:1である請求項5~10のいずれかに記載の非水系二次電池用負極活物質の製造方法。
- 請求項5~11のいずれかに記載の製造方法により得られることを特徴とする非水系二次電池用負極活物質。
- 正極と、請求項1~4および12のいずれかに記載の非水系二次電池用負極活物質を含む負極と、非水電解質と、を備えることを特徴とする非水系二次電池。
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CN201080060349.4A CN102714307B (zh) | 2009-12-21 | 2010-12-08 | 非水系二次电池用负极活性物质及其制造方法 |
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WO2019131724A1 (ja) * | 2017-12-27 | 2019-07-04 | パナソニックIpマネジメント株式会社 | 二次電池用負極活物質及び二次電池 |
JP7257626B2 (ja) | 2017-12-27 | 2023-04-14 | パナソニックIpマネジメント株式会社 | 二次電池用負極活物質及び二次電池 |
KR20210092234A (ko) | 2018-11-16 | 2021-07-23 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | 양극 활물질, 이차 전지, 전자 기기, 및 차량 |
DE112019005722T5 (de) | 2018-11-16 | 2021-07-29 | Semiconductor Energy Laboratory Co., Ltd. | Positivelektrodenaktivmaterial, Sekundärbatterie, elektronisches Gerät und Fahrzeug |
KR20210103470A (ko) | 2018-12-17 | 2021-08-23 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | 양극 활물질 및 이차 전지 |
DE112019006253T5 (de) | 2018-12-17 | 2021-09-09 | Semiconductor Energy Laboratory Co., Ltd. | Positivelektrodenaktivmaterial und Sekundärbatterie |
JP2020202068A (ja) * | 2019-06-10 | 2020-12-17 | 昭和電工マテリアルズ株式会社 | リチウムイオン二次電池用負極活物質、リチウムイオン二次電池およびリチウムイオン二次電池用負極活物質の製造方法 |
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KR101424544B1 (ko) | 2014-07-31 |
CN102714307A (zh) | 2012-10-03 |
US9184439B2 (en) | 2015-11-10 |
EP2518799A4 (en) | 2015-06-17 |
CN102714307B (zh) | 2014-12-10 |
EP2518799B1 (en) | 2016-08-24 |
KR20120092668A (ko) | 2012-08-21 |
JPWO2011077654A1 (ja) | 2013-05-02 |
EP2518799A1 (en) | 2012-10-31 |
JP5557059B2 (ja) | 2014-07-23 |
US20120258370A1 (en) | 2012-10-11 |
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