WO2019131864A1 - Matériau d'électrode négative pour batterie secondaire au lithium-ion - Google Patents

Matériau d'électrode négative pour batterie secondaire au lithium-ion Download PDF

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WO2019131864A1
WO2019131864A1 PCT/JP2018/048102 JP2018048102W WO2019131864A1 WO 2019131864 A1 WO2019131864 A1 WO 2019131864A1 JP 2018048102 W JP2018048102 W JP 2018048102W WO 2019131864 A1 WO2019131864 A1 WO 2019131864A1
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particles
negative electrode
lithium ion
ion secondary
secondary battery
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PCT/JP2018/048102
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English (en)
Japanese (ja)
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貴行 栗田
石井　伸晃
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昭和電工株式会社
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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
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a negative electrode material for a lithium ion secondary battery.
  • the speed-up of the power saving of the electronic components has advanced the multifunctionalization of portable electronic devices, and the power consumption of the portable electronic devices is increasing. Therefore, there is a strong demand for higher capacity and smaller size of the lithium ion secondary battery, which is the main power source of portable electronic devices. In addition, demand for electric vehicles is increasing, and there is a strong demand for higher capacity in lithium ion secondary batteries used therein.
  • Patent Document 1 is a negative electrode material made of a Si-based alloy for a storage device accompanied by migration of lithium ions during discharge, and the negative electrode material made of the Si-based alloy is Si main phase and other than Si and Si.
  • the negative electrode material which consists of Si type alloys for electrical storage devices whose crystallite size of the compound phase which consists of Cu is 40 nm or less is disclosed.
  • Patent Document 2 is silicon mainly used as a negative electrode active material for a lithium ion secondary battery, and has a crystallite size of 1 to 200 nm by powder X-ray diffraction, and an average particle diameter of 0.1 by a laser method. It discloses silicon fine particles having a specific surface area of up to 5 ⁇ m and a BET surface area of at least 10 m 2 / g.
  • Patent Document 1 attempts to reduce the crystalline size, it is unclear which crystal plane is focused on, and the Si particle size is not described.
  • the invention of Patent Document 2 has an allowable Si crystallite size too large compared to Patent Document 1, and may not lead to expansion suppression.
  • the expansion suppression of the negative electrode is the point that the negative electrode material is formed of Si alone or the Si particle diameter is 0.1 ⁇ m or more.
  • An object of the present invention is to provide a negative electrode material for a lithium ion secondary battery, which has a small expansion of the electrode with use and a long life.
  • the present invention includes the following aspects.
  • Si particles (A1) having an average particle diameter d AV of 5 nm or more and 95 nm or less, an amorphous carbon coating layer (A1 C) with a thickness of 1 nm or more and 20 nm or less, which covers the particles (A1);
  • a negative electrode material for a lithium ion secondary battery comprising a composite (A) comprising particles (A2) comprising a material containing graphite and a carbonaceous material (A3), wherein the composite (A) is a powder X-ray
  • the negative electrode material for a lithium ion secondary battery wherein a half value width of a (111) plane diffraction peak of the Si particles (A1) by diffraction measurement is 0.40 degrees or more.
  • the particles (A2) have a 50% particle diameter DV50 in the volume-based cumulative particle size distribution of 2.0 ⁇ m to 20.0 ⁇ m, and a BET specific surface area (S BET ) of 1.0 m 2 / g to 10
  • the ratio I 110 / I 004 of the peak intensity I 110 of the ( 110 ) plane to the peak intensity I 004 of the (004) plane by powder X-ray diffraction method is 0.10 or more 0.35 or less
  • the average interplanar spacing d 002 of the (002) plane by powder X-ray diffraction is 0.3360 nm or less
  • the total fineness of pores with a diameter of 0.4 ⁇ m or less measured by nitrogen gas adsorption The negative electrode material for a lithium ion secondary battery according to the above 1 or 2, wherein the pore volume is 5.0 ⁇ L / g or more and 40.0 ⁇ L / g or less.
  • Material. [5] A sheet-like current collector and a negative electrode layer for covering the current collector, the negative electrode layer comprising a binder, a conductive additive and the negative electrode for lithium ion secondary battery according to any one of the above 1 to 4 Material containing negative electrode sheet. [6] A lithium ion secondary battery having the negative electrode sheet described in the preceding item 5.
  • a negative electrode material for a lithium ion secondary battery according to an embodiment of the present invention is a composite (particles (A1), an amorphous carbon coating layer (A1C), particles (A2), and a carbonaceous material (A3) A) is included.
  • the particles (A1) used in one embodiment of the present invention contain Si as a main component capable of inserting and extracting lithium ions.
  • the content of Si is preferably 90% by mass or more, more preferably 95% by mass or more.
  • the particles (A1) may be composed of a simple substance of Si or a compound containing a Si element, a mixture, a eutectic or a solid solution.
  • the particles (A1) before being complexed with the particles (A2) and the carbonaceous material (A3) may be aggregations of a plurality of fine particles, that is, secondary particles.
  • grains (A1) a lump shape, scale shape, spherical shape, fibrous shape etc. can be mentioned. Among these, spherical or massive is preferable.
  • the material containing Si element, the general formula and a element M other than Si alone or Si and Li: be mentioned M ( M a + M b + M c + M d ⁇ ) material represented by m Si it can.
  • the substance is a compound, a mixture, a eutectic or a solid solution containing the element M in a ratio of m moles to 1 mole of Si.
  • the element M which is an element other than Li include B, C, N, O, S, P, Na, Mg, Al, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, Ru, Rh, Pd, Pt, Be, Nb, Nd, Ce, W, Ta, Ag, Au, Cd, Ga, In, Sb, Ba and the like can be mentioned.
  • m is preferably 0.01 or more, more preferably 0.10 or more, and still more preferably 0.30 or more.
  • the substance containing Si element include elemental Si, an alloy of Si and an alkaline earth metal; an alloy of Si and a transition metal; an alloy of Si and a semimetal; Si, Be, Ag, Al, Au , Cd, Ga, in, solid-solution alloys or KyoTorusei alloy of Sb or Zn; CaSi, CaSi 2, Mg 2 Si, BaSi 2, Cu 5 Si, FeSi, FeSi 2, CoSi 2, Ni 2 Si, NiSi 2, MnSi, MnSi 2, MoSi 2, CrSi 2, Cr 3 Si, TiSi 2, Ti 5 Si 3, NbSi 2, NdSi 2, CeSi 2, WSi 2, W 5 Si 3, TaSi 2, Ta 5 Si 3, It may be mentioned SiO 2, SiC, Si 3 N 4 and the like; PtSi, V 3 Si, VSi 2, PdSi, RuSi, silicides such RhSi.
  • the lower limit of the average particle diameter d AV of the primary particles of the particles (A1) is 5 nm, preferably 10 nm, and more preferably 35 nm. Further, the upper limit value of d AV of the primary particles is 95 nm, preferably 70 nm.
  • the d AV of the primary particles of the particles (A1) is larger than 95 nm, the particles (A1) expand and shrink in volume due to charge and discharge and the influence on the structure of the composite (A) containing the particles (A1) increases. Maintenance rate decreases.
  • the d AV of the primary particles is smaller than 5 nm, the specific surface area of the particles (A1) is increased, and the amount of side reaction is increased.
  • Average particle diameter d AV [nm] 6 x 10 3 / ( ⁇ x S BET ) Defined by Here, [[g / cm 3 ] is the true density of Si particles, and the theoretical value of 2.3 [g / cm 3 ] was adopted. S BET [m 2 / g] is a specific surface area measured by the BET method using N 2 gas as an adsorption gas.
  • the particles (A1) are coated on their surface with a thin amorphous carbon coating layer (A1C).
  • the upper limit of the thickness of the amorphous carbon coating layer (A1C) is 20 nm, preferably 10 nm, more preferably 5 nm. This is to suppress the side reaction between the electrolytic solution and the amorphous carbon coating layer (A1C).
  • the lower limit of the thickness of the amorphous carbon coating layer (A1C) is 1 nm, preferably 2 nm, and more preferably 3 nm. This is because the oxidation of the particles (A1) and the aggregation of the particles (A1) are suppressed.
  • the thickness of the amorphous carbon coating layer (A1C) can be determined by measuring the film thickness in an image taken by observation with a transmission electron microscope (TEM). An example of a specific TEM observation is shown below.
  • Device H9500 manufactured by Hitachi, Ltd. Acceleration voltage: 300 kV.
  • Preparation of sample A small amount of sample is taken in ethanol and dispersed by ultrasonic irradiation, and then placed on a microgrid observation mesh (without a supporting film) to make an observation sample.
  • Observation magnification 50,000 times (at the time of particle shape observation) and 400,000 times (at the time of thickness observation of an amorphous carbon layer)
  • the core-shell structure (hereinafter referred to as a structure ( ⁇ )) comprising particles (A1) and an amorphous carbon coating layer (A1C) covering the particles preferably has a BET specific surface area of 25 m 2 / g to 70 m. It is 2 / g or less, more preferably 52 m 2 / g or more and 67 m 2 / g or less. Moreover, the density of primary particles is 2.2 g / cm 3 or more.
  • the BET specific surface area (S BET ) of the structure ( ⁇ ) is 25 m 2 / g or more, the particle diameter of the structure ( ⁇ ) does not become too large, and the electron transfer path in the solid of the structure ( ⁇ ) and Li The ion diffusion path will not be long. That is, the resistance at the time of charge and discharge is kept low. Furthermore, the absolute value of the amount of expansion per particle of the structure ( ⁇ ) does not increase, and the possibility of destruction of the structure of the complex (A) around the structure ( ⁇ ) is low. In addition, when the density of the structure ( ⁇ ) is 2.2 g / cm 3 or more, it is also advantageous in terms of volumetric energy density.
  • the content of particles (A1) in the composite (A) is preferably 2% by mass to 95% by mass, more preferably 5% by mass to 80% by mass, and still more preferably 10% by mass to 70% by mass It is.
  • the content of the particles (A1) is 95% by mass or less, no problem occurs in the battery performance due to the increase in the electrical resistance.
  • the content of the particles (A1) is 2% by mass or more, the superiority in terms of volume or mass energy density is maintained.
  • the structure ( ⁇ ) composed of the particles (A1) and the amorphous carbon coating layer (A1C) can be produced by any of the solid phase method, liquid phase method and gas phase method, but the gas phase method is preferable.
  • the graphite particles contained in the particles (A2) in the preferred embodiment of the present invention are preferably artificial graphite particles.
  • the size and shape of the optical structure are in a specific range, and an artificial graphite particle having an appropriate degree of graphitization can provide an electrode material having both excellent crushing characteristics and battery characteristics.
  • D V 50 represents a 50% particle size in a volume-based particle size distribution measured by a laser diffraction particle size distribution analyzer, and represents an apparent diameter of particles.
  • the 50% particle diameter D V50 in the volume-based cumulative particle size distribution of the graphite particles contained in the particles (A2) in the preferred embodiment of the present invention is preferably 2.0 ⁇ m or more and 20.0 ⁇ m or less, more preferably 5.0 ⁇ m or more 18 .0 ⁇ m or less. If the D V 50 is 2.0 ⁇ m or more, it is not necessary to grind with a special device at the time of grinding, and energy can be saved. Moreover, since it is hard to cause aggregation, the handling property at the time of coating is also good. Furthermore, since the specific surface area does not become excessively large, the decrease in the initial charge and discharge efficiency does not occur.
  • D V 50 is 20.0 ⁇ m or less, it does not take time to diffuse lithium in the negative electrode material, and hence the input / output characteristics are good. Further, since silicon-containing particles are uniformly compounded on the surface of the graphite particles, good cycle characteristics can be obtained.
  • Graphite particles contained in the particle (A2) in a preferred embodiment of the present invention BET specific surface area of preferably 1.0 m 2 / g or more 10.0 m 2 / g or less by N 2 gas adsorption method, 3.0 m 2 / g or more and 7.5 m 2 / g or less is more preferable.
  • BET specific surface area of the graphite particles is in the above range, a large area in contact with the electrolytic solution can be secured while suppressing an irreversible side reaction as a negative electrode material, so that the input / output characteristics are improved.
  • the artificial graphite particles contained in the particles (A2) in the preferred embodiment of the present invention have peak intensities I 110 of the (110) plane of the graphite crystal and peaks of the (004) plane in the diffraction peak profile obtained by powder X-ray diffraction. It preferably has a specific I 110 / I 004 intensity I 004 is 0.10 or more 0.35 or less.
  • the ratio is more preferably 0.18 or more and 0.30 or less, and still more preferably 0.21 or more and 0.30 or less. If the ratio is 0.10 or more, the orientation is not too high, and the current collector surface of the electrode is due to expansion and contraction associated with insertion and desorption (occluding and releasing) of lithium ions to Si and graphite in the negative electrode material.
  • the average interplanar spacing d 002 of the (002) plane according to powder X-ray diffraction method is preferably 0.3360 nm or less.
  • the thickness Lc in the C-axis direction of the crystallite of the artificial graphite particle is preferably 50 nm or more and 1000 nm or less from the viewpoint of mass energy density and crushability.
  • d 002 and Lc can be measured by powder X-ray diffraction (XRD) according to a known method (Michio Inagaki, “carbon”, 1963, No. 36, pages 25-34; Iwashita et al., Carbon vol. 42 (2004), p. 701-714).
  • XRD powder X-ray diffraction
  • the artificial graphite particles contained in the particles (A2) in the preferred embodiment of the present invention have a total pore volume of 5.0 ⁇ L / g or more of pores with a diameter of 0.4 ⁇ m or less according to nitrogen gas adsorption BET method under liquid nitrogen cooling. It is preferably 40.0 ⁇ L / g or less. More preferably, it is 25.0 ⁇ L / g or more and 40.0 ⁇ L / g or less.
  • An artificial graphite particle having a total pore volume of 5.0 ⁇ L / g or more tends to be complexed with the particle (A1) and the carbonaceous material (A3), and is preferable in terms of improvement of the cycle capacity retention rate.
  • the artificial graphite particles contained in the particles (A2) in a preferred embodiment of the present invention have a peak intensity I D of 1580 to 1620 cm of the peak derived from the amorphous component in the range of 1300 to 1400 cm.sup.- 1 measured by Raman spectroscopy.
  • the ratio I D / I G (R value) to the intensity I G of the peak derived from the graphite component in the range of -1 is preferably 0.04 or more and 0.18 or less, preferably 0.08 or more and 0.16 or less It is further preferred that If the R value is 0.04 or more, the crystallinity of graphite is not too high, and good rapid charge / discharge characteristics can be obtained.
  • the Raman spectrum can be measured, for example, by observing with a microscope attached using a laser Raman spectrophotometer (NRS-5100 manufactured by JASCO Corporation).
  • the graphite particles contained in the particles (A2) may be produced by heating particles obtained by crushing coke having a heat history of 1000 ° C. or less. it can.
  • a raw material of coke for example, petroleum pitch, coal pitch, coal pitch coke, petroleum coke and mixtures thereof can be used. That is, as the graphite particles contained in the particles (A2), it is preferable to use a material derived from petroleum-based coke and / or coal-based coke. Among these, those subjected to delayed coking under specific conditions are desirable.
  • the raw material to be passed through a delayed coker is a decanted oil from which the catalyst has been removed after fluid bed catalytic cracking has been performed on heavy fractions at the time of crude oil refining, coal tar extracted from bituminous coal, etc. And those obtained by sufficiently distilling the tar obtained by raising the temperature to 100 ° C. or higher.
  • the temperature of these liquids be raised to 450 ° C. or higher, 500 ° C. or higher, or even 510 ° C. or higher at least at the entrance of the drum.
  • the carbon content increases and the yield improves.
  • the pressure in the drum is preferably maintained at normal pressure or higher, more preferably 300 kPa or higher, and still more preferably 400 kPa or higher. This further increases the capacity as the negative electrode. As described above, by performing coking under more severe conditions than usual, the liquid can be reacted more and coke having a higher degree of polymerization can be obtained.
  • the obtained coke is cut out from the inside of the drum by a jet water flow, and the obtained mass is roughly crushed to about 5 cm with a gold crucible or the like.
  • a twin-roll crusher or a jaw crusher can also be used for the coarse grinding, it is preferable that the 1 mm sieve is ground to have 90% by mass or more.
  • the coke is then crushed.
  • the pulverization property is significantly reduced, so it is preferable to previously dry it at about 100 to 1000.degree. More preferably, it is 100 to 500 ° C.
  • the crushing strength becomes strong and the crushability deteriorates, and the crystal anisotropy develops, so that the cleavage property becomes strong and it becomes easy to be a scaly powder.
  • a known jet mill, hammer mill, roller mill, pin mill, vibration mill or the like can be used. Milling is preferably carried out as D V50 becomes 2.0 ⁇ m or 20.0 ⁇ m or less, and more preferably more than 5.0 .mu.m 18.0.
  • Graphitization is preferably performed at a temperature of 2400 ° C. or higher, more preferably 2800 ° C. or higher, still more preferably 3050 ° C. or higher, still more preferably 3150 ° C. or higher under an inert atmosphere (eg, nitrogen gas or argon gas atmosphere) Do.
  • an inert atmosphere eg, nitrogen gas or argon gas atmosphere
  • the graphitization temperature is preferably 3600 ° C. or less.
  • the carbon raw material be calcined to remove organic volatile components, that is, the fixed carbon content is 95% or more, more preferably 98% or more, and still more preferably 99% or more.
  • This firing can be performed, for example, by heating at 700 to 1500.degree. Since the reduction in mass at the time of graphitization is reduced by firing, the throughput of the graphitization processing apparatus can be increased once.
  • the carbonaceous material (A3) in a preferred embodiment of the present invention is a carbon material which is different from the particles (A2) and in which the development of crystals formed by carbon atoms is low, and a Raman spectrum by Raman scattering spectroscopy. Has a peak near 1360 cm -1 .
  • the carbonaceous material (A3) may be the same as the amorphous carbon coating layer (A1C).
  • the carbonaceous material (A3) can be produced, for example, by carbonizing a carbon precursor.
  • the carbon precursor is not particularly limited, but includes, but not limited to, thermal heavy oil, pyrolysis oil, straight asphalt, blown asphalt, petroleum-derived substances such as tar or petroleum pitch by-produced during ethylene production, coal tar produced during coal distillation,
  • the heavy component obtained by distilling off the low-boiling component of coal tar, and coal-derived materials such as coal tar pitch (coal pitch) are preferred, and petroleum pitch or coal pitch is particularly preferred.
  • Pitch is a mixture of multiple polycyclic aromatic compounds. When pitch is used, a carbonaceous material (A3) with few impurities can be produced at a high carbonization rate. Since the pitch has a low oxygen content, when the particles (A1) are coated with the carbonaceous material, the particles (A1) are less likely to be oxidized.
  • the pitch as a precursor of the carbonaceous material (A3) preferably has a softening point of 80 ° C. or more and 300 ° C. or less. If the softening point of pitch is 80 ° C. or higher, the average molecular weight of the polycyclic aromatic compound constituting it is not too small, and the volatile content is also relatively small, so the carbonization rate decreases, the manufacturing cost increases, and further There is no problem that a carbonaceous material (A3) having a large specific surface area containing many pores can be easily obtained. If the softening point of the pitch is 300 ° C. or less, the viscosity is not too high, so that it can be uniformly mixed with the particles (A1). The softening point of pitch can be measured by the Mettler method described in ASTM-D 3104-77.
  • the pitch of the carbonaceous material (A3) as a precursor is preferably 20% by mass to 70% by mass, and more preferably 25% by mass to 60% by mass, as a residual carbon ratio.
  • the residual carbon ratio of the pitch is 20% by mass or more, problems such as an increase in manufacturing cost and a carbonaceous material having a large specific surface area do not occur.
  • the residual carbon ratio of the pitch is 70% by mass or less, the viscosity is not too high, and therefore, it can be uniformly mixed with the particles (A1).
  • the residual coal rate is determined by the following method.
  • the solid pitch is ground in a mortar or the like, and the ground product is subjected to mass thermal analysis under a nitrogen gas flow.
  • the ratio of mass to charged mass at 1100 ° C. is defined as the residual carbon ratio.
  • the pitch used in the present invention preferably has a QI (quinoline insoluble content) content of 10% by mass or less, more preferably 5% by mass or less, and still more preferably 2% by mass or less.
  • the QI content of pitch is a value corresponding to the amount of free carbon.
  • the pitch containing a large amount of free carbon is heat-treated, the free carbon adheres to the surface of the sphere to form a three-dimensional network in the process of appearance of mesophase spheres, thereby hindering the growth of the sphere, and thus it tends to be a mosaic structure.
  • heat treatment is performed on a pitch having a small amount of free carbon, mesophase spheres grow large and tend to generate needle coke.
  • the QI content is in the above range, the electrode characteristics are further improved.
  • the pitch used in the present invention preferably has a TI (toluene insoluble content) content of 10% by mass to 70% by mass.
  • the pitch with low TI content has a low average carbon weight and high volatile content because the polycyclic aromatic compound constituting it has a low carbonization rate, an increase in production cost, and a large specific surface area including many pores. Carbonaceous materials are easily obtained.
  • the pitch with a high TI content has a high carbonization rate because the average molecular weight of the polycyclic aromatic compound constituting it is high, but the pitch with a high TI content is uniformly mixed with the particles (A1) since the viscosity is high. It tends to be difficult. When the TI content is in the above-mentioned range, it is possible to uniformly mix the pitch and the other components, and to obtain a negative electrode material having characteristics suitable as a battery active material.
  • the QI content and the TI content of the pitch used in the present invention can be measured by the method described in JIS K2425 or a method according thereto.
  • the mass ratio of the carbonaceous material (A3) to the total mass of the particles (A1), the particles (A2) and the carbonaceous material (A3) is preferably 2% by mass to 40% by mass, and more preferably 4% % Or more and 30% by mass or less.
  • the proportion of the carbonaceous material (A3) is 2% by mass or more, sufficient bonding between the particles (A1) and the particles (A2) can be obtained, and the surface of the particles (A1) can be a carbonaceous material (A3)
  • conductivity is easily imparted to the particles (A1), and an effect of suppressing surface reactivity of the particles (A1) and an effect of alleviating expansion and contraction are obtained, and good cycle characteristics are obtained.
  • the proportion of the carbonaceous material (A3) is 40% by mass or less, the initial efficiency does not decrease even if the proportion of the carbonaceous material (A3) is high.
  • the composite (A) comprises a structure ( ⁇ ) comprising particles (A1) and an amorphous carbon coating layer (A1C), particles (A2), and a carbonaceous material (A3). It is preferable that at least a part of the structure ( ⁇ ), the particles (A2) and the carbonaceous material (A3) be complexed with each other.
  • the complexing is, for example, a state in which the structure ( ⁇ ) and the particle (A2) are fixed by the carbonaceous material (A3) and bound, or the structure ( ⁇ ) and / or the particle (A2) is carbon The state covered with the quality material (A3) can be mentioned.
  • the structure ( ⁇ ) is completely covered with the carbonaceous material (A3) and the surface of the structure ( ⁇ ) is not exposed, among which the structure ( ⁇ ) And particles (A2) are linked via the carbonaceous material (A3), and the whole is covered with the carbonaceous material (A3), and the structure ( ⁇ ) and particles (A2) are in direct contact It is preferable that the whole is covered with the carbonaceous material (A3).
  • the surface of the structure ( ⁇ ) is not exposed, so that the electrolytic solution decomposition reaction is suppressed and the coulombic efficiency can be maintained high, and particles (the carbonaceous material (A3) A2) and the structure ( ⁇ ) can increase the conductivity between each other, and the structure ( ⁇ ) is covered with the carbonaceous material (A3) to be accompanied by its expansion and contraction. Volume changes can be buffered.
  • the composite (A) according to an embodiment of the present invention may contain the particles (A2), the carbonaceous material (A3) or the structure ( ⁇ ) alone, which are not complexed. It is preferable that the amount of the particles (A2), the carbonaceous material (A3), or the structures ( ⁇ ) contained alone without being complexed is small, and specifically, to the mass of the complex (A) On the other hand, it is preferably 10% by mass or less.
  • DV50 of the complex (A) which concerns on one Embodiment of this invention
  • 2.0 micrometers or more and 20.0 micrometers or less are preferable. More preferably, it is 2.0 micrometers or more and 18.0 micrometers or less. If DV50 is 2.0 micrometers or more, economical manufacture is possible. Also, there is no difficulty in increasing the electrode density. Furthermore, since the specific surface area is not excessively increased, the decrease in the initial charge and discharge efficiency due to the side reaction with the electrolytic solution does not occur. Further, if the DV50 is 20.0 ⁇ m or less, good input / output characteristics and cycle characteristics can be obtained.
  • the BET specific surface area (S BET ) of the composite (A) is preferably 1.0 m 2 / g or more and 10.0 m 2 / g or less. More preferably, it is 1.0 m 2 / g or more and 5.0 m 2 / g or less. If the BET specific surface area (S BET ) is 1.0 m 2 / g or more, uniform distribution in the electrode is maintained without deterioration of input / output characteristics, and good cycle characteristics can be obtained. When the BET specific surface area (S BET ) is 10.0 m 2 / g or less, the coating property is not lowered and the handling property is also good. In addition, it is easy to increase the electrode density without requiring a large amount of binder for electrode production, and it is possible to suppress a decrease in initial charge and discharge efficiency due to a side reaction with the electrolytic solution.
  • the half value width of the (111) plane diffraction peak of the Si particle (A1) measured by the X-ray diffraction method is 0.40 to 0.71 degrees. Preferably it is 0.40 degree or more and 0.65 degree or less, More preferably, it is 0.40 degree or more and 0.65 degree or less.
  • the half value width of the (111) plane diffraction peak of the Si particle (A1) is less than 0.40 degrees, the crystallite size of the Si particle (A1) becomes large and the expansion of the Si particle (A1) becomes anisotropic. . As a result, the electrode expansion rate increases and the cycle capacity retention rate decreases.
  • the half value width of the diffraction peak of the particles (A1) can be measured using the powder X-ray diffraction (XRD) method described above (Michio Inagaki, “carbon”, 1963, No. 36, pages 25-34; Iwashita et al., Carbon vol. 42 (2004), p. 701-714). In this measurement, when the half value width of the (111) plane diffraction peak of the Si particle (A1) exceeds 0.71 degrees, the crystallite size becomes less than 0 nm, which can not occur.
  • XRD powder X-ray diffraction
  • the complex (A) has a peak intensity I D of a peak in the range of 1300 to 1400 cm ⁇ 1 in a Raman spectrum obtained by measuring the particle end face with a microscopic Raman spectrometer.
  • the ratio I D / I G (R value) of the peak intensity to the peak intensity I G in the range of 1580 to 1620 cm -1 is preferably 0.15 or more and 1.0 or less. More preferably, it is 0.2 or more and 1.0 or less, still more preferably 0.4 or more and 1.0 or less.
  • the fact that the R value is too small means that the surface of the particles (A2) is exposed to a certain amount.
  • the particles (A2) and the particles (A1) are covered with the carbonaceous material (A3), and the effect of suppressing the surface reactivity of the particles (A1) or expansion and contraction Good cycle characteristics can be obtained because the effect of relieving is increased.
  • the R value is too large, it indicates that the carbonaceous material (A3) containing a large amount of amorphous carbon having a large initial irreversible capacity covers the surface of the particles (A2). Therefore, if R value is 1.0 or less, the fall of initial stage discharge efficiency is suppressed.
  • the complex (A) according to an embodiment of the present invention can be produced according to a known method.
  • the structure ( ⁇ ) consisting of the particles (A1) and the amorphous carbon coating layer (A1C), the particles (A2) and the precursor of the carbonaceous material (A3) are mixed, and the obtained mixture is heat-treated Complex (A) can be obtained by the method including making the said precursor into carbonaceous material (A3).
  • the mixture of the structure ( ⁇ ), the particles (A2) and the precursor of the carbonaceous material (A3) melts the pitch which is one of the precursors of the carbonaceous material (A3), and the molten pitch and structure
  • melts the pitch which is one of the precursors of the carbonaceous material (A3), and the molten pitch and structure
  • the body ( ⁇ ) in an inert atmosphere, solidifying and then grinding the mixture, and mixing the ground product with the particles (A2); the structure ( ⁇ ) and the particles (A2)
  • a known device such as a hybridizer (registered trademark, manufactured by Nara Machinery Co., Ltd.) can be used.
  • the means of grinding mainly by impact and shear such as a pin mill and a rotary cutter mill, tends to transmit shear force preferentially to large particle size particles and less to small particle size particles.
  • Such an apparatus can be used to grind or mix the particles (A1) and the structure ( ⁇ ) without promoting oxidation.
  • the non-oxidizing atmosphere an atmosphere filled with an inert gas such as argon gas or nitrogen gas can be mentioned.
  • the heat treatment for converting the carbonaceous material (A3) precursor to the carbonaceous material (A3) is preferably 200 ° C. or more and 2000 ° C. or less, more preferably 500 ° C. or more and 1500 ° C. or less, particularly preferably 600 ° C. or more and 1200 ° C. or less At a temperature of By this heat treatment, the carbonaceous material (A3) coats the structural body ( ⁇ ) and / or the particles (A2), and the carbonaceous material (A3) is between the structural bodies ( ⁇ ) and the particles (A2) And between the structure ( ⁇ ) and the particles (A2) to connect them.
  • the heat treatment is preferably performed in a non-oxidative atmosphere.
  • a non-oxidative atmosphere an atmosphere filled with an inert gas such as argon gas or nitrogen gas can be mentioned.
  • an inert gas such as argon gas or nitrogen gas
  • a crushing method a pulperizer using an impact force such as a hammer, a jet mill using a collision of objects to be crushed and the like are preferable.
  • a material containing the composite (A) and carbon for the purpose of improving battery performance as the negative electrode material for lithium ion secondary batteries and for the purpose of adjusting the capacity of the negative electrode material for lithium ion secondary batteries May be mixed.
  • a plurality of types of materials containing carbon to be mixed may be used.
  • As a material containing carbon graphite having a high capacity is preferable.
  • the graphite can be selected from natural graphite and artificial graphite.
  • the material containing carbon for adjusting the volume may be mixed with the composite (A) in advance, and additives such as a binder, a solvent, and a conductive additive may be added thereto to prepare a negative electrode paste.
  • the negative electrode paste may be prepared by simultaneously mixing the composite (A), a material containing carbon, a binder, a solvent, an additive such as a solvent, a conductive additive, and the like. The order and method of mixing may be appropriately determined in consideration of powder handling and the like.
  • the paste for an anode according to one embodiment of the present invention contains the above-mentioned anode material, a binder, a solvent, and, if necessary, an additive such as a conductive aid.
  • This negative electrode paste can be obtained, for example, by kneading the negative electrode material, the binder, the solvent, and the conductive auxiliary agent as needed.
  • the negative electrode paste can be formed into a sheet, a pellet, or the like.
  • Examples of the material used as the binder include polyethylene, polypropylene, ethylene propylene terpolymer, butadiene rubber, styrene butadiene rubber, butyl rubber, acrylic rubber, and a polymer compound having a large ion conductivity.
  • Examples of the polymer compound having large ion conductivity include polyvinylidene fluoride, polyethylene oxide, polyepichlorohydrin, polyphasphazen, polyacrylonitrile and the like.
  • the amount of the binder is preferably 0.5 parts by mass to 100 parts by mass with respect to 100 parts by mass of the negative electrode material.
  • the conductive aid is not particularly limited as long as it plays the role of imparting conductivity and electrode stability (buffering action against volume change in insertion and detachment of lithium ions) to the electrode.
  • carbon nanotubes, carbon nanofibers, vapor-grown carbon fibers for example, “VGCF (registered trademark)” manufactured by Showa Denko KK
  • conductive carbon for example, “Denka Black (registered trademark)” Electric Chemical Industry Co., Ltd.
  • the amount of the conductive additive is preferably 10 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the negative electrode material.
  • the solvent is not particularly limited, and N-methyl-2-pyrrolidone, dimethylformamide, isopropanol, water and the like can be used.
  • the binder which uses water as a solvent it is preferable to use a thickener together.
  • the amount of the solvent may be adjusted to have a viscosity such that the paste can be easily applied to the current collector.
  • Negative electrode sheet The negative electrode sheet which concerns on one Embodiment of this invention has a collector and the electrode layer which coat
  • a collector sheet-like things, such as nickel foil, copper foil, nickel mesh, or a copper mesh, are mentioned, for example.
  • the electrode layer contains a binder and the above-mentioned negative electrode material.
  • the electrode layer can be obtained, for example, by applying the above-mentioned paste on a current collector and drying it.
  • the application method of the paste is not particularly limited.
  • the thickness of the electrode layer is preferably 50 to 200 ⁇ m. If the electrode layer is too thick, it may not be possible to accommodate the negative electrode sheet in a standardized battery container. The thickness of the electrode layer can be adjusted by the amount of paste applied.
  • the electrode density of the negative electrode sheet can be calculated as follows. That is, the negative electrode sheet after pressing is punched into a circular shape having a diameter of 16 mm, and its mass and thickness are measured. The mass and thickness of the current collector foil (punched into a circular shape of 16 mm in diameter) separately measured therefrom are subtracted to obtain the mass and thickness of the electrode layer, and the electrode density is calculated based on the values.
  • a lithium ion secondary battery according to an embodiment of the present invention comprises at least one selected from the group consisting of a non-aqueous electrolytic solution and a non-aqueous polymer electrolyte, a positive electrode sheet and the negative electrode sheet.
  • a positive electrode sheet a sheet conventionally used in lithium ion secondary batteries, specifically, a sheet containing a positive electrode active material can be used.
  • the positive electrode active material include LiNiO 2 , LiCoO 2 , LiMn 2 O 4 , LiNi 0.34 Mn 0.33 Co 0.33 O 2 , LiFePO 4 and the like.
  • the non-aqueous electrolytic solution and the non-aqueous polymer electrolyte used for the lithium ion secondary battery are not particularly limited.
  • lithium carbonates such as LiClO 4 , LiPF 6 , LiAsF 6 , LiBF 4 , LiSO 3 CF 3 , CH 3 SO 3 Li, CF 3 SO 3 Li, ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, propylene Organic electrolytes dissolved in non-aqueous solvents such as carbonate, butylene carbonate, acetonitrile, propionitrile, dimethoxyethane, tetrahydrofuran, ⁇ -butyrolactone, etc. containing polyethylene oxide, polyacrylonitrile, polyfluorinated bilinidene, polymethyl methacrylate and the like Examples thereof include solid polymer electrolytes containing gel-like polymer electrolytes, polymers having ethylene oxide bonds, and the like.
  • a small amount of a substance that causes a decomposition reaction when charging a lithium ion secondary battery may be added to the electrolytic solution.
  • the substance include vinylene carbonate (VC), biphenyl, propane sultone (PS), fluoroethylene carbonate (FEC), ethylene sultone (ES) and the like.
  • VC vinylene carbonate
  • PS propane sultone
  • FEC fluoroethylene carbonate
  • ES ethylene sultone
  • the lithium ion secondary battery can be provided with a separator between the positive electrode sheet and the negative electrode sheet.
  • a separator for example, non-woven fabric mainly made of polyolefin such as polyethylene and polypropylene, cloth, microporous film, or a combination thereof can be mentioned.
  • Lithium-ion secondary batteries are used to power electronic devices such as mobile phones, personal computers and personal digital assistants; power sources for electric drills, electric vacuum cleaners and electric motors such as electric cars; fuel cells, solar power, wind power, etc. It can be used for storage of stored power.
  • the average particle diameter d AV of the primary particles of the particles (A1), the thickness of the amorphous carbon coating layer (A1C), and the (002) plane of the artificial graphite particles by X-ray diffraction method The average interplanar spacing d 002 , the thickness L C of the crystallite in the C-axis direction, the half value width of the (111) diffraction peak of the Si particle (A1), and the R value in the Raman spectrum It measures by the method described in "form". Moreover, the measurement of other physical properties and battery evaluation were performed as follows.
  • the resulting (004) intensity ratio becomes orientation index from the peak intensity I 110 between the peak intensity I 004 (110) plane of the surface was calculated I 110 / I 004.
  • the peak of each surface selected the thing of the largest intensity among the following ranges as each peak. (004) plane: 54.0 to 55.0 deg. (110) plane: 76.5 to 78.0 deg
  • Specific surface area Specific surface area / pore distribution measurement device (Quantam Chrome Instruments, NOVA 4200e), using nitrogen gas as a probe, BET specific surface area according to BET multipoint method with relative pressure of 0.1, 0.2, and 0.3 S BET (m 2 / g) was measured.
  • Carboxymethylcellulose (CMC; manufactured by Daicel, CMC 1300) was used as a binder. Specifically, an aqueous solution in which CMC powder having a solid content ratio of 2% was dissolved was obtained. Prepare carbon black, carbon nanotubes (CNT), and vapor grown carbon fiber (VGCF (registered trademark) -H, Showa Denko KK) as a conductive additive, and each is 3: 1: 1 (mass ratio) The mixture was used as a mixed conductive aid.
  • CMC carboxymethylcellulose
  • CMC 1300 Carboxymethylcellulose
  • the negative electrode paste was uniformly coated on a copper foil with a thickness of 20 ⁇ m using a doctor blade with a gap of 300 ⁇ m, dried on a hot plate, and then vacuum dried to obtain a negative electrode sheet.
  • the dried electrode was pressed by a uniaxial press at a pressure of 300 MPa to obtain a negative electrode sheet for battery evaluation.
  • the negative electrode sheet evaluates the amount of discharge per mass of active material in the half cell of the counter electrode Li in advance, and the negative electrode with respect to the capacity (Q C ) of the positive electrode sheet
  • the capacity of the negative electrode sheet was finely adjusted so that the ratio of the sheet capacity (Q A ) was a constant value of 1.2.
  • the electrolytic solution was prepared by mixing 1% by mass of vinylene carbonate (VC) and 10 parts of fluoroethylene carbonate (FEC) in a solvent in which ethylene carbonate, ethyl methyl carbonate and diethyl carbonate were mixed in a volume ratio of 3: 5: 2. mixed mass%, a further liquid electrolyte LiPF 6 was dissolved to a concentration of 1 mol / L to this.
  • VC vinylene carbonate
  • FEC fluoroethylene carbonate
  • Charging refers to applying a voltage to the cell
  • discharging refers to an operation that consumes the voltage of the cell.
  • the counter electrode is not Li metal, and a material having a higher redox potential than the negative electrode sheet is applied. Therefore, the negative electrode sheet is treated as a negative electrode. Therefore, in the bipolar laminate full cell, charging means an operation of inserting Li into the negative electrode sheet, and discharging means an operation of releasing Li from the negative electrode operation.
  • the discharge was carried out in CC mode up to 2.7 V with a current value of 0.1C.
  • the third cycle and the fourth cycle of the aging were under the same condition, and the current value in the second and the fifth cycle of the aging was replaced with 0.1 C to 0.2 C.
  • a charge / discharge cycle test was performed by the following method. The charging was performed to a voltage of 4.3 V in the CC mode with a current value of 1 C, and then switched to the discharge in the CV mode, and was performed with a cutoff current value of 0.05 C. Discharge was performed up to 3.0 V in CC mode with a current value of 1C.
  • This charge / discharge operation was performed as one cycle for 20 cycles, and at the 21st cycle, a low rate test was performed in which 1 C of the charge / discharge was replaced with 0.1 C. This 21 cycle test was repeated for a total of 500 cycles.
  • the first discharge capacity in this equation means the first cycle after the end of aging.
  • the bipolar laminate type full cell after discharge was recovered, and then disassembled in a glove box maintained in a dry argon gas atmosphere with a dew point of ⁇ 80 ° C. or less, and the negative electrode was taken out.
  • EMC ethyl methyl carbonate
  • the thickness of the electrode was measured using a dial gauge (manufactured by Mitutoyo Co., Ltd .; Code No. 547-401, scale 0.001 mm). The measurement locations were nine locations along the short side of the tab-attached side electrode, and the average value of the measured values was taken as the electrode thickness.
  • the electrode immediately after pressing was used as an electrode serving as a reference in determining the electrode expansion coefficient.
  • the electrode thickness here means the value which deducted the thickness of the copper foil collector altogether.
  • Si fine particles Silicon-containing particles
  • Table 1 Physical properties of Si particles and Si (1) to Si (3) used for the particles (A1) in Examples and Comparative Examples are shown in Table 1.
  • ⁇ is the true density (2.3 [g / cm 3 as theoretical value) of Si particles
  • S BET is the specific surface area [m 2 / g] measured by the BET method.
  • Pitch Petroleum pitch (softening point 220 ° C.) was used. It was 52 mass% when the residual carbon rate in 1100 degreeC was measured by thermal analysis under nitrogen gas distribution about this petroleum pitch. Further, the QI content of the petroleum pitch measured by the method described in JIS K2425 or a method according to the same was 0.62% by mass, and the TI content was 48.9% by mass.
  • Example 1 After petroleum-based coke is crushed by a bantam mill (manufactured by Hosokawa Micron Corporation), it is further crushed by a jet mill (manufactured by Seishin Enterprise Co., Ltd.) and heat-treated at 3000 ° C. in an Achison furnace to give a D V 50 of 7.5 ⁇ m. Artificial graphite particles (A2) -a having a BET specific surface area of 4.9 m 2 / g were obtained. Next, 16.4 parts by mass of the structure ( ⁇ ) -1 and 15.4 parts by mass of the petroleum pitch (as a mass after carbonizing the petroleum pitch), which is a precursor of the carbonaceous material (A3), are separated. It was charged into a bull flask.
  • Nitrogen gas was circulated to maintain an inert atmosphere, and the temperature was raised to 250 ° C.
  • the mixer was rotated at 500 rpm for agitation to uniformly mix the pitch and the silicon-containing particles. It was cooled and solidified to obtain a mixture.
  • 68.2 parts by mass of the above-mentioned artificial graphite particles which are particles (A2) -a are added to this mixture, charged into a rotary cutter mill, and mixed at a high speed of 25000 rpm and mixed while maintaining an inert atmosphere by flowing nitrogen gas. I did. This was put into a baking furnace, heated to 1100 ° C. at 150 ° C./h under nitrogen gas flow, and held at 1100 ° C.
  • a negative electrode sheet was produced using a mixture of 67.0 parts by mass of composite (A) -a, 16.5 parts by mass of graphite (1) and 16.5 parts by mass of graphite (2), and battery characteristics were measured. The results are shown in Table 3.
  • Comparative Example 1 A complex (A) -b was obtained in the same manner as in Example 1 except that the structure ( ⁇ ) -1 was changed to Si (2) in Table 1.
  • a negative electrode sheet was produced using a mixture of 67.0 parts by mass of the composite (A) -b, 16.5 parts by mass of graphite (1) and 16.5 parts by mass of graphite (2), and battery characteristics were measured. The results are shown in Table 3.
  • Comparative example 2 A complex (A) -c was obtained in the same manner as in Example 1 except that the structure ( ⁇ ) -1 was changed to Si (3) in Table 1.
  • a negative electrode sheet was produced using a mixture of 67.0 parts by mass of the composite (A) -c, 16.5 parts by mass of the graphite (1) and 16.5 parts by mass of the graphite (2), and battery characteristics were measured. The results are shown in Table 3.
  • the composite of Comparative Example 2 not only has a large Si (111) crystallite size but also the average particle diameter of Si particles. Also very big.
  • the average particle size of the Si particles is large, the amount of expansion per Si particle increases and at the same time the expanded portion is localized. As a result, the electrode mixture layer is largely destroyed.
  • the average particle diameter of the Si particles is small, the amount of expansion around the Si1 particles is reduced, and at the same time, the expansion superlocation is delocalized. As a result, breakage of the electrode mixture layer can be reduced. Accordingly, the electrode mixture layer expansion coefficient and capacity retention ratio of Comparative Example 2 are worse than those of Example 1 and Comparative Example 1.

Abstract

La présente invention concerne un matériau d'électrode négative pour une batterie secondaire au lithium-ion, le matériau d'électrode négative comprenant : un composite (A) comprenant des particules de Si (A1) ayant un diamètre moyen de particule dAV de particules primaires de 5 à 95 nm ; une couche de revêtement de carbone amorphe (A1C) ayant une épaisseur de 1 nm à 20 nm et recouvrant les particules (A1) ; des particules (A2) constituées d'un matériau comprenant du graphite ; et un matériau carboné (A3), la largeur de demi-valeur du pic de diffraction de plan (111) de la particule de Si (A1) dans le composite (A) étant de 0,40 degrés ou plus telle que déterminée par la mesure de diffraction des rayons X sur poudre. La présente invention concerne également une feuille d'électrode négative et une batterie secondaire au lithium-ion. Dans l'agent d'électrode négative de la présente invention, la taille des cristallites est réduite tout en réduisant la taille des particules de Si, ce qui permet d'obtenir une batterie secondaire au lithium-ion ayant un faible coefficient d'expansion d'électrode et une longue durée de vie de la batterie.
PCT/JP2018/048102 2017-12-28 2018-12-27 Matériau d'électrode négative pour batterie secondaire au lithium-ion WO2019131864A1 (fr)

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CN111180712A (zh) * 2020-01-22 2020-05-19 佛山科学技术学院 一种纳米硅/碳纳米管微球/石墨复合结构负极材料及其制备方法
CN114094077A (zh) * 2021-11-15 2022-02-25 珠海冠宇电池股份有限公司 一种负极材料及包含该负极材料的负极片
JP7424555B1 (ja) 2022-09-01 2024-01-30 Dic株式会社 負極活物質および二次電池
WO2024048051A1 (fr) * 2022-09-01 2024-03-07 Dic株式会社 Matériau actif d'électrode négative et batterie secondaire

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WO2015159935A1 (fr) * 2014-04-16 2015-10-22 昭和電工株式会社 Matériau d'électrode négative pour batterie au lithium-ion, et son utilisation
WO2017002959A1 (fr) * 2015-07-02 2017-01-05 昭和電工株式会社 Matériau d'électrode négative pour piles lithium-ion et son utilisation

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WO2008102712A1 (fr) * 2007-02-21 2008-08-28 Jfe Chemical Corporation Matériau d'électrode négative pour une batterie secondaire lithium-ion, son procédé de fabrication, électrode négative pour une batterie secondaire lithium-ion et batterie secondaire lithium-ion
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Publication number Priority date Publication date Assignee Title
CN111180712A (zh) * 2020-01-22 2020-05-19 佛山科学技术学院 一种纳米硅/碳纳米管微球/石墨复合结构负极材料及其制备方法
CN114094077A (zh) * 2021-11-15 2022-02-25 珠海冠宇电池股份有限公司 一种负极材料及包含该负极材料的负极片
JP7424555B1 (ja) 2022-09-01 2024-01-30 Dic株式会社 負極活物質および二次電池
WO2024048051A1 (fr) * 2022-09-01 2024-03-07 Dic株式会社 Matériau actif d'électrode négative et batterie secondaire

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