WO2020166599A1 - 活物質 - Google Patents

活物質 Download PDF

Info

Publication number
WO2020166599A1
WO2020166599A1 PCT/JP2020/005305 JP2020005305W WO2020166599A1 WO 2020166599 A1 WO2020166599 A1 WO 2020166599A1 JP 2020005305 W JP2020005305 W JP 2020005305W WO 2020166599 A1 WO2020166599 A1 WO 2020166599A1
Authority
WO
WIPO (PCT)
Prior art keywords
active material
negative electrode
peak
less
silicon
Prior art date
Application number
PCT/JP2020/005305
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
拓也 甲斐
秀雄 上杉
徹也 光本
仁彦 井手
Original Assignee
三井金属鉱業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 三井金属鉱業株式会社 filed Critical 三井金属鉱業株式会社
Priority to JP2020572269A priority Critical patent/JPWO2020166599A1/ja
Publication of WO2020166599A1 publication Critical patent/WO2020166599A1/ja

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
    • 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 an active material, a negative electrode using the same, and a solid-state battery.
  • the Si-containing active material has a potential that the capacity per mass is 5 to 10 times that of graphite.
  • it has a problem that the electron conductivity is not higher than that of graphite. Therefore, in order to increase the electron conductivity of the Si-containing active material, it has been proposed to add a conductive auxiliary agent, for example, for the purpose of imparting electron conductivity between the current collector and the active material.
  • Patent Document 1 discloses that the periphery of a core particle containing silicon is coated with a silicon solid solution such as Mg 2 Si, CoSi, or NiSi, and the surface thereof is further coated with a conductive material such as graphite or acetylene black. There is.
  • the Si-containing active material also undergoes a large volume change due to the insertion and desorption of lithium ions, and repeats expansion and contraction during charge and discharge cycles, so separation with the conductive auxiliary agent tends to occur as charge and discharge are repeated, and as a result, cycle
  • the battery performance is deteriorated and the safety of the battery is deteriorated by causing deterioration of the battery and a decrease in energy density.
  • Patent Document 2 discloses active material particles containing silicon and having an average particle diameter of 5 ⁇ m or more and 25 ⁇ m or less. By setting the average particle diameter of the active material particles to 5 ⁇ m or more, the specific surface area of the original active material can be reduced, and thus the contact area between the electrolyte and the new surface of the active material can be reduced. It is described that the suppression effect of is increased.
  • an electrode material for a lithium secondary battery which comprises particles of a solid-state alloy containing silicon as a main component, is used as an electrode material having a high efficiency of lithium insertion/desorption.
  • an electrode material for a lithium secondary battery characterized in that particles are microcrystalline silicon or amorphized silicon, in which microcrystalline or amorphous particles composed of elements other than silicon are dispersed. ..
  • Patent Document 4 a negative electrode active material for a lithium secondary battery containing silicon, copper and oxygen as main constituent elements, wherein Cu 3 Si and an average crystallite diameter (Dx) measured by an X-ray diffraction method are used.
  • a negative electrode active material for a lithium secondary battery which contains silicon particles of 50 nm or less and has a peak intensity ratio (Cu 3 Si/Si) of 0.05 to 1.5 calculated from XRD measurement results. ..
  • charge/discharge characteristics in a high current range are also required. That is, it is important that the battery has a high rate characteristic, and improvement of the rate characteristic is required.
  • the present invention can improve the cycle characteristics of the active material containing silicon, reduce or eliminate the plateau region in the discharge profile, and discharge at a high rate while maintaining the profile. It aims to provide a new active material that can.
  • the present invention relates to silicon and a chemical formula M x Si y (where x and y satisfy 0.1 ⁇ x/y ⁇ 7.0, and M is a metalloid element other than Si and a metal element).
  • a compound represented by one or two or more kinds) and a content of the M in the active material is more than 5 wt% and less than 38 wt%, and Raman spectroscopic measurement in the Raman spectrum obtained by measuring by law, the wave number 200 cm -1 ⁇ has at least one or more peaks P a to 420 cm -1, at least one peak P at a wavenumber 450 cm -1 ⁇ 490 cm -1 has a B, and the wave number 500 cm -1 peak PC to ⁇ 525 cm -1 appears at least one, the active material of the peak area ratio of the PB and PC I PB / I PC is 0.5 or more suggest.
  • the active material proposed by the present invention can be used as a negative electrode active material.
  • the active material of the present invention can be used in batteries such as liquid batteries and solid batteries, and can be preferably used in solid batteries.
  • the active material of the present invention is advantageously used in a solid battery containing a sulfide solid electrolyte as the solid electrolyte.
  • the solid-state battery using the active material of the present invention can have improved cycle characteristics and high rate characteristics. Moreover, the plateau region in the discharge profile can be reduced or eliminated.
  • the active material proposed by the present invention not only exhibits the effect in a single use, but, for example, in combination with a carbon material (Graphite), a battery, particularly a solid battery, a solid secondary battery such as a solid lithium secondary battery among them. It can be suitably used as a negative electrode active material of a secondary battery.
  • a carbon material Graphite
  • a battery particularly a solid battery, a solid secondary battery such as a solid lithium secondary battery among them. It can be suitably used as a negative electrode active material of a secondary battery.
  • the active material (hereinafter referred to as “main active material”) according to an example of the present embodiment includes silicon and a chemical formula MxSiy (where x and y satisfy 0.1 ⁇ x/y ⁇ 7.0, M Is one kind or two or more kinds of metalloid elements and metal elements other than Si.).
  • silicon also means Si capable of inserting and releasing lithium ions. That is, the present active material has a function as an active material by containing silicon.
  • silicon mainly refers to pure silicon, but it may contain an element that forms a solid solution with silicon to form a solid solution. In this case, the solid solution may have a function as an active material.
  • the proportion of silicon in the main active material is preferably 30 wt% or more of the main active material, and more preferably 40 wt% or more.
  • silicon is preferably the main component of the active material in order for the proportion of silicon to affect the charge/discharge capacity and increase the charge/discharge capacity.
  • the proportion of silicon in the substance is preferably 50 wt% or more, and particularly preferably 60 wt% or more.
  • This active material has a chemical formula M x Si y (where x and y satisfy 0.1 ⁇ x/y ⁇ 7.0, and M is one of a metalloid element other than Si and a metal element). Or two or more kinds).
  • M x Si y By containing the compound represented by M x Si y , the present active material can further improve the cycle characteristics, and can further reduce or eliminate the plateau region in the discharge profile, and further, have high rate characteristics. Can be improved.
  • M The compound represented by the chemical formula M x Si y (0.1 ⁇ x/y ⁇ 7.0) is called so-called silicide.
  • M in the chemical formula M x Si y is one or more of metalloid elements and metal elements other than Si. That is, M may be a metalloid element, a metal element, or a combination of two or more metalloid elements and metal elements.
  • the metalloid element and the metal element include elements such as B, Ti, V, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Ta, and W, and among them, B, Ti, Mn, Fe, Co, Ni, Y, Zr, Nb, Mo, Ta and W are preferable. Further, among them, B, Ti, Mn, Fe, Co and Ni are preferable, and among them, B, Ti, Mn and Fe are particularly preferable.
  • “X/y” in the chemical formula M x Si y is preferably 0.1 or more and 7.0 or less, particularly 0.2 or more or 4.0 or less, and among them 0.3 or more or 3.0 or less, Among them, 0.4 or more or 2.0 or less is more preferable.
  • “x” in the chemical formula M x Si y is preferably 0.5 or more and 15 or less, more preferably 0.75 or more or 13 or less, and further preferably 1 or more or 11 or less.
  • “y” is preferably 0.5 or more and 27 or less, more preferably 0.75 or more or 23 or less, and even more preferably 1 or more or 19 or less.
  • silicide examples include titanium silicide (TiSi 2 , TiSi, Ti 5 Si 4 , Ti 5 Si 3 ), cobalt silicide (CoSi 2 , CoSi, CoSi, Co 2 Si, Co 3 Si), nickel silicide ( NiSi 2 , NiSi, Ni 3 Si 2 , Ni 2 Si, Ni 5 Si 2 , Ni 3 Si), manganese silicide (Mn 11 Si 19 , MnSi, Mn 5 Si 3 , Mn 5 Si 2 , Mn 3 Si), iron Silicide (FeSi 3 , FeSi, Fe 5 Si 3 , Fe 3 Si), Niobium silicide (NbSi 2 , Nb 5 Si 3 , Nb 3 Si), Copper silicide (Cu 3 Si, Cu 6 Si, Cu 7 Si), Boron silicide (B 3 Si, B 6 Si ) zirconium silicide (ZrSi 2, ZrSi, Zr 5 Si 4, Zr 3 Si 2, Zr 5 Si 3, Zr 3
  • the active material may contain "other components” as necessary.
  • the “other components” include silicon-containing substances such as silicon compounds.
  • examples of the silicon compound include Si 3 N 4 and SiC.
  • the “other component” for example, not a constituent element of the compound represented by the chemical formula M x Si y , but a metal having one or more elements of a metalloid element and a metal element, an oxide It may be contained as a substance, a carbide and a nitride.
  • one of H, Li, B, C, O, N, F, Na, Mg, Al, P, K, Cu, Ca, Ga, Ge, Ag, In, Sn and Au for example, one of H, Li, B, C, O, N, F, Na, Mg, Al, P, K, Cu, Ca, Ga, Ge, Ag, In, Sn and Au.
  • the content of components other than silicon (Si) and compound A is preferably less than 15 at %, more than 0 at% or less than 12 at %, of which 1 at% or more. It is preferable that the amount is large or less than 10 at %, and more preferably more than 2 at% or less than 7 at %.
  • the active material contains a carbon (C) element as the “other component”
  • the content thereof is preferably less than 5 wt% of the amount of the active material, particularly preferably less than 3 wt %.
  • the content of C element in the active material has the above upper limit, it is possible to suppress the decrease in capacity.
  • the active material may contain unavoidable impurities derived from the raw materials.
  • the content of unavoidable impurities in the active material is preferably, for example, less than 2 wt %, more preferably less than 1 wt %, and most preferably less than 0.5 wt.
  • the content of the unavoidable impurities in the active material has the above upper limit, it is possible to suppress the decrease in capacity.
  • the active material may contain a Si oxide containing a Si element.
  • the Si oxide include SiO a (0 ⁇ a ⁇ 2). Specifically, SiO, SiO 2, etc. can be mentioned.
  • the content of the Si element in the active material is preferably more than 50 wt %. Above all, it is preferably more than 52 wt %, particularly preferably more than 60 wt %, more preferably more than 63 wt %, and even more preferably more than 65 wt %.
  • the content of the Si element in the active material is, for example, preferably less than 95 wt%, more preferably less than 88 wt%, further preferably less than 82 wt%, and further preferably 78 wt%. It is preferably less than.
  • the content of the Si element here means the total amount of the Si element contained in the active material.
  • the content of the Si element can be the total amount of the Si element mainly derived from silicon and the Si element derived from the compound represented by M x Si y .
  • the content of Si element having the above lower limit makes it possible to suppress the decrease in capacity.
  • the content of the Si element has the upper limit, expansion and contraction of the active material can be suppressed, and cycle characteristics can be improved.
  • the oxygen (O) element content in the active material is preferably less than 30 wt %. Above all, it is preferably less than 20 wt%, particularly preferably less than 15 wt%, further preferably less than 10 wt%, and further preferably less than 5 wt%.
  • the content of the oxygen (O) element in the active material is, for example, preferably more than 0 wt%, more preferably more than 0.1 wt%, and particularly preferably more than 0.2 wt%. Above all, it is preferably more than 0.6 wt %.
  • the content of the oxygen (O) element in the present active material has the above upper limit, it is possible to suppress an increase in the ratio of the oxygen (O) element that does not contribute to charging and discharging, and suppress a decrease in capacity and charging/discharging efficiency. it can.
  • So-called SiO silicon monoxide
  • SiO silicon monoxide
  • the content of the oxygen (O) element has the above lower limit, it is possible to prevent a rapid reaction with oxygen in the atmosphere.
  • the content of M in the active material is preferably more than 5 wt% and less than 38 wt %. Above all, it is more preferably more than 8% by weight, particularly preferably more than 12% by weight, further preferably more than 15% by weight. On the other hand, the content of M in the active material is, for example, preferably less than 35 wt%, more preferably less than 32 wt%, and particularly preferably less than 29 wt%.
  • the content of M in the active material has the above lower limit, expansion and contraction of the active material can be suppressed, and cycle characteristics can be improved.
  • the content of M in the active material has the above upper limit, it becomes possible to suppress the decrease in capacity.
  • the ratio (M/Si) of the content (wt%) of M to the content (wt%) of the Si element in the active material is preferably, for example, more than 0.05, and is 0.06 or more. It is preferably large, particularly preferably larger than 0.07, and particularly preferably larger than 0.10.
  • the ratio of the content of M to the content of Si element (M/Si) is, for example, preferably less than 0.96, more preferably less than 0.86, and particularly less than 0.76. Is preferable, and particularly preferably less than 0.56.
  • the ratio of the content of M to the content of Si element in the active material has the above lower limit, expansion and contraction of the active material can be suppressed, and cycle characteristics can be improved.
  • the ratio of the content of M to the content of Si element in the active material has the above upper limit, the capacity can be maintained.
  • the content of each element other than oxygen is an element ratio determined by chemical analysis such as inductively coupled plasma (ICP) emission spectroscopic analysis in which the active material is completely dissolved.
  • the oxygen element content can be measured using an oxygen/nitrogen analyzer (for example, manufactured by LECO).
  • the amount of oxygen obtained by such a measuring method means that the amount of oxygen as SiOa (0 ⁇ a ⁇ 2) and an oxygen compound with a metalloid element other than Si and a metal element M are included. ..
  • the active material has a Raman spectrum measured by Raman spectroscopy, and has at least one peak P A derived from the compound represented by the chemical formula M x Si y at a wave number of 200 cm ⁇ 1 to 420 cm ⁇ 1. appear, the wave number 450 cm -1 ⁇ 490 cm -1, tensile strain peak P B derived from the silicon occurs appears at least one, and peaks P C at a wavenumber 500 cm -1 ⁇ 525 cm -1 appears at least one.
  • This active material is P A, P B, by the P C appears, tensile strain occurs in the active material particles, so that the state interatomic distance between Si-Si is extended. As a result, distortion of the crystal structure at the time of initial Li insertion can be eliminated, and both durability and rate characteristics can be improved.
  • the present active material is also an active material having an area ratio of the peaks of P B and P C of I PB /I PC of 0.5 or more.
  • the I PB /I PC is, for example, preferably 1.0 or more, and more preferably 1.5 or more.
  • the I PB /I PC may be, for example, 10.0 or less, 8.0 or less, or 5.0 or less.
  • peaks due to Si defects may appear at wave numbers of 200 cm ⁇ 1 to 420 cm ⁇ 1, and whether or not silicide exists can be examined by an electron diffraction method using a transmission electron microscope (TEM). ..
  • TEM transmission electron microscope
  • P B indicates that the tensile strain in the active material particles is relatively large, and represents the state in which the interatomic distance between Si and Si is extended.
  • P C indicates that tensile strain in the active material particles is relatively small, indicating a state in which shrinks interatomic distance between Si-Si.
  • the full width at half maximum of the peak P B is preferably 40 cm ⁇ 1 or more, more preferably 45 cm ⁇ 1 or more, and even more preferably 50 cm ⁇ 1 or more, while 90 cm ⁇ 1 or less, Among them, 80 cm -1 or less is more preferable.
  • the above M is added to a raw material in a predetermined amount, melted, cast, and further modified as described below. Good.
  • the method is not limited to this.
  • the “peak” in the Raman spectrum obtained by measurement by Raman spectroscopy means a spectrum having a peak top in the Raman spectrum and a full width at half maximum of 5.0 cm ⁇ 1 or more. Therefore, a spectrum having a full width at half maximum of 4.9 cm ⁇ 1 or less is regarded as noise.
  • the full width at half maximum and the peak area can be obtained by setting a baseline for the obtained Raman spectrum and separating the peaks.
  • the laser diffraction/scattering particle size distribution measuring method is a measuring method in which agglomerated powder particles are regarded as one particle (aggregated particle) and the particle size is calculated.
  • the D 50 according to this measuring method means a diameter corresponding to 50% cumulative from the smallest cumulative percentage of the volume-measured particle size measured values in the volume-based particle size distribution chart.
  • the D 50 of the active material is preferably less than 4.0 ⁇ m, more preferably less than 3.8 ⁇ m, particularly preferably less than 3.4 ⁇ m, and further preferably less than 3.2 ⁇ m. It is more preferably less than 3.0 ⁇ m, and further preferably less than 2.8 ⁇ m.
  • the D 50 of the active material is preferably larger than 0.01 ⁇ m, more preferably larger than 0.05 ⁇ m, particularly preferably larger than 0.1 ⁇ m, and further preferably larger than 0.5 ⁇ m. Furthermore, it is preferable that it is larger than 1.0 ⁇ m.
  • the D 50 of the present active material has the above upper limit, the influence of expansion and contraction can be reduced, and the contact with the solid electrolyte in the solid battery electrode can be secured.
  • the D 50 of the present active material has the above lower limit, an increase in the number of contacts with the solid electrolyte due to an increase in the specific surface area can be suppressed, and an increase in contact resistance can be suppressed.
  • the D 50 of the present active material can be adjusted by changing the crushing condition and the crushing condition. However, the adjustment method is not limited to these.
  • D max of the active material is preferably D max less than 25 ⁇ m by and volume particle size distribution measurement obtained by the measurement by a laser diffraction scattering particle size distribution measuring method, more preferably among them less than 20 [mu] m, in particular 15 ⁇ m It is preferably less than 10 ⁇ m, and more preferably less than 10 ⁇ m.
  • D max of the present active material is, for example, preferably larger than 0.5 ⁇ m, more preferably larger than 1.0 ⁇ m, particularly preferably larger than 3.0 ⁇ m, and further preferably 5.0 ⁇ m. It is preferably large.
  • the D 50 according to this measurement method means a diameter corresponding to 100% cumulative from the smallest cumulative percentage of volume-converted particle size measurement values in the volume-based particle size distribution chart.
  • the active material is an aggregate of particles, and can be in the form of powder, lump, or the like.
  • the particle shape of the active material is not particularly limited.
  • a spherical shape, a polyhedral shape, a spindle shape, a plate shape, a scaly shape, an amorphous shape, or a combination thereof can be used.
  • the particles have a spherical shape, and when they are pulverized by a jet mill or the like, the particles are broken along the grain boundaries and thus have an irregular shape.
  • the true density of the present active material is, for example, preferably more than 2.4 g/cm 3, more preferably more than 2.5 g/cm 3 , particularly preferably more than 2.7 g/cm 3 , and further 2 It is preferably larger than 0.9 g/cm 3 .
  • the true density of the active material that for example, preferably less than 3.9 g / cm 3, preferably less than Above all 3.8 g / cm 3, in particular less than 3.7 g / cm 3 preferable.
  • the true density of the present active material has the above lower limit, the electrode density can be improved and the energy density can be improved.
  • the true density of the present active material has the upper limit described above, it is possible to suppress the occurrence of the problem that the content of Si element in the active material decreases and the capacity decreases.
  • the true density of the present active material can be adjusted by the amount of M, for example. However, the method is not limited to this.
  • the specific surface area (SSA) of the present active material is, for example, preferably larger than 2.0 m 2 /g, more preferably larger than 2.5 m 2 /g, particularly preferably larger than 3.0 m 2 /g, Further, it is preferably larger than 3.3 m 2 /g.
  • the specific surface area (SSA) of the present active material is, for example, preferably less than 140 m 2 /g, more preferably less than 60 m 2 /g, and particularly preferably less than 30 m 2 /g. It is preferably less than 10 m 2 /g.
  • the active material SSA has the above upper limit, it is possible to suppress an increase in the number of contacts with the solid electrolyte and suppress an increase in contact resistance.
  • the SSA of the active material can be adjusted by, for example, pulverizing conditions or modifying conditions. However, the adjustment method is not limited to these.
  • the active material is obtained by mixing silicon or a silicon (Si)-containing substance, M or an M-containing substance, and optionally other raw materials, heating and melting to alloy them, and crushing or crushing as necessary. It is preferable to carry out the above-mentioned process and, if necessary, classify it, and then carry out a reforming treatment by using a reforming apparatus utilizing a strong impact force.
  • the method is not limited to this.
  • the above-mentioned "silicon or silicon (Si)-containing substance” is meant to include pure silicon and silicon oxide, as well as silicon-containing substances such as silicon compounds such as Si 3 N 4 and SiC.
  • this active material is obtained by mixing silicon or a silicon (Si)-containing substance, the above M or the above M-containing substance, and optionally other raw materials and heating them to obtain a molten liquid, and then an atomizing method.
  • the alloy may be alloyed by the above method, or may be melted as described above, cast by a roll casting method, and further pulverized in a non-oxygen atmosphere to be alloyed. Other alloying methods may be used.
  • the apparatus shown in FIG. 2 of WO 01/081033 pamphlet is used, and the pressure wave generated by causing boiling due to spontaneous nucleation is used and dropped into the cooling medium. It is preferable to employ a method of alloying molten metal (this alloying method is referred to as "steam explosion atomizing method" in the present specification).
  • the reforming treatment using a reforming device that uses a strong impact force is a reforming treatment that uses a device that can perform mechanical milling or mechanical alloying depending on the condition settings. (SSA) can be increased. Further, when the treatment is carried out by a planetary ball mill, a vibrating ball mill, an attritor, a ball mill, etc., particularly in an active material having a small amount of silicide as in the present application, stronger agglomeration occurs, so that D 50 and D max are targeted values. Will be bigger than This is not suitable as a negative electrode active material used for solid-state batteries.
  • a treatment device having rotary blades in a reaction tank is used, and the peripheral speed of the rotating blades is set to, for example, 3.0 m/s or more and 20 m/s or less and charged into the reaction tank.
  • the peripheral speed of the rotating blades is set to, for example, 3.0 m/s or more and 20 m/s or less and charged into the reaction tank.
  • beads having a particle size of, for example, 1500 times or more and 4000 times or less with respect to D 50 of the active material is, for example, about 100 m/s or more and 130 m/s or less, it can be said that the peripheral speed of the rotary blade is slower than the peripheral speed at the time of fine pulverization processing.
  • the peripheral speed of the rotary blade is, for example, 4.0 m/s or more or 17 m/s or less, particularly 4.5 m/s or more or 15 m/s or less, and among them 5.0 m/s or more, or It is preferably 12 m/s or less. Even when the size of the stirring blade is changed, the same effect can be obtained by adjusting the peripheral speeds.
  • the medium put into the reaction tank can be crushed to about 1/1000 of its size. Therefore, the use of beads having a particle size of, for example, 1500 times or more and 4000 times or less with respect to D 50 of the present active material means that the surface modification is performed preferentially over the pulverization.
  • the particle size of the medium charged into the reaction vessel is preferably 4 mm ⁇ or more and 10 mm ⁇ or less, more preferably 5 mm ⁇ or more or 8 mm ⁇ or less, and further preferably 5 mm ⁇ or more or 7 mm ⁇ or less.
  • the material of the medium for example SiO 2, Al 2 O 3, ZrO 2, SiC, Si 3 N 4, WC , etc. can be cited, among others, Al 2 O 3, ZrO 2 , SiC, Si 3 N 4 is preferable.
  • the above-mentioned reforming treatment is preferably carried out in an inert atmosphere such as a nitrogen atmosphere or an argon gas atmosphere, and further, it is preferable to carry out gradual oxidation when collecting the treated product.
  • an inert atmosphere such as a nitrogen atmosphere or an argon gas atmosphere
  • the inside of the reaction tank at the time of carrying out the reforming treatment is set to the above-mentioned inert atmosphere, and when the treated product is recovered from the reaction tank after the reforming treatment, air or the like is gradually introduced into the reaction tank to gradually remove the treated product.
  • Gradual oxidation that is, gradual oxidation is preferably performed.
  • the present active material can be preferably used as a negative electrode active material for batteries, especially solid batteries, and solid secondary batteries such as solid lithium secondary batteries.
  • a negative electrode active material of a solid battery containing a sulfide solid electrolyte as the solid electrolyte can be suitably used as a negative electrode active material of a solid battery containing a sulfide solid electrolyte as the solid electrolyte.
  • the negative electrode according to this embodiment contains the present active material.
  • the present negative electrode is a member composed of a negative electrode mixture.
  • the negative electrode mixture is, for example, a main active material, a binder if necessary, a conductive material if necessary, a solid electrolyte if necessary, and an active material different from the main active material if necessary. It may contain graphite.
  • the present negative electrode can be formed by applying a negative electrode mixture on a negative electrode current collector.
  • the present negative electrode can be used, for example, in a solid state battery. More specifically, it can be used for a lithium solid state battery.
  • the lithium solid state battery may be a primary battery or a secondary battery, but among them, it is preferably used for a lithium secondary battery.
  • a pellet obtained by press-molding a dry powder composed of an active material, a conductive material and an electrolyte is used as a negative electrode, and the negative electrode does not include a binder and a current collector.
  • solid state battery includes not only a solid state battery that does not contain any liquid substance or gelled substance as an electrolyte, but also a solid state battery that contains a small amount, for example, 10 wt% or less of a liquid substance or gelled substance as an electrolyte.
  • the binder is not particularly limited as long as it is a material that can be used for the negative electrode.
  • polyimide, polyamide, polyamide imide, etc. may be mentioned. These may be used alone or in combination of two or more (hereinafter, these may be collectively referred to as "polyimide or the like").
  • a binder other than these may be used in combination.
  • the details of the binder can be the same as those of known binders, and thus the description thereof is omitted here.
  • Solid electrolyte examples include a sulfide solid electrolyte, an oxide solid electrolyte, a nitride solid electrolyte, a halide solid electrolyte, and the like. Among them, a sulfide solid electrolyte containing a sulfur (S) element is preferable. ..
  • the sulfide solid electrolyte may be any of a crystalline material, glass ceramics and glass.
  • a crystalline material glass ceramics and glass.
  • the oxide solid electrolyte, the nitride solid electrolyte, and the halide solid electrolyte can be the same as known ones, and thus the description thereof is
  • the binder is not particularly limited as long as it is a material that can be used for the negative electrode.
  • examples thereof include fine metal powder and powder of conductive carbon material such as acetylene black.
  • metal fine powder it is preferable to use fine powder of a metal having lithium ion conductivity such as Sn, Zn, Ag and In, or an alloy of these metals.
  • the content of the binder is preferably 1 to 25 parts by mass, and more preferably 2 parts by mass or more or 20 parts by mass or less based on 100 parts by mass of the active material.
  • the content of the conductive material is preferably 1 to 15 parts by mass, and particularly 2 parts by mass or more or 10 parts by mass or less based on 100 parts by mass of the active material. Is more preferable.
  • graphite is blended as the negative electrode active material, the content of graphite is 0.5:95 to 50:50, particularly 0.5:95 to 20:50 in terms of the mixing mass ratio of the main active material and graphite. It is preferably 80.
  • the present negative electrode includes, for example, a carbon material (an active material different from the present active material (particulate), a binder, a conductive material, an electrolyte if necessary, a solvent, and optionally the present active material (Graphite) and other materials are mixed to prepare a negative electrode mixture, and the negative electrode mixture is applied to the surface of a current collector made of Cu or the like and dried to form a negative electrode mixture. It can be formed by pressing. Further, as the present negative electrode for an all-solid-state battery, it is preferable to press-mold a dry powder containing an active material, a conductive material, and an electrolyte, and use the obtained pellet as the negative electrode. At this time, the negative electrode preferably does not include a binder and a current collector.
  • Drying after applying the negative electrode mixture to the surface of the current collector is preferably performed for 1 hour to 10 hours, particularly 1 hour to 7 hours in a non-oxygen atmosphere such as a nitrogen atmosphere or an argon atmosphere.
  • the main active material (particulate), a polyimide precursor compound, an organic solvent such as N-methyl-2-pyrrolidone, and if necessary, a conductive material such as fine metal powder or acetylene black or a carbon material (Graphite) And the like are mixed to prepare a negative electrode mixture, and this negative electrode mixture is applied to the surface of a current collector made of Cu or the like.
  • a polyamic acid (polyamic acid) can be used as the polyimide precursor compound.
  • the coating film can be heated to volatilize the organic solvent, and at the same time, the polyimide precursor compound can be polymerized to obtain a polyimide.
  • the polyimide can be planarly adhered to the surface of the active material particles, and the active materials can be connected in a beaded shape via the connection site made of the polyimide.
  • the first-step heating is preferably performed at 100 to 150°C
  • the second-step heating is preferably performed at 200 to 400°C.
  • the heating time it is preferable that the heating time of the first step is the same as or longer than the heating time of the second step. For example, it is preferable to set the heating time for the first step to 120 to 300 minutes, particularly 180 minutes or more or 240 minutes or less, and the heating time for the second step to 30 to 120 minutes, especially 30 to 60 minutes.
  • an intermediate heating temperature between the first stage and the second stage in the above-described two-stage heating is preferably performed at 150 to 190°C.
  • the heating time is preferably the same as the time of the first step and the second step or an intermediate time between the first step and the second step. That is, when performing heating in three stages, it is preferable that the heating time be the same in each stage, or that the heating time be shortened as the stages progress. Further, when performing heating in four stages, it is preferable to adopt a heating temperature higher than that in the third stage.
  • the heating is preferably performed in an inert atmosphere such as nitrogen or argon. Further, during the heat treatment, it is also preferable to press the active material layer with a pressing member such as a glass plate.
  • a pressing member such as a glass plate.
  • Polyimide can be fixed on a wide range of the surface of the particle, and three-dimensional mesh-like voids can be formed in the active material layer over the entire thickness direction.
  • the non-aqueous electrolyte battery examples include a battery that can be composed of the present negative electrode, a positive electrode, a separator, a non-aqueous electrolyte solution, and the like. You can The non-aqueous electrolyte battery may be a primary battery or a secondary battery, but is preferably a secondary battery.
  • the positive electrode in the present non-aqueous electrolyte battery has, for example, a positive electrode active material layer formed on at least one surface of a current collector.
  • the positive electrode active material layer contains a positive electrode active material.
  • the positive electrode active material those known in the art can be used without particular limitation.
  • various lithium transition metal composite oxides can be used. Examples of such substances include LiCoO 2 , LiNiO 2 , LiMnO 2 , LiMn 2 O 4 , LiCo 1/3 Ni 1/3 Mn 1/3 O 2 , LiCo 0.5 Ni 0.5 O 2 , LiNi 0.7 Co 0.2 Mn 0.1.
  • Li(Li x Mn 2x Co 1-3x )O 2 in the formula, 0 ⁇ x ⁇ 1/3)
  • LiFePO 4 LiMn 1-z M z PO 4 (in the formula, 0 ⁇ z ⁇ 0.1
  • M is at least one metal element selected from the group consisting of Co, Ni, Fe, Mg, Zn, and Cu).
  • a synthetic resin non-woven fabric As the separator used together with the present negative electrode and the positive electrode, a synthetic resin non-woven fabric, a polyolefin such as polyethylene or polypropylene, or a porous film of polytetrafluoroethylene is preferably used.
  • the non-aqueous electrolytic solution in the present non-aqueous electrolytic solution battery is composed of a solution in which a lithium salt as a supporting electrolyte is dissolved in an organic solvent.
  • the organic solvent include carbonate-based organic solvents such as ethylene carbonate, propylene carbonate, dimethyl carbonate, ethylmethyl carbonate and diethyl carbonate, and fluorine-based organic solvents obtained by fluorinating a part of the carbonate-based organic solvent such as fluoroethylene carbonate. Or a combination of two or more thereof is used. Specifically, fluoroethylene carbonate, diethyl fluorocarbonate, dimethyl fluorocarbonate or the like can be used.
  • the lithium salt CF 3 SO 3 Li, ( CF 3 SO 2) NLi, (C 2 F 5 SO 2) 2 NLi, LiClO 4, LiA1Cl 4, LiPF 6, LiAsF 6, LiSbF 6, LiCl, LiBr, LiI , LiC 4 F 9 SO 3 and the like. These may be used alone or in combination of two or more.
  • the solid-state battery according to the present embodiment may include a positive electrode, the present negative electrode, and a solid electrolyte layer provided between the positive electrode and the negative electrode. That is, the present active material can be used as a negative electrode active material included in the negative electrode. In other words, the active material can be used in a solid state battery. More specifically, it can be used for a lithium all-solid-state battery.
  • the lithium all-solid-state battery may be a primary battery or a secondary battery, but among them, it is preferably used for the lithium secondary battery. Examples of the shape of the present solid state battery include a laminate type, a cylindrical type and a square type.
  • the solid electrolyte layer is, for example, a method of dropping a slurry containing a solid electrolyte, a binder and a solvent onto a substrate and scraping it off with a doctor blade, a method of cutting the substrate with the slurry and then cutting with an air knife, a screen printing method, etc. It can be manufactured by a method in which a coating film is formed by, followed by heating and drying to remove the solvent. Alternatively, the solid electrolyte powder may be press-molded and then appropriately processed to be manufactured. What was mentioned above can be used as a solid electrolyte.
  • a positive electrode active material for the positive electrode, a positive electrode active material (particulate), a binder, a conductive material, a solid electrolyte, and a solvent are mixed to prepare a positive electrode mixture, and this positive electrode mixture is applied to the surface of a current collector and dried. It can be formed by pressing and then pressing if necessary.
  • the positive electrode active material porosity
  • the conductive material for the positive electrode, the positive electrode active material (particulate), the conductive material, and the powder of the solid electrolyte may be mixed, press-molded, and then appropriately processed to be manufactured.
  • the positive electrode the same one as the above-mentioned non-aqueous electrolyte battery can be used.
  • Example 1 Silicon (Si) and nickel (Ni) ingots are mixed, heated and melted, and the melt heated to 1700° C. is rapidly cooled using a liquid rapid solidification device (single roll type) to obtain a quenched ribbon alloy. It was The obtained quenched ribbon alloy is roughly crushed using a dry ball mill, and then further dry crushed under a nitrogen atmosphere (atmosphere of less than 1%, the balance being vaporized nitrogen from liquid nitrogen (purity of 99.999% or more)). The particle size was adjusted using to obtain an alloy powder.
  • a liquid rapid solidification device single roll type
  • the obtained alloy powder was subjected to a reforming treatment by using a nanoparticle surface reforming device (product name “Simroyer”, equipped with a rotary blade in the reaction device). That is, 2 kg of ZrO 2 beads and 50 g of the alloy powder were placed in a container having a volume of 2 L, and the mixture was treated under an argon atmosphere at 1500 rpm for 3 hours.
  • the alloy powder after the treatment was crushed or crushed using a dry crusher to adjust the particle size, and then classified with a sieve having an opening of 75 ⁇ m to obtain an alloy powder (sample) as a negative electrode active material.
  • an alloy powder sample
  • it was Si: 63 wt% and Ni: 31 wt %.
  • Example 2 Silicon (Si), titanium (Ti), and nickel (Ni) ingots are mixed, heated and melted, and the molten liquid heated to 1700° C. is rapidly cooled using a liquid rapid solidification device (single roll type) and then rapidly cooled. A ribbon alloy was obtained. The obtained quenched ribbon alloy is roughly crushed using a dry ball mill, and then further dry crushed under a nitrogen atmosphere (atmosphere of less than 1%, the balance being vaporized nitrogen from liquid nitrogen (purity of 99.999% or more)). The particle size was adjusted using to obtain an alloy powder.
  • the obtained alloy powder was subjected to a reforming treatment using a nanoparticle surface reforming device (product name "Shimoloyer", equipped with a rotary blade in the reaction device). That is, 2 kg of ZrO 2 beads and 50 g of alloy powder were placed in a container having a capacity of 2 L, and treatment was performed at 1500 rpm for 3 hours in an argon atmosphere.
  • the alloy powder after the treatment was crushed or crushed using a dry crusher to adjust the particle size, and then classified with a sieve having an opening of 75 ⁇ m to obtain an alloy powder (sample) as a negative electrode active material.
  • an alloy powder sample
  • Example 3 Silicon (Si), titanium (Ti) and cobalt (Co) ingots are heated and melted, and the molten liquid heated to 1700° C. is rapidly cooled using a liquid rapid solidification device (single roll type), and a quenched ribbon alloy Got The obtained quenched ribbon alloy is roughly crushed using a dry ball mill, and then further dry crushed under a nitrogen atmosphere (atmosphere of less than 1%, the balance being vaporized nitrogen from liquid nitrogen (purity of 99.999% or more)). The particle size was adjusted by using to obtain an alloy powder.
  • the obtained alloy powder was subjected to a reforming treatment using a nanoparticle surface reforming device (product name “SIMOLOYER”, equipped with a rotary blade in the reaction device). That is, 2 kg of ZrO 2 beads and 50 g of alloy powder were placed in a container having a volume of 2 L, and treatment was carried out at 1500 rpm for 3 hours in an argon atmosphere.
  • the alloy powder after the treatment was crushed or crushed using a dry crusher to adjust the particle size, and then classified with a sieve having an opening of 75 ⁇ m to obtain an alloy powder (sample) as a negative electrode active material.
  • an alloy powder sample
  • it was Si: 71 wt %
  • Ti 20 wt %
  • Co 7 wt %.
  • Example 4 A silicon (Si) and titanium (Ti) ingot was heated and melted, and the melt heated to 1700° C. was rapidly cooled using a liquid rapid solidification device (single roll type) to obtain a quenched ribbon alloy. Other than that, coarse pulverization and grain size adjustment were performed in the same manner as in Example 1 to obtain an alloy powder.
  • the obtained alloy powder was subjected to a reforming treatment in the same manner as in Example 1 by using a nanoparticle surface reforming device (product name "Shimoloyer", equipped with a rotary blade in the reaction device).
  • the treated alloy powder was crushed or crushed using a wet crusher to adjust the particle size, and then an alloy powder (sample) as a negative electrode active material was obtained.
  • Si: 71 wt% and Ti: 22 wt% were found.
  • ⁇ Comparative Example 1> A silicon (Si) ingot was heated and melted, and the molten liquid heated to 1700° C. was rapidly cooled using a liquid rapid solidification device (single roll type) to obtain a quenched thin strip metal.
  • the obtained quenched thin strip metal is roughly crushed by using a dry ball mill, and then further dry crusher under a nitrogen atmosphere (atmosphere less than 1%, and the balance being vaporized nitrogen from liquid nitrogen (purity 99.999% or more)).
  • the particle size was adjusted using to obtain a metal powder (sample). When a chemical analysis of the obtained metal powder (sample) was performed, it was Si: 99 wt %.
  • Silicon (Si) ingot and massive titanium are mixed at an atomic ratio of 85:15 (weight ratio of 76.8:23.2) and melted using a liquid rapid solidification device (single roll type), and the molten metal is argon gas. Then, it was sprayed on a rotating copper roll and rapidly cooled to produce a Si—Ti alloy. Next, the Si—Ti alloy was crushed for 2 hours in a planetary ball mill using a silicon nitride ball in an argon gas atmosphere to obtain an alloy powder electrode material.
  • composition analysis With respect to the alloy powders (samples) obtained in Examples and Comparative Examples, the content of each element was measured by inductively coupled plasma (ICP) emission spectroscopy. However, regarding oxygen, the content was measured using an oxygen/nitrogen analyzer (manufactured by LECO).
  • ICP inductively coupled plasma
  • the dispersion was put into a water-soluble solvent (ion-exchanged water containing 20 vol% of ethanol) using an automatic sample feeder for a laser diffraction particle size distribution measuring device (“Microtorac SDC” manufactured by Microtrac Bell Co., Ltd.). .. Flow rate in 70 mL / sec, and measuring the particle size distribution using a Microtrac Bell Co. laser diffraction particle size distribution measuring instrument "MT3300II", from the chart of the resulting volume-based particle size distribution was determined D 50.
  • a water-soluble solvent ion-exchanged water containing 20 vol% of ethanol
  • the water-soluble solvent used in the measurement was passed through a 60 ⁇ m filter, the solvent refractive index was 1.33, the particle permeability condition was reflection, the measurement range was 0.021 to 2000 ⁇ m, and the measurement time was 10 seconds.
  • the obtained values were defined as the respective measured values.
  • the specific surface area (SSA) of the alloy powders (samples) obtained in Examples and Comparative Examples was measured as follows. First, 1.0 g of a sample (powder) was weighed in a glass cell (standard cell) for a fully automatic specific surface area measuring apparatus Macsorb (manufactured by Mountech Co., Ltd.) and set in an auto sampler. After replacing the inside of the glass with nitrogen gas, heat treatment was performed at 250° C. for 15 minutes in the nitrogen gas atmosphere. Then, the mixture was cooled for 4 minutes while flowing a mixed gas of nitrogen and helium. After cooling, the sample was measured by the BET single point method. A mixed gas of 30 vol% nitrogen and 70 vol% helium was used as the adsorption gas during cooling and measurement.
  • the true densities of the alloy powders (samples) obtained in Examples and Comparative Examples were measured as follows. First, the sample (powder) was put into a sample basket of 10 cm 3 until the 7th minute, and the amount of the put sample was measured. Next, the sample basket containing the sample was set in the true density measuring device BELPycno (manufactured by Mountech Co., Ltd.), the lid of the device was closed, and the measurement was started. Helium gas was used for the measurement, and the temperature of the measurement part was controlled at 25° C. ⁇ 0.1° C.
  • Raman spectra of the alloy powders (samples) obtained in the examples and comparative examples were obtained by Raman spectroscopy under the following conditions using a Raman spectroscope.
  • Raman measurement is performed on a powder sample, the smaller the unevenness of the sample surface and the higher the density of particles, the more particles are present in the space in which the excitation light and the Raman light are focused, and the lower laser excitation power is used. High Raman light intensity can be obtained.
  • a mini hydraulic press manufactured by Specac and a pellet forming die having a diameter of 7 mm the sample powder was pressed into 1 ton to form a pellet.
  • the wave number calibration Si, which is a standard sample contained in the apparatus body, was measured and calibrated so that the main peak appeared at 520.0 cm -1 .
  • the Raman spectrum was obtained by averaging the spectra measured at four points. If the S/N ratio of the spectrum is poor and it is difficult to determine whether it is a sample-derived peak or noise, the number of measurement points may be increased to average the spectrum.
  • the spectrum may include peaks due to cosmic rays. It is possible to determine whether or not it is a cosmic ray peak, and it can be determined that the peak is a cosmic ray if the peak does not appear in the wave number with good reproducibility when the measurement is repeated.
  • Comparative Example 1 the excitation power was set to 1.0 mW, the exposure time was set to 1 second, and the other conditions were set to the above measurement conditions.
  • the exposure time was set to 10 seconds, and the other conditions were measured as described above.
  • the exposure time was set to 5 seconds, and the other conditions were measured as above.
  • the peak intensity was too strong to exceed the detection limit when measured with the same excitation power and exposure time as those in Examples, so the measurement was performed under the conditions not exceeding.
  • Peak analysis The peaks in the Raman spectrum were fitted by "Peak Fitting", which is a peak fitting program of Nanophoton. The parameters of peak wavenumber, full width at half maximum, and area were obtained by peak fitting.
  • the baseline was set to draw a tangent line to the spectrum with a first-order straight line in the range of 200 to 610 cm ⁇ 1 .
  • Function used for fitting the peak of 500 cm -1 ⁇ 525 cm -1 is used Lorentzian peak of 450 cm -1 ⁇ 490 cm -1 was used a Gaussian function. For the peak at 200 to 420 cm ⁇ 1, a Lorentz function or a Gaussian function with which the fitting converges was used.
  • the peak peak top exists at a wavenumber 450cm -1 ⁇ 490cm -1 P B, the peak peak top is present in the range of wave number 500 cm -1 ⁇ 525 cm -1 was P C.
  • the area ratio of the peaks of P B and P C was defined as I PB /I PC .
  • a spectrum having a peak top in the Raman spectrum and having a full width at half maximum of 5.0 cm ⁇ 1 or more was determined as a “peak”. Therefore, a spectrum having a full width at half maximum of 4.9 cm ⁇ 1 or less was regarded as noise.
  • the surface capacity was set to 2.8 mAh/cm 2 for evaluation.
  • the charge capacity is set to 4200 mAh/g
  • 85 wt% of the sample is contained in the negative electrode active material, so the negative electrode active material layer has a coating amount of 0.78 mg/cm 2 . If the charge capacity of the sample is lower than 4200 mAh/g, the coating amount is increased to adjust the same surface capacity.
  • the negative electrode obtained as described above was punched into a circle having a diameter of 14 mm ⁇ , and vacuum dried at 160° C. for 6 hours. Then, the electrochemical evaluation cell TOMCEL (registered trademark) was assembled in a glove box under an argon atmosphere. Metal lithium was used as the counter electrode.
  • As the electrolytic solution an electrolytic solution prepared by dissolving LiPF 6 in a carbonate-based mixed solvent so as to be 1 mol/l was used. A polypropylene porous film was used as the separator.
  • discharge profile shape was determined based on the discharge curve of the first cycle obtained above. That is, the obtained discharge curves were linearly approximated, the heights of the correlation coefficients were compared, and they were used as an index of the “discharge profile shape”. In addition, in Table 2, it is shown as an index when the numerical value of Comparative Example 3 is 100. At this time, if the potential changes continuously from the beginning of discharge to the end of discharge, that is, if the linearity is high, the correlation coefficient at the time of linear approximation becomes high and there is no plateau or the plateau can be reduced. Will be shown.
  • the discharge rate characteristics were evaluated using the electrochemically evaluated cell TOMCEL (registered trademark) that was initially activated by the method described above.
  • constant-current constant-potential charging was performed at 25C at 0.1C to 0.01V (charging was completed when the current value reached 0.01C)
  • constant-current discharging was performed at 5C to 1.0V.
  • the recording interval during charging/discharging was set so that recording was performed when either 300 s or 5.0 mV change was satisfied. With such a setting, it is recorded every 300 s in the region where the voltage fluctuation is small and is recorded every 5.0 mV change in the region where the voltage fluctuation is large.
  • the cell was placed in an environmental tester set so that the environmental temperature for charging/discharging the battery was 45° C., the battery was prepared for charging/discharging, and the cell was allowed to stand for 5 hours so as to reach the environmental temperature.
  • the charging/discharging range is set to 0.01V-1.0V
  • charging is performed at 0.1C constant current/constant potential and discharging is performed at 0.1C constant current for 1 cycle, and then 1C is charged/discharged 98 times.
  • one charge/discharge cycle was performed at 0.1C.
  • the C rate was calculated based on the discharge capacity at 25° C. at the time of initial activation and the third cycle.
  • the percentage (%) of the numerical value obtained by dividing the discharge capacity at the 100th cycle by the discharge capacity at the second cycle was determined as the 45°C cycle characteristic value.
  • Table 2 it is shown as an index when the numerical value of Comparative Example 3 is 100.
  • the alloy powders (samples) obtained in the examples and comparative examples were used as the negative electrode active material to prepare an electrode mixture, to prepare a sulfide-based all-solid-state battery, and to evaluate the battery characteristics.
  • a foil of In and Li was used as the counter electrode, and a powder represented by the composition formula: Li 5.4 PS 4.4 Cl 0.8 Br 0.8 was used as the solid electrolyte powder.
  • the electrode mixture powder is prepared by mixing the active material powder, the solid electrolyte powder, and the conductive agent (VGCF (registered trademark)) powder in a mortar in a mass ratio of 4.5:86.2:9.3. Uniaxial press molding was performed at 10 MPa to obtain a mixture pellet.
  • VGCF registered trademark
  • ⁇ Battery performance evaluation test> Evaluation of charge capacity
  • the capacity confirmation in the battery characteristic evaluation was evaluated by putting the all-solid-state battery in an environmental tester kept at 25° C. and connecting it to a charge/discharge measuring device. Since the cell capacity is 1.6 mAh, 1 C is 1.6 mA.
  • the charge/discharge of the battery was 0.1 C, and the CCCV system was charged to -0.62 V (charging was completed when the current value reached 0.01 C) to obtain the initial charge capacity.
  • the discharge was 0.1 C, and CC discharge was performed up to 0.88 V.
  • the recording interval during charging/discharging was set so that one point was recorded when either 10 s or 1 mV change was satisfied.
  • a sample having an initial charge capacity of more than 3000 mAh/g is shown in Table 3 as “A”, a sample “B” of 1200 mAh/g or more and 3000 mAh/g or less, and a sample “C” of less than 1200 mAh/g.
  • the materials classified into C do not have sufficient capacity because of insufficient capacity, the subsequent measurements were stopped.
  • discharge profile shape was determined based on the discharge curve obtained above. That is, the obtained discharge curves were linearly approximated, the heights of the correlation coefficients were compared, and they were used as an index of the “discharge profile shape”. In addition, in Table 3, it is shown as an index when the numerical value of Comparative Example 2 is 100. At this time, if the potential changes continuously in the section from the initial stage of discharge to the final stage of discharge, that is, if the linearity is high, the correlation coefficient at the time of linear approximation becomes high and there is no plateau region, or there is a plateau region. Is small.
  • High-rate characteristic evaluation was performed using the above-mentioned charged and discharged cells. The evaluation was carried out continuously in the environmental tester kept at 25°C. The battery capacity was calculated based on the above-mentioned charge capacity, and the C rate was determined. Next, after charging to -0.62V by the 0.1C, CCCV method (charging ends when the current value reaches 0.01C), discharging is performed to 0.88V by the 0.1C, CC method. .. The discharge capacity at this time was set to 0.1 C discharge capacity (A).
  • Cycle evaluation was performed using the cell that underwent the high rate characteristic evaluation described above. The evaluation was carried out continuously in the environmental tester kept at 25°C.
  • the initial current value is set to 5 C, and the CV method is used to perform discharge at 0.88 V (discharge is completed when the current value reaches 0.01 C). It was Next, after charging to -0.62V by the 0.1C, CCCV method (charging ends when the current value reaches 0.01C), discharging is performed to 0.88V by the 0.1C, CC method. ..
  • the discharge capacity at this time was set to 0.1 C discharge capacity (B). “0.1 C discharge capacity (B)”/0.1 C discharge capacity (A) ⁇ 100” was calculated and evaluated as a cycle characteristic value.
  • the index of Comparative Example 2 is set as 100 and shown as an index.

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
PCT/JP2020/005305 2019-02-13 2020-02-12 活物質 WO2020166599A1 (ja)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2020572269A JPWO2020166599A1 (ko) 2019-02-13 2020-02-12

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2019-023491 2019-02-13
JP2019023491 2019-02-13

Publications (1)

Publication Number Publication Date
WO2020166599A1 true WO2020166599A1 (ja) 2020-08-20

Family

ID=72044922

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/005305 WO2020166599A1 (ja) 2019-02-13 2020-02-12 活物質

Country Status (2)

Country Link
JP (1) JPWO2020166599A1 (ko)
WO (1) WO2020166599A1 (ko)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007273182A (ja) * 2006-03-30 2007-10-18 Sony Corp 集電体、負極及び電池
JP2013179033A (ja) * 2012-02-01 2013-09-09 Sanyo Special Steel Co Ltd Ｓｉ系合金負極材料
JP2014078400A (ja) * 2012-10-10 2014-05-01 Toyota Motor Corp 硫化物系固体電池用負極用スラリー、硫化物系固体電池用負極及びその製造方法、並びに、硫化物系固体電池及びその製造方法
JP2014086222A (ja) * 2012-10-22 2014-05-12 Idemitsu Kosan Co Ltd 二次電池の製造方法
JP2016225143A (ja) * 2015-05-29 2016-12-28 エルジー・ケム・リミテッド 二次電池用負極材料及びそれを用いた非水電解質二次電池

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007273182A (ja) * 2006-03-30 2007-10-18 Sony Corp 集電体、負極及び電池
JP2013179033A (ja) * 2012-02-01 2013-09-09 Sanyo Special Steel Co Ltd Ｓｉ系合金負極材料
JP2014078400A (ja) * 2012-10-10 2014-05-01 Toyota Motor Corp 硫化物系固体電池用負極用スラリー、硫化物系固体電池用負極及びその製造方法、並びに、硫化物系固体電池及びその製造方法
JP2014086222A (ja) * 2012-10-22 2014-05-12 Idemitsu Kosan Co Ltd 二次電池の製造方法
JP2016225143A (ja) * 2015-05-29 2016-12-28 エルジー・ケム・リミテッド 二次電池用負極材料及びそれを用いた非水電解質二次電池

Also Published As

Publication number Publication date
JPWO2020166599A1 (ko) 2020-08-20

Similar Documents

Publication Publication Date Title
JP4865556B2 (ja) リチウムイオン電池用の多相ケイ素含有電極
KR101884476B1 (ko) 리튬 이온 전지용 부극재
KR100790271B1 (ko) 비수전해질 2차전지 및 그 제조방법
JP5790282B2 (ja) リチウム二次電池用負極活物質およびリチウム二次電池用負極
CA2752844A1 (en) Method for preparing a particulate of si or siox-based anode material, and material thus obtained
JP5513689B1 (ja) 非水電解液二次電池用負極活物質
JP6601937B2 (ja) 負極活物質、それを採用した負極及び該リチウム電池、並びに該負極活物質の製造方法
TWI635645B (zh) Si-based eutectic alloy for negative electrode active material of power storage device and method for producing same
WO2015041063A1 (ja) ケイ素相含有物黒鉛複合粒子およびその製造方法
JP2014107132A (ja) リチウムイオン二次電池用負極材料、リチウムイオン二次電池用負極、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材料の製造方法
US10483531B2 (en) Negative electrode active material for nonaqueous electrolyte secondary batteries
JP6978563B2 (ja) Ｓｉ系負極活物質
WO2020166658A1 (ja) 活物質
JP2016035825A (ja) リチウムイオン二次電池用負極活物質およびその製造方法並びに負極および電池
WO2020166655A1 (ja) 活物質
WO2020166599A1 (ja) 活物質
WO2015163398A1 (ja) 非水電解液二次電池用負極活物質
JP2019179731A (ja) 全固体電池負極及び全固体型リチウム二次電池
JP7337580B2 (ja) 多元系シリサイドおよびケイ素を含むリチウムイオン電池用負極材料
WO2020166601A1 (ja) 活物質
JP2018098018A (ja) リチウムイオン二次電池用負極活物質およびその製造方法並びに負極および電池
WO2022202357A1 (ja) 活物質及びその製造方法
JP7443851B2 (ja) リチウムイオン電池の負極用粉末材料およびその製造方法
JP2015138625A (ja) リチウムイオン電池用負極活物質

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20755116

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2020572269

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20755116

Country of ref document: EP

Kind code of ref document: A1