WO2014129346A1 - 蓄電デバイス用Ｓｉ系合金負極材料およびそれを用いた電極 - Google Patents

蓄電デバイス用Ｓｉ系合金負極材料およびそれを用いた電極 Download PDF

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WO2014129346A1
WO2014129346A1 PCT/JP2014/053039 JP2014053039W WO2014129346A1 WO 2014129346 A1 WO2014129346 A1 WO 2014129346A1 JP 2014053039 W JP2014053039 W JP 2014053039W WO 2014129346 A1 WO2014129346 A1 WO 2014129346A1
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phase
negative electrode
electrode material
crystallite size
based alloy
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PCT/JP2014/053039
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English (en)
French (fr)
Japanese (ja)
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友紀 廣野
哲嗣 久世
哲朗 仮屋
澤田　俊之
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山陽特殊製鋼株式会社
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Priority to CN201480008723.4A priority Critical patent/CN104995771B/zh
Priority to KR1020157021216A priority patent/KR102120238B1/ko
Publication of WO2014129346A1 publication Critical patent/WO2014129346A1/ja

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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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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 uses a Si-based alloy negative electrode material having excellent conductivity for an electricity storage device that involves movement of lithium ions during charging and discharging, such as a lithium ion secondary battery, a hybrid capacitor, and an all solid lithium ion secondary battery, and the same. It relates to an electrode.
  • Si has attracted attention as a material that can replace carbonaceous materials.
  • the reason is that Si can form a compound represented by Li 22 Si 5 and occlude a large amount of lithium, so that the capacity of the negative electrode can be greatly increased compared to the case of using a carbonaceous material.
  • the storage capacity of the lithium ion secondary battery, the hybrid capacitor, or the all solid state battery can be increased.
  • the Si phase is pulverized by repetition of expansion when alloying with lithium during charging and contraction when dealloying with lithium during discharging.
  • problems such as the Si phase dropping off from the electrode substrate or the electrical conductivity between the Si phases being lost may occur. For this reason, there has been a problem that the life as an electricity storage device is extremely short.
  • Si has poor electrical conductivity compared to carbonaceous materials and metal-based materials, and the efficient movement of electrons associated with charge / discharge is limited. Therefore, as a negative electrode material, a material that supplements conductivity, such as a carbonaceous material. Often used in combination. However, even in such a case, particularly initial charge / discharge and charge / discharge characteristics with high efficiency are problems.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2001-297757
  • Patent Document 2 Japanese Patent Application Laid-Open No. 10-318044
  • the problem to be solved by the present invention is to control lithium ion secondary batteries and hybrids by highly controlling the chemical composition, structure, structure size, etc. of the Si phase and intermetallic compound phase in the Si-based alloy. It is to propose a Si-based alloy negative electrode material that is excellent in charge / discharge characteristics with respect to an electricity storage device that moves lithium ions during charge / discharge, such as a capacitor and an all solid state battery.
  • the inventors have intensively developed, and as a result, refinement of the structure, excellent ion conductivity and electron conductivity, control of the component system that enhances the stress relaxation effect, Si phase and
  • the present inventors have found a Si-based alloy negative electrode material capable of obtaining excellent battery characteristics by controlling the crystallite size of the intermetallic compound phase.
  • a negative electrode material made of a Si-based alloy for an electricity storage device accompanied by movement of lithium ions during charge and discharge has a Si main phase made of Si, and a compound phase made of one or more elements other than Si and Si, The compound phase comprises a phase composed of Si and Cr or Si, Cr and Ti;
  • a negative electrode material made of a Si-based alloy for an electricity storage device accompanied by movement of lithium ions during charge / discharge wherein the negative electrode material made of the Si-based alloy is composed of a Si main phase made of Si and one or more elements other than Si and Si. And the compound phase has a phase comprising Si and Cr, or a phase composed of Si, Cr and Ti, and the Si main phase has a Si crystallite size of 30 nm or less, and There is provided a negative electrode material comprising a Si-based alloy for an electricity storage device, wherein the crystallite size of a compound phase comprising Si and Cr or Si, Cr and Ti is 40 nm or less.
  • the total content of Cr and Ti of the negative electrode material made of the Si-based alloy is 12 to 21 at.
  • a negative electrode material made of a Si-based alloy for an electricity storage device is provided, in which Cr% / (Cr% + Ti%), which is a ratio of Cr and Ti, is 0.15 to 1.00. .
  • At least one selected from the group consisting of Cu, V, Mn, Fe, Ni, Nb, Zn, and Al is used as the compound phase of the negative electrode material made of the Si-based alloy for power storage devices.
  • the total content is 0.05 at. % To 5 at. %, A negative electrode material made of a Si-based alloy for power storage devices is provided.
  • the compound phase of the negative electrode material made of the Si-based alloy for an electricity storage device includes at least one element selected from the group consisting of Mg, B, P, and Ga, and contains the total amount The amount is 0.05 at. % To 5 at. %, A negative electrode material made of a Si-based alloy for power storage devices is provided.
  • a negative electrode made of an Si-based alloy for an electricity storage device characterized in that, in the electrode using the negative electrode material made of the Si-based alloy for an electricity storage device, a polyimide-based binder is included. .
  • Cr is an essential element for generating Si 2 Cr effective for forming a fine eutectic structure with the Si phase
  • Ti is substituted for Cr to increase the lattice constant of Si 2 Cr, thereby increasing the lithium ion. Presumed to increase conductivity.
  • crystallite size of the Si phase to 30 nm or less, and the crystallite size of the compound phase of Si and Cr or the compound phase of Si, Cr and Ti to 40 nm or less, when lithium is occluded / released in Si It is presumed that excellent charge / discharge cycle characteristics can be obtained because it relieves the stress caused by the volume expansion of the metal and prevents electrical isolation due to the atomization of Si.
  • charge / discharge cycle characteristics can be obtained by controlling the chemical components of the Si-based alloy negative electrode material for power storage devices.
  • the total content of Cr and Ti in the phase composed of Si and Cr or Si, Cr and Ti is 12 to 21 at. %, And Cr% / (Cr% + Ti%) is controlled within the range of 0.15 to 1.00, the effect is large.
  • a first sample comprising Cu, V, Mn, Fe, Ni, Nb, Pd, Zn, and Al in a sample containing Si and Cr or a sample containing Si, Cr and Ti as a Si-based alloy negative electrode material for an electricity storage device.
  • One or more additive elements in the group with a total amount of 0.05 at. % To 5 at.
  • the compound phase surrounds the fine Si phase and relieves stress caused by Si pulverization and volume expansion during the insertion and extraction of lithium into and from Si.
  • it plays the role of preventing the collapse of the electrode and the electrical isolation of Si.
  • excellent battery characteristics are provided.
  • a sample containing Si and Cr, or a sample containing Si, Cr and Ti, of the Si-based alloy negative electrode material for an electricity storage device a total of one or more additive elements of the second group consisting of Mg, B, P and Ga
  • the amount is 0.05 at. % To 5 at.
  • the compound phase surrounds the periphery of the fine Si phase and relieves the stress caused by Si pulverization and volume expansion when lithium is absorbed into and released from Si. And it plays the role which prevents the collapse of an electrode and the electrical isolation of Si. Also, by taking a P-type semiconductor structure by adding B, it plays a role of improving the electrical conductivity of Si.
  • the present invention has an excellent effect of providing a Si-based alloy negative electrode material for an electricity storage device having a high capacity and excellent cycle characteristics during repeated charge and discharge.
  • Cross-sectional SEM image of the Si-Si 2 Cr eutectic alloy is a diagram showing a. 3 is an XRD spectrum of a Si—Si 2 Cr eutectic alloy with a changed Cr / Ti ratio. SEM images of Cr and the total amount of change in the Si-Si 2 Cr eutectic alloy was of Ti is a diagram showing a. (A) is an image when the total amount of Cr and Ti is 17%, and (b) is an image when the total amount of Cr and Ti is 19%.
  • the charge / discharge capacity of a lithium ion secondary battery is determined by the amount of lithium transferred. Therefore, there is a demand for a substance that can occlude and release a large amount of lithium. It is most efficient to use lithium metal for the negative electrode material, but there is a possibility of battery ignition caused by the formation of dendrites accompanying charging and discharging. Therefore, studies on alloys that can occlude and release more lithium are currently underway, and among these alloys, Si is promising as a substance that can occlude and release lithium in large quantities. Therefore, Si is adopted as the main phase of the alloy phase.
  • Si causes volume expansion of about 400% when lithium is occluded / released, Si is peeled off or dropped from the electrode, or Si cannot maintain contact with the current collector. A sudden drop in capacity occurs.
  • Si phase size is too large, Si does not react with lithium up to the internal Si phase, expands from the surface layer where Si and lithium easily react, cracks occur, and then the internal unreacted Si phase expands.
  • repeated generation of cracks causes fine powdering of Si. As a result, Si peels off from the electrode, or Si cannot maintain contact with the current collector, resulting in a rapid decrease in charge / discharge capacity associated with the cycle.
  • FIG. 1 is a cross-sectional structure diagram of a Si—Si 2 Cr eutectic alloy according to the present invention, taken by a scanning electron micrograph, wherein the black phase is the Si phase and the white phase is the Si 2 Cr phase. As shown in FIG. 1, both the Si phase and the CrSi 2 phase are extremely fine. In addition, compared with other elements, such as Fe and V, the following is estimated about the cause by which Cr addition produces an extremely fine eutectic structure
  • the amount of additive element necessary to obtain the eutectic of the Si phase and silicide is determined by the type of element, for example, 26.5% for Fe and 3% for V. These can be read from the phase diagrams of Si and additive elements.
  • an element that requires a relatively large amount of addition, such as Fe is used in order to obtain a eutectic, the amount of silicide is inevitably increased, and it tends to be coarse. Therefore, the ratio of the Si phase that occludes / releases Li decreases, and a high discharge capacity cannot be obtained.
  • the Si—Si 2 Cr eutectic alloy can have both a high discharge capacity and an excellent cycle life.
  • charge / discharge characteristics can be further improved by substituting a part of Cr with Ti.
  • the inventor conducted detailed studies on replacing Cr with Ti in the Si—Si 2 Cr eutectic alloy. As a result, Ti was replaced with Cr in Si 2 Cr, and the lattice constant was changed without changing the crystal structure. I thought it would increase.
  • FIG. 2 is a diagram showing X-ray diffraction of a Si—Si 2 Cr eutectic alloy with a changed Cr / Ti ratio. As shown in this figure, by replacing a part of Cr with Ti, the diffraction peak position of Si 2 Cr is shifted to the lower angle side without changing the crystal structure, and the lattice constant is increased. It is considered a thing.
  • the increase in the lattice constant of Si 2 Cr due to the substitution of Ti with Cr in the present invention may play a role of smoothing the passage of Li in the silicide and reducing the accompanying volume change.
  • the characteristics of the lithium ion secondary battery can be further improved by controlling the crystallite size. If the Si phase size is too large, Si does not react with lithium up to the internal Si phase, but expands from the surface layer that easily reacts with lithium in the Si phase, causing cracks, and then the internal unreacted Si phase expands. In addition, repeated generation of cracks causes fine powdering of Si. As a result, Si peels off from the electrode, or Si cannot maintain contact with the current collector, resulting in a rapid decrease in charge / discharge capacity associated with the cycle.
  • the crystallite size of the Si phase of the negative electrode material for lithium ion secondary batteries is controlled to 25 nm or less. In particular, it is desirable to control to 10 nm or less.
  • the crystallite size of the Si phase can be controlled by controlling the cooling rate during solidification after dissolving the raw material powder in addition to the control of the components defined above.
  • Examples of the production method include water atomization, single-roll quenching method, twin-roll quenching method, gas atomization method, disk atomization method, and centrifugal atomization, but are not limited thereto.
  • mechanical milling or the like can be performed.
  • Examples of the milling method include a ball mill, a bead mill, a planetary ball mill, an attritor, and a vibration ball mill, but are not limited thereto.
  • TEM transmission electron microscope
  • XRD powder X-ray diffraction
  • the crystallite size not only the Si main phase but also the crystallite size of the intermetallic compound phase is important.
  • an intermetallic compound such as Si and Cr or Si, Cr and Ti
  • the crystallite size of the intermetallic compound it is possible to contact the Si phase with a larger specific surface area than large particles, and to efficiently absorb and relax the stress due to the volume expansion and contraction of the Si phase. .
  • the crystallite size is controlled to 40 nm or less.
  • the crystallite size is controlled to 20 nm or less. In particular, it is desirable to control to 10 nm or less.
  • the crystallite size of the intermetallic compound can also be directly observed with a transmission electron microscope (TEM). Or it can also confirm by using powder X-ray diffraction.
  • TEM transmission electron microscope
  • a relatively broad diffraction peak is observed as the crystallite size decreases.
  • the crystallite size of the intermetallic compound can be controlled by controlling the cooling rate during solidification after dissolving the raw material powder.
  • Examples of the production method include water atomization, single-roll quenching method, twin-roll quenching method, gas atomization method, disk atomization method, and centrifugal atomization, but are not limited thereto. Further, when the cooling effect is insufficient in the above process, mechanical milling or the like can be performed. Examples of the milling method include a ball mill, a bead mill, a planetary ball mill, an attritor, and a vibration ball mill, but are not limited thereto.
  • the normal eutectic structure is a unique structure with a single additive element amount. If the added amount fluctuates back and forth, it becomes a hypoeutectic or hypereutectic alloy, and an extremely coarse primary crystal is crystallized. Therefore, a high production technique is required to obtain a eutectic structure strictly.
  • a fine structure is obtained in a wide range where the total of Cr and Ti is about 12 to 21%, and the added amount fluctuates back and forth depending on the production lot. But there is no extreme organizational change. FIG.
  • FIG. 3 is a cross-sectional structure diagram of a scanning electron micrograph of a Si—Si 2 Cr eutectic alloy in which the total amount of Cr and Ti is changed.
  • FIG. 3A shows a case where the total amount of Cr and Ti is 17%
  • FIG. 3B shows a case where the total amount of Cr and Ti is 19%.
  • Cr is an essential element that forms Si 2 Cr that forms a fine eutectic structure with the Si phase
  • Ti is an effective element that replaces Cr and increases the lattice constant of Si 2 Cr.
  • Cr% / (Cr% + Ti%) to that in the range 0.15 to 1.00 It is suppressed that Si 2 Ti phase is produced in addition to the Si 2 Cr phase, the coarsening of the Si phase This is preferable in that the effect on the cycle life can be suppressed as described above. Therefore, a more preferable range of the total of Cr and Ti is set to 13 to 20%, and more preferably set to 14 to 19%. Further, a more preferable range of Cr% / (Cr% + Ti%) is 0.15 to 0.90, and more preferably 0.20 to 0.80.
  • the Si x (Cr, Ti) y phase Is preferably x> y.
  • the negative electrode material for a lithium ion secondary battery besides Cr and Ti, an eutectic alloy is formed with Si to obtain a fine Si phase, and a flexible intermetallic compound having better conductivity than Si is obtained.
  • One or more selected from an additive element of the first group consisting of Cu, V, Mn, Fe, Ni, Nb, Zn and Al to be formed can be further contained.
  • the compound phase surrounds the periphery of the fine Si phase, relieving the stress caused by volumetric expansion when Si is pulverized and lithium is absorbed into and released from Si. And it plays the role which prevents the collapse of an electrode and the electrical isolation of Si.
  • the negative electrode material for a lithium ion secondary battery besides Cr and Ti, an eutectic alloy is formed with Si to obtain a fine Si phase, and a flexible intermetallic compound having better conductivity than Si is obtained.
  • One or more elements selected from the second group of additive elements consisting of Mg, B, P and Ga are formed at 0.05 at. % To 5 at. % Can be contained.
  • the compound phase surrounds the periphery of the fine Si phase, mitigating stress caused by volumetric expansion at the time of Si pulverization and insertion / extraction of lithium to / from Si, It plays a role in preventing collapse and electrical isolation of Si.
  • a P-type semiconductor structure by adding B it plays a role of improving the electrical conductivity of Si.
  • By taking an N-type semiconductor structure by adding P it plays a role of improving the electrical conductivity of Si.
  • the total content of Cu, V, Mn, Fe, Ni, Nb, Pd, Zn and Al is 0.05 at. % Or more is necessary, but 5 at. If it exceeds 50%, the amount of lithium inert elements increases, which causes a decrease in charge / discharge capacity. For this reason, the total content of at least one additive element selected from the first group consisting of Cu, V, Mn, Fe, Ni, Nb, Pd, Zn, and Al is 0.05 at. % To 5 at. % Is desirable. More preferably, 0.1 at. % To 3 at. %. In addition, Co, Zr, Pd, Bi, In, Sb, Sn, and Mo aiming at the same effect are also set to 0.05 at. % To 5 at. % Is desirable.
  • the total content of Mg, B, P and Ga is 0.05 at. % Or more is necessary, but 5 at. If it exceeds 50%, the amount of lithium inactive elements increases, which causes a decrease in charge / discharge capacity. For this reason, the total content of at least one additive element selected from the second group consisting of Mg, B, P and Ga is 0.05 at. % To 5 at. % Is desirable. More preferably, 0.1 at. % To 3 at. %. In addition, for Co, Zr, Pd, Bi, In, Sb, Sn, and Mo aiming at similar effects, the total content of at least one additive element is 0.05 at. % To 5 at. % Is desirable.
  • the lithium ion secondary battery negative electrode material according to the present invention By using the lithium ion secondary battery negative electrode material according to the present invention described above, battery characteristics with high capacity, excellent cycle characteristics during repeated charge / discharge, and excellent charge / discharge efficiency at the initial cycle are exhibited.
  • the electrode using the lithium ion secondary battery negative electrode material by including a polyimide-based binder having excellent binding properties, the adhesion with a current collector such as Cu is improved, and charging and discharging are performed while maintaining a high capacity. The effect of improving cycle characteristics is expected.
  • Negative electrode material powders for lithium ion secondary batteries having the compositions shown in Tables 1 and 2 were prepared by a single roll quenching method, a gas atomizing method, or the like described below.
  • a liquid quenching method which is a single roll quenching method
  • a raw material having a predetermined composition is placed in a quartz tube having pores at the bottom, melted at a high frequency in an Ar atmosphere to form a molten metal, and a copper roll that rotates this molten metal.
  • a quenching ribbon was prepared in which the crystallite size of the Si phase was refined by the quenching effect of the copper roll.
  • the milled ribbon is then sealed in an Ar atmosphere together with zirconia balls, SUS304 balls, or SUJ2 balls in a zirconia, SUS304, or SUJ2 pot container and milled for the purpose of processing into particles. It was.
  • a ball mill, a bead mill, a planetary ball mill, an attritor, a vibrating ball mill, and the like can be given.
  • a raw material having a predetermined composition is placed in a quartz crucible having pores at the bottom, heated and melted in a high-frequency induction melting furnace in an Ar gas atmosphere, and then subjected to gas injection in an Ar gas atmosphere and a tapping hot water. Then, gas atomized fine powder was obtained by rapid solidification.
  • a raw material having a predetermined composition is placed in a quartz crucible having pores at the bottom, heated and melted in a high-frequency induction melting furnace in an Ar gas atmosphere, and then in an Ar gas atmosphere, 40000 to 60000 r. p. m.
  • Hot water was poured onto a (revolutions per minute) rotating disk and rapidly solidified to obtain a disk atomized fine powder.
  • the atomized fine powder produced is sealed in a zirconia or SUS304 / SUJ2 pot container with zirconia balls, SUS304 balls, or SUJ2 balls in an Ar atmosphere, and powdered by mechanical milling to control the crystallite size. went.
  • mechanical milling include a ball mill, a bead mill, a planetary ball mill, an attritor, and a vibrating ball mill.
  • the crystallite size of the atomized powder and the intermetallic compound using rapid solidification can be controlled by setting the milling time and the number of rotations.
  • a so-called bipolar coin-type cell using lithium metal as a counter electrode was used.
  • a negative electrode active material Si—Cr—Ti, etc.
  • a conductive material acetylene black
  • a binder material polyimide, polyvinylidene fluoride, etc.
  • a dispersion N-methylpyrrolidone
  • the solvent was evaporated under reduced pressure in a vacuum dryer, and then roll-pressed as necessary, and then punched into a shape that fits the coin cell. Similarly, lithium for the counter electrode was punched into a shape that fits the coin cell.
  • the vacuum drying of the slurry-coated electrode when the polyimide binder material was used, it was dried at a temperature of 200 ° C. or higher in order to fully exhibit the performance. When using polyvinylidene fluoride or the like, it was dried at a temperature of about 160 ° C.
  • the electrolyte used for the lithium ion battery was a 3: 7 mixed solvent of ethylene carbonate and dimethyl carbonate, LiPF 6 (lithium hexafluorophosphate) was used as the supporting electrolyte, and 1 mol was dissolved in the electrolyte. Since the electrolyte solution must be handled in an inert atmosphere with dew point control, the cells were all assembled in a glove box with an inert atmosphere. The separator was cut out in a shape suitable for a coin cell and then held in the electrolyte for several hours under reduced pressure in order to sufficiently permeate the electrolyte into the separator. Thereafter, the negative electrode punched out in the previous step, the separator, and the counter electrode lithium were combined in this order, and the inside of the battery was sufficiently filled with the electrolytic solution.
  • LiPF 6 lithium hexafluorophosphate
  • the measurement of the charge capacity and the discharge capacity is carried out using the above-mentioned bipolar cell, at a temperature of 25 ° C., charging at a current density of 0.50 mA / cm 2 until the potential is equal to the metal lithium electrode (0 V), Furthermore, discharging was performed up to 1.5 V at the same current value (0.50 mA / cm 2 ), and this charging-discharging was made one cycle. In addition, as the cycle life, the above measurement was repeated.
  • No. Nos. 1 to 55 are examples of the present invention.
  • Reference numerals 56 to 126 show comparative examples. These characteristics are judged based on the initial discharge capacity and the discharge capacity maintenance ratio after 50 cycles.
  • the standard is that the initial discharge capacity is 1000 mAh / g or more and the cycle life is 60% or more [discharge capacity maintenance ratio (%) after 50 cycles].
  • example 1 to 12 include the Si main phase and the phase composed of Si, Cr and Ti, the crystallite size of Si is 30 nm or less, and the crystallite size of the compound phase composed of Si, Cr and Ti satisfies the condition of 40 nm or less is doing.
  • Invention Example No. 4 includes Si main phase, Si, Cr, and Ti, the crystallite size of Si is 4 nm, and the crystallite size of Si is 30 nm or less.
  • the crystallite size of the compound phase composed of Si, Cr and Ti is 30 nm, and the crystallite size of the compound phase composed of Si, Cr and Ti satisfies the condition of 40 nm or less.
  • the conditions of the present invention were satisfied, the initial discharge capacity was 1289 mAh / g, the discharge capacity retention rate after 50 cycles was 72%, and both the charge / discharge capacity and the cycle life showed good characteristics.
  • No. of the invention example 13 to 18 include a Si main phase and a phase composed of Si and Cr, the crystallite size of Si is 30 nm or less, and the crystallite size of the compound phase composed of Si and Cr satisfies the condition of 40 nm or less.
  • No. No. 14 contains a Si main phase, Si, and Cr, the crystallite size of Si is 7 nm, and the crystallite size of Si is 30 nm or less. Moreover, the crystallite size of the compound phase consisting of Si and Cr is 15 nm, and the crystallite size of the compound phase consisting of Si and Cr satisfies the condition of 40 nm or less. Further, as described above, the conditions of the present invention were satisfied, the discharge capacity was 1389 mAh / g, the discharge capacity retention rate after 50 cycles was 68%, and both the charge / discharge capacity and the cycle life showed good characteristics.
  • No. of the invention example. 19 to 24 include a Si main phase and a phase composed of Si, Cr, and Ti.
  • the crystallite size of Si is 30 nm or less, and the crystallite size of the compound phase composed of Si, Cr, and Ti is 40 nm or less. is doing.
  • No. No. 23 includes a Si main phase and a phase composed of Si, Cr, and Ti, the Si crystallite size is 8 nm, and satisfies the condition that the Si crystallite size is 30 nm or less. And the crystallite size of the compound phase consisting of Si, Cr and Ti is 16 nm, and the crystallite size of the compound phase consisting of Si, Cr and Ti is 40 nm or less. Further, as described above, the present invention conditions were satisfied, the discharge capacity was 1174 mAh / g, the discharge capacity retention rate after 50 cycles was 87%, and both the charge / discharge capacity and the cycle life showed good characteristics.
  • No. of the invention example 25 to 55 include a Si main phase and a phase composed of Si and Cr, or Si, Cr and Ti.
  • the Si main phase has a Si crystallite size of 30 nm or less, and is composed of Si and Cr, or Si, Cr and Ti.
  • the crystallite size of the compound phase satisfies the condition of 40 nm or less.
  • the total content of at least one additive element selected from the first group consisting of Cu, V, Mn, Fe, Ni, Nb, Zn, and Al is 0.05 at. % To 5 at. %.
  • the total content of at least one additive element selected from the second group consisting of Mg, B, P, and Ga is 0.05 at. % To 5 at. %.
  • No. No. 39 includes a Si main phase and a phase composed of Si, Cr, and Ti, the crystallite size of Si is 17 nm, and the crystallite size of Si is 30 nm or less.
  • the crystallite size of the compound phase composed of Si, Cr and Ti is 38 nm, and the crystallite size of the compound phase composed of Si, Cr and Ti satisfies the condition of 40 nm or less.
  • 0.01 at. % Cu, 0.03 at. % V, 0.01 at. % Mn, 0.01 at. % Fe, 0.01 at. % Ni, 0.02 at. % Zn and 0.02 at. % Al is contained.
  • % B, 1.03 at. % P and 1.12 at. % Ga is contained. As described above, the conditions of the present invention were satisfied, the discharge capacity was 1179 mAh / g, the discharge capacity retention rate after 50 cycles was 80%, and both the charge / discharge capacity and the cycle life showed good characteristics.
  • Comparative Example No. 73 to 90 include a phase composed of Si and Cr or Si, Cr and Ti, and the crystallite size of the compound phase composed of Si and Cr or Si, Cr and Ti satisfies the condition of 40 nm or less. Since the Si crystallite size of the Si main phase does not satisfy the condition of 30 nm or less, the conditions of the present invention are not satisfied. Comparative Example No. 91 to 108 include a phase composed of Si and Cr, or Si, Cr and Ti, and the Si crystallite size of the Si main phase satisfies the condition of 30 nm or less. However, Si and Cr, or Si and Cr Since the crystallite size of the compound phase composed of Ti does not satisfy the condition of 40 nm or less, the present invention condition is not satisfied.
  • Comparative Example No. 109 to 126 include a phase composed of Si and Cr or Si and Cr and Ti, but the Si main phase does not satisfy the condition that the Si crystallite size is 30 nm or less, and Si and Cr, or Si and Cr and Ti. Since the crystallite size of the compound phase consisting of does not satisfy the condition of 40 nm or less, the condition of the present invention is not satisfied.

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PCT/JP2014/053039 2013-02-19 2014-02-10 蓄電デバイス用Ｓｉ系合金負極材料およびそれを用いた電極 WO2014129346A1 (ja)

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JP6329888B2 (ja) * 2013-12-13 2018-05-23 エルジー・ケム・リミテッド 二次電池用負極材及びこれを用いた二次電池
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