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CN105409040A - Graphite composite particle containing silicon phase and manufacturing method thereof - Google Patents

Graphite composite particle containing silicon phase and manufacturing method thereof Download PDF

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Publication number
CN105409040A
CN105409040A CN201480041817.1A CN201480041817A CN105409040A CN 105409040 A CN105409040 A CN 105409040A CN 201480041817 A CN201480041817 A CN 201480041817A CN 105409040 A CN105409040 A CN 105409040A
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China
Prior art keywords
silicon
composite particles
phase
particles
graphite
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CN201480041817.1A
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Chinese (zh)
Inventor
山本浩司
祢宜教之
永田辰夫
西原克浩
藤原徹
小林幸司
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Chuo Denki Kogyo Co Ltd
Nippon Steel Corp
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Chuo Denki Kogyo Co Ltd
Nippon Steel Corp
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Priority claimed from JP2013191941A external-priority patent/JP2015060640A/en
Priority claimed from JP2013191947A external-priority patent/JP2015060642A/en
Priority claimed from JP2013191944A external-priority patent/JP2015060641A/en
Application filed by Chuo Denki Kogyo Co Ltd, Nippon Steel Corp filed Critical Chuo Denki Kogyo Co Ltd
Publication of CN105409040A publication Critical patent/CN105409040A/en
Pending legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/21—After-treatment
    • 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
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/06—Metal silicides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

本发明的课题在于，提供能够提高锂离子二次电池等非水电解质二次电池的充放电循环特性的复合颗粒及其制造方法。本发明所述的硅相含有物石墨复合颗粒具备多个鳞片状石墨颗粒和含硅相颗粒。多个鳞片状石墨颗粒排列成层状。含硅相颗粒包含硅相和非硅相。并且，该含硅相颗粒被多个鳞片状石墨颗粒夹持。并且，由该硅相含有物石墨复合颗粒制作电极密度为1.70±0.02g/cm3的电极时，在该电极的X射线衍射图像中，“归属于(110)面的峰的强度I(110)”相对于“归属于(004)面的峰的强度I(004)”之比优选在0.0010以上且0.0300以下的范围内。

An object of the present invention is to provide composite particles capable of improving the charge-discharge cycle characteristics of nonaqueous electrolyte secondary batteries such as lithium ion secondary batteries, and a method for producing the same. The silicon-phase-containing graphite composite particle of the present invention includes a plurality of flaky graphite particles and silicon-containing phase particles. Multiple flaky graphite particles are arranged in layers. Silicon-containing phase particles comprise a silicon phase and a non-silicon phase. And, the silicon-containing phase particles are sandwiched by a plurality of flaky graphite particles. In addition, when an electrode having an electrode density of 1.70 ± 0.02 g/cm 3 is produced from the graphite composite particles containing the silicon phase, in the X-ray diffraction image of the electrode, the intensity of the peak belonging to the (110) plane I (110 )" to "the intensity I(004) of the peak assigned to the (004) plane" is preferably in the range of 0.0010 to 0.0300.

Description

Silicon is mutually containing thing graphite composite particles and manufacture method thereof
Technical field
The present invention relates to silicon mutually containing thing graphite composite particles and manufacture method thereof.
Background technology
In the past, as lithium rechargeable battery negative electrode active material and usually use the particle etc. of graphite, silicon, tin.Among these negative electrode active materials, silicon grain receives much concern because making the negative pole of high discharge capacity.But the change in volume of the silicon grain accompanied with lithium ion of attracting deposit/discharge is greatly to about 4 times.Therefore, for when repeating discharge and recharge using silicon grain as the battery of negative electrode active material, the conductive network of silicon grain is destroyed gradually, its result, and the discharge capacity of battery reduces.
Thus, in recent years, in order to take into account " raising of discharge capacity " and " suppressing the discharge capacity caused because of charge and discharge cycles to reduce " of the negative pole of lithium rechargeable battery, propose " making the 3 SiC 2/graphite composite particles that silicon and graphite are composited ".As this 3 SiC 2/graphite composite particles, include, for example out: " a kind of composite graphite particles, it contains silicon, flaky graphite and Carbonaceous matter, Carbonaceous matter containing quantity not sufficient 20 quality %, the D bands of a spectrum 1360cm recorded by the Raman spectroscopy employing argon laser -1peak intensity ID and G bands of a spectrum 1580cm -1the ratio I D/IG (R value) of peak intensity IG is less than 0.4 (such as with reference to Japanese Unexamined Patent Publication 2005-243508 publication etc.) "; " a kind of composite material; it comprises silicon grain, graphite material and carbonaceous material; implement the process for giving compression stress and shearing force and possess silicon grain and the closely sealed structure of graphite material, the surface at least partially of described silicon grain has the overlay film (such as with reference to Japanese Unexamined Patent Publication 2008-235247 publication etc.) formed by carbonaceous material " etc.But, be difficult to be sufficient using these 3 SiC 2/graphite composite particles as the charge/discharge cycle characteristics of the lithium rechargeable battery of negative electrode active material.
In addition, proposing Si oxides such as utilizing silicon monoxide in recent years replaces silicon grain as electrode active material.Si oxide has by the mutually fine tissue mixed of silicon phase and silicon dioxide.Further, fine silicon suppresses the Particle attrition caused with the absorption/release of lithium expansion/contraction together mutually.In addition, the silicon phase containing ratio of silicon oxide particles is lower than pure silicon granules, and the change in volume therefore accompanied with discharge and recharge also diminishes, and the cycle characteristics of battery improves.
A large amount of compounding conductive auxiliary agent in Si oxide when making thin electrodes (electrode that the coating weight of the blend of unit are is few) by this blend, the cycle characteristics of this electrode is excellent.But, conductive auxiliary agent is reduced to can be practical level, when increasing its thickness, the change in volume accompanied with discharge and recharge becomes greatly simultaneously, cycle characteristics is impaired.Thus, attempted Si oxide and graphite to carry out recently mixing or Composite to suppress the charge/discharge capacity of electrode.Such as, exist and make Si oxide be carried on the near surface of globular graphite thus the product this Si oxide and carbon Composite obtained (such as reference Japanese Unexamined Patent Publication 2012-124116 publication etc.).But, in order to increase discharge capacity increase the combined amount of Si oxide time, there is denseization to globular graphite surface portion in Si oxide, the expansion/contraction accompanied with discharge and recharge is concentrated to local, thus fully cannot meet cycle characteristics.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2005-243508 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2008-235247 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2012-124116 publication
Summary of the invention
the problem that invention will solve
Problem of the present invention is, provides composite particles and the manufacture method thereof that can improve the charge/discharge cycle characteristics of the rechargeable nonaqueous electrolytic batteries such as lithium rechargeable battery.
for the scheme of dealing with problems
Silicon described in one aspect of the present invention possesses multiple flaky graphite particle and siliceous phase particle containing thing graphite composite particles mutually.Multiple flaky graphite particle is arranged in stratiform.Multiple flaky graphite particle preferably carries out orientation along equidirectional or roughly the same direction.Siliceous phase particle comprises silicon phase and non-silicon phase.Further, this siliceous phase particle is clamped by multiple flaky graphite particle.
The present inventor etc. conduct in-depth research, and result specify that: silicon as described above can improve the charge/discharge cycle characteristics of rechargeable nonaqueous electrolytic battery mutually further containing thing graphite composite particles.The present inventor etc. infer that its reason is as follows.
By comprise silicon of the present invention forms electrode containing the electrode mix paste of thing graphite composite particles mutually time, the stacked direction that silicon contains thing graphite composite particles containing thing graphite composite particles with silicon mutually mutually carries out stacked along the mode in thickness of electrode direction.Its result, its electrode is such as formed along thickness of electrode direction ... // graphite linings/siliceous phase stratum granulosum/graphite linings // graphite linings/siliceous phase stratum granulosum/graphite linings // ... repeat layer (in foregoing teachings, the symbol of " // " represents intergranular boundary line, and "/" represents the boundary line of silicon mutually containing the layer in thing graphite composite particles.)。Due to this electrode structure, the change in volume of silicon mutually containing thing graphite composite particles is concentrated to thickness of electrode direction.Further, in inside battery, electrode is applied to the power of vertically compression electrodes constantly.Therefore, be suppressed because of this compression stress containing the destruction of thing graphite composite particles as the electrode of electrode active material mutually using this silicon, and then the charge/discharge cycle characteristics of rechargeable nonaqueous electrolytic battery is improved further (it should be noted that, usually there is hole in the electrodes, therefore, when silicon change in volume occurs containing thing graphite composite particles to all directions mutually, the destruction of suppressing electrode is difficult to.)。
Above-mentioned silicon is mutually containing in thing graphite composite particles, and non-silicon is preferably the nonactive phase of alkali metal ion mutually.The nonactive phase of alkali metal ion is such as that metal silicide is equal.Alkali metal ion is such as lithium ion, sodium ion, potassium ion etc.
Above-mentioned silicon mutually containing in thing graphite composite particles, preferably, siliceous phase particle by multiple flaky graphite particle clampings and siliceous phase particle be attached on the outer surface of outermost flaky graphite particle by the low-temperature heat handled thing of organic compound.At the temperature of " the low-temperature heat handled thing of organic compound " expression in the scope of 300 DEG C ~ 600 DEG C mentioned, organic compound is carried out to the handled thing of heat treated herein.This is because, by silicon is made this structure containing thing graphite composite particles mutually, silicon can be increased mutually containing the siliceous phase granule content in thing graphite composite particles, and then the discharge capacity/charging capacity improving the rechargeable nonaqueous electrolytic batteries such as lithium rechargeable battery can be contributed to.
By the way, by comprise above-mentioned silicon form electrode containing the electrode mix paste of thing graphite composite particles mutually time, such as formed along thickness of electrode direction in this electrode ... // siliceous phase stratum granulosum/graphite linings/siliceous phase stratum granulosum/graphite linings/siliceous phase stratum granulosum // siliceous phase stratum granulosum/graphite linings/siliceous phase stratum granulosum/graphite linings/siliceous phase stratum granulosum // ... repeat layer (in foregoing teachings, the symbol of " // " represents intergranular boundary line, and "/" represents the boundary line of silicon mutually containing the layer in thing graphite composite particles.)。
Above-mentioned silicon is mutually containing in thing graphite composite particles, and the mass ratio of the heat treated thing of flaky graphite particle, siliceous phase particle and organic compound is preferably 97 ~ 60:1 ~ 30:2 ~ 10.Herein, the statement of " 97 ~ 60 " refers to less than 97 and more than 60, and the statement of " 1 ~ 30 " refers to more than 1 and less than 30, and the statement of " 2 ~ 10 " refers to more than 2 and less than 10 (following identical).This is because, if silicon contains the as mentioned above compounding of thing graphite composite particles mutually, then can form the electrode of the balancing good of discharge capacity, efficiency for charge-discharge and charge/discharge cycle characteristics.
Above-mentioned silicon is mutually containing in thing graphite composite particles, and the median particle diameter d50 of siliceous phase particle is preferably less than 2 μm.It should be noted that, the median particle diameter d50 of siliceous phase particle is more little more preferred.This is because, can disperse due to attract deposit/discharge the change in volume that alkali metal ion (such as lithium ion etc.) accompanies and the stress produced.
Above-mentioned silicon is mutually containing in thing graphite composite particles, and siliceous phase particle is preferably SiOx particle (wherein, 0<x≤0.9).By the way, this SiOx particle is preferably specific area 40m 2the case of wet attrition thing of/more than g.It should be noted that, this specific area is preferably 200m 2/ below g.Attempted in the past pulverizing and reduced silicon grain to improve cycle characteristics.This is because, when the particle diameter of silicon grain is large, silicon grain produces breakage etc. because of expansion/contraction during discharge and recharge, in each circulation, silicon grain generates newborn face, this newborn face and electrolyte react, and all consume electrolyte in each circulation, and therefore circulation deterioration occurs, if but with regard to reducing the particle diameter of silicon grain from first, then this problem can not be there is.This can lowly by the efficiency for charge-discharge in cyclic process infer.Further, when reducing the particle diameter of silicon grain, the specific area of silicon grain increases and the oxidation in newborn face aggravation, thus this silicon grain possesses the line and staff control of silicon phase and silicon dioxide phase.In the present invention, this silicon grain is called " silicon oxide particles " or " SiOx particle ".Further, in the present invention, " x " of SiOx as implied above be greater than 0 and be less than 0.9 scope in.Multiple flaky graphite particle is arranged in stratiform.
Above-mentioned silicon is mutually containing in thing graphite composite particles, and siliceous phase particle is preferably SiOx particle (wherein, 0.9<x<1.3).
Above-mentioned silicon is mutually containing in thing graphite composite particles, and preferably, SiOx particle is clamped by multiple flaky graphite particle and SiOx particle is attached on the outer surface of outermost flaky graphite particle by non-graphite matter carbon.This is because, by silicon is made this structure containing thing graphite composite particles mutually, silicon can be increased mutually containing the SiOx granule content in thing graphite composite particles, and then the discharge capacity/charging capacity improving the rechargeable nonaqueous electrolytic batteries such as lithium rechargeable battery can be contributed to.
By the way, by comprise above-mentioned silicon form electrode containing the electrode mix paste of thing graphite composite particles mutually time, in this electrode, such as formed along thickness of electrode direction ... //SiOx stratum granulosum/graphite linings/SiOx stratum granulosum/graphite linings/SiOx stratum granulosum //SiOx stratum granulosum/graphite linings/SiOx stratum granulosum/graphite linings/SiOx stratum granulosum // ... repeat layer (in foregoing teachings, the symbol of " // " represents intergranular boundary line, and "/" represents the boundary line of silicon mutually containing the layer in thing graphite composite particles.)。
Above-mentioned silicon is mutually containing in thing graphite composite particles, and the mass ratio of flaky graphite particle, SiOx particle and non-graphite matter carbon is preferably 97 ~ 55:1 ~ 30:2 ~ 15, is more preferably 97 ~ 70:1 ~ 15:2 ~ 15.Herein, the statement of " 97 ~ 55 " refers to less than 97 and more than 55, and the statement of " 1 ~ 30 " refers to more than 1 and less than 30, and the statement of " 2 ~ 15 " refers to " more than 2 and less than 15 " (following identical).This is because, if silicon contains the as mentioned above compounding of thing graphite composite particles mutually, then can form the electrode of the balancing good of discharge capacity, efficiency for charge-discharge and charge/discharge cycle characteristics.
Making electrode density containing thing graphite composite particles mutually by above-mentioned silicon is 1.70 ± 0.02g/cm 3electrode time, in the X-ray diffraction image of this electrode, " belonging to the intensity I (110) at the peak in graphite (110) face " is relative to the ratio of " belonging to the intensity I (004) at the peak in graphite (004) face " preferably more than 0.0010 and in the scope of less than 0.0300.This is because if silicon meets this condition containing thing graphite composite particles mutually, then the degree of orientation of the flaky graphite particle in electrode becomes good, can more effectively realize above-mentioned effect.
Above-mentioned silicon mutually containing in thing graphite composite particles, the long axis length of flaky graphite particle be preferably more than 1.5 relative to stacked direction length ratio (so-called draw ratio) and in the scope of less than 10, be more preferably more than 1.5 and in the scope of less than 5.This is because if above-mentioned silicon meets this condition containing thing graphite composite particles mutually, then the degree of orientation of the flaky graphite particle in electrode becomes good, can more effectively realize above-mentioned effect.
The manufacture method of silicon described in another aspect of the present invention mutually containing thing graphite composite particles possesses once-combined particle preparation section, mixed-powder preparation section and heating process.It should be noted that, once-combined particle preparation section and mixed-powder preparation section carry out with dry type.In once-combined particle preparation section, give compression stress and shearing force to the hybrid particles of siliceous phase particle and flaky graphite particle, thus prepare once-combined particle.It should be noted that, siliceous phase particle comprises silicon phase and non-silicon phase.In this once-combined particle preparation section, preferably, carry out MECHANOCHEMICAL (registered trade mark) to the hybrid particles of siliceous phase particle and flaky graphite particle to process.In mixed-powder preparation section, once-combined particle prepares mixed-powder with the organic compound of solid through mixing.In heating process, heat treated is carried out to mixed-powder.Its result, organifying polymer melt is attached to once-combined particle, and then this organic compound conversions becomes carbon precursor or changes into non-graphite matter carbon whole or in part.
Above-mentioned silicon is manufactured mutually containing thing graphite composite particles by the manufacture method of this silicon mutually containing thing graphite composite particles.That is, this silicon can show above-mentioned effect containing thing graphite composite particles mutually.
Above-mentioned silicon is mutually containing in the manufacture method of thing graphite composite particles, and non-silicon is preferably metal silicide phase mutually.In described situation, in heating process, at the temperature preferably within the scope of 300 DEG C ~ 600 DEG C, heat treated is carried out to mixed-powder.
Above-mentioned silicon is mutually containing in the manufacture method of thing graphite composite particles, and siliceous phase particle is preferably SiOx (wherein, 0<x<1.3).In described situation, organic compound is preferably non-graphite matter carbon raw material.
The manufacture method of silicon described in another aspect of the present invention mutually containing thing graphite composite particles possesses middle composite particles preparation section and heating process.It should be noted that, middle composite particles preparation section carries out with dry type.In middle composite particles preparation section, give compression stress and shearing force at temperature more than the softening point of organic compound of the mixture of the organic compound of siliceous phase particle, flaky graphite particle and solid, thus composite particles in the middle of preparation.It should be noted that, siliceous phase particle comprises silicon phase and non-silicon phase.In this middle composite particles preparation section, preferably, carry out MECHANOCHEMICAL (registered trade mark) to the mixture of the organic compound of siliceous phase particle, flaky graphite particle and solid to process.This is because under the situation that compression stress works, the organic compound of melting plays the effect of bonding agent and makes flaky graphite particle increase with the stacked quantity of siliceous phase particle.In heating process, heat treated is carried out to middle composite particles.Its result, organic compound conversions becomes carbon precursor or changes into non-graphite matter carbon whole or in part.
Above-mentioned silicon is manufactured mutually containing thing graphite composite particles by the manufacture method of this silicon mutually containing thing graphite composite particles.That is, this silicon can show above-mentioned effect containing thing graphite composite particles mutually.
Above-mentioned silicon is mutually containing in the manufacture method of thing graphite composite particles, and non-silicon is preferably metal silicide phase mutually.In described situation, in heating process, at the temperature preferably within the scope of 300 DEG C ~ 600 DEG C, heat treated is carried out to middle composite particles.
Above-mentioned silicon is mutually containing in the manufacture method of thing graphite composite particles, and siliceous phase particle is preferably SiOx (wherein, 0<x<1.3).In described situation, organic compound is preferably non-graphite matter carbon raw material.
The manufacture method of above-mentioned silicon mutually containing thing graphite composite particles can also possess case of wet attrition operation, mixed processes and drying process.In case of wet attrition operation, the coarse granule of siliceous phase particle prepares particulate slurry through case of wet attrition.In mixed processes, in particulate slurry, mix flaky graphite particle and prepare mixed slurry.In drying process, mixed slurry drying and prepare mixed-powder.Further, in middle composite particles preparation section, compression stress and shearing force is given at temperature more than the softening point of organic compound of the mixture of the organic compound of mixed-powder and solid, thus composite particles in the middle of preparation.It should be noted that, in drying process, without the need to make to use in case of wet attrition solvent evaporate completely, be dried to the degree that can be used as powder and carry out processing.In described situation, siliceous phase particle is preferably SiOx (wherein, 0<x≤0.9), and organic compound is preferably non-graphite matter carbon raw material.
Above-mentioned silicon can be used as containing thing graphite composite particles the active material forming electrode mutually, especially can be used as the active material of the electrode forming rechargeable nonaqueous electrolytic battery.The rechargeable nonaqueous electrolytic battery herein mentioned with lithium rechargeable battery representatively.
Accompanying drawing explanation
Fig. 1 is the schematic side elevation of silicon mutually containing thing graphite composite particles described in embodiments of the present invention.
Fig. 2 is the figure that the silicon schematically shown described in embodiments of the present invention contains the structure of the electrode that thing graphite composite particles is formed mutually.
Fig. 3 is the reflected electron image photo of the section of Si oxide graphite composite particles described in embodiment 12.It should be noted that, in photo, gray area represents flaky graphite particle, and white portion represents silicon oxide particles.
description of reference numerals
100 silicon are mutually containing thing graphite composite particles
110 siliceous phase particles
120 flaky graphite particles
200 electrodes
210 active material layers
220 collector bodies
Embodiment
The formation > of < silicon mutually containing thing graphite composite particles
As illustrated in figures 1 and 2, the silicon described in embodiments of the present invention is formed containing the heat treated thing (not shown) of thing graphite composite particles 100 primarily of siliceous phase particle 110, flaky graphite particle 120 and organic compound mutually.This silicon is mutually containing in thing graphite composite particles 100, as illustrated in figures 1 and 2, multiple flaky graphite particle 120 holds siliceous phase particle 110 and the outer surface of outermost flaky graphite particle 120 adheres to siliceous phase particle 110 (with reference to Fig. 1).Below, describe in detail for each inscape of silicon mutually containing thing graphite composite particles 100.
(1) siliceous phase particle
In present embodiment, siliceous phase particle 110 is containing silicon phase and non-silicon phase.As so siliceous phase particle 110, such as silicon alloy particle, SiOx particle (0<x<1.3) can be listed.Below, be described for silicon alloy particle and SiOx particle (0<x<1.3) respectively.
(1-1) silicon alloy particle
Silicon alloy particle is as mentioned above containing silicon phase and non-silicon phase.Below, for each describe in detail mutually after, the manufacture method for silicon alloy particle is described.
Silicon is be active phase relative to alkali metal ions such as lithium ion, sodium ion, potassium ions mutually.This silicon mutually in import and be difficult to be the strain (dislocation) of complete crystalline.
The maximum particle diameter of silicon phase is preferably being greater than 0nm and in the scope of below 500nm, more preferably be greater than 0nm and for below 200nm scope in, further preferred be greater than 0nm and for below 100nm scope in, particularly preferably in be greater than 0nm and for below 50nm scope in.Herein, when the maximum particle diameter of silicon phase refers to and utilizes transmission electron microscope (TEM) to observe, the maximum among the major diameter of the silicon phase crystal grain in the visual field.
Non-silicon is be inactive phase for alkali metal ion mutually, is the phase not absorbing in fact alkali metal ion.When alkali metal ion is lithium ion, as non-silicon phase, preferably comprise the phase (hereinafter referred to as metal silicide phase) of metal silicide.Metal silicide is formed by silicon atom and at least one metallic atom.It should be noted that, metal silicide can be intermetallic compound.In addition, preferably this metal silicide mutually in import and be difficult to be the strain (dislocation) of crystalline completely.
This metal silicide MSix represents.Herein, M is more than one metallic element, and Si is silicon.And, M is preferably selected from by aluminium (Al), iron (Fe), nickel (Ni), titanium (Ti), copper (Cu), cobalt (Co), chromium (Cr), vanadium (V), manganese (Mn), zinc (Zn), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), indium (In), hafnium (Hf), tantalum (Ta), tungsten (W), platinum (Pt), lanthanum (La), cerium (Ce), at least one metallic element in the group that praseodymium (Pr) and neodymium (Nd) form.
The example of the metal silicide represented with MSix is TiSi 2, Ni 4ti 4si 7and NiSi 2deng.In the scope not damaging purport of the present invention, metal silicide mutually in can comprise tissue beyond MSix.In described situation, metal silicide mutually in MSix content be preferably 20 more than volume %, be more preferably 30 more than volume %.
Non-silicon can be such as Al mutually 2cu, NiAl 3, Ni 2al 3, Al 3ce, Mn 3sn, Ti 6sn 5etc. the compound comprising Al, Sn element; Also can be TiCo 2, Cu 4ti, Fe 2ti, Co 2niV etc. are by the transition metal intermetallic compound be combined to form each other.
The manufacture method of silicon alloy particle does not limit.Preferred employing can manufacture the method for the material with fine crystal particle diameter.As such manufacture method, the quenching freezing method that such as atomization, roller quenching method, rotary electrode method etc. are representative can be listed; Improve the casting (such as, thin strand continuous metal cast process) of cooling rate; Employ MA (mechanical alloying) method and MG (mechanical lapping) method etc. of solid phase reaction.Further, in embodiments of the present invention, silicon alloy particle preferably solidifies operation, pulverizing process and mechanical grinding processes via metal melting operation, quenching and manufactures.Below, describe in detail for each operation.
(a) metal melting operation
In metal melting operation, the multiple raw metals comprising silicon (Si) are made into specific molten metal through melting.In described situation, silicon is added in raw metal to make silicon separate out mutually.If utilize equilibrium state diagram, then easily can determine the addition of silicon.It should be noted that, raw metal not necessarily needs melting simultaneously, also can periodically melting.
Raw metal makes molten condition because of heating usually.Raw metal preferably carries out heating and melting under non-active gas or vacuum environment.
As heating means, high-frequency induction heating, arc discharge heating (electric arc melting), plasma discharge heating (plasma melting), resistance heating etc. can be listed.It should be noted that, in this operation, importantly form the uniform liquation of composition.
B operation is solidified in () quenching
Quenching is solidified in operation, and particular alloy liquation solidifies through quenching and generates specific alloy solidfied material.It should be noted that, this quenching is solidified in operation, and particular alloy liquation preferably carries out quenching with cooling rate more than 100K/ second and solidifies, and particular alloy liquation more preferably carries out quenching with cooling rate more than 1000K/ second and solidifies.
As quench condensation solid method (quenching casting method), gas atomization, roller quenching method, dull and stereotyped casting, rotary electrode method, atomization of liquid method, melt spinning method method etc. can be listed.
Gas atomization is following method: the molten metal in tundish is flowed out from the pore of tundish bottom, and the thread to this molten metal blows argon gas (Ar), nitrogen (N 2) and the non-active gas of the high pressure such as helium (He), crushing metal liquation also makes it be frozen into pulverous method, can obtain spherical particle.
Roller quenching method drops on single roller of High Rotation Speed or two roller under making molten metal or carried out lifting by molten metal roller and obtain the method for thin strand.It should be noted that, the thin strand of gained is ground into suitable size in subsequent handling and pulverizing process.
Dull and stereotyped casting is cast into make the method for the lower thickness of ingot casting to tabular mold when being cast metal liquation, and it is compared with block ingot casting, and cooling rate accelerates.It should be noted that, gained tabular ingot casting is ground into suitable size in subsequent handling and pulverizing process.
(c) pulverizing process
In pulverizing process, particular alloy solidfied material forms specific alloy powder through pulverizing.This pulverizing process is preferably implemented under non-oxidizing environment.This is because in pulverizing process, when particular alloy solidfied material is pulverized, while the newborn face of formation, specific area also increases.It should be noted that, as non-oxidizing environment, be preferably non-reactive gas ambient, as long as the oxygen comprising 2 ~ 5 volume about % does not have special problem yet.
(d) mechanical grinding processes
In mechanical grinding processes, specific alloy powder manufactures above-mentioned silicon alloy particle through mechanical lapping process (hereinafter referred to as " MG process ").It should be noted that, the particular alloy powder for MG process preferably have below 5mm average grain diameter, more preferably have below 1mm average grain diameter, more preferably there is the average grain diameter of less than 500 μm, further preferably there is the average grain diameter of less than 100 μm.
In MG process, compression stress and shear strength are applied to the powder as processed material, grinds destruction and granulation that powder repeats powder.Its result, powder tissue is originally destroyed, thus formation has the particle having carried out the tissue of ultra tiny dispersion with nanometer scale existed before treatment.Wherein, form the kind of the phase of this micro organization, content and be in fact identical before process, new phase can not be formed because of process.Due to the characteristic of this MG process, when the silicon described in embodiments of the present invention is used as the negative material of rechargeable nonaqueous electrolytic battery containing thing graphite composite particles mutually, this negative pole shows stable discharge capacity.From this point of view, MG process from there is alloying reaction between element and the MA method (mechanical alloying method) that the content of phase is changed because of process is different.It should be noted that, in the process of MG process, the pole sub-fraction of alloy powder can produce the mechanical alloying of local.
On the other hand, in simple pulverizing, tissue (being more specifically crystal structure) can not be destroyed, and therefore, the particle after pulverizing maintains the tissue before pulverizing.That is, in pulverizing, only particle diameter diminishes and the miniaturization of tissue does not occur.To grind and the pulverizing being destroyed, organizing the MG process that miniaturization occurs is different from organizing in processes in this.
Any pulverizer of the enough ground material of MG process utilizable energy is implemented.Among this pulverizer, preferably use the pulverizer of spherical crushing medium, i.e. ball milling type pulverizer.Ball milling type pulverizer tool has the following advantages: structure is simple; Easily can obtain the crushing medium ball of various material; Pulverize at ball contact point each other/grind and thus carry out equably at very many positions grinding (viewpoint of this high uniformity from reaction and goods stability is particular importance) etc., be particularly suitable for adopting in the present invention.In addition, among ball milling type pulverizer, preferably, not only make pulverization cylinder merely rotate, also improve the vibrator of size reduction energy by applying vibration; The pulverizing mill by crushed material and crushing medium ball is forcibly stirred with the bar rotated; Revolving force and centrifugal force is utilized to improve the planetary ball mill etc. of size reduction energy.
In order to prevent the oxidation of the material in process, MG process is preferably carried out in the non-reactive gas ambient such as argon gas.Wherein, in the same manner as the situation that operation is solidified in quenching, when material does not contain the metallic element of easily oxidizable, also under air ambient, MG process can be carried out to material.In present embodiment, from fully guaranteeing this viewpoint of discharge capacity, the silicon in the silicon alloy particle preferably after MG process mutually in the least possible person of oxygen content.Specifically, the oxygen content in silicon alloy particle is preferably below 20 quality %, is more preferably below 10 quality %, more preferably below 5 quality %.
In MG process, when the temperature of silicon alloy rises because processing heat, the tissue size likely coarsening of the silicon alloy granule interior finally obtained.Therefore, pulverizer is preferably provided with cooling body.In described situation, carry out MG process on system inner edge cooling limit.
It should be noted that, for more than one metal silicide phase, silicon phase, also can the separately prepared silicon alloy powder by the operation of above-mentioned (a) ~ (c), MG process is carried out to the hybrid alloys powder mixed.This is because, manufacture silicon alloy particle can obtain following advantage by operating like this: (i) can with the good chemical composition raw materials alloy of dissolubility/castability, can produce with high production rate; (ii), when manufacturing multiple, that capacity is slightly different because of purposes silicon alloy powder, the blending ratio only changing pre-prepd silicon alloy powder can separately make.
(1-2) SiOx particle
As mentioned above, SiOx particle contains silicon phase and non-silicon phase.Non-silicon is silica phase mutually.The little as far as possible person of this SiOx particle preferable particle size.This is because, the stress produced with the change in volume together of attracting deposit/discharge of lithium ion can be disperseed.Specifically, the particle diameter (median particle diameter) during volume fraction 50% is preferably less than 2 μm, is more preferably below 500nm, more preferably below 200nm, is particularly preferably below 100nm.X be greater than 0 and be less than 0.9 time, it is 40m that SiOx particle is preferably specific area 2the case of wet attrition thing of/more than g.It should be noted that, this specific area is preferably 200m 2/ below g.
(2) flaky graphite particle
Flaky graphite particle 120 is arranged in stratiform, is clamped with siliceous phase particle 110 (with reference to Fig. 1) as described above.This flaky graphite particle 120 can be any one in natural graphite particles, synthetic graphite particles, kish (Kishgraphite) particle, from the view point of economy and guarantee discharge capacity, is preferably natural graphite particles.As flaky graphite particle 120, the mixture of above-mentioned graphite granule can be used.The graphite granule that flaky graphite particle 120 carries out heat treated with high temperature in advance also can be used as flaky graphite particle.Particle diameter (median particle diameter) during the volume fraction 50% of flaky graphite particle 120 is preferably more than 5 μm and less than 30 μm.In addition, the draw ratio of this flaky graphite particle 120 is preferably more than 3 and less than 50.In embodiments of the present invention, when flaky graphite particle 120 clamps alloying pellet 110, be preferably rich in flexibility, high crystallization and there is dimensional instability.Therefore, the galvanized hexagonal wire mesh interplanar of the flaky graphite particle 120 used in embodiments of the present invention every d002 preferably at more than 0.3354nm and in the scope of below 0.3370nm, pellet density is preferably at 1.80g/cm 3above and 2.00g/cm 3in following scope.
(3) the heat treated thing of organic compound
The heat treated thing of organic compound, using at least one in non-graphite matter carbon and carbon precursor as principal component, makes siliceous phase particle 110 be attached to flaky graphite particle 120.In present embodiment, the heat treated thing of organic compound can be only made up of non-graphite matter carbon.
Non-graphite matter carbon be in amorphous carbon and Turbostratic carbon (turbostraticcarbon) at least any one.It should be noted that, herein, " amorphous carbon " has even if refer to the carbon that short-range order (short-rangeorder) (order of magnitude of several atom ~ tens atom) does not have long-range order (long-distanceorder) (order of magnitude of hundreds of ~ several thousand atom).Herein, " Turbostratic carbon " refers to, by having the Turbostratic parallel with galvanized hexagonal wire mesh in-plane but the carbon that formed of the carbon atom not observing crystallography regularity on three-dimensional.In X-ray diffraction figure, there will not be and 101,103 corresponding hkl diffracted rays.But the diffracted ray of the graphite as base material of silicon mutually containing thing graphite composite particles 100 of embodiments of the present invention is strong, is therefore difficult to the existence being confirmed Turbostratic carbon by X-ray diffraction.Therefore, Turbostratic carbon preferably utilizes transmission electron microscope (TEM) etc. to confirm.
Carbon precursor refers to that thermoplasticity organic compound conversions becomes the material being rich in carbon before non-graphite matter carbon when heating thermoplastic organic compound.
But this non-graphite matter carbon and carbon precursor obtain by carrying out heat treated to the organic compound of solid.It should be noted that, in present embodiment, when siliceous phase particle 110 is SiOx particle, preferably at the temperature being fully converted to non-graphite matter carbon, organic compound is heated.Turbostratic carbon obtains by burning till organic compounds such as such as petroleum asphalt powder, carbobitumen powder, thermoplastic resin powders.Organic compound can be the mixture of above-mentioned powder.Among these, be particularly preferably asphalt powder.This is because asphalt powder, in temperature-rise period, melting and carbonization occurs simultaneously, its result, can compatibly be fixed on flaky graphite particle 120 by SiOx particle.Even if also little from the view point of carrying out easy fired irreversible capacity, be preferably asphalt powder.As an example of the heat-treat condition in burning till, can list and heat treatment temperature is set in the scope of 800 DEG C ~ 1200 DEG C.This heat treatment time is considered the characteristic of heat treatment temperature and organic compound etc. and suitably determines, typical case is 1 hours.Environment during heat treatment is preferably non-oxidizing atmosphere (non-reactive gas ambient, vacuum environment), from the view point of economy, is preferably nitrogen environment.Amorphous carbon can be formed by the such as vapor phase method such as vacuum vapour deposition, plasma CVD method.
On the other hand, when siliceous phase particle 110 is silicon alloy particle, at the temperature preferably within the scope of 300 DEG C ~ 600 DEG C, heat treated is carried out to organic compound.In described situation, heating treatment time considers that the characteristic etc. of heat treatment temperature and organic compound is suitably determined, typical case is 1 hours.Environment during heat treated is preferably non-oxidizing atmosphere (non-reactive gas ambient, vacuum environment), from the view point of economy, is preferably nitrogen environment.In embodiments of the present invention, thermoplastic resin is such as petroleum asphalt powder, carbobitumen powder, thermoplastic synthetic resin powder, native thermoplastic's toner and their mixed-powder.Among these, be particularly preferably asphalt powder.This is because asphalt powder, in temperature-rise period, melting occurs, silicon alloy particle compatibly can be fixed on flaky graphite particle 120.Even if also little from the view point of carrying out heat treated irreversible capacity with low temperature, be preferably asphalt powder.
It should be noted that, in the scope not damaging purport of the present invention, the heat treated thing of organic compound can also comprise other compositions such as conductivity carbonaceous particulate.Conductivity carbonaceous particulate is directly attached to graphite.Conductivity carbonaceous particulate is such as the carbon blacks such as Ketjen black, furnace black, acetylene black; Carbon nano-tube, carbon nano-fiber, carbon nanocoil etc.It should be noted that, among these conductivity carbonaceous particulates, be particularly preferably acetylene black.In addition, conductivity carbonaceous particulate can be the mixture of diverse carbon black etc.
< silicon contains composition and the physical property > of thing graphite composite particles mutually
Silicon described in embodiments of the present invention is mutually containing in thing graphite composite particles 100, when siliceous phase particle 110 is silicon alloy particle, the mass ratio of the heat treated thing of silicon alloy particle, flaky graphite particle 120 and organic compound is preferably 1 ~ 30:97 ~ 60:2 ~ 10.This is because, by silicon is made for this composition containing thing graphite composite particles 100 mutually, silicon alloy particle firmly can be fixed on the outer surface of the outermost flaky graphite particle 120 of silicon mutually containing thing graphite composite particles 100, and discharge capacity, efficiency for charge-discharge and charge/discharge cycle characteristics can be optimized when making electrode.When siliceous phase particle 110 is SiOx particle, the mass ratio of the heat treated thing of SiOx particle, flaky graphite particle 120 and organic compound is preferably 1 ~ 30:97 ~ 55:2 ~ 15, is more preferably 1 ~ 15:97 ~ 70:2 ~ 15.This is because, by silicon is made for this composition containing thing graphite composite particles 100 mutually, SiOx particle firmly can be fixed on the outer surface of the outermost flaky graphite particle 120 of silicon mutually containing thing graphite composite particles 100 and optimizes discharge capacity, efficiency for charge-discharge and charge/discharge cycle characteristics when making electrode.
Silicon described in embodiments of the present invention is mutually containing the particle diameter (median particle diameter) during the volume fraction 50% of thing graphite composite particles 100 preferably more than 10 μm and in the scope of less than 35 μm.This is because, by making particle diameter within the scope of this, efficiency for charge-discharge and charge/discharge cycle characteristics can be optimized when making electrode.
Silicon described in present embodiment mutually containing the draw ratio of thing graphite composite particles 100 and the long axis length (being equivalent to " W " of Fig. 1) of flaky graphite particle 120 relative to the length (being equivalent to " H " of Fig. 1) of stacked direction ratio preferably more than 1.5 and in the scope of less than 10, more preferably more than 1.5 and in the scope of less than 8, preferred more than 1.5 and in the scope of less than 6, particularly preferably in more than 1.5 and in the scope of less than 5 further.This is because, by making draw ratio be this scope, can charge/discharge cycle characteristics be optimized and easily can make electrode.
Making electrode density containing thing graphite composite particles 100 mutually by the silicon described in present embodiment is 1.70 ± 0.02g/cm 3electrode time (with reference to Fig. 2), in the X-ray diffraction image of this electrode 200, " belonging to the intensity I (110) at the peak in (110) face " be preferably less than 0.0300 relative to the ratio of " belonging to the intensity I (004) at the peak in (004) face ", be more preferably less than 0.0200, more preferably less than 0.0150, be particularly preferably less than 0.0100.This is because if this silicon can meet this condition containing thing graphite composite particles 100 mutually, the degree of orientation of the flaky graphite particle 120 in electrode becomes well, can more effectively realize above-mentioned effect.It should be noted that, in Fig. 2, symbol 210 represents active material layer, and symbol 220 represents collector body.
The manufacture > of < silicon mutually containing thing graphite composite particles
Silicon described in embodiments of the present invention manufactures by following manufacture method arbitrarily containing thing graphite composite particles 100 mutually.
(1) first manufacture method
In first manufacture method, manufacture silicon mutually containing thing graphite composite particles 100 via once-combined particle preparation section, mixed-powder preparation section and heating process.It should be noted that, once-combined particle preparation section and mixed-powder preparation section are implemented in the dry state.
In once-combined particle preparation section, by process such as MECHANOCHEMICAL (registered trade mark) process, MECHANOFUSION (registered trade mark) process, give compression stress and shearing force to the hybrid particles of siliceous phase particle 110 and flaky graphite particle 120, thus prepare once-combined particle.It should be noted that, now, siliceous phase particle 110 can be fed into MECHANOCHEMICAL (registered trade mark) system with the hybrid particles of flaky graphite particle 120, MECHANOFUSION (registered trade mark) system, also siliceous phase particle 110 and flaky graphite particle 120 can be fed into MECHANOCHEMICAL (registered trade mark) system respectively successively, after MECHANOFUSION (registered trade mark) system, two kinds of particles are mixed while carry out MECHANOCHEMICAL (registered trade mark) process, the process such as MECHANOFUSION (registered trade mark) process.It should be noted that, in once-combined particle, siliceous phase particle 110 is attached to the surface of flaky graphite particle 120 with more weak power.
In mixed-powder preparation section, the organic compound of once-combined particle and solid prepares mixed-powder through solid phase mixing.
In mixed-powder preparation section, as the method that once-combined particle and the organic compound of solid are carried out mixing, as long as particle can Homogeneous phase mixing and the method be not damaged, be just not particularly limited.Such as there is the method using common mixer.As mixer, such as rotary container type mixer, fixed container type mixer, airflow mixer, high velocity stream ejector half mixer etc. can be listed.As rotary container type mixer, such as V-Mixer can be listed.
In heating process, under non-oxidizing atmosphere, (under non-reactive gas ambient, vacuum environment inferior) carries out heat treated to mixed-powder.Its result, organic compound melting is attached to once-combined particle, and then organic compound conversions becomes carbon precursor or changes into non-graphite matter carbon whole or in part, thus the silicon obtained as target contains thing graphite composite particles 100 mutually.When siliceous phase particle 110 is silicon alloy particle, heating-up temperature is preferably the temperature within the scope of 300 DEG C ~ 600 DEG C.By making heating-up temperature be less than 600 DEG C, the coarse of silicon phase can be suppressed, therefore, it is possible to form the electrode of cycle characteristics excellence.By making heating-up temperature be more than 300 DEG C, the electrode of efficiency for charge-discharge excellence can be formed.Like this, when heating-up temperature is above-mentioned scope, the electrode of the balancing good of cycle characteristics and efficiency for charge-discharge can be formed.On the other hand, when siliceous phase particle 110 is SiOx particle, heating-up temperature is preferably organifying compound and changes into temperature within the scope of the temperature such as 800 DEG C ~ 1200 DEG C of non-graphite matter carbon completely.By making heating-up temperature be less than 1200 DEG C, the growing amount of carborundum (SiC) can be suppressed, therefore, it is possible to form the electrode of discharge capacity excellence.By making heating-up temperature be more than 800 DEG C, the electrode of efficiency for charge-discharge excellence can be formed.Like this, when heating-up temperature is above-mentioned scope, the electrode of the balancing good of discharge capacity and efficiency for charge-discharge can be formed.
(2) second manufacture methods
In second manufacture method, manufacture silicon via middle composite particles preparation section and heating process mutually containing thing graphite composite particles 100.It should be noted that, middle composite particles preparation section is implemented in the dry state.
In middle composite particles preparation section, by process such as MECHANOCHEMICAL (registered trade mark) process, MECHANOFUSION (registered trade mark) process, compression stress and shearing force is given at temperature more than the softening point of organic compound of the mixture of the organic compound of siliceous phase particle 110, flaky graphite particle 120 and solid, thus composite particles in the middle of preparation.Now, under the situation that compression stress works, the organic compound of melting plays the effect of bonding agent, and flaky graphite particle 120 is increased with the stacked quantity of siliceous phase particle 110.It should be noted that, now, siliceous phase particle 110, flaky graphite particle 120 can be fed into MECHANOCHEMICAL (registered trade mark) system with the mixture of the organic compound of solid, MECHANOFUSION (registered trade mark) system, also can by siliceous phase particle 110, the organic compound of flaky graphite particle 120 and solid is fed into MECHANOCHEMICAL (registered trade mark) system respectively successively, after MECHANOFUSION (registered trade mark) system, these particles are mixed while carry out MECHANOCHEMICAL (registered trade mark) process, the process such as MECHANOFUSION (registered trade mark) process.In the former case, after flaky graphite particle 120 can also being mixed in the pulverizing slurry that obtain by carrying out case of wet attrition to siliceous phase particle 110, carry out drying, then hybrid solid organic compound and obtain mixture.Now, even if drying is the solvent that uses in the case of wet attrition not degree that processes of evaporation but also can carry out in the form of a powder completely.
In heating process, mixture (under non-reactive gas ambient, vacuum environment inferior) under non-oxidizing atmosphere carries out heat treated.Its result, organic compound conversions becomes carbon precursor or changes into non-graphite matter carbon whole or in part, thus the silicon obtained as target contains thing graphite composite particles 100 mutually.When siliceous phase particle 110 is silicon alloy particle, heating-up temperature is preferably the temperature within the scope of 300 DEG C ~ 600 DEG C.By making heating-up temperature be less than 600 DEG C, the coarse of silicon phase can be suppressed, therefore, it is possible to form the electrode of cycle characteristics excellence.By making heating-up temperature be more than 300 DEG C, the electrode of efficiency for charge-discharge excellence can be formed.Like this, when heating-up temperature is in above-mentioned scope, the electrode of the balancing good of cycle characteristics and efficiency for charge-discharge can be formed.On the other hand, when siliceous phase particle 110 is SiOx particle, heating-up temperature is preferably organifying compound and changes into temperature within the scope of the temperature such as 800 DEG C ~ 1200 DEG C of non-graphite matter carbon completely.By making heating-up temperature be less than 1200 DEG C, the growing amount of carborundum (SiC) can be suppressed, therefore, it is possible to form the electrode of discharge capacity excellence.By making heating-up temperature be more than 800 DEG C, the electrode of efficiency for charge-discharge excellence can be formed.Like this, when heating-up temperature is above-mentioned scope, the electrode of the balancing good of discharge capacity and efficiency for charge-discharge can be formed.
The feature > of < silicon mutually containing thing graphite composite particles
When silicon described in embodiments of the present invention is used as the electrode active material of rechargeable nonaqueous electrolytic battery containing thing graphite composite particles 100 mutually, its charge/discharge cycle characteristics can be improved.
< embodiment and comparative example >
Embodiment and comparative example are below shown, the present invention is described in detail for pin.
Embodiment 1
The manufacture > of < silicon alloy graphite composite particles
(1) preparation of silicon alloy particle
First, reach the mode of 13.5:21.5:65.0 with the mass ratio of nickel (Ni), titanium (Ti) and silicon (Si), the pure raw material of nickel, titanium and silicon is fed into the melting crucible of metatitanic acid aluminum.Then, after making to become argon gas (Ar) environment in this melting crucible, high-frequency induction heating is utilized the pure raw material (metal mixture) melted in crucible to be heated to 1500 DEG C and make it melt completely.Then, by making this liquefactent contact with the copper water cooled rolls rotated with the peripheral speed of 90m/ minute, its quenching is solidified, thus obtain laminar strand (thin strap continuous casting (SC) method).It should be noted that, infer that cooling rate is now approximately about 500 ~ 2000 DEG C/sec.Further, the strand obtained operating like this carries out classification with the sieves of 63 μm after pulverizing, thus makes the powder that average grain diameter is 25 ~ 30 μm.And, further this powder is fed into planetary ball mill (Kurimoto, Ltd.'s system, BX384E), this powder is carried out mechanical lapping process (hereinafter referred to as " MG process ") with the rotating speed of 500rpm, thus prepare silicon alloy powder (following, to be sometimes called of silicon alloy powder " silicon alloy particle ").It should be noted that, for MG process, in the glove box of nitrogen environment (oxygen is less than 1%), by a powder and ball (material: SUS304, sphere diameter 4mm, ball ratio, a powder: graphite (preventing silicon alloy powder to be consolidated in ball, outer wall): ball (mixing)=36g:4.0g:600g) be fed into after in container (material: SUS304, internal diameter: 100mm, the degree of depth: 67mm), this container is added a cover, carries out MG process in 10 hours with the rotating speed of 500rpm.After MG process, in the glove box of nitrogen environment (oxygen is less than 1%), take out silicon alloy powder, and carry out sieve classification (63 μm).
Utilize transmission electron microscope photo (brightfield image), directly measure the diameter of the silicon phase of the nm order of magnitude (less than 1 μm).The diameter of the silicon phase in silicon alloy particle is 10 ~ 40nm.
(2) preparation of composite particles in the middle of
First, with flake natural graphite powder (middle Yueshi ink Industrial Co., Ltd system, average grain diameter: 10 μm, d002:0.3357nm, pellet density: 1.82g/cm 3) reach the mode of 70.4:23.9:9.5 with the mass ratio of silicon alloy powder and carbobitumen powder (softening point be 86 DEG C, average grain diameter be 20 μm), flake natural graphite powder and silicon alloy powder and carbobitumen powder are fed into after the gap of rotor and internal stator is set to the circular form MECHANOFUSION system (HOSOKAWAMICRONGROUP AMS-30F) of 5mm, temperature be adjusted to 95 DEG C ~ 130 DEG C and with the rotating speed of 2600rpm, this mixed-powder carried out to the mechanochemistry process of 15 minutes, thus composite particles in the middle of preparation.
It should be noted that, the pellet density of flake natural graphite powder is obtained by following method.
It is in the mould of 15mm that 1.00g flake natural graphite powder is filled to diameter, pressurizes after 5 seconds, weaken to 0.15kN by this moulding pressure by this mould single shaft pressuring machine with the moulding pressure of 8.7kN, reads the displacement of upper punch now.It should be noted that, pressing speed is set to 10mm/ second.In addition, flake natural graphite powder is not filled to above-mentioned mould, is utilized by this mould this single shaft pressuring machine to be forced into after moulding pressure reaches 8.7kN, this moulding pressure is weakened to 0.15kN, obtains the displacement of now upper punch.By this displacement as a reference.Further, the displacement obtaining upper punch when filling flake natural graphite powder is used as sample thickness with the difference with reference to displacement, calculates pressed density and pellet density by this thickness.
(3) heat treated of carbobitumen powder
Then, after middle composite particles is fed into graphite crucible, by this middle composite particles in stream of nitrogen gas with the heating temperatures 1 hour of 500 DEG C.
(4) break process
Finally, the middle composite particles after heat treated is crushed to till its more than 98 quality % by mesh size is the sieve of 75 μm, thus obtains the silicon alloy graphite composite particles of target.It should be noted that, the mass ratio of the flake natural graphite powder in this silicon alloy graphite composite particles and the heat treated thing of silicon alloy powder and pitch is 70.4:23.9:5.7 (with reference to table 1).Herein, the weight change before and after heat treated is all derived from pitch.
The evaluating characteristics > of < silicon alloy graphite composite particles
(1) mensuration of particle diameter
Use laser diffraction/diffuse transmission type particle size distribution meter (Horiba Ltd's system, LA-910), utilize light scattering diffraction approach to measure the particle size distribution of the volume reference of silicon alloy graphite composite particles.Thereafter, use gained particle size distribution obtains the particle diameter (median particle diameter) when volume fraction is 50%.Its result, this particle diameter is 17 μm (with reference to table 1).
(2) battery behavior evaluation
(2-1) electrode fabrication
The aqueous liquid dispersion of compounding AB (acetylene black) and CMC (sodium carboxymethylcellulose) powder and SBR (butadiene-styrene rubber) and water in above-mentioned silicon alloy graphite composite particles, thus obtain electrode mix paste.Herein, AB is conductive auxiliary agent, CMC and SBR is binding agent.The compounding ratio of silicon alloy graphite composite particles, AB, CMC and SBR is 97.0:1.0:1.0:1.0 by quality ratio.Further, with scraping the skill in using a kitchen knife in cookery, this electrode mix paste to be coated on thickness be that upper (coating weight is 7 ~ 8mg/cm for the Copper Foil (collector body) of 17 μm 2).Make coating fluid dry and after obtaining film, this film be die-cut into the plate-like that diameter is 13mm.Further, utilize Press forming machine to pressurize to this dish, thus making have 1.70 ± 0.02g/cm 3the electrode of electrode density.It should be noted that, by utilizing micrometer to measure thickness and calculate volume, and the quality measuring this dish (part except Copper Foil) is to obtain the electrode density of the electrode obtained.
(2-2) battery makes
Configure above-mentioned electrode in the both sides of polyolefin barrier film and as the Li metal forming to electrode, make electrode assemblies.Further, the inside injection electrolyte to this electrode assemblies makes the non-water test battery unit of Coin shape that cell sizes is 2016.It should be noted that, the composition of electrolyte is set to: ethylene carbonate (EC): methyl ethyl carbonate (EMC): dimethyl carbonate (DMC): vinylene carbonate (VC): fluoroethylene carbonate (FEC): LiPF 6=23:4:48:1:8:16 (mass ratio).
(2-3) evaluation of discharge capacity, efficiency for charge-discharge and charge and discharge cycles
In this non-water test battery unit, first, with the current value of 0.33mA for electrode being carried out to constant current doping (embed lithium ion to electrode, be equivalent to the charging of lithium rechargeable battery), after till potential difference reaches 0 (zero) V, adulterating till reaching 5 μ A for proceeding electrode with constant voltage under the state keeping 0V further, measuring doping capacity.Then, carry out dedoping (lithium ion departs from, is equivalent to the electric discharge of lithium rechargeable battery from electrode) till potential difference reaches 1.5V with the constant current of 0.33mA, measure dedoping capacity.Doping capacity now, dedoping capacity are equivalent to charging capacity, discharge capacity when this electrode being used as the negative pole of lithium rechargeable battery, therefore it can be used as charging capacity, discharge capacity.The discharge capacity of the non-water test battery unit described in the present embodiment is 486mAh/g (with reference to table 1).The ratio of dedoping capacity/doping capacity is equivalent to the ratio of the discharge capacity/charging capacity of lithium rechargeable battery, therefore using this ratio as efficiency for charge-discharge.The efficiency for charge-discharge of the non-water test battery unit described in the present embodiment was 87.1% (with reference to table 1).
The mensuration of cycle characteristics uses the non-water test battery unit of the Coin shape formed as described above to carry out.In this test cell unit, after the 2nd circulation and the 2nd circulation, with the constant current of 1.33mA, (charging is equivalent to) for adulterating to electrode after till potential difference reaches 5mV, further under the state keeping 5mV, continue doping till reaching 50 μ A with constant voltage.Then, carry out dedoping with the constant current of 1.33mA and (be equivalent to electric discharge) till potential difference reaches 1.5V, measure dedoping capacity.Using dedoping capacity now as discharge capacity.
Under condition same as described above, repeat 31 doping and dedoping, carry out evaluation cycle characteristic by " discharge capacity during dedoping circulated for the 31st time " with the ratio (capacity dimension holdup) of " discharge capacity during dedoping circulated for the 2nd time ".It should be noted that, if this capacity dimension holdup is more than 90%, then can regard as well as practical battery.It should be noted that, the capacity dimension holdup of the non-water test battery unit described in the present embodiment was 96.8% (with reference to table 1).
(3) mensuration of the degree of orientation of the flake natural graphite particle in silicon alloy graphite composite particles
The degree of orientation of the flake natural graphite particle in silicon alloy graphite composite particles can utilize the powder X-ray diffractometry of reflection diffraction formula to obtain.Specifically, circular electrode double faced adhesive tape after the pressurization made in above-mentioned " (2-1) electrode fabrication " is fixed on areflexia plate, and use the RINT-1200V that Co., Ltd. of science manufactures, using copper (Cu) as target, with the tube current of the tube voltage of 40kV, 30mA, CuK alpha ray is irradiated to circular electrode, and measure.Thereafter, carry out the separation at peak, obtain the powder x-ray diffraction spectrogram utilizing CuK α 1 ray.Obtain 2 θ and be in the respective intensity that the diffraction maximum in (004) face within the scope of 52 ~ 57 ° and 2 θ are in the diffraction maximum in (110) face within the scope of 75 ~ 80 °.Further, the diffraction peak intensity in (110) face divided by the diffraction peak intensity in (004) face, thus calculates the degree of orientation of the flake natural graphite particle in silicon alloy graphite composite particles.The degree of orientation of the flake natural graphite particle in the silicon alloy graphite composite particles described in the present embodiment was 0.0081 (with reference to table 1).It should be noted that, this degree of orientation is less, then the orientation of the flake natural graphite particle in silicon alloy graphite composite particles becomes higher.
(4) mensuration of draw ratio
After circular electrode before the pressurization made in above-mentioned " (2-1) electrode fabrication " is embedded into resin, this resin is cut off and grinds its cross section.And, with this cross section of observation by light microscope (electrode section), measure the size of 50 silicon alloy graphite composite particles, for each silicon alloy graphite composite particles, calculate draw ratio (the long axis length W of the flaky graphite particle in Fig. 1 is relative to the ratio of stacked direction length H).Further, using the draw ratio of the mean value of the draw ratio of these 50 silicon alloy graphite composite particles as silicon alloy graphite composite particles.It should be noted that, the draw ratio of the silicon alloy graphite composite particles described in the present embodiment is 3.4.
Embodiment 2
The manufacture > of < silicon alloy graphite composite particles
(1) preparation of silicon alloy particle
The mode of 16.8:13.6:69.6 is reached with the mass ratio of nickel (Ni), titanium (Ti) and silicon (Si), the pure raw material of nickel, titanium and silicon is fed into the melting crucible of metatitanic acid aluminum, in addition, silicon alloy powder is prepared in operation similarly to Example 1, operates the silicon phase size measured in silicon alloy particle similarly to Example 1.The diameter of the silicon phase in silicon alloy particle is 10 ~ 40nm (with reference to table 1).
(2) preparation of composite particles in the middle of
The mass ratio of flake natural graphite powder and silicon alloy powder and carbobitumen powder is set to 83.8:10.5:9.5, and in addition, middle composite particles is prepared in operation similarly to Example 1.
(3) heat treated of carbobitumen powder
Operate similarly to Example 1, composite particles in the middle of heating.
(4) break process
Operate similarly to Example 1, obtain the silicon alloy graphite composite particles as target.It should be noted that, the mass ratio of the flake natural graphite powder in this silicon alloy graphite composite particles and the heat treated thing of silicon alloy powder and pitch is 83.8:10.5:5.7 (with reference to table 1).
Further, the particle diameter when volume fraction of silicon alloy graphite composite particles is 50% is 16 μm.The draw ratio of silicon alloy graphite composite particles is 3.3.The degree of orientation of the flake natural graphite particle in silicon alloy graphite composite particles is 0.0075.The discharge capacity of non-water test battery unit is 500mAh/g, and efficiency for charge-discharge is 87.4%, and capacity dimension holdup was 95.5% (with reference to table 1).
Embodiment 3
The manufacture > of < silicon alloy graphite composite particles
(1) preparation of silicon alloy particle
The mode of 32.7:30.1:37.2 is reached with the mass ratio of nickel (Ni), aluminium (Al) and silicon (Si), the pure raw material of nickel, aluminium and silicon is fed into the melting crucible of metatitanic acid aluminum, in addition, silicon alloy powder is prepared in operation similarly to Example 1, operates the silicon phase size measured in silicon alloy particle similarly to Example 1.The diameter of the silicon phase in silicon alloy particle is 10 ~ 40nm (with reference to table 1).
(2) preparation of composite particles in the middle of
The mass ratio of flake natural graphite powder and silicon alloy powder and carbobitumen powder is set to 69.8:24.5:9.5, and in addition, middle composite particles is prepared in operation similarly to Example 1.
(3) heat treated of carbobitumen powder
Operate similarly to Example 1, composite particles in the middle of heating.
(4) break process
Operate similarly to Example 1, obtain the silicon alloy graphite composite particles as target.It should be noted that, the mass ratio of the flake natural graphite powder in this silicon alloy graphite composite particles and the heat treated thing of silicon alloy powder and pitch is 69.8:24.5:5.7 (with reference to table 1).
Further, the particle diameter when volume fraction of silicon alloy graphite composite particles is 50% is 18 μm.The draw ratio of silicon alloy graphite composite particles is 3.0.The degree of orientation of the flake natural graphite particle in silicon alloy graphite composite particles is 0.0093.The discharge capacity of non-water test battery unit is 486mAh/g, and efficiency for charge-discharge is 87.1%, and capacity dimension holdup was 94.0% (with reference to table 1).
Embodiment 4
The manufacture > of < silicon alloy graphite composite particles
(1) preparation of silicon alloy particle
The mode of 26.1:21.6:52.3 is reached with the mass ratio of aluminium (Al), iron (Fe) and silicon (Si), the pure raw material of aluminium, iron and silicon is fed into the melting crucible of metatitanic acid aluminum, in addition, silicon alloy powder is prepared in operation similarly to Example 1, operates the silicon phase size measured in silicon alloy particle similarly to Example 1.The diameter of the silicon phase in silicon alloy particle is 10 ~ 40nm (with reference to table 1).
(2) preparation of composite particles in the middle of
The mass ratio of flake natural graphite powder and silicon alloy powder and carbobitumen powder is set to 68.2:26.1:9.5, and in addition, middle composite particles is prepared in operation similarly to Example 1.
(3) heat treated of carbobitumen powder
Operate similarly to Example 1, composite particles in the middle of heating.
(4) break process
Operate similarly to Example 1, obtain the silicon alloy graphite composite particles as target.It should be noted that, the mass ratio of the flake natural graphite powder in this silicon alloy graphite composite particles and the heat treated thing of silicon alloy powder and pitch is 68.2:26.1:5.7 (with reference to table 1).
Further, the particle diameter when volume fraction of silicon alloy graphite composite particles is 50% is 16 μm.The draw ratio of silicon alloy graphite composite particles is 3.5.The degree of orientation of the flake natural graphite particle in silicon alloy graphite composite particles is 0.0071.The discharge capacity of non-water test battery unit is 487mAh/g, and efficiency for charge-discharge is 86.8%, and capacity dimension holdup was 93.5% (with reference to table 1).
Embodiment 5
The manufacture > of < silicon alloy graphite composite particles
(1) preparation of silicon alloy particle
The mode of 16.8:12.6:1.0:69.6 is reached with the mass ratio of nickel (Ni), titanium (Ti), iron (Fe) and silicon (Si), the pure raw material of nickel, titanium, iron and silicon is fed into the melting crucible of metatitanic acid aluminum, in addition, silicon alloy powder is prepared in operation similarly to Example 1, operates the silicon phase size measured in silicon alloy particle similarly to Example 1.The diameter of the silicon phase in silicon alloy particle is 10 ~ 40nm (with reference to table 1).
(2) preparation of composite particles in the middle of
The mass ratio of flake natural graphite powder and silicon alloy powder and carbobitumen powder is set to 69.8:24.5:9.5, and in addition, middle composite particles is prepared in operation similarly to Example 1.
(3) heat treated of carbobitumen powder
Operate similarly to Example 1, composite particles in the middle of heating.
(4) break process
Operate similarly to Example 1, obtain the silicon alloy graphite composite particles as target.It should be noted that, the mass ratio of the flake natural graphite powder in this silicon alloy graphite composite particles and the heat treated thing of silicon alloy powder and pitch is 69.8:24.5:5.7 (with reference to table 1).
Further, the particle diameter when volume fraction of silicon alloy graphite composite particles is 50% is 17 μm.The draw ratio of silicon alloy graphite composite particles is 3.1.The degree of orientation of the flake natural graphite particle in silicon alloy graphite composite particles is 0.0101.The discharge capacity of non-water test battery unit is 650mAh/g, and efficiency for charge-discharge is 87.5%, and capacity dimension holdup was 92.1% (with reference to table 1).
Embodiment 6
The manufacture > of < silicon alloy graphite composite particles
The heating-up temperature during heat treated of carbobitumen powder is set to 300 DEG C, in addition, operates the silicon alloy graphite composite particles obtained as target similarly to Example 2.It should be noted that, the mass ratio of the flake natural graphite powder in this silicon alloy graphite composite particles and the heat treated thing of silicon alloy powder and pitch is 83.8:10.5:8.8 (with reference to table 1).
Further, the particle diameter when volume fraction of silicon alloy graphite composite particles is 50% is 16 μm.The draw ratio of silicon alloy graphite composite particles is 3.3.The degree of orientation of the flake natural graphite particle in silicon alloy graphite composite particles is 0.0085.The discharge capacity of non-water test battery unit is 470mAh/g, and efficiency for charge-discharge is 81.5%, and capacity dimension holdup was 96.0% (with reference to table 1).
Embodiment 7
The manufacture > of < silicon alloy graphite composite particles
The heating-up temperature during heat treated of carbobitumen powder is set to 700 DEG C, in addition, operates the silicon alloy graphite composite particles obtained as target similarly to Example 2.It should be noted that, the mass ratio of the flake natural graphite powder in this silicon alloy graphite composite particles and the heat treated thing of silicon alloy powder and pitch is 83.8:10.5:5.2 (with reference to table 1).
Further, the particle diameter when volume fraction of silicon alloy graphite composite particles is 50% is 16 μm.The draw ratio of silicon alloy graphite composite particles is 3.4.The degree of orientation of the flake natural graphite particle in silicon alloy graphite composite particles is 0.0075.The discharge capacity of non-water test battery unit is 500mAh/g, and efficiency for charge-discharge is 88.1%, and capacity dimension holdup was 85.0% (with reference to table 1).
Embodiment 8
The manufacture > of < silicon alloy graphite composite particles
In " preparation of (2) middle composite particles ", the mass ratio of flake natural graphite powder and silicon alloy powder and carbobitumen powder is set to 86.3:10.8:4.8, in addition, the silicon alloy graphite composite particles obtained as target is operated similarly to Example 2.It should be noted that, the mass ratio of the flake natural graphite powder in this composite particles and the heat treated thing of silicon alloy powder and pitch is 86.3:10.8:2.9 (with reference to table 1).
Further, the particle diameter when volume fraction of silicon alloy graphite composite particles is 50% is 14 μm.The draw ratio of silicon alloy graphite composite particles is 4.5.The degree of orientation of the flake natural graphite particle in silicon alloy graphite composite particles is 0.0070.The discharge capacity of non-water test battery unit is 492mAh/g, and efficiency for charge-discharge is 89.5%, and capacity dimension holdup was 85.0% (with reference to table 1).
Embodiment 9
The manufacture > of < silicon alloy graphite composite particles
In " preparation of (2) middle composite particles ", the mass ratio of flake natural graphite powder and silicon alloy powder and carbobitumen powder is set to 79.3:10.0:17.8, in addition, the silicon alloy graphite composite particles obtained as target is operated similarly to Example 2.It should be noted that, the mass ratio of the flake natural graphite powder in this composite particles and the heat treated thing of silicon alloy powder and pitch is 79.3:10.0:10.7 (with reference to table 1).
Further, the particle diameter when volume fraction of silicon alloy graphite composite particles is 50% is 24 μm.The draw ratio of silicon alloy graphite composite particles is 2.5.The degree of orientation of the flake natural graphite particle in silicon alloy graphite composite particles is 0.0085.The discharge capacity of non-water test battery unit is 500mAh/g, and efficiency for charge-discharge is 83.8%, and capacity dimension holdup was 97.2% (with reference to table 1).
(comparative example 1)
Silicon alloy graphite composite particles is replaced to " material (without carbobitumen powder) that the silicon alloy particle of preparation in embodiment 2 and spheroidal natural graphite (average grain diameter be 20 μm, draw ratio be 1.4) mix with the mass ratio of 11:89 ", in addition, operate similarly to Example 1, and evaluate each characteristic (with reference to table 1).
Further, the degree of orientation of hybrid particles is 0.0350.The discharge capacity of non-water test battery unit is 480mAh/g, and efficiency for charge-discharge is 91.2%, and capacity dimension holdup was 75.8% (with reference to table 1).
[table 1]
Can be clear and definite by the above results: when the silicon alloy graphite composite particles described in embodiments of the invention is used as the negative electrode active material of lithium rechargeable battery, effectively improve the charge/discharge cycle characteristics of this lithium rechargeable battery.
Embodiment 10
The manufacture > of < Si oxide graphite composite particles
(1) pulverizing of silicon monoxide
The silicon monoxide powder (SiO, i.e. x=1) that Wako Pure Chemical Industries, Ltd. manufactures is pulverized with ball mill.It should be noted that, the average grain diameter (median particle diameter) of silicon monoxide powder is now 1 μm.
(2) preparation of composite particles in the middle of
With flake natural graphite powder (middle Yueshi ink Industrial Co., Ltd system, average grain diameter: 10 μm, d002:0.3357nm, pellet density: 1.82g/cm 3) with pulverize after silicon monoxide powder and carbobitumen powder (softening point is 86 DEG C, average grain diameter is 20 μm, with the carbon yield after 1000 DEG C of heating for 50%) mass ratio reach the mode of 80:11:18, flake natural graphite powder and silicon monoxide powder and carbobitumen powder are fed into circular form MECHANOFUSION system (the HOSOKAWAMICRONGROUP system gap of rotor and internal stator being set to 5mm, AMS-30F) after, temperature be adjusted to 95 DEG C ~ 130 DEG C and this mixed-powder carried out to the mechanochemistry process of 15 minutes with the rotating speed of 2600rpm, thus composite particles in the middle of preparation.
It should be noted that, the pellet density of flake natural graphite powder is obtained by following method.
It is in the mould of 15mm that 1.00g flake natural graphite powder is filled to diameter, pressurizes after 5 seconds, weaken to 0.15kN by this moulding pressure by this mould single shaft pressuring machine with the moulding pressure of 8.7kN, reads the displacement of upper punch now.It should be noted that, pressing speed is set to 10mm/ second.In addition, flake natural graphite powder be not filled to above-mentioned mould and utilized by this mould this single shaft pressuring machine to be heated to after moulding pressure reaches 8.7kN, this moulding pressure being weakened to 0.15kN, obtain the displacement of now upper punch.By this displacement as a reference.Further, the displacement obtaining upper punch when filling flake natural graphite powder is used as sample thickness with the difference with reference to displacement, calculates pressed density and pellet density by this thickness.
(3) heat treated of carbobitumen powder
Then, after middle composite particles is fed into graphite crucible, by this middle composite particles in stream of nitrogen gas with the heating temperatures 1 hour of 1000 DEG C.
(4) break process
Finally, the middle composite particles after heat treated is crushed to its more than 98 quality % through till mesh size is the sieve of 75 μm, obtains the Si oxide graphite composite particles as target.It should be noted that, the mass ratio of the flake natural graphite powder in this Si oxide graphite composite particles and the heat treatment thing of silicon monoxide powder and pitch is 80:11:9 (with reference to table 2).Herein, the weight change of burning till front and back is all derived from pitch.
The evaluating characteristics > of < Si oxide graphite composite particles
(1) mensuration of particle diameter
Use laser diffraction/diffuse transmission type particle size distribution meter (Horiba Ltd's system, LA-910), utilize light scattering diffraction approach to measure the particle size distribution of the volume reference of Si oxide graphite composite particles.Thereafter, use gained particle size distribution obtains the particle diameter (median particle diameter) when volume fraction is 50%.Its result, this particle diameter is 21 μm (with reference to table 2).
(2) battery behavior evaluation
(2-1) electrode fabrication
The aqueous liquid dispersion of compounding AB (acetylene black) and CMC (sodium carboxymethylcellulose) powder and SBR (butadiene-styrene rubber) and water in above-mentioned Si oxide graphite composite particles, thus obtain electrode mix paste.Herein, AB is conductive auxiliary agent, CMC and SBR is binding agent.The compounding ratio of Si oxide graphite composite particles, AB, CMC and SBR is 97.0:1.0:1.0:1.0 by quality ratio.Further, with scraping the skill in using a kitchen knife in cookery, this electrode mix paste to be coated on thickness be that upper (coating weight is 7 ~ 8mg/cm for the Copper Foil (collector body) of 17 μm 2).Make coating fluid dry and after obtaining film, this film be die-cut into the plate-like that diameter is 13mm.Further, utilize Press forming machine to pressurize to this dish, thus making have 1.70 ± 0.02g/cm 3the electrode of electrode density.It should be noted that, by utilizing micrometer to measure thickness and calculate volume, and the quality measuring this dish (not comprising the part of Copper Foil) is to obtain the electrode density of the electrode obtained.
(2-2) battery makes
Configure above-mentioned electrode in the both sides of polyolefin barrier film and as the Li metal forming to electrode, make electrode assemblies.Further, the inside injection electrolyte to this electrode assemblies makes the non-water test battery unit of Coin shape that cell sizes is 2016.It should be noted that, the composition of electrolyte is set to: ethylene carbonate (EC): methyl ethyl carbonate (EMC): dimethyl carbonate (DMC): vinylene carbonate (VC): fluoroethylene carbonate (FEC): LiPF 6=23:4:48:1:8:16 (mass ratio).
(2-3) evaluation of discharge capacity, efficiency for charge-discharge and charge and discharge cycles
In this non-water test battery unit, first, with the current value of 0.33mA for electrode being carried out to constant current doping (embed lithium ion to electrode, be equivalent to the charging of lithium rechargeable battery), after till potential difference reaches 0 (zero) V, adulterate for proceeding electrode with constant voltage under the state keeping 0V further, till reaching 5 μ A, measure doping capacity.Then, carry out dedoping (lithium ion departs from, is equivalent to the electric discharge of lithium rechargeable battery from electrode) with the constant current of 0.33mA, till potential difference reaches 1.5V, measure dedoping capacity.Doping capacity now, dedoping capacity are equivalent to charging capacity, discharge capacity when this electrode being used as the negative pole of lithium rechargeable battery, therefore it can be used as charging capacity, discharge capacity.The discharge capacity of the non-water test battery unit described in the present embodiment is 480mAh/g (with reference to table 2).The ratio of dedoping capacity/doping capacity is equivalent to the ratio of the discharge capacity/charging capacity of lithium rechargeable battery, therefore using this ratio as efficiency for charge-discharge.The efficiency for charge-discharge of the non-water test battery unit described in the present embodiment was 84.8% (with reference to table 2).
The mensuration of cycle characteristics uses the non-water test battery unit of the Coin shape formed as described above to carry out.In this test cell unit, after the 2nd circulation and the 2nd circulation, with the constant current of 1.33mA, (charging is equivalent to) for adulterating to electrode after till potential difference reaches 5mV, further under the state keeping 5mV, doping is continued, till reaching 50 μ A with constant voltage.Then, carry out dedoping with the constant current of 1.33mA and (be equivalent to electric discharge) till potential difference reaches 1.5V, measure dedoping capacity.Using dedoping capacity now as discharge capacity.
Under condition same as described above, repeat 31 doping and dedoping, carry out evaluation cycle characteristic by " discharge capacity during dedoping circulated for the 31st time " with the ratio (capacity dimension holdup) of " discharge capacity during dedoping circulated for the 2nd time ".It should be noted that, if this capacity dimension holdup is more than 90%, then can regard as well as practical battery.It should be noted that, the capacity dimension holdup of the non-water test battery unit described in the present embodiment was 95.0% (with reference to table 2).
(3) mensuration of draw ratio
After circular electrode before the pressurization made in above-mentioned " (2-1) electrode fabrication " is embedded into resin, this resin is cut off and grinds its cross section.With this cross section of observation by light microscope (electrode section), measure the size of 50 Si oxide graphite composite particles, for each Si oxide graphite composite particles, calculate draw ratio (the long axis length W of the flake natural graphite particle in Fig. 1 is relative to the ratio of stacked direction length H).Further, using the draw ratio of the mean value of the draw ratio of these 50 Si oxide graphite composite particles as Si oxide graphite composite particles.It should be noted that, the draw ratio of the Si oxide graphite composite particles described in the present embodiment was 2.2 (with reference to table 2).
(4) mensuration of the degree of orientation of the flake natural graphite particle in Si oxide graphite composite particles
The degree of orientation of the flake natural graphite particle in Si oxide graphite composite particles can utilize the powder X-ray diffractometry of reflection diffraction formula to obtain.Specifically, circular electrode double faced adhesive tape after the pressurization made in above-mentioned " (2-1) electrode fabrication " is fixed on areflexia plate, and use the RINT-1200V that Co., Ltd. of science manufactures, using copper (Cu) as target, with the tube current of the tube voltage of 40kV, 30mA, CuK alpha ray is irradiated to circular electrode, and measure.Thereafter, carry out the separation at peak, obtain the powder x-ray diffraction spectrogram based on CuK α 1 ray.Obtain 2 θ and be in each intensity that the diffraction maximum in (004) face within the scope of 52 ~ 57 ° and 2 θ are in the diffraction maximum in (110) face within the scope of 75 ~ 80 °.Further, the diffraction peak intensity in (110) face divided by the diffraction peak intensity in (004) face, thus calculates the degree of orientation of the flake natural graphite particle in Si oxide graphite composite particles.The degree of orientation of the flake natural graphite particle in the Si oxide graphite composite particles described in the present embodiment was 0.0091 (with reference to table 2).It should be noted that, this degree of orientation is less, then the orientation of the flake natural graphite particle in Si oxide graphite composite particles becomes higher.
(comparative example 2)
Si oxide graphite composite particles is replaced to " material (without carbobitumen powder) that the silicon monoxide powder after pulverizing and spheroidal natural graphite (average grain diameter (median particle diameter) is 20 μm) mix with the mass ratio of 12:88 ", in addition, operate similarly to Example 10, and evaluate each characteristic (with reference to table 2).
The discharge capacity of non-water test battery unit is now 460mAh/g, and efficiency for charge-discharge is 78.0%, and capacity dimension holdup was 71.0% (with reference to table 2).
(comparative example 3)
First, the silicon monoxide powder (SiO, i.e. x=1) that Wako Pure Chemical Industries, Ltd. manufactures is pulverized using ethanol as solvent ball mill, thus slurry is pulverized in preparation.Then, this pulverizing slurry is fed into and is dissolved with in the oxolane of asphalt powder, stir this mixed liquor and obtain mixed slurry.Then, after mixed slurry is mixed with spheroidizing native graphite (average grain diameter (median particle diameter) is 20 μm), drying is carried out to this mixture and obtains mixed-powder.Further, after this mixed-powder is fed into graphite crucible, by this mixed-powder in stream of nitrogen gas with the heating temperatures 1 hour of 1000 DEG C, thus make asphalt powder convert non-graphite matter carbon to.Finally, the mixed-powder after heat treated is crushed to the sieve that its more than 98 quality % through mesh size is 75 μm, thus obtains comparing mixed-powder.
Operate similarly to Example 10, when comparing the evaluating characteristics of mixed-powder, the degree of orientation comparing mixed-powder is 0.0420.The discharge capacity of non-water test battery unit is 479mAh/g, and efficiency for charge-discharge is 84.3%, and capacity dimension holdup was 89.2% (with reference to table 2).
[table 2]
Can be clear and definite by the above results: when the Si oxide graphite composite particles described in embodiments of the invention is used as the negative electrode active material of lithium rechargeable battery, effectively improve the charge/discharge cycle characteristics of this lithium rechargeable battery.
Embodiment 11
The manufacture > of < Si oxide graphite composite particles
(1) pulverizing of silicon grain
By Si powder, (specific area is 20m 2/ g) pulverize 1 hour to prepare pulverizing slurry with ball mill.It should be noted that, now use ethanol as solvent, use zirconia ball as medium.Now, the newborn face of Si powder is oxidized and become SiOx powder.Only make this pulverizing slurry natural drying in an atmosphere, and reclaim SiOx powder, use the KantaSorb that YuasaIonicsCo., Ltd manufacture, when utilizing BET1 point method to obtain the specific area of SiOx powder, the BET specific surface area of SiOx powder is 40m 2/ g (with reference to table 3).
(2) preparation of mixed slurry
By flake natural graphite powder (middle Yueshi ink Industrial Co., Ltd system, average grain diameter: 10 μm, d002:0.3357nm, pellet density: 1.82g/cm 3) be fed into the Pneugra-machine matching new spectra Co., Ltd. and manufacture, rotate this machine and add above-mentioned pulverizing slurry and mix, thus prepare mixed slurry.It should be noted that, now, reach the mode of 84:7 with the mass ratio of flake natural graphite powder and SiOx powder, to flake natural graphite powder with pulverize slurry and mix.
It should be noted that, the pellet density of flake natural graphite powder can profit be obtained with the following method.
It is in the mould of 15mm that 1.00g flake natural graphite powder is filled to diameter, pressurizes after 5 seconds, weaken to 0.15kN by this moulding pressure by this mould single shaft pressuring machine with the moulding pressure of 8.7kN, reads the displacement of upper punch now.It should be noted that, pressing speed is set to 10mm/ second.In addition, flake natural graphite powder be not filled to above-mentioned mould and utilized by this mould this single shaft pressuring machine to be forced into after moulding pressure reaches 8.7kN, this moulding pressure being weakened to 0.15kN, obtain the displacement of now upper punch.By this displacement as a reference.Further, the displacement obtaining upper punch when filling flake natural graphite powder is used as sample thickness with the difference with reference to displacement, calculates pressed density and pellet density by this thickness.
(3) preparation of composite particles in the middle of
Make mixed slurry natural drying and after obtaining mixed-powder, by the carbobitumen powder of the mixed-powder of 91 mass parts and 18 mass parts (softening point is 86 DEG C, average grain diameter is 20 μm, heat with 1000 DEG C after carbon yield for 50%) be fed into the circular form MECHANOFUSION system (HOSOKAWAMICRONGROUP system, the AMS-mini) gap of rotor and internal stator being set to 1mm.Further, the temperature of this circular form MECHANOFUSION system is adjusted to 90 DEG C ~ 120 DEG C, and the mechanochemistry process of 15 minutes is carried out with the rotating speed of 7000rpm to this mixed-powder, thus composite particles in the middle of preparation.
(4) heat treated of carbobitumen powder
Then, after middle composite particles is fed into graphite crucible, by this middle composite particles in stream of nitrogen gas with the heating temperatures 1 hour of 1000 DEG C, make carbobitumen powder convert non-graphite matter carbon to.
(5) break process
Finally, the middle composite particles after heat treated is crushed to its more than 98 quality % through till mesh size is the sieve of 75 μm, thus obtains the Si oxide graphite composite particles (with reference to Fig. 3) of target.It should be noted that, the flake natural graphite powder in this Si oxide graphite composite particles and SiOx powder (silicon oxide powder) are 84:7:9 (with reference to table 3) with the mass ratio of the heat treatment thing of pitch.Herein, the weight change of burning till front and back is all derived from pitch.
The evaluating characteristics > of < Si oxide graphite composite particles
(1) mensuration of the oxidizability of silicon grain
After acid decomposition is carried out to Si oxide graphite composite particles, melt its residue and make sample.Further, use emission spectroanalysis device to carry out the elementary analysis of this sample, obtain silicon atom content and zirconium atom content.It should be noted that, (zirconium dioxide, by ZrO by zirconia ball for zirconium atom 2formed) abrasion and be mixed into.In addition, utilizing non-active gas to transport melting method makes other Si oxide graphite composite particles melt and after making sample, use infrared-ray absorption process to obtain the oxygen atom content of this sample.Further, according to being deducted the oxygen atom part of zirconium dioxide by oxygen atom content and the value obtained and silicon atom content, the ratio of components " x " of SiOx (i.e.) of oxygen atom relative to silicon atom is obtained.In Si oxide graphite composite particles described in the present embodiment, this ratio of components was 0.41 (with reference to table 3).
(2) mensuration of particle diameter
Use laser diffraction/diffuse transmission type particle size distribution meter (Horiba Ltd's system, LA-910), utilize light scattering diffraction approach to measure the particle size distribution of the volume reference of Si oxide graphite composite particles.Thereafter, use gained particle size distribution, obtain the particle diameter (median particle diameter) when volume fraction is 50%.Its result, this particle diameter is 21 μm (with reference to table 3).
(3) battery behavior evaluation
(3-1) electrode fabrication
The aqueous liquid dispersion of compounding AB (acetylene black) and CMC (sodium carboxymethylcellulose) powder and SBR (butadiene-styrene rubber) and water in above-mentioned Si oxide graphite composite particles, thus obtain electrode mix paste.Herein, AB is conductive auxiliary agent, CMC and SBR is binding agent.The compounding ratio of Si oxide graphite composite particles, AB, CMC and SBR is 97.0:1.0:1.0:1.0 by quality ratio.Further, with scraping the skill in using a kitchen knife in cookery, this electrode mix paste to be coated on thickness be that upper (coating weight is 7 ~ 8mg/cm for the Copper Foil (collector body) of 17 μm 2).Make coating fluid dry and after obtaining film, this film be die-cut into the plate-like that diameter is 13mm.Further, utilize Press forming machine to pressurize to this dish, thus making have 1.70 ± 0.02g/cm 3the electrode of electrode density.It should be noted that, by utilizing micrometer to measure thickness and calculate volume, and the quality measuring this dish (not comprising the part of Copper Foil) is to obtain the electrode density of the electrode obtained.
(3-2) battery makes
Configure above-mentioned electrode in the both sides of polyolefin barrier film and as the Li metal forming to electrode, make electrode assemblies.Further, the inside injection electrolyte to this electrode assemblies makes the non-water test battery unit of Coin shape that cell sizes is 2016.It should be noted that, the composition of electrolyte is set to: ethylene carbonate (EC): methyl ethyl carbonate (EMC): dimethyl carbonate (DMC): vinylene carbonate (VC): fluoroethylene carbonate (FEC): LiPF 6=23:4:48:1:8:16 (mass ratio).
(3-3) evaluation of discharge capacity, first efficiency for charge-discharge, deterioration of battery degree and charge and discharge cycles
In this non-water test battery unit, first, with the current value of 0.33mA for electrode being carried out to constant current doping (embed lithium ion to electrode, be equivalent to the charging of lithium rechargeable battery), after till potential difference reaches 0 (zero) V, adulterate for proceeding electrode with constant voltage under the state keeping 0V further, till reaching 5 μ A, measure doping capacity.Then, carry out dedoping (lithium ion departs from, is equivalent to the electric discharge of lithium rechargeable battery from electrode) with the constant current of 0.33mA, till potential difference reaches 1.5V, measure dedoping capacity.Doping capacity now, dedoping capacity are equivalent to charging capacity, discharge capacity when this electrode being used as the negative pole of lithium rechargeable battery, therefore it can be used as charging capacity, discharge capacity.The discharge capacity of the non-water test battery unit described in the present embodiment is 472mAh/g (with reference to table 3).The ratio of dedoping capacity/doping capacity is now equivalent to the ratio of the discharge capacity/charging capacity of first lithium rechargeable battery, therefore using this ratio as first efficiency for charge-discharge.The first efficiency for charge-discharge of the non-water test battery unit described in the present embodiment was 88.5% (with reference to table 3).
The mensuration of cycle characteristics uses the non-water test battery unit of the Coin shape formed as described above to carry out.In this test cell unit, after the 2nd circulation and the 2nd circulation, with the constant current of 1.33mA, (charging is equivalent to) for adulterating to electrode after till potential difference reaches 5mV, further under the state keeping 5mV, doping is continued, till reaching 50 μ A with constant voltage.Then, carry out dedoping with the constant current of 1.33mA and (be equivalent to electric discharge) till potential difference reaches 1.5V, measure dedoping capacity.Using dedoping capacity now as discharge capacity.
Under condition same as described above, repeat doping and the dedoping of 31 times, obtain the mean value of efficiency for charge-discharge of the 10th circulation ~ the 15 circulation to evaluate deterioration of battery degree, and obtain " discharge capacity during dedoping of the 31st circulation " and carry out evaluation cycle characteristic relative to the ratio (capacity dimension holdup) of " discharge capacity during dedoping of the 2nd circulation ".It should be noted that, when the mean value of efficiency for charge-discharge of the 10th circulation ~ the 15 circulation is less than 100%, electrode destroyed or active material and electrolyte between this circulation there occurs reaction.In addition, when capacity dimension holdup is more than 90%, can regard as well as practical battery.It should be noted that, the mean value of the efficiency for charge-discharge of the 10th circulation ~ the 15 circulation of the non-water test battery unit described in the present embodiment is 99.6%, and capacity dimension holdup was 96.1% (with reference to table 3).
(4) mensuration of the degree of orientation of the flake natural graphite particle in Si oxide graphite composite particles
The degree of orientation of the flake natural graphite particle in Si oxide graphite composite particles can utilize the powder X-ray diffractometry of reflection diffraction formula to obtain.Specifically, circular electrode double faced adhesive tape after the pressurization made in above-mentioned " (3-1) electrode fabrication " is fixed on areflexia plate, and use the RINT-1200V that Co., Ltd. of science manufactures, using copper (Cu) as target, with the tube current of the tube voltage of 40kV, 30mA, CuK alpha ray is irradiated to circular electrode, and measure.Thereafter, carry out the separation at peak, obtain the powder x-ray diffraction spectrogram based on CuK α 1 ray.Obtain 2 θ and be in each intensity that the diffraction maximum in (004) face within the scope of 52 ~ 57 ° and 2 θ are in the diffraction maximum in (110) face within the scope of 75 ~ 80 °.Further, the diffraction peak intensity in (110) face divided by the diffraction peak intensity in (004) face, thus calculates the degree of orientation of the flake natural graphite particle in Si oxide graphite composite particles.The degree of orientation of the flake natural graphite particle in the Si oxide graphite composite particles described in the present embodiment was 0.0075 (with reference to table 1).It should be noted that, this degree of orientation is less, then the orientation of the flake natural graphite particle in Si oxide graphite composite particles becomes higher.
(5) mensuration of draw ratio
After circular electrode before the pressurization made in above-mentioned " (3-1) electrode fabrication " is embedded into resin, this resin is cut off and grinds its cross section.And, with this cross section of observation by light microscope (electrode section), measure the size of 50 Si oxide graphite composite particles, for each Si oxide graphite composite particles, calculate draw ratio (the long axis length W of the flaky graphite particle in Fig. 1 is relative to the ratio of stacked direction length H).Further, using the draw ratio of the mean value of the draw ratio of these 50 Si oxide graphite composite particles as Si oxide graphite composite particles.It should be noted that, the draw ratio of the Si oxide graphite composite particles described in the present embodiment was 2.4 (with reference to table 3).
Embodiment 12
When pulverizing silicon grain, by Si powder, (specific area is 20m 2/ g) pulverize 2 hours with ball mill and prepare pulverizing slurry, when powder mixes, the mass ratio of flake natural graphite powder and Si powder is set to 83:8, in addition, operate similarly to Example 11 and prepare Si oxide graphite composite particles, evaluating each characteristic.It should be noted that, the flake natural graphite powder in this Si oxide graphite composite particles and Si powder (silicon oxide powder) are 83:8:9 (with reference to table 3) with the mass ratio of the heat treatment thing of pitch.
The oxygen atom of SiOx particle is now 54m relative to the BET specific surface area that the ratio of components (i.e. " x ") of silicon atom is 0.69, SiOx particle 2/ g.The draw ratio of Si oxide graphite composite particles is 2.5.Particle diameter (median particle diameter) during the volume fraction 50% of this Si oxide graphite composite particles is 20 μm.The degree of orientation of this Si oxide graphite composite particles is 0.0078.The discharge capacity of non-water test battery unit is 470mAh/g, and first efficiency for charge-discharge is the mean value of the efficiency for charge-discharge of the 87.4%, 10th circulation ~ the 15 circulation is 99.7%, and capacity dimension holdup was 96.8% (with reference to table 3).
Embodiment 13
When pulverizing silicon grain, by Si powder, (specific area is 20m 2/ g) pulverize 5 hours with ball mill and prepare pulverizing slurry, when powder mixes, the mass ratio of flake natural graphite powder and Si powder is set to 77:14, in addition, operate similarly to Example 11 and prepare Si oxide graphite composite particles, evaluating each characteristic.It should be noted that, the flake natural graphite powder in this Si oxide graphite composite particles and Si powder (silicon oxide powder) are 77:14:9 (with reference to table 3) with the mass ratio of the heat treatment thing of pitch.
The oxygen atom of SiOx particle is now 82m relative to the BET specific surface area that the ratio of components (i.e. " x ") of silicon atom is 0.85, SiOx particle 2/ g.The draw ratio of Si oxide graphite composite particles is 2.7.Particle diameter (median particle diameter) during the volume fraction 50% of this Si oxide graphite composite particles is 20 μm.The degree of orientation of this Si oxide graphite composite particles is 0.0081.The discharge capacity of non-water test battery unit is 471mAh/g, and first efficiency for charge-discharge is the mean value of the efficiency for charge-discharge of the 86.0%, 10th circulation ~ the 15 circulation is 99.6%, and capacity dimension holdup was 95.5% (with reference to table 3).
(comparative example 4)
< compares the manufacture > of Si oxide graphite composite particles
(1) pulverizing of silicon grain
Similarly to Example 12, by Si powder, (specific area is 20m 2/ g) pulverize 2 hours with ball mill and prepare pulverizing slurry.The BET specific surface area of the SiOx powder now obtained is 54m 2/ g (with reference to table 3).
(2) preparation of mixed slurry
Similarly to Example 12, by flake natural graphite powder (middle Yueshi ink Industrial Co., Ltd system, average grain diameter: 10 μm, d002:0.3357nm, pellet density: 1.82g/cm 3) be fed into the Pneugra-machine matching new spectra Co., Ltd., rotate this machine and add above-mentioned pulverizing slurry and mix, thus prepare mixed slurry.It should be noted that, now, similarly to Example 12, reach the mode of 83:8 with the mass ratio of flake natural graphite powder and SiOx powder, by flake natural graphite powder with pulverize slurry and mix.
(3) preparation of aggregation
Then, in above-mentioned mixed slurry, mix oxolane and carbobitumen powder (softening point is 86 DEG C, average grain diameter is 20 μm, with the carbon yield after 1000 DEG C of heating for 50%) prepare dispersion liquid.Further, make this dispersion liquid dry and obtain dried powder.Then, after this dried powder is fed into graphite crucible, by constantly little for the heating temperatures 1 of this dried powder with 450 DEG C in stream of nitrogen gas, aggregation can be obtained.
(4) preparation of composite particles in the middle of
Then, the powder obtained pulverizing the aggregation after heat treated with electric coffee grinder is fed into the circular form MECHANOFUSION system (HOSOKAWAMICRONGROUP AMS-mini) gap of rotor and internal stator being set to 1mm.Further, utilize this circular form MECHANOFUSION system, this powder is carried out the mechanochemistry process of 15 minutes with the rotating speed of 7000rpm, thus composite particles in the middle of preparation.
(5) heat treated of carbobitumen powder
Then, after middle composite particles is fed into graphite crucible, by this middle composite particles in stream of nitrogen gas with the heating temperatures 1 hour of 1000 DEG C, thus make carbobitumen powder convert non-graphite matter carbon to.
(6) break process
Finally, the middle composite particles after heat treatment is crushed to the sieve that its more than 98 quality % through mesh size is 75 μm, thus obtains the comparison 3 SiC 2/graphite composite particles of target.It should be noted that, this compares flake natural graphite powder in Si oxide graphite composite particles and SiOx powder (silicon oxide powder) is 83:8:9 (with reference to table 3) with the mass ratio of the heat treatment thing of pitch.Herein, the weight change of burning till front and back is all derived from pitch.
Further, the comparison 3 SiC 2/graphite composite particles obtained for as above operating, operation is when evaluating its characteristic similarly to Example 11, the oxygen atom of SiOx particle relative to silicon atom ratio of components (i.e. " x ") be 0.69.Relatively the draw ratio of Si oxide graphite composite particles is 1.9.Particle diameter (median particle diameter) when this compares the volume fraction 50% of Si oxide graphite composite particles is 30 μm.This degree of orientation comparing Si oxide graphite composite particles is 0.0350.The discharge capacity of non-water test battery unit is 460mAh/g, and first efficiency for charge-discharge is the mean value of the efficiency for charge-discharge of the 86.0%, 10th circulation ~ the 15 circulation is 96.0%, and capacity dimension holdup was 87.1% (with reference to table 3).
(comparative example 5)
< compares the manufacture > of Si oxide graphite composite particles
(1) pulverizing of silicon grain
Similarly to Example 12, by Si powder, (specific area is 20m 2/ g) pulverize 2 hours with ball mill and prepare pulverizing slurry.The BET specific surface area of the SiOx powder now obtained is 54m 2/ g (with reference to table 3).
(2) preparation of mixed slurry
Then, mix the tetrahydrofuran solution of coal measures asphalt powder (softening point is 86 DEG C, average grain diameter is 20 μm, with the carbon yield after 1000 DEG C of heating for 50%) in above-mentioned pulverizing slurry after, in its fraction, mix spheroidizing native graphite (average grain diameter is 20 μm) further, thus prepare mixed slurry.
(3) heat treated of carbobitumen powder
Then, make mixed slurry dry and after this dry thing is fed into graphite crucible, by this dry thing in stream of nitrogen gas with the heating temperatures 1 hour of 1000 DEG C, thus make carbobitumen powder convert non-graphite matter carbon to.
(4) break process
Finally, the middle composite particles after heat treated is crushed to the sieve that its more than 98 quality % through mesh size is 75 μm, thus obtains the comparison 3 SiC 2/graphite composite particles of target.It should be noted that, this compares flake natural graphite powder in Si oxide graphite composite particles and SiOx powder (silicon oxide powder) is 83:8:9 (with reference to table 3) with the mass ratio of the heat treatment thing of pitch.Herein, the weight change of burning till front and back is all derived from pitch.
Further, the comparison 3 SiC 2/graphite composite particles obtained for as above operating, operation is when evaluating its characteristic similarly to Example 11, the oxygen atom of SiOx particle relative to silicon atom ratio of components (i.e. " x ") be 0.69.Relatively the draw ratio of Si oxide graphite composite particles is 1.3.Particle diameter (median particle diameter) when this compares the volume fraction 50% of Si oxide graphite composite particles is 21 μm.This degree of orientation comparing Si oxide graphite composite particles is 0.0420.The discharge capacity of non-water test battery unit is 470mAh/g, and first efficiency for charge-discharge is the mean value of the efficiency for charge-discharge of the 88.6%, 10th circulation ~ the 15 circulation is 98.2%, and efficiency for charge-discharge was 89.0% (with reference to table 3).
[table 3]
Can be clear and definite by the above results: when the Si oxide graphite composite particles described in embodiments of the invention is used as the negative electrode active material of lithium rechargeable battery, effectively can improve the charge/discharge cycle characteristics of this lithium rechargeable battery.

Claims (24)

1.一种硅相含有物石墨复合颗粒，其具备：1. A silicon phase containing graphite composite particle, which possesses: 排列成层状的多个鳞片状石墨颗粒；以及a plurality of flaky graphite particles arranged in layers; and 包含硅相和非硅相且被所述多个鳞片状石墨颗粒夹持的含硅相颗粒。Silicon-containing phase particles comprising a silicon phase and a non-silicon phase and sandwiched by the plurality of flaky graphite particles. 2.根据权利要求1所述的硅相含有物石墨复合颗粒，其中，所述非硅相为碱金属离子非活性相。2. The silicon phase-containing graphite composite particles according to claim 1, wherein the non-silicon phase is an alkali metal ion inactive phase. 3.根据权利要求1或2所述的硅相含有物石墨复合颗粒，其中，所述非硅相为金属硅化物相。3. The silicon phase-containing graphite composite particles according to claim 1 or 2, wherein the non-silicon phase is a metal silicide phase. 4.根据权利要求2或3所述的硅相含有物石墨复合颗粒，其中，所述含硅相颗粒被所述多个鳞片状石墨颗粒夹持且所述含硅相颗粒借助加热处理物附着在最外层的所述鳞片状石墨颗粒的外表面上，所述加热处理物是在300℃～600℃范围内的温度下对有机化合物进行加热处理而得到的。4. The silicon phase-containing graphite composite particles according to claim 2 or 3, wherein the silicon-containing phase particles are sandwiched by the plurality of scaly graphite particles and the silicon-containing phase particles are attached by heat treatment The heat-treated product is obtained by heat-treating an organic compound at a temperature in the range of 300°C to 600°C on the outer surface of the flaky graphite particles in the outermost layer. 5.根据权利要求4所述的硅相含有物石墨复合颗粒，其中，所述鳞片状石墨颗粒、所述含硅相颗粒与所述加热处理物的质量比为97～60:1～30:2～10。5. The graphite composite particles containing silicon phase according to claim 4, wherein the mass ratio of the scaly graphite particles, the silicon-containing phase particles and the heat-treated product is 97～60:1～30: 2 to 10. 6.根据权利要求1～5中任一项所述的硅相含有物石墨复合颗粒，其中，所述含硅相颗粒的中值粒径d50为2μm以下。6 . The silicon phase-containing graphite composite particles according to claim 1 , wherein the silicon phase-containing particles have a median diameter d50 of 2 μm or less. 7.根据权利要求1所述的硅相含有物石墨复合颗粒，其中，所述含硅相颗粒为SiOx颗粒，其中，0<x≤0.9。7 . The graphite composite particles containing silicon phase according to claim 1 , wherein the silicon-containing phase particles are SiOx particles, wherein 0<x≤0.9. 8.根据权利要求7所述的硅相含有物石墨复合颗粒，其中，所述含硅相颗粒的比表面积在40m2/g以上且200m2/g以下的范围内。8 . The silicon phase-containing graphite composite particles according to claim 7 , wherein the specific surface area of the silicon phase-containing particles is in the range of not less than 40 m 2 /g and not more than 200 m 2 /g. 9.根据权利要求1所述的硅相含有物石墨复合颗粒，其中，所述含硅相颗粒为SiOx颗粒，其中，0.9<x<1.3。9 . The graphite composite particles containing silicon phase according to claim 1 , wherein the silicon-containing phase particles are SiOx particles, wherein 0.9<x<1.3. 10.根据权利要求7～9中任一项所述的硅相含有物石墨复合颗粒，其中，所述含硅相颗粒被所述多个鳞片状石墨颗粒夹持，且所述含硅相颗粒借助非石墨质碳附着在最外层的所述鳞片状石墨颗粒的外表面上。10. The graphite composite particles containing silicon phases according to any one of claims 7 to 9, wherein the silicon-containing phase particles are sandwiched by the plurality of scaly graphite particles, and the silicon-containing phase particles Attached to the outer surface of the flaky graphite particles in the outermost layer by means of non-graphitic carbon. 11.根据权利要求10所述的硅相含有物石墨复合颗粒，其中，所述鳞片状石墨颗粒、所述含硅相颗粒与所述非石墨质碳的质量比为97～55:1～30:2～15。11. The silicon phase-containing graphite composite particles according to claim 10, wherein the mass ratio of the flake graphite particles, the silicon-containing phase particles to the non-graphitic carbon is 97-55:1-30 :2～15. 12.根据权利要求1～11中任一项所述的硅相含有物石墨复合颗粒，其中，制作电极密度为1.70±0.02g/cm3的电极时的所述电极的X射线衍射图像中，“归属于(110)面的峰的强度I(110)”相对于“归属于(004)面的峰的强度I(004)”之比在0.0010以上且0.0300以下的范围内。12. The silicon phase inclusion graphite composite particles according to any one of claims 1 to 11, wherein, in the X-ray diffraction image of the electrode when the electrode density is 1.70±0.02g/cm 3 , The ratio of "the intensity I(110) of the peak assigned to the (110) plane" to the "intensity I(004) of the peak assigned to the (004) plane" is within the range of 0.0010 to 0.0300. 13.根据权利要求1～12中任一项所述的硅相含有物石墨复合颗粒，其中，所述鳞片状石墨颗粒的长轴长度相对于层叠方向长度之比为1.5以上且10以下。13 . The silicon phase-containing graphite composite particles according to claim 1 , wherein the ratio of the length of the major axis of the flaky graphite particles to the length in the stacking direction is 1.5 to 10. 14 . 14.一种硅相含有物石墨复合颗粒的制造方法，其具备如下工序：14. A method for manufacturing graphite composite particles containing a silicon phase, comprising the following steps: 一次复合颗粒制备工序：对包含硅相和非硅相的含硅相颗粒与鳞片状石墨颗粒的混合颗粒赋予压缩力和剪切力，从而制备一次复合颗粒；Preparation of primary composite particles: applying compressive force and shear force to the mixed particles of silicon-containing phase particles and scaly graphite particles including silicon phase and non-silicon phase, thereby preparing primary composite particles; 混合粉末制备工序：使所述一次复合颗粒与固体的有机化合物混合而制备混合粉末；以及A mixed powder preparation process: mixing the primary composite particles with a solid organic compound to prepare a mixed powder; and 加热工序：对所述混合粉末进行加热处理。Heating process: heat treatment is performed on the mixed powder. 15.根据权利要求14所述的硅相含有物石墨复合颗粒的制造方法，其中，所述非硅相为金属硅化物相，15. The method for producing graphite composite particles containing silicon phases according to claim 14, wherein the non-silicon phase is a metal silicide phase, 所述加热工序中，在300℃～600℃范围内的温度下对所述混合粉末进行加热处理。In the heating step, the mixed powder is heat-treated at a temperature ranging from 300°C to 600°C. 16.根据权利要求14所述的硅相含有物石墨复合颗粒的制造方法，其中，所述含硅相颗粒为SiOx，其中，0<x<1.3，16. The method for producing graphite composite particles containing silicon phases according to claim 14, wherein the silicon-containing phase particles are SiOx, wherein, 0<x<1.3, 所述有机化合物为非石墨质碳原料。The organic compound is a non-graphitic carbon raw material. 17.一种硅相含有物石墨复合颗粒的制造方法，其具备如下工序：17. A method for manufacturing graphite composite particles containing a silicon phase, comprising the following steps: 中间复合颗粒制备工序：对包含硅相和非硅相的含硅相颗粒、鳞片状石墨颗粒与固体的有机化合物的混合物在所述有机化合物的软化点以上的温度下施加压缩力和剪切力，从而制备中间复合颗粒；以及，Preparation of intermediate composite particles: Applying compressive force and shearing force to a mixture of silicon-containing phase particles including a silicon phase and a non-silicon phase, flake graphite particles, and a solid organic compound at a temperature above the softening point of the organic compound , thereby preparing intermediate composite particles; and, 加热工序：对所述中间复合颗粒进行加热处理。Heating step: heat-treating the intermediate composite particles. 18.根据权利要求17所述的硅相含有物石墨复合颗粒的制造方法，其中，所述非硅相为金属硅化物相，18. The method for producing graphite composite particles containing silicon phases according to claim 17, wherein the non-silicon phase is a metal silicide phase, 所述加热工序中，在300℃～600℃范围内的温度下对所述中间复合颗粒进行加热处理。In the heating step, the intermediate composite particles are heat-treated at a temperature ranging from 300°C to 600°C. 19.根据权利要求17所述的硅相含有物石墨复合颗粒的制造方法，其中，所述含硅相颗粒为SiOx，其中，0<x<1.3，19. The method for producing graphite composite particles containing silicon phases according to claim 17, wherein the silicon-containing phase particles are SiOx, wherein, 0<x<1.3, 所述有机化合物为非石墨质碳原料。The organic compound is a non-graphitic carbon raw material. 20.根据权利要求17～19中任一项所述的硅相含有物石墨复合颗粒的制造方法，其还具备如下工序：20. The method for producing the graphite composite particles containing silicon phases according to any one of claims 17 to 19, further comprising the steps of: 湿式粉碎工序：对所述含硅相颗粒的粗颗粒进行湿式粉碎而制备微粒浆料；Wet pulverization process: wet pulverizing the coarse particles of the silicon-containing phase particles to prepare a particle slurry; 混合工序：向所述微粒浆料中混合所述鳞片状石墨颗粒而制备混合浆料；以及mixing process: mixing the flaky graphite particles into the fine particle slurry to prepare a mixed slurry; and 干燥工序：使所述混合浆料干燥而制备混合粉末，Drying process: drying the mixed slurry to prepare mixed powder, 所述中间复合颗粒制备工序中，对所述混合粉末与所述固体的有机化合物的混合物在所述有机化合物的软化点以上的温度下施加压缩力和剪切力，从而制备中间复合颗粒。In the intermediate composite particle preparation step, compressive force and shear force are applied to the mixture of the mixed powder and the solid organic compound at a temperature equal to or higher than the softening point of the organic compound to prepare intermediate composite particles. 21.根据权利要求20所述的硅相含有物石墨复合颗粒的制造方法，其中，所述含硅相颗粒为SiOx，其中，0<x≤0.9，21. The method for producing graphite composite particles containing silicon phases according to claim 20, wherein the silicon-containing phase particles are SiOx, wherein, 0<x≤0.9, 所述有机化合物为非石墨质碳原料。The organic compound is a non-graphitic carbon raw material. 22.一种硅相含有物石墨复合颗粒，其是通过权利要求14～21中任一项所述的硅相含有物石墨复合颗粒的制造方法而得到的。22. Graphite composite particles containing silicon phases obtained by the method for producing graphite composite particles containing silicon phases according to any one of claims 14 to 21. 23.一种电极，其以权利要求1、2、3、4、5、6、7、8、9、10、11、12、13和22中任一项所述的硅相含有物石墨复合颗粒作为活性物质。23. An electrode, which is composited with the silicon phase inclusion graphite according to any one of claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 and 22 Granules as active substance. 24.一种非水电解质二次电池，其具备权利要求23所述的电极。24. A nonaqueous electrolyte secondary battery comprising the electrode according to claim 23.
CN201480041817.1A 2013-09-17 2014-09-04 Graphite composite particle containing silicon phase and manufacturing method thereof Pending CN105409040A (en)

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JP2013-191947 2013-09-17
JP2013191941A JP2015060640A (en) 2013-09-17 2013-09-17 Alloy-graphite composite particle and method for producing the same
JP2013191947A JP2015060642A (en) 2013-09-17 2013-09-17 Silicon oxide-graphite composite particle and method for producing the same
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JP2013191944A JP2015060641A (en) 2013-09-17 2013-09-17 Silicon oxide-graphite composite particle and method for producing the same
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PCT/JP2014/073344 WO2015041063A1 (en) 2013-09-17 2014-09-04 Composite particles of silicon phase-containing substance and graphite, and method for producing same

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US20200411844A1 (en) * 2019-06-26 2020-12-31 Samsung Sdi Co., Ltd. Composite anode and lithium secondary battery including the same
CN114335687A (en) * 2021-12-30 2022-04-12 横店集团东磁股份有限公司 Lithium ion battery and preparation method thereof
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