CN114883558B - Negative electrode material for lithium ion secondary battery, negative electrode for lithium ion secondary battery, and lithium ion secondary battery - Google Patents
Negative electrode material for lithium ion secondary battery, negative electrode for lithium ion secondary battery, and lithium ion secondary battery Download PDFInfo
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- CN114883558B CN114883558B CN202210750544.4A CN202210750544A CN114883558B CN 114883558 B CN114883558 B CN 114883558B CN 202210750544 A CN202210750544 A CN 202210750544A CN 114883558 B CN114883558 B CN 114883558B
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Classifications
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/13—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
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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
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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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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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- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
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Abstract
本发明提供锂离子二次电池用负极材、锂离子二次电池用负极和锂离子二次电池，该锂离子二次电池用负极材包含碳材料，所述碳材料通过X射线衍射法求出的平均面间隔d002为0.335nm～0.339nm，通过在77K进行的氮吸附测定而求出的比表面积为0.5m2/g～6.0m2/g，且满足下述(1)和(2)。(1)在个数基准的粒度分布中，差分的相对粒子量q0成为最频值时的粒径小于或等于11.601μm。(2)在个数基准的粒度分布中，粒径为11.601μm时的差分的相对粒子量q0A与粒径为7.806μm时的差分的相对粒子量q0B之比(q0A/q0B)为1.20～3.00。The present invention provides a negative electrode material for a lithium ion secondary battery, a negative electrode for a lithium ion secondary battery, and a lithium ion secondary battery. The negative electrode material for a lithium ion secondary battery comprises a carbon material, wherein the carbon material has an average interplanar spacing d002 of 0.335 nm to 0.339 nm as determined by an X-ray diffraction method, a specific surface area of 0.5 m2 /g to 6.0 m2 /g as determined by nitrogen adsorption at 77K, and satisfies the following (1) and (2). (1) In a particle size distribution based on number, the particle size at which the differential relative particle amount q0 becomes the most frequent value is less than or equal to 11.601 μm. (2) In a particle size distribution based on number, the ratio of the differential relative particle amount q0A when the particle size is 11.601 μm to the differential relative particle amount q0B when the particle size is 7.806 μm (q0A/q0B) is 1.20 to 3.00.
Description
The present invention is a divisional application of the invention application having the application number 201680090827.3, the application date 2016, 11 and 14, and the invention name "negative electrode material for lithium ion secondary battery, negative electrode for lithium ion secondary battery and lithium ion secondary battery".
Technical Field
The present invention relates to a negative electrode material for a lithium ion secondary battery, a negative electrode for a lithium ion secondary battery, and a lithium ion secondary battery.
Background
Lithium ion secondary batteries are lightweight and have high input/output characteristics as compared with other secondary batteries such as nickel-metal hydride batteries and lead-acid batteries, and have recently been attracting attention as high input/output power sources for use in electric vehicles, hybrid electric vehicles, and the like.
Since the commercialization of lithium ion secondary batteries in 1991, further improvements in energy density and input/output characteristics have been strongly desired. As a method for achieving this, a technique of improving a negative electrode material contained in a negative electrode of a lithium ion secondary battery occupies an important position (for example, refer to patent document 1 and patent document 2).
Prior art literature
Patent literature
Patent document 1 Japanese patent laid-open No. 4-370662
Patent document 2 Japanese patent laid-open No. 5-307956
Disclosure of Invention
Problems to be solved by the invention
As a material of the negative electrode material of the lithium ion secondary battery, carbon materials such as graphite and amorphous carbon are widely used.
Graphite has a structure in which hexagonal network surfaces of carbon atoms are regularly stacked, and lithium ions are intercalated and deintercalated from the end portions of the stacked network surfaces to perform charge and discharge.
Further, since amorphous carbon has irregular lamination of hexagonal network surfaces or no mesh structure, intercalation/deintercalation reaction of lithium ions proceeds over the entire surface, and lithium ions having excellent input/output characteristics are easily obtained. In contrast to graphite, amorphous carbon has characteristics such as low crystallinity, low reaction with an electrolyte, and excellent life characteristics.
Since the intercalation/deintercalation reaction of lithium ions proceeds only at the end, the graphite cannot be said to have sufficient input/output performance. Further, since the crystallinity is high and the reactivity of the surface is high, the reactivity with the electrolyte may be high particularly at high temperature, and there is room for improvement in the life characteristics of the lithium ion secondary battery. On the other hand, amorphous carbon has a lower crystallinity than graphite, and therefore has an irregular crystal structure, and therefore cannot be said to have a sufficient energy density.
As a carbon material that can achieve both high energy density derived from graphite and high life characteristics derived from amorphous carbon, a carbon material in which a layer of amorphous carbon is formed on the surface of a core material made of graphite has been proposed.
In recent years, particularly in vehicle-mounted applications, there has been a further increase in the demand for a battery having a higher capacity in order to extend the travel distance. Therefore, in the same manner as in the civil use, the densification of the electrode is being studied in the vehicle-mounted use. Among them, there is a concern that the input/output characteristics are degraded due to the high density of the electrode, and it is a problem to achieve both the high capacity and the input/output characteristics. That is, there is a demand for addressing the problem that is difficult to solve by simply compositing graphite with amorphous carbon.
The purpose of the present invention is to provide a negative electrode material for a lithium ion secondary battery, a negative electrode for a lithium ion secondary battery, and a lithium ion secondary battery produced using the same, wherein the negative electrode material and the negative electrode are capable of producing a lithium ion secondary battery that has excellent input/output characteristics and life characteristics while maintaining high charge/discharge efficiency.
Means for solving the problems
The following embodiments are included in the means for solving the above problems.
<1> An anode material for a lithium ion secondary battery comprising a carbon material having an average surface interval d 002 of 0.335nm to 0.399 nm as measured by an X-ray diffraction method, and a specific surface area of 0.5m 2/g～6.0m2/g as measured by nitrogen adsorption at 77K, and satisfying the following (1) and (2).
(1) In the number-based particle size distribution, the particle diameter at which the differential relative particle quantity q0 becomes the most frequent value is 11.601 μm or less.
(2) In the number-based particle size distribution, the ratio (q 0A/q 0B) of the differential relative particle quantity q0A at a particle size of 11.601 [ mu ] m to the differential relative particle quantity q0B at a particle size of 7.806 [ mu ] m is 1.20 to 3.00.
<2> An anode material for a lithium ion secondary battery, comprising a carbon material, wherein the carbon material has an average surface interval d 002 as measured by an X-ray diffraction method of 0.335nm to 0.339nm, and an R value as measured by Raman spectroscopy of 0.1 to 1.0, and satisfies the following (1) and (2).
(1) In the number-based particle size distribution, the particle diameter at which the differential relative particle quantity q0 becomes the most frequent value is 11.601 μm or less.
(2) In the number-based particle size distribution, the ratio (q 0A/q 0B) of the differential relative particle quantity q0A at a particle size of 11.601 [ mu ] m to the differential relative particle quantity q0B at a particle size of 7.806 [ mu ] m is 1.20 to 3.00.
<3> An anode material for a lithium ion secondary battery, comprising a carbon material having an average surface interval d 002 of 0.335nm to 0.399 nm as determined by an X-ray diffraction method, comprising a first carbon phase which becomes a core, and a second carbon phase which is disposed on at least a part of the surface of the first carbon phase and is different from the first carbon phase, and satisfying the following (1) and (2).
(1) In the number-based particle size distribution, the particle diameter at which the differential relative particle quantity q0 becomes the most frequent value is 11.601 μm or less.
(2) In the number-based particle size distribution, the ratio (q 0A/q 0B) of the differential relative particle quantity q0A at a particle size of 11.601 [ mu ] m to the differential relative particle quantity q0B at a particle size of 7.806 [ mu ] m is 1.20 to 3.00.
<4> The negative electrode material for a lithium ion secondary battery according to any one of <1> to <3>, wherein when the volume cumulative distribution curve is drawn from the small particle diameter side in the volume-based particle size distribution of the carbon material, the cumulative value Q3 at a particle diameter of 9.516 μm is 4.0% or more of the entire volume.
<5> The negative electrode material for a lithium ion secondary battery according to any one of <1> to <4>, wherein, in the particle size distribution based on the volume of the carbon material, when a volume cumulative distribution curve is drawn from the small particle size side, the particle size (50% D) when the cumulative content is 50% is 1 μm to 20 μm.
<6> The negative electrode material for a lithium ion secondary battery according to any one of <1> to <5>, wherein in the particle size distribution based on the volume of the carbon material, when a volume cumulative distribution curve is drawn from the small particle size side, the particle size (99.9% D) when the cumulative amount is 99.9% is 63 μm or less.
<7> The negative electrode material for a lithium ion secondary battery according to any one of <1> to <6>, wherein the carbon material has a tap density of 0.90g/cm 3～2.00g/cm3.
<8> The negative electrode material for a lithium ion secondary battery according to any one of <1> to <7>, wherein the carbon material has a particle density of 1.55g/cm 3 or less.
<9> A negative electrode for a lithium ion secondary battery comprising a negative electrode material layer and a current collector, wherein the negative electrode material layer comprises the negative electrode material for a lithium ion secondary battery according to any one of <1> to <8 >.
<10> A lithium ion secondary battery comprising the negative electrode, positive electrode, and electrolyte for a lithium ion secondary battery of <9 >.
Effects of the invention
According to the present invention, it is possible to provide a negative electrode material for a lithium ion secondary battery and a negative electrode for a lithium ion secondary battery, which can produce a lithium ion secondary battery having excellent input/output characteristics and life characteristics while maintaining high charge/discharge efficiency, and a lithium ion secondary battery produced using the same.
Detailed Description
The mode for carrying out the present invention will be described in detail below. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (including the element steps) are not necessarily required unless otherwise specifically indicated. The numerical values and the ranges thereof are also not limiting.
In the present specification, the term "process" includes not only a process independent of other processes, but also a process which cannot be clearly distinguished from other processes, as long as the object of the process can be achieved.
In the present specification, the numerical range expressed by "-" includes numerical values described before and after "-" as the minimum value and the maximum value, respectively.
In the numerical ranges described in stages in the present specification, the upper limit or the lower limit described in one numerical range may be replaced with the upper limit or the lower limit of the numerical range described in other stages. In the numerical ranges described in the present specification, the upper limit or the lower limit of the numerical range may be replaced with the values shown in the examples.
In the present specification, when a plurality of substances corresponding to the respective components are present in the composition, unless otherwise specified, the content or content of the respective components in the composition means the total content or content of the plurality of substances present in the composition.
In the present specification, when a plurality of particles corresponding to each component are present in the composition, unless otherwise specified, the particle size of each component in the composition refers to the value of the mixture of the plurality of particles present in the composition.
In the present specification, the term "layer" or "film" includes a case where the film is formed only in a part of the region, as well as a case where the film is formed in the entire region when the region where the layer or film is present is observed.
In the present specification, the term "stacked" means that layers are stacked, and two or more layers may be combined, or two or more layers may be detachable.
< Negative electrode Material (1) for lithium ion Secondary Battery >
The negative electrode material for a lithium ion secondary battery (hereinafter, sometimes simply referred to as "negative electrode material") of the present embodiment contains a carbon material, has an average surface interval d 002 of 0.335nm to 0.399 nm as determined by an X-ray diffraction method, has a specific surface area of 0.5m 2/g～6.0m2/g as determined by nitrogen adsorption measurement at 77K, and satisfies the following (1) and (2).
(1) In the number-based particle size distribution, the particle diameter at which the differential relative particle quantity q0 becomes the most frequent value is 11.601 μm or less.
(2) In the number-based particle size distribution, the ratio (q 0A/q 0B) of the differential relative particle quantity q0A at a particle size of 11.601 [ mu ] m to the differential relative particle quantity q0B at a particle size of 7.806 [ mu ] m is 1.20 to 3.00.
By using the negative electrode material according to the present embodiment, a lithium ion secondary battery having excellent input/output characteristics and life characteristics while maintaining high charge/discharge efficiency can be manufactured.
The composition of the anode material of the present embodiment is not particularly limited as long as the anode material contains a carbon material satisfying the above conditions. From the viewpoint of obtaining the effect of the present embodiment, the proportion of the carbon material in the entire negative electrode material is preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and particularly preferably 100% by mass.
(Carbon Material)
The average surface interval d 002 of the carbon material obtained by an X-ray diffraction method is 0.335-0.339 nm.
The value of the average surface interval d 002 is 0.3354nm, which is a theoretical value of graphite crystals, and the energy density tends to be higher as the value approaches. When the average surface interval d 002 is within the above range, the initial charge/discharge efficiency and the energy density of the lithium ion secondary battery tend to be excellent.
In the present embodiment, the average surface interval d 002 of the carbon material can be calculated by irradiating a sample of the carbon material with an X-ray (cukα ray), based on a diffraction pattern obtained by measuring a diffraction line with a goniometer, and based on diffraction peaks corresponding to the carbon 002 surface, which occur in the vicinity of the diffraction angles 2θ=24° to 27 °.
The value of the average plane interval d 002 of the carbon material is preferably small from the viewpoint of the energy density of the lithium ion secondary battery. Specifically, for example, it is preferably 0.335nm to 0.337nm.
Since the value of the average surface interval d 002 of the carbon material tends to be small by increasing the temperature of the heat treatment performed on the carbon material, the average surface interval d 002 can be adjusted to be within the above range by utilizing the property.
The specific surface area of the carbon material (hereinafter, referred to as "N 2 specific surface area") obtained by nitrogen adsorption measurement at 77K was 0.5m 2/g～6.0m2/g.
If the specific surface area of N 2 of the carbon material is within the above range, the balance between the input/output characteristics and the primary efficiency tends to be maintained well.
The specific surface area of N 2 of the carbon material can be determined by the BET method based on the adsorption isotherm obtained by nitrogen adsorption measurement at 77K.
The specific surface area of N 2 is preferably 1.0m 2/g～5.0m2/g from the viewpoint of balance between the input/output characteristics and the primary efficiency of the lithium ion secondary battery.
The N 2 specific surface area tends to be small by, for example, increasing the volume average particle diameter of the carbon material, increasing the temperature of the heat treatment of the carbon material, modifying the surface of the carbon material, and the like, and therefore, the N 2 specific surface area can be set within the above range by utilizing this property.
In the particle size distribution of the carbon material based on the number, the particle size when the differential relative particle quantity q0 becomes the most frequent value is 11.601 μm or less. If the particle diameter exceeds 11.601 μm when the differential relative particle quantity q0 becomes the maximum frequency value, the proportion of the carbon material having a large particle diameter increases, and therefore the diffusion distance of lithium ions from the particle surface of the carbon material to the inside increases, and the input/output characteristics of the lithium ion secondary battery tend to decrease.
The particle diameter at which the differential relative particle amount q0 becomes the most frequent value is preferably 11.601 μm or 9.516 μm, more preferably 11.601 μm.
In the carbon material, the total value of the differential relative particle amount q0 at a particle diameter of 11.601 μm and the differential relative particle amount q0 at a particle diameter of 9.516 μm is preferably 25 or more, more preferably 30 or more, and even more preferably 32 or more.
In the particle size distribution of the carbon material based on the number, the ratio (q 0A/q 0B) of the differential relative particle quantity q0A at a particle size of 11.601 [ mu ] m to the differential relative particle quantity q0B at a particle size of 7.806 [ mu ] m is 1.20-3.00.
If the value of q0A/q0B is less than 1.20, the input/output characteristics tend to be degraded.
If the value of q0A/q0B exceeds 3.00, the contact between the particles of the carbon material becomes poor, and the life characteristics of the lithium ion secondary battery tend to be degraded.
The value of q0A/q0B is preferably in the range of 1.20 to 2.20, more preferably in the range of 1.25 to 2.10, from the viewpoints of input/output characteristics and lifetime characteristics.
The particle size distribution of the carbon material in the present specification based on the number can be obtained by dividing the range of particle diameters of 0.1 μm to 2000 μm into 50 pieces by number. For example, n= (2000/0.1)/(1/50) can be obtained and the particle size can be obtained based on 0.1×n, 0.1×n ζ2,... The total value of the relative particle amounts q0 for each particle diameter in the range of 0.1 μm to 2000 μm is 100.
Table 1 also shows the values of the relative particle amounts q0 and the particle diameters of the differences in the number references of the carbon materials used in example 2.
TABLE 1
In the case where a volume-based particle size distribution of the carbon material is obtained by drawing a volume cumulative distribution curve from the small particle diameter side, the cumulative value Q3 at a particle diameter of 9.516 μm is preferably 4.0% or more, more preferably 9.0% or more of the entire particle size.
If the cumulative value Q3 at a particle diameter of 9.516 μm is 4.0% or more of the entire, the contact points between particles can be sufficiently ensured by the fine particles contained in the carbon material, and the life characteristics of the lithium ion secondary battery tend to be improved.
The upper limit of the integrated value Q3 is not particularly limited, but is preferably 30% or less, more preferably 20% or less.
In the case of drawing a volume accumulation distribution curve from the small particle diameter side in the volume-based particle size distribution of the carbon material, the particle diameter (50% d, hereinafter also referred to as volume average particle diameter) at 50% accumulation is preferably 1 μm to 20 μm, more preferably 3 μm to 18 μm, and even more preferably 5 μm to 15 μm.
If the volume average particle diameter of the carbon material is 1 μm or more, the decrease in the primary charge/discharge efficiency of the lithium ion secondary battery due to the excessive specific surface area tends to be suppressed. On the other hand, if the volume average particle diameter of the carbon material is 20 μm or less, the diffusion distance of Li from the particle surface to the inside becomes long due to the excessively large particle diameter, and the input/output characteristics of the lithium ion secondary battery tend to be degraded.
In the case where a volume accumulation distribution curve is drawn from the small particle diameter side in the volume-based particle size distribution of the carbon material, the particle diameter (99.9% d, hereinafter also referred to as maximum particle diameter) at 99.9% accumulation is preferably 63 μm or less, more preferably 50 μm or less, and even more preferably 45 μm or less.
If the maximum particle diameter of the carbon material is 63 μm or less, the electrode plate is easily thinned at the time of manufacturing the electrode, and the influence on the input/output characteristics tends to be suppressed.
In the present specification, the volume-based particle size distribution of the carbon material can be obtained by dividing the range of 0.1 μm to 2000 μm into 50 pieces by the logarithmic ratio, as in the number-based particle size distribution. The volume-based particle size distribution can be measured by the same method as the number-based particle size distribution.
In the present specification, the particle size distribution of the carbon material can be measured by a known method. For example, a dispersion prepared by dispersing a sample of a carbon material together with a surfactant in purified water is placed in a sample water tank of a laser diffraction particle size distribution measuring apparatus, and ultrasonic waves are applied for 1 minute while circulating the dispersion by a pump, and the dispersion is measured by a laser diffraction method under the following measurement conditions. As a laser diffraction type particle size distribution measuring apparatus, for example, "SALD-3000J" manufactured by Shimadzu corporation may be used. Here, the number-based particle size distribution or the volume-based particle size distribution may be obtained by selecting "number" or "volume" as the output condition.
(Setting of measurement conditions)
Number of measurements 1 time
Measurement interval of 2 seconds
Average number of times of 64 times
Measuring absorbance range of 0.01-0.2
(Arbitrary particle size ·% Table set)
In the range of 0.1 μm to 2000 μm
Number of divisions 50
The carbon material of the present embodiment can be obtained by combining two or more carbon materials having different particle diameters, for example.
Examples of such combinations of carbon materials include combinations of carbon materials having a volume average particle diameter of 8 μm to 12 μm and carbon materials having a volume average particle diameter of 14 μm to 18 μm, and combinations of carbon materials having a volume average particle diameter of 9 μm to 11 μm and carbon materials having a volume average particle diameter of 15 μm to 17 μm.
The ratio of the two kinds of carbon materials having different particle diameters when combined may be, for example, in the range of 7:3 to 3:7 by mass ratio, in the range of 6:4 to 4:6 by mass ratio, or the like.
The tap density of the carbon material is preferably 0.90g/cm 3～2.00g/cm3, more preferably 1.00g/cm 3～1.50g/cm3, and further preferably 1.05g/cm 3～1.30g/cm3.
If the tap density of the carbon material is 0.90g/cm 3 or more, the amount of organic matters such as a binder used in manufacturing the negative electrode can be reduced, and the energy density of the lithium ion secondary battery tends to be increased. On the other hand, if the tap density of the carbon material is 2.00g/cm 3 or less, the input-output characteristics tend to become good.
The tap density of the carbon material tends to be high by increasing the volume average particle diameter of the carbon material, for example, and the tap density can be set within the above range by utilizing this property.
The bulk tap density of the negative electrode material as a whole containing the carbon material may be 0.90g/cm 3～3.00g/cm3. As a method for adjusting the tap density of the negative electrode material, there is a method in which a metal component or the like described later is contained in the negative electrode material in addition to the carbon material.
In the present specification, the tap density of the carbon material or the negative electrode material is a value (g/cm 3) obtained by slowly charging 100cm 3 of the sample powder into a measuring cylinder having a capacity of 100cm 3, plugging the measuring cylinder, dropping the measuring cylinder 250 times from a height of 5cm, and dividing the mass (g) of the sample powder after the dropping 250 times by the volume (cm 3).
The particle density of the carbon material is preferably less than or equal to 1.55g/cm 3, more preferably less than or equal to 1.50g/cm 3. If the particle density is 1.55g/cm 3 or less, the gaps between particles of the carbon material at the time of densification of the electrode are too small and the ion concentration in the vicinity of the particles tends to be reduced, so that the input/output characteristics of the lithium ion secondary battery tend to be reduced.
The particle density of the carbon material tends to be low by, for example, reducing the volume average particle diameter of the carbon material, and the particle density can be set within the above range by utilizing this property.
The particle density of the negative electrode material as a whole containing the carbon material may be 1.10g/cm 3～2.00g/cm3. As a method for adjusting the particle density of the negative electrode material, a method of controlling the temperature of the heat treatment performed on the carbon material is exemplified.
In the present invention, the particle density of the carbon material or the negative electrode material is a value (g/cm 3) obtained by charging 1.00g of the sample powder into a former, pressurizing the sample powder with a hydraulic press at a pressure of 1.0t, and dividing the mass (g) by a volume obtained from the thickness (cm) and the cross-sectional area (cm 2) of the pressurized sample.
The R value of the carbon material measured by Raman spectroscopy is preferably 0.1 to 1.0, more preferably 0.2 to 0.8, and even more preferably 0.3 to 0.7. If the R value is 0.1 or more, the graphite lattice defect used for intercalation and deintercalation of lithium ions is sufficiently present, and the deterioration of the input/output characteristics tends to be suppressed. If the R value is 1.0 or less, the decomposition reaction of the electrolytic solution can be sufficiently suppressed, and the primary efficiency tends to be suppressed from decreasing.
The R value is defined as the intensity ratio (Id/Ig) of the intensity Ig of the largest peak near 1580cm -1 to the intensity Id of the largest peak near 1360cm -1 in the Raman spectrum obtained in the Raman spectroscopy. Here, the peak appearing near 1580cm -1 is generally a peak identified as corresponding to the crystal structure of graphite, and for example, refers to a peak observed at 1530cm -1～1630cm-1. The peak appearing near 1360cm -1 is usually a peak identified as corresponding to an amorphous structure of carbon, and for example, is a peak observed at 1300cm -1～1400cm-1.
In this specification, a laser raman spectrometer (model: NRS-1000, japan spectroscopy corporation) was used for raman spectrometry, and a sample plate provided with a negative electrode material for a lithium ion secondary battery in a flat form was irradiated with an argon laser beam (excitation wavelength: 532 nm) for measurement.
Examples of the material of the carbon material include carbon materials such as graphite (artificial graphite, natural graphite, graphitized mesophase carbon, graphitized carbon fiber, etc.), low-crystalline carbon, and mesophase carbon. From the viewpoint of increasing the charge and discharge capacity, it is preferable that at least a part of the carbon material is graphite.
The shape of the carbon material is not particularly limited. Examples thereof include scales, spheres, and blocks. From the viewpoint of obtaining a high tap density, it is preferably spherical. The carbon material having the above physical properties may be appropriately selected from these carbon materials. The carbon material may be used alone or in combination of two or more different materials, shapes, and the like.
The carbon material may be a composite material including a first carbon phase which becomes a core and a second carbon phase which is disposed on at least a part of the surface (for example, a coating core) and is different from the first carbon phase. By constituting the carbon material from a plurality of different carbon phases, a carbon material that can more effectively exhibit desired physical properties or properties can be obtained.
In the case where the carbon material is a composite material including a first carbon phase which is a core and a second carbon phase which is disposed on at least a part of the surface of the carbon material, a combination of the first carbon phase and the second carbon phase having a crystallinity different from that of the first carbon phase is exemplified as a combination of the first carbon phase and the second carbon phase having a crystallinity lower than that of the first carbon phase (d 002 is larger than that of the first carbon phase).
In the case where the carbon material is a composite material including a first carbon phase which becomes a core and a second carbon phase which has lower crystallinity than the first carbon phase, the material of the first carbon phase which becomes the core is preferably selected from the above-mentioned graphites. In this case, the second carbon phase is preferably selected from carbon phases having lower crystallinity than the first carbon phase (hereinafter, also referred to as low-crystalline carbon phase).
The material of the second carbon phase having lower crystallinity than the first carbon phase is not particularly limited, and may be appropriately selected according to the desired properties. As a preferable example of the second carbon phase, a carbon phase obtained from an organic compound (carbon precursor) which becomes carbonaceous by heat treatment can be cited. Specifically, there may be mentioned ethylene heavy-end asphalt, crude oil asphalt, coal tar asphalt, asphalt produced by thermally decomposing an organic compound such as polyvinyl chloride, synthetic asphalt produced by polymerizing naphthalene or the like in the presence of a super acid, and the like. In addition, thermoplastic synthetic polymers such as polyvinyl chloride, polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, and natural polymers such as starch and cellulose can be used as the carbon precursor.
In the case where the carbon material is the composite material, from the viewpoint of increasing the charge/discharge capacity, the first carbon phase serving as a core is preferably a graphite material having an average surface interval d 002 in the range of 0.335nm to 0.339 nm. Particularly, when a graphite material having d 002 to 0.338nm, preferably 0.335 to 0.335nm is used, the charge/discharge capacity tends to be large, and 330 to 370mAh/g, and a good lithium ion secondary battery tends to be obtained.
The volume average particle diameter (50% D) of the graphite material to be the first carbon phase is preferably 1 μm to 20. Mu.m. If the volume average particle diameter of the graphite material is 1 μm or more, the fine powder is contained in an appropriate amount in the raw graphite, and thus, aggregation in the step of adhering the organic compound as a carbon precursor to the core material can be suppressed, and the two materials tend to be mixed more uniformly. If the volume average particle diameter of the graphite material is 20 μm or less, coarse particles are prevented from being mixed in the negative electrode material, and the occurrence of streaks or the like tends to be prevented when the negative electrode material is coated.
The specific surface area of the graphite material to be the first carbon phase, that is, the BET specific surface area (N 2 specific surface area) obtained by nitrogen adsorption measurement at 77K is preferably 0.1m 2/g～30m2/g, more preferably 0.5m 2/g～25m2/g, and even more preferably 0.5m 2/g～15m2/g. If the specific surface area of the graphite material N 2 is 0.1m 2/g or more, aggregation tends to be less likely to occur in the step of attaching the organic compound as a carbon precursor to the core material. If the specific surface area of the graphite material N 2 is 30m 2/g or less, the specific surface area can be maintained in a proper range, and the organic compound tends to be more uniformly attached.
Examples of the shape of the graphite material to be the first carbon phase include a flake shape, a sphere shape, and a block shape, and from the viewpoint of increasing the tap density, the shape is preferably a sphere shape.
As an index indicating the sphericity of the graphite material, an aspect ratio is exemplified. The aspect ratio of the graphite material in this specification is a value obtained by "maximum length vertical length/maximum length", and the maximum value thereof is 1. Here, the "maximum length" is the maximum value of the distance between two points on the contour line of the graphite material particle, and the "maximum length vertical length" is the length of the longest line segment among line segments that are perpendicular to the line segment connecting the two points on the contour line of the particle and that will become the maximum length.
The aspect ratio of the graphite material can be measured, for example, using a flow-type particle image analyzer. Examples of the flow type particle image analyzer include "FPIA-3000" of Sysmex corporation.
The average aspect ratio of the graphite material to become the first carbon phase is preferably 0.1 or more, more preferably 0.3 or more. If the average aspect ratio of the graphite material is 0.1 or more, the proportion of the flaky graphite in the graphite material is not excessive, and the amount of the edge surface of the graphite material can be suppressed to be within an appropriate range. Since the edge surface is active as compared with the basal plane, there is a concern that the organic compound is more attached to the edge surface in the step of attaching the organic compound as a carbon precursor to the core material, but if the average aspect ratio is 0.1 or more, there is a concern that the organic compound is more uniformly attached to the core material. As a result, the distribution of low crystalline carbon and crystalline carbon in the obtained carbon material tends to be more uniform.
The negative electrode material may contain other components in addition to the carbon material as necessary. For example, may comprise a metal component.
The metal component may be, if necessary, a metal powder composed of an element that alloys with lithium such as Al, si, ga, ge, in, sn, sb, ag, a multi-element alloy powder containing at least an element that alloys with lithium such as Al, si, ga, ge, in, sn, sb, ag, or a lithium alloy powder in order to increase the capacity. The metal component may be used alone or in combination of two or more. In the case where the negative electrode material contains a metal component, the metal component may be added separately from the carbon material or may be added in a state of being combined with the carbon material.
When the negative electrode material contains a metal component in addition to the carbon material, the tap density of the negative electrode material as a whole tends to be increased as compared with the case where the negative electrode material contains only the carbon material. For example, the tap density of the negative electrode material as a whole may be set to 0.3g/cm 3～3.0g/cm3. If the tap density of the negative electrode material is large, the charge-discharge reaction can be promoted, the negative electrode resistance can be reduced, and good input-output characteristics can be obtained.
In the case where the negative electrode material contains a metal component in addition to the carbon material, the amount thereof is not particularly limited. For example, the amount of the negative electrode material may be 1 to 50 mass%.
< Negative electrode Material (2) for lithium ion Secondary Battery >
The negative electrode material for a lithium ion secondary battery according to the present embodiment contains a carbon material, has an average surface interval d 002 as measured by an X-ray diffraction method of 0.335nm to 0.339nm, has an R value of 0.1 to 1.0 as measured by raman spectroscopy, and satisfies the following (1) and (2).
(1) In the number-based particle size distribution, the particle diameter at which the differential relative particle quantity q0 becomes the most frequent value is 11.601 μm or less.
(2) In the number-based particle size distribution, the ratio (q 0A/q 0B) of the differential relative particle quantity q0A at a particle size of 11.601 [ mu ] m to the differential relative particle quantity q0B at a particle size of 7.806 [ mu ] m is 1.20 to 3.00.
In the negative electrode material of the present embodiment, details and preferred embodiments of each condition can be referred to the description of the negative electrode material of the above embodiment.
< Negative electrode Material (3) for lithium ion Secondary Battery >
The negative electrode material for a lithium ion secondary battery according to the present embodiment contains a carbon material having an average surface interval d 002 as measured by an X-ray diffraction method of 0.335nm to 0.399 nm, contains a first carbon phase as a core, and a second carbon phase which is disposed on at least a part of the surface of the first carbon phase and is different from the first carbon phase, and satisfies the following (1) and (2).
(1) In the number-based particle size distribution, the particle diameter at which the differential relative particle quantity q0 becomes the most frequent value is 11.601 μm or less.
(2) In the number-based particle size distribution, the ratio (q 0A/q 0B) of the differential relative particle quantity q0A at a particle size of 11.601 [ mu ] m to the differential relative particle quantity q0B at a particle size of 7.806 [ mu ] m is 1.20 to 3.00.
In the negative electrode material of the present embodiment, details and preferred embodiments of each condition can be referred to the description of the negative electrode material of the above embodiment.
< Method for producing negative electrode Material >
The method for producing the negative electrode material of the present embodiment is not particularly limited, and a method generally used in producing a negative electrode material can be employed.
In the case where the carbon material is a composite material comprising a first carbon phase which becomes a core and a second carbon phase which is disposed on at least a part of the surface thereof, for example, a method of attaching an organic compound which becomes a carbon precursor to the surface of the core material which becomes the first carbon phase, and then firing the core material in an inert atmosphere at 750 ℃ to 1200 ℃ to carbonize the carbon precursor is mentioned as a production method thereof. As the organic compound used as the carbon precursor, the above-described organic compounds described as examples of the carbon precursor can be cited.
The method of attaching the carbon precursor to the surface of the first carbon phase is not particularly limited. Examples of the method include a wet method in which a core material of a first carbon phase is mixed with a liquid obtained by dissolving or dispersing a carbon precursor in a solvent and then the solvent is removed, a dry method in which a core material and a carbon precursor are mixed in a solid state to obtain a mixture, and mechanical energy is applied to the mixture to adhere the mixture, and a gas phase method such as a CVD method. From the viewpoint of controlling the specific surface area of the carbon material, it is preferably performed by a dry method.
The method of attaching the carbon precursor to the surface of the first carbon phase by the dry method is not particularly limited. For example, the mixture of the first carbon and the carbon precursor may be filled into a container having a structure capable of at least one of mixing and stirring the content, and the adhesion may be performed by applying mechanical energy and at least one of mixing and stirring. Specifically, the present invention can be carried out using a container having a blade, a screw, or the like. The amount of mechanical energy applied to the mixture is not particularly limited. For example, the amount is preferably 0.360 to 36000kJ/kg, more preferably 0.360 to 7200kJ/kg, and still more preferably 2.50 to 2000kJ/kg.
Here, the mechanical energy applied to the mixture is a value obtained by dividing a value obtained by multiplying the time (h) by the load (kW) by the mass (kg) of the filled mixture. By setting the mechanical energy applied to the mixture to the above range, the carbon precursor is more uniformly attached to the surface of the first carbon, and the distribution of the low-crystalline carbon and the crystalline carbon in the obtained carbon material tends to become more uniform.
The substance (intermediate product) in a state in which the carbon precursor is attached to the surface of the first carbon phase is further heated and burned. The firing temperature is not particularly limited as long as it is a temperature at which the carbon precursor can be carbonized. For example, 750 ℃ to 2000 ℃, more preferably 800 ℃ to 1800 ℃, and still more preferably 900 ℃ to 1400 ℃. If the firing temperature is 750 ℃ or higher, the charge/discharge efficiency, the input/output characteristics, and the cycle characteristics of the lithium ion secondary battery tend to be well maintained, and if the firing temperature is 2000 ℃ or lower, the crystallinity of the low crystalline carbon portion tends to be suppressed from becoming too high. As a result, characteristics such as quick charge characteristics, low-temperature charge characteristics, and overcharge safety tend to be maintained satisfactorily. The atmosphere at the time of firing is not particularly limited as long as it is an atmosphere in which the intermediate product is hardly oxidized. For example, a nitrogen atmosphere, an argon atmosphere, a self-decomposing gas atmosphere, or the like may be applied. The form of the furnace used for firing is not particularly limited. For example, a batch furnace, a continuous furnace, or the like using at least one of electricity and gas as a heat source is preferable.
< Negative electrode for lithium ion Secondary Battery >
The negative electrode for a lithium ion secondary battery according to the present embodiment includes a negative electrode material layer including the negative electrode material, and a current collector. This makes it possible to construct a lithium ion secondary battery excellent in input/output characteristics and lifetime characteristics while maintaining high charge/discharge efficiency. The negative electrode for a lithium ion secondary battery may contain other components as necessary in addition to the negative electrode material layer containing the negative electrode material and the current collector.
The method for producing the negative electrode for a lithium ion secondary battery is not particularly limited. For example, a method of kneading a negative electrode material and an organic binder together with a solvent using a dispersing device such as a stirrer, a ball mill, a super sand mill, or a pressure kneader to prepare a slurry-like negative electrode composition and applying the slurry-like negative electrode composition to the surface of a current collector to form a negative electrode layer, a method of preparing a paste-like negative electrode composition in the same manner as described above, molding the paste-like negative electrode composition into a sheet-like or pellet-like shape, and integrating the paste-like negative electrode composition with the current collector, and the like can be mentioned.
The organic binder is not particularly limited. Examples thereof include ethylenically unsaturated carboxylic acid esters such as styrene-butadiene copolymer, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, acrylonitrile, and hydroxyethyl (meth) acrylate, ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, and maleic acid, and polymer compounds having high ion conductivity such as polyvinylidene fluoride, polyethylene oxide, polyepichlorohydrin, polyphosphazene, and polyacrylonitrile. (meth) acrylate means at least one of acrylate and methacrylate.
The amount of the organic binder contained in the negative electrode composition is not particularly limited, but is preferably 0.5 to 20 parts by mass based on 100 parts by mass of the total of the negative electrode material and the organic binder.
The negative electrode composition may also contain a thickener for adjusting the viscosity. Examples of the thickener include carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, polyacrylic acid (salt), oxidized starch, phosphorylated starch, casein, and the like.
The negative electrode composition may also contain a conductive auxiliary material. Examples of the conductive auxiliary material include carbon materials such as carbon black, graphite, and acetylene black, and oxides and nitrides that exhibit conductivity. The amount of the conductive auxiliary agent is not particularly limited, and may be 0.5 mass% to 15 mass% with respect to 100 parts by mass of the negative electrode material.
The material and shape of the current collector are not particularly limited. Examples of the current collector include a current collector formed by forming a metal material such as aluminum, copper, nickel, titanium, or stainless steel into a foil shape, a perforated foil shape, or a mesh shape. Further, a porous material such as a porous metal (foamed metal), carbon paper, or the like may be used.
The method of imparting the negative electrode composition to the current collector is not particularly limited. Examples thereof include a metal mask printing method, an electrostatic coating method, a dip coating method, a spray coating method, a roll coating method, a doctor blade method, a corner-roll coating method, a gravure coating method, a screen printing method, and the like. After the negative electrode composition is applied to the current collector, the negative electrode composition is dried by a hot air dryer, an infrared dryer, or a dryer combining them in order to remove the solvent contained in the negative electrode composition. Further, a rolling treatment is performed by a platen press, a rolling roll, or the like as needed.
The method of forming the negative electrode material composition into a sheet, pellet, or other shape and integrating it with the current collector is not particularly limited. For example, rolls, presses or combinations thereof may be used and performed by well known methods. The pressure during integration is preferably 1Pa to 200 mPa.
The negative electrode density of the negative electrode for a lithium ion secondary battery is preferably 1.3g/cm 3～1.8g/cm3, more preferably 1.4g/cm 3～1.8g/cm3, and still more preferably 1.5g/cm 3～1.7g/cm3. If the negative electrode density is 1.3g/cm 3 or more, the resistance value tends to be less likely to decrease and the capacity can be maintained high, and if it is 1.8g/cm 3 or less, the rate characteristics and cycle characteristics tend to be suppressed from decreasing.
< Lithium ion Secondary Battery >
The lithium ion secondary battery of the present embodiment includes the negative electrode, the positive electrode, and the electrolyte for a lithium ion secondary battery. The lithium ion secondary battery can be obtained, for example, by disposing a negative electrode and a positive electrode for the lithium ion secondary battery in a container so as to face each other with a separator interposed therebetween, and injecting an electrolyte prepared by dissolving an electrolyte in a solvent into the container.
The positive electrode can be obtained by forming a positive electrode layer by applying a positive electrode material to the surface of the current collector, as in the case of the negative electrode described above. As the current collector, a strip-shaped current collector in which a metal material such as aluminum, titanium, or stainless steel is formed into a foil shape, a perforated foil shape, or a mesh shape can be used.
The material for the positive electrode is not particularly limited. Examples thereof include positive electrode active materials such as metal compounds, metal oxides, metal sulfides, and phosphoric acid compounds capable of doping or intercalating lithium ions, and other materials.
Examples of the positive electrode active material include lithium cobalt oxide (LiCoO 2), lithium nickel oxide (LiNiO 2), lithium manganese oxide (LiMnO 2), a composite oxide in which at least a part of cobalt in lithium cobalt oxide is substituted with at least one of nickel and manganese (LiCo xNiyMnzO2, x+y+z=1), a composite oxide in which at least a part of cobalt, nickel and manganese in these compounds is substituted with an additive element M '(LiCo aNibMncM'dO2, a+b+c+d=1, M': al, mg, ti, zr or Ge), lithium manganese spinel (LiMn 2O4), lithium vanadium compound 、V2O5、V6O13、VO2、MnO2、TiO2、MoV2O8、TiS2、V2S5、VS2、MoS2、MoS3、Cr3O8、Cr2O5、, and olivine-type LiMPO 4 (M: co, ni, mn, fe).
Examples of the other materials include conductive polymers such as polyacetylene, polyaniline, polypyrrole, polythiophene, and polyacene, and porous carbon.
Examples of the separator include nonwoven fabrics, cloths, microporous films, and separators comprising polyolefin such as polyethylene and polypropylene as a main component, and combinations thereof. In the structure of the lithium ion secondary battery, the separator may be omitted when the positive electrode and the negative electrode are not in contact.
Examples of the electrolyte include lithium salts such as LiClO 4、LiPF6、LiAsF6、LiBF4、LiSO3CF3.
Examples of the solvent for dissolving the electrolyte include nonaqueous solvents such as ethylene carbonate, fluoroethylene carbonate, chloroethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, cyclopentanone, cyclohexylbenzene, sulfolane, propane sultone, 3-methyl sulfolane, 2, 4-dimethyl sulfolane, 3-methyl-1, 3-oxazolidin-2-one, γ -butyrolactone, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, butyl methyl carbonate, ethyl propyl carbonate, butyl ethyl carbonate, dipropyl carbonate, 1, 2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dioxolane, methyl acetate, ethyl acetate, trimethyl phosphate, and triethyl phosphate.
The structure of the electrode in the lithium ion secondary battery is not particularly limited. In general, a structure (wound electrode group) in which a positive electrode and a negative electrode, and a separator provided between the positive electrode and the negative electrode as needed, are stacked and wound in a spiral state, and a structure (stacked electrode group) in which the separator is not wound in a spiral plate shape are exemplified.
The type of the lithium ion secondary battery is not particularly limited. Examples thereof include laminated batteries, paper batteries, button batteries, coin batteries, laminated batteries, cylindrical batteries, prismatic batteries, and the like.
The negative electrode material of the present embodiment is excellent in input/output characteristics and life characteristics during charge/discharge, and therefore can be suitably used for lithium ion secondary batteries requiring a large capacity, such as electric vehicles, power tools, and electric storage applications. Among them, in the middle of automobiles such as Electric Vehicles (EV), hybrid Electric Vehicles (HEV), plug-in hybrid electric vehicles (PHEV), etc., in order to improve acceleration performance and braking regeneration performance, charge and discharge of a large current are required, and it is desired to use a negative electrode material of the present embodiment that satisfies such requirements and also has excellent input and output characteristics.
Examples
The present invention will be further specifically described with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
A mixture obtained by mixing 100 parts by mass of spherical natural graphite (d 002 =0.336 nm, average aspect ratio=0.8) having a volume average particle diameter of 10 μm and 5 parts by mass of coal tar pitch (softening point 98 ℃ and carbon residue (carbonization rate) of 50%) was placed in a cylinder provided with rotary blades, and the inner wall of the cylinder and the rotary blades were rubbed against each other, thereby causing the coal tar pitch to adhere to the surface of the spherical natural graphite. The step of rubbing against each other was carried out under a load of 24kW for 5 minutes (load: 1800 kJ/kg). Then, the temperature was raised to 1000℃at a temperature rise rate of 20℃per hour under nitrogen flow, and the mixture was kept for 1 hour to carbonize the coal tar pitch. Then, the resultant was pulverized by a cutter mill, and sieved by a 300-mesh sieve, whereby an undersize portion thereof was obtained as composite material 1.
Composite material 2 was obtained in the same manner as composite material 1, except that 100 parts by mass of spherical natural graphite having a volume average particle diameter of 16 μm (d 002 =0.336 nm, average aspect ratio=0.8) was used instead of spherical natural graphite having a volume average particle diameter of 10 μm.
The composite material 1 and the composite material 2 were mixed at a mass ratio of 5:5 (composite material 1: composite material 2) to prepare a carbon material. The obtained carbon material was subjected to XRD analysis, specific surface area measurement, particle size distribution measurement, tap density measurement, and particle density measurement by the methods shown below.
XRD analysis (measurement of average surface spacing d 002)
A concave portion of a quartz sample holder was filled with a carbon material, and the sample holder was placed on a measurement table. The measurement was performed under the following measurement conditions by using a wide-angle X-ray diffraction apparatus (manufactured by the company corporation).
Radiation source CuK alpha ray (wavelength=0.15418 nm)
Output of 40kV and 20mA
Sampling amplitude of 0.010 DEG
The scanning range is 10-35 DEG
Scanning speed 0.5 DEG/min
[ Determination of N 2 specific surface area ]
The carbon material was calculated by measuring nitrogen adsorption at a liquid nitrogen temperature (77K) by a multipoint method using a high specific surface area/pore distribution measuring device (MICROMERITICS, "ASAP 2010") and by a BET method (relative pressure range: 0.05 to 0.2).
[ Measurement of particle size distribution ]
The carbon material was dispersed in purified water together with a surfactant to obtain a solution, and the solution was placed in a sample water tank of a laser diffraction particle size distribution measuring apparatus (SALD-3000J, manufactured by Shimadzu corporation) and circulated by a pump while applying ultrasonic waves for 1 minute, and was measured by a laser diffraction method under the following measurement conditions. At this time, the output conditions were set to the number or volume basis, and values satisfying the following (1) to (5) were investigated.
(Setting of measurement conditions)
Number of measurements 1 time
Measurement interval of 2 seconds
Average number of times of 64 times
Measuring absorbance range of 0.01-0.2
(Arbitrary particle size ·% Table set)
In the range of 0.1 μm to 2000 μm
Number of divisions 50
(1) The particle diameter at which the differential relative particle quantity q0 becomes the most frequent value in the number-based particle size distribution obtained by setting the distribution reference of the output condition to "number" in the particle size distribution measurement was examined.
(2) The ratio (q 0A/q 0B) of the differential relative particle quantity q0A at a particle diameter of 11.601 μm to the differential relative particle quantity q0B at a particle diameter of 7.806 μm in the number-based particle size distribution obtained by setting the distribution standard of the output condition as the "number" in the particle size distribution measurement was calculated.
(3) In the particle size distribution measurement, the cumulative value Q3 at a particle size of 9.516 μm was examined when a cumulative volume distribution curve was drawn from the small particle size side in the particle size distribution of the volume basis obtained by setting the basis of the distribution of the output condition as "volume".
(4) In the particle size distribution measurement, the particle size (50% d) at 50% is accumulated when a volume accumulation distribution curve is drawn from the small particle size side in the particle size distribution on the volume basis obtained by setting the distribution basis of the output condition as "volume".
(5) In the particle size distribution measurement, the particle size (99.9% d) at 99.9% was accumulated when a volume accumulation distribution curve was drawn from the small particle size side in the particle size distribution based on the volume obtained by setting the distribution base of the output condition as "volume".
[ Tap Density determination ]
Carbon material 100cm 3 was slowly poured into a measuring cylinder of capacity 100cm 3 and the cylinder was stoppered. The measuring cylinder was dropped 250 times from a height of 5cm, and the value obtained by the mass and volume of the carbon material after the drop 250 times was set as tap density.
[ Determination of particle Density ]
1.00G of a carbon material was charged into a 13mm diameter former (13 mm pellet die model 3619 from Carver Co.) and pressurized at a pressure of 1.0t by a hydraulic press (CARVER STANDARD PRESS from Carver Co.), and the volume obtained by dividing the volume obtained based on the thickness and cross-sectional area of the pressurized carbon material by the mass of the carbon material was set as the particle density.
[ Average aspect ratio ]
The average aspect ratio of the carbon material was determined using a flow type particle image analyzer (FPIA-3000, sysmex Co.).
[ Measurement of Primary charging and discharging efficiency ]
An aqueous solution of CMC (carboxymethyl cellulose, "Cellogen WS-C" from first industrial pharmaceutical co., ltd.) was added as a thickener to 98 parts by mass of the produced carbon material so that the solid content of CMC became 1 part by mass, and the aqueous solution was kneaded for 10 minutes at a CMC concentration of 2% by mass. Then, purified water was added so that the solid content concentration (total of the negative electrode material and CMC) in the kneaded material became 40 mass% to 50 mass%, and kneading was performed for 10 minutes. Then, an aqueous dispersion of SBR (BM-400B from ZEON Co., ltd.) as a binder was added so that the solid content of SBR became 1 part by mass, and the mixture was mixed for 10 minutes at an SBR concentration of 40% by mass to prepare a paste-like negative electrode material composition. The negative electrode material composition was applied to an electrolytic copper foil having a thickness of 40 μm in a circular shape having a diameter of 9.5mm using a mask having a thickness of 200. Mu.m. Further, the sample electrode (negative electrode) was produced by drying at 105 ℃.
Next, the sample electrode, the separator, and the counter electrode were sequentially stacked and placed in a battery container, and an electrolyte obtained by dissolving LiPF 6 in a mixed solvent of Ethylene Carbonate (EC) and Methyl Ethyl Carbonate (MEC) (the volume ratio of EC to MEC is 1:3) so as to be 1.5 mol/l was injected, thereby producing a coin cell. The counter electrode used lithium metal and the separator used a polyethylene microporous membrane with a thickness of 20 μm.
Between the sample electrode and the counter electrode of the obtained coin cell, the battery was charged to 0V (Vvs. Li/Li +) at a constant current of 0.2mA/cm 2, and then charged to a constant voltage of 0V until the current reached 0.02 mA. Next, after a rest time of 30 minutes, 1 cycle test of discharging to 2.5V (vvs.li/Li +) at a constant current of 0.2mA/cm 2 was performed, and the initial charge-discharge efficiency was measured. The initial charge-discharge efficiency (%) is calculated as (discharge capacity)/(charge capacity) ×100. Here, the case of absorbing lithium ions in the sample electrode of the negative electrode material is referred to as charging, and the case of discharging lithium ions from the sample electrode in contrast is referred to as discharging.
[ Evaluation of Life characteristics ]
The negative electrode composition prepared by the same method as that used for measuring the initial charge/discharge efficiency was applied to an electrolytic copper foil having a thickness of 40. Mu.m, using a corner-wheel coater having a gap adjusted so that the coating amount per unit area became 9.0mg/cm 2. Then, the electrode density was adjusted to 1.5g/cm 3 by a manual press. The electrode was punched out into a disk shape having a diameter of 14mm, and a sample electrode (negative electrode) was produced. A coin cell was produced in the same manner as in the measurement of the initial charge/discharge efficiency except that the sample electrode was used.
Using the coin cell manufactured as described above, the life characteristics were evaluated according to the following procedure.
(1) Charging to 0V (Vvs. Li/Li +) at a constant current of 0.48mA, and then charging to 0.048mA at a constant voltage of 0V.
(2) After a rest time of 30 minutes, 1 cycle test of discharging to 1.5V (Vvs. Li/Li +) at a constant current of 0.48mA was performed, and the discharge capacity was measured.
(3) The charge was carried out at a constant current of 4.8mA to 0V (Vvs. Li/Li +), and at a constant voltage of 0V until the current reached 0.48 mA.
(4) After a rest time of 30 minutes, discharge was carried out at a constant current of 4.8mA to 1.5V (Vvs. Li/Li +).
(5) The charge-discharge cycle test of (3) and (4) above was carried out for 50 cycles.
The discharge capacity maintenance rate (= discharge capacity of 50 th cycle/cycle discharge capacity of 1 st cycle×100) from 1 st cycle when the above cycle was repeated for 50 cycles was measured. The higher the discharge capacity maintenance rate, the more excellent the life characteristics can be judged.
(Evaluation of input/output characteristics)
A coin cell was produced by the same method as the life characteristics, and the input/output characteristics were evaluated according to the following procedure.
(1) Charging was performed at a constant current of 0.96mA to 0V (Vvs. Li/Li +), and then charging was performed at a constant voltage of 0V until the current value reached 0.096 mA.
(2) After a rest time of 30 minutes, discharge was carried out at a constant current of 0.96mA to 1.5V (Vvs. Li/Li +).
(3) Charging was performed at a constant current of 0.96mA until half of the capacity.
(4) The discharge was performed for 10 seconds at current values of 4.8mA, 14.4mA, and 24mA, and the voltage drop (. DELTA.V) at this time was confirmed. A rest time of 30 minutes was set during the test at each current value.
Δv is plotted against each current value, and the slope thereof is set as a resistance value (Ω). The smaller the value, the more excellent the input-output characteristics can be judged.
Example 2
A carbon material was produced in the same manner as in example 1 except that composite material 1 and composite material 2 were mixed so that the mass ratio was 4:6 (composite material 1: composite material 2), and the properties thereof were examined. In addition, coin cells were fabricated and evaluated for performance. The results are shown in table 2.
Example 3
A carbon material was produced in the same manner as in example 1 except that composite material 1 and composite material 2 were mixed so that the mass ratio was 3:7 (composite material 1: composite material 2), and the properties thereof were examined. In addition, coin cells were fabricated and evaluated for performance. The results are shown in table 2.
Example 4
A carbon material was produced in the same manner as in example 1 except that composite material 1 and composite material 2 were mixed so that the mass ratio was 6:4 (composite material 1: composite material 2), and the properties thereof were examined. In addition, coin cells were fabricated and evaluated for performance. The results are shown in table 2.
Comparative example 1
A carbon material was produced in the same manner as in example 1 except that composite material 1 and composite material 2 were mixed so that the mass ratio was 2:8 (composite material 1: composite material 2), and the properties thereof were examined. In addition, coin cells were fabricated and evaluated for performance. The results are shown in table 2.
Comparative example 2
A carbon material was produced in the same manner as in example 1 except that only the composite material 2 was used, and the characteristics thereof were examined. In addition, coin cells were fabricated and evaluated for performance. The results are shown in table 2.
Comparative example 3
A carbon material was produced in the same manner as in example 1 except that only composite material 1 was used, and the characteristics thereof were examined. In addition, coin cells were fabricated and evaluated for performance. The results are shown in table 2.
Comparative example 4
Composite material 3 was obtained in the same manner as composite material 1, except that 100 parts by mass of spherical natural graphite having a volume average particle diameter of 22 μm (d 002 =0.336 nm, average aspect ratio=0.7) was used instead of spherical natural graphite having a volume average particle diameter of 10 μm.
A carbon material was produced in the same manner as in example 1 except that the composite material 3 and the composite material 2 were mixed so that the mass ratio was 5:5 (composite material 3: composite material 2), and the properties thereof were examined. In addition, coin cells were fabricated and evaluated for performance. The results are shown in table 2.
Comparative example 5
A carbon material was produced in the same manner as in example 1, except that spherical natural graphite (d 002 =0.336 nm, average aspect ratio=0.7) having a volume average particle diameter of 22 μm was passed through a 300-mesh sieve, and the obtained undersize portion was mixed with composite material 2 so that the mass ratio was 5:5 (undersize portion: composite material 2), and the properties thereof were examined. In addition, coin cells were fabricated and evaluated for performance. The results are shown in table 2.
Comparative example 6
The coal-based coal tar is subjected to heat treatment at 400 ℃ by utilizing an autoclave, and coarse coke is obtained. The coarse coke was pulverized and then calcined in an inert atmosphere at 1200 ℃. The coke cake was crushed to an average particle diameter of 15 μm using an impact crusher equipped with a classifier, and then passed through a 200-mesh sieve to obtain an undersize fraction as carbon particles (d 002 =0.342 nm). Composite material 4 was obtained in the same manner as composite material 1, except that a mixture obtained by mixing 100 parts by mass of the carbon particles with 20 parts by mass of polyvinyl alcohol (polymerization degree 1700, total saponification, carbonization rate 15 mass%) was used.
A carbon material was produced in the same manner as in example 1 except that the composite material 4 and the composite material 2 were mixed so that the mass ratio was 5:5 (composite material 4: composite material 2), and the properties thereof were examined. In addition, coin cells were fabricated and evaluated for performance. The results are shown in table 2.
Comparative example 7
A carbon material was produced in the same manner as in example 1, except that spherical natural graphite having a volume average particle diameter of 10 μm (d 002 =0.336 nm, average aspect ratio=0.8) and spherical natural graphite having a volume average particle diameter of 16 μm (d 002 =0.336 nm, average aspect ratio=0.8) were mixed so that the mass ratio became 5:5, and the characteristics thereof were examined. In addition, coin cells were fabricated and evaluated for performance. The results are shown in table 2.
Comparative example 8
100 Parts by mass of the carbon particles (d 002 =0.342 nm) produced in comparative example 6, 30 parts by mass of coal tar pitch and 5 parts by mass of iron oxide powder were mixed at 250 ℃ for 1 hour. The obtained cake was pulverized by a pin mill, and then molded into a cake having a density of 1.52g/cm 3 by a molding press. After the obtained block was fired at a maximum temperature of 800 ℃ using a muffle furnace, graphitization was performed at 2900 ℃ using an acheson furnace under a self-decomposition gas atmosphere. Then, the graphitized block was coarsely pulverized by a hammer, and then, graphite powder having an average particle diameter of 30 μm was obtained by a pin mill. Further, the graphite powder was subjected to a treatment for 10 minutes at a grinding speed of 1800 revolutions per minute (rpm) and a classification speed of 7000 revolutions per minute (rpm) by using a spheroidizing apparatus (Faculty, manufactured by fine chemical). The spherical artificial graphite powder was passed through a 200-mesh sieve to obtain an undersize fraction as a carbon material. The properties of the carbon material were examined in the same manner as in example 1. In addition, coin cells were fabricated and evaluated for performance. The results are shown in table 2.
TABLE 2
As is clear from the results shown in table 2, the lithium ion secondary batteries of examples 1 to 4 manufactured using the negative electrode material containing the carbon material according to the present embodiment were excellent in input/output characteristics and lifetime characteristics while maintaining high charge/discharge efficiency.
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