KR102608550B1 - Carbonaceous particles, negative electrode material for lithium ion secondary batteries, negative electrode for lithium ion secondary batteries, and lithium ion secondary batteries - Google Patents
Carbonaceous particles, negative electrode material for lithium ion secondary batteries, negative electrode for lithium ion secondary batteries, and lithium ion secondary batteries Download PDFInfo
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- KR102608550B1 KR102608550B1 KR1020207025939A KR20207025939A KR102608550B1 KR 102608550 B1 KR102608550 B1 KR 102608550B1 KR 1020207025939 A KR1020207025939 A KR 1020207025939A KR 20207025939 A KR20207025939 A KR 20207025939A KR 102608550 B1 KR102608550 B1 KR 102608550B1
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- Prior art keywords
- lithium ion
- ion secondary
- negative electrode
- carbonaceous particles
- secondary battery
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- 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
Abstract
라만 매핑 측정으로 얻어지는 흑연의 G밴드(1580 cm-1)와 D밴드(1360 cm-1)의 피크 강도비(G/D)를 나타내는 R값의 도수 분포에 있어서, 하기 조건 (1) 및 (2)를 만족시키는, 리튬 이온 이차 전지의 음극재용 탄소질 입자.
(1) R값의 최빈값(Rc)가 0.87~0.96이다.
(2) R값이 작은 측으로부터의 빈도의 누적이 50%일 때의 R값(R50)이 0.88~0.92이다. In the frequency distribution of the R value representing the peak intensity ratio (G/D) of the G band (1580 cm -1 ) and D band (1360 cm -1 ) of graphite obtained by Raman mapping measurement, the following conditions (1) and ( Carbonaceous particles for a negative electrode material of a lithium ion secondary battery that satisfy 2).
(1) The mode of R value (Rc) is 0.87 to 0.96.
(2) The R value (R 50 ) when the accumulation of frequencies from the side with the smaller R value is 50 % is 0.88 to 0.92.
Description
본 발명은, 탄소질 입자, 리튬 이온 이차 전지용 음극재, 리튬 이온 이차 전지용 음극 및 리튬 이온 이차 전지에 관한 것이다. The present invention relates to carbonaceous particles, negative electrode materials for lithium ion secondary batteries, negative electrodes for lithium ion secondary batteries, and lithium ion secondary batteries.
리튬 이온 이차 전지는, 니켈카드뮴 전지, 니켈수소 전지, 납 축전지 등의 다른 이차 전지에 비해 높은 입출력 특성을 갖는 점에서, 최근, 전기 자동차, 하이브리드형 전기 자동차 등의 전원 등의 고입출력이 요구되는 용도에 사용하는 전원으로서의 기대가 높아지고 있다. Lithium ion secondary batteries have higher input/output characteristics compared to other secondary batteries such as nickel cadmium batteries, nickel metal hydride batteries, and lead storage batteries. Recently, high input/output is required for power supplies such as electric vehicles and hybrid electric vehicles. Expectations as a power source for various purposes are increasing.
리튬 이온 이차 전지의 음극재(음극 활물질)로서 일반적으로 사용되는 탄소 재료는, 흑연계와 비정질 탄소계로 대별된다. 흑연은 탄소 원자의 육각망면이 규칙바르게 적층된 구조를 갖는 것으로, 적층된 망면의 단부로부터 리튬 이온의 삽입 탈리 반응이 진행되어 충방전을 실시한다. 그러나, 삽입 탈리 반응이 육각망면의 단부에서만 진행되기 때문에, 입출력 성능의 향상에 한계가 있다. 또한, 결정성이 높아 표면의 결함이 적기 때문에, 전해액과의 친화성이 나쁘고, 리튬 이온 이차 전지의 수명 특성이 저하된다는 문제점을 갖는다. Carbon materials commonly used as negative electrode materials (negative electrode active materials) of lithium ion secondary batteries are roughly divided into graphite-based and amorphous carbon-based. Graphite has a structure in which hexagonal networks of carbon atoms are stacked regularly, and an insertion/desorption reaction of lithium ions proceeds from the ends of the stacked networks to carry out charging and discharging. However, because the insertion/desorption reaction occurs only at the ends of the hexagonal network surface, there is a limit to the improvement of input/output performance. In addition, since crystallinity is high and there are few surface defects, affinity with the electrolyte solution is poor and the lifespan characteristics of lithium ion secondary batteries are reduced.
비정질 탄소는, 육각망면의 적층이 불규칙하거나, 망목 구조를 가지지 않기 때문에, 리튬의 삽입 탈리 반응은 입자의 전표면에서 진행되게 되어, 입출력 특성이 우수한 리튬 이온 이차 전지를 얻기 쉽다. Since amorphous carbon has irregular hexagonal layering or does not have a network structure, lithium insertion/desorption reactions proceed on the entire surface of the particle, making it easy to obtain a lithium ion secondary battery with excellent input/output characteristics.
리튬 이온 이차 전지의 음극 활물질로서 사용되는 비정질 탄소로는, 코크스, 카본블랙 등을 원료로 하는 것이 알려져 있다(예를 들어, 특허문헌 1 및 특허문헌 2 참조). It is known that amorphous carbon used as a negative electrode active material for lithium ion secondary batteries is made from coke, carbon black, etc. (for example, see Patent Document 1 and Patent Document 2).
상술한 바와 같이 비정질 탄소를 음극재로서 사용한 리튬 이온 이차 전지는 입출력 특성이 우수하지만, 전기 자동차, 하이브리드형 전기 자동차 등의 전원 등의 고입출력이 요구되는 용도에 대한 수요 확대에 따라, 가일층 저(低)저항화가 요구된다. As mentioned above, lithium-ion secondary batteries using amorphous carbon as a negative electrode material have excellent input/output characteristics, but with the expansion of demand for applications requiring high input/output, such as power sources for electric vehicles, hybrid electric vehicles, etc., they are becoming even lower ( Low) resistance is required.
본 발명은 상기 사정을 감안하여, 저저항인 리튬 이온 이차 전지를 제조 가능한 탄소질 입자 및 리튬 이온 이차 전지용 음극재, 그리고 리튬 이온 이차 전지용 음극 및 리튬 이온 이차 전지를 제공하는 것을 과제로 한다. In consideration of the above circumstances, the present invention aims to provide carbonaceous particles capable of producing a low-resistance lithium ion secondary battery, a negative electrode material for a lithium ion secondary battery, and a negative electrode for a lithium ion secondary battery and a lithium ion secondary battery.
상기 과제를 해결하기 위한 수단에는 이하의 실시 양태가 포함된다. Means for solving the above problems include the following embodiments.
<1> 라만 매핑 측정으로 얻어지는 흑연의 G밴드(1580 cm-1)와 D밴드(1360 cm-1)의 피크 강도비(G/D)를 나타내는 R값의 도수 분포에 있어서, 하기 조건 (1) 및 (2)를 만족시키는, 리튬 이온 이차 전지의 음극재용 탄소질 입자. <1> In the frequency distribution of the R value representing the peak intensity ratio (G/D) of the G band (1580 cm -1 ) and D band (1360 cm -1 ) of graphite obtained by Raman mapping measurement, the following conditions (1) ) and (2), carbonaceous particles for a negative electrode material of a lithium ion secondary battery.
(1) R값의 최빈값(Rc)가 0.87~0.96이다. (1) The mode of R value (Rc) is 0.87 to 0.96.
(2) R값이 작은 측으로부터의 빈도의 누적이 50%일 때의 R값(R50)이 0.88~0.92이다. (2) The R value (R 50 ) when the accumulation of frequencies from the side with the smaller R value is 50 % is 0.88 to 0.92.
<2> 핵으로서의 제1 탄소재와, 상기 제1 탄소재 표면의 적어도 일부에 존재하며, 상기 제1 탄소재보다도 결정성이 낮은 제2 탄소재를 갖는, <1>에 기재된 탄소질 입자. <2> The carbonaceous particle according to <1>, which has a first carbon material as a nucleus, and a second carbon material that exists on at least a part of the surface of the first carbon material and has a lower crystallinity than the first carbon material.
<3> c축 방향의 결정자 사이즈(Lc)가 4.5 nm~5.2 nm인, <1> 또는 <2>에 기재된 탄소질 입자. <3> The carbonaceous particle according to <1> or <2>, wherein the crystallite size (Lc) in the c-axis direction is 4.5 nm to 5.2 nm.
<4> 비표면적이 2.0 ㎡/g~5.0 ㎡/g인, <1>~<3> 중 어느 한 항에 기재된 탄소질 입자. <4> The carbonaceous particle according to any one of <1> to <3>, wherein the specific surface area is 2.0 m2/g to 5.0 m2/g.
<5> 평균 입경(50%D)가 5 ㎛~20 ㎛인, <1>~<4> 중 어느 한 항에 기재된 탄소질 입자. <5> The carbonaceous particles according to any one of <1> to <4>, wherein the average particle diameter (50% D) is 5 μm to 20 μm.
<6> <1>~<5> 중 어느 한 항에 기재된 탄소질 재료를 포함하는, 리튬 이온 이차 전지용 음극재. <6> A negative electrode material for a lithium ion secondary battery containing the carbonaceous material according to any one of <1> to <5>.
<7> 흑연 입자를 더 포함하는, <6>에 기재된 리튬 이온 이차 전지용 음극재. <7> The negative electrode material for a lithium ion secondary battery according to <6>, further comprising graphite particles.
<8> <6> 또는 <7>에 기재된 리튬 이온 이차 전지용 음극재를 포함하는, 리튬 이온 이차 전지용 음극. <8> A negative electrode for a lithium ion secondary battery, comprising the negative electrode material for a lithium ion secondary battery according to <6> or <7>.
<9> <8>에 기재된 리튬 이온 이차 전지용 음극을 구비하는, 리튬 이온 이차 전지. <9> A lithium ion secondary battery comprising the negative electrode for a lithium ion secondary battery according to <8>.
본 발명에 의하면, 저저항인 리튬 이온 이차 전지를 제조 가능한 탄소질 입자 및 리튬 이온 이차 전지용 음극재, 그리고 리튬 이온 이차 전지용 음극 및 리튬 이온 이차 전지가 제공된다. According to the present invention, carbonaceous particles capable of producing a low-resistance lithium ion secondary battery, a negative electrode material for a lithium ion secondary battery, and a negative electrode for a lithium ion secondary battery and a lithium ion secondary battery are provided.
도 1은, 실시예 1, 비교예 1 및 비교예 2에서 제작한 탄소질 입자에 있어서의 R값의 도수 분포를 나타내는 그래프이다.
도 2는, 실시예 1, 비교예 1 및 비교예 2에서 제작한 탄소질 입자에 있어서의 R값의 누적 곡선을 나타내는 그래프이다. Figure 1 is a graph showing the frequency distribution of R values in carbonaceous particles produced in Example 1, Comparative Example 1, and Comparative Example 2.
Figure 2 is a graph showing the cumulative curve of R values for carbonaceous particles produced in Example 1, Comparative Example 1, and Comparative Example 2.
이하, 본 발명을 실시하기 위한 형태에 관하여 상세하게 설명한다. 다만, 본 발명은 이하의 실시 형태에 한정되는 것은 아니다. 이하의 실시형태에 있어서, 그 구성 요소(요소 스텝 등도 포함한다)는, 특별히 명시한 경우를 제외하고, 필수는 아니다. 수치 및 그 범위에 관하여도 동일하며, 본 발명을 제한하는 것은 아니다. Hereinafter, modes for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps, etc.) are not essential, unless specifically stated. The values and ranges are the same and do not limit the present invention.
본 개시에 있어서 "공정"이라는 단어에는, 다른 공정으로부터 독립된 공정에 더하여, 다른 공정과 명확히 구별할 수 없는 경우여도 그 공정의 목적이 달성되면, 당해 공정도 포함된다. In the present disclosure, the word "process" includes processes that are independent from other processes, as long as the purpose of the process is achieved even if the process cannot be clearly distinguished from other processes.
본 개시에 있어서 "~"을 사용하여 나타낸 수치 범위에는, "~"의 전후에 기재되는 수치가 각각 최소값 및 최대값으로서 포함된다. In the present disclosure, the numerical range indicated using “~” includes the numerical values written before and after “~” as the minimum and maximum values, respectively.
본 개시 중에 단계적으로 기재되어 있는 수치 범위에 있어서, 하나의 수치 범위에서 기재된 상한값 또는 하한값은, 다른 단계적인 기재의 수치 범위의 상한값 또는 하한값으로 치환해도 된다. 또한, 본 개시 중에 기재되어 있는 수치 범위에 있어서, 그 수치 범위의 상한값 또는 하한값은, 실시예에 나타내고 있는 값으로 치환해도 된다. In the numerical range described stepwise during the present disclosure, the upper limit or lower limit value described in one numerical range may be replaced with the upper limit or lower limit value of another numerical range described stepwise. In addition, in the numerical range described in the present disclosure, the upper or lower limit of the numerical range may be replaced with the value shown in the examples.
본 개시에 있어서 각 성분은 해당하는 물질을 복수종 포함하고 있어도 된다. 조성물 중에 각 성분에 해당하는 물질이 복수종 존재하는 경우, 각 성분의 함유율 또는 함유량은, 특별히 언급하지 않는 한, 조성물 중에 존재하는 당해 복수종의 물질 합계의 함유율 또는 함유량을 의미한다. In this disclosure, each component may contain multiple types of corresponding substances. When multiple types of substances corresponding to each component exist in the composition, the content rate or content of each component means the content rate or content of the total of the multiple types of substances present in the composition, unless otherwise specified.
본 개시에 있어서 각 성분에 해당하는 입자는 복수종 포함하고 있어도 된다. 조성물 중에 각 성분에 해당하는 입자가 복수종 존재하는 경우, 각 성분의 입경은, 특별히 언급하지 않는 한, 조성물 중에 존재하는 당해 복수종의 입자의 혼합물에 관한 값을 의미한다. In the present disclosure, plural types of particles corresponding to each component may be included. When multiple types of particles corresponding to each component exist in the composition, the particle size of each component means a value related to the mixture of the multiple types of particles present in the composition, unless otherwise specified.
본 개시에 있어서 "층" 또는 "막"이라는 단어에는, 당해 층 또는 막이 존재하는 영역을 관찰했을 때에, 당해 영역의 전체에 형성되어 있는 경우에 더하여, 당해 영역의 일부에만 형성되어 있는 경우도 포함된다. In the present disclosure, the word "layer" or "film" includes cases where the layer or film is formed in the entire area when observing the area where the layer or film exists, as well as cases where it is formed only in a part of the area. do.
<탄소질 입자><Carbonaceous particles>
본 개시의 탄소질 입자는, 라만 매핑 측정으로 얻어지는 흑연의 G밴드(1580 cm-1)와 D밴드(1360 cm-1)의 피크 강도비(G/D)를 나타내는 R값의 도수 분포에 있어서, 하기 조건 (1) 및 (2)를 만족시키는, 리튬 이온 이차 전지의 음극재용 탄소질 입자이다. The carbonaceous particles of the present disclosure are, in the frequency distribution of the R value representing the peak intensity ratio (G/D) of the G band (1580 cm -1 ) and D band (1360 cm -1 ) of graphite obtained by Raman mapping measurement. , carbonaceous particles for a negative electrode material of a lithium ion secondary battery that satisfy the following conditions (1) and (2).
(1) R값의 최빈값(Rc)가 0.87~0.96이다. (1) The mode of R value (Rc) is 0.87 to 0.96.
(2) R값이 작은 측으로부터의 빈도의 누적이 50%일 때의 R값(R50)이 0.88~0.92이다. (2) The R value (R 50 ) when the accumulation of frequencies from the side with the smaller R value is 50 % is 0.88 to 0.92.
본 발명자들의 검토 결과, 상기 조건 (1) 및 (2)를 만족시키는 탄소질 입자를 포함하는 음극재를 사용하여 얻어지는 리튬 이온 이차 전지는 입출력 특성이 우수하고, 또한 저저항인 것이 밝혀졌다. As a result of examination by the present inventors, it was found that a lithium ion secondary battery obtained by using a negative electrode material containing carbonaceous particles that satisfies the above conditions (1) and (2) has excellent input/output characteristics and low resistance.
본 개시에 있어서 탄소질 입자의 R값의 도수 분포는, 라만 매핑에 의해 얻을 수 있다. 라만 매핑의 측정 조건은, 대물 렌즈의 배율: 50배, 노광 시간: 2초, 적산 횟수: 4회, 샘플링 범위: 100 ㎛×100 ㎛, 측정 간격: 2 ㎛로 한다. 측정 장치로서는, 예를 들어, 서모피셔 사이언티픽사의 DXR 현미 레이저 라만을 사용할 수 있다. In the present disclosure, the frequency distribution of the R value of carbonaceous particles can be obtained by Raman mapping. The measurement conditions for Raman mapping are: objective lens magnification: 50 times, exposure time: 2 seconds, number of integrations: 4, sampling range: 100 ㎛ × 100 ㎛, and measurement interval: 2 ㎛. As a measuring device, for example, DXR microscopic laser Raman from Thermo Fisher Scientific can be used.
리튬 이온 이차 전지의 저저항화의 관점에서는, Rc는 0.90~0.92인 것이 바람직하다. From the viewpoint of lowering the resistance of the lithium ion secondary battery, Rc is preferably 0.90 to 0.92.
불가역 용량, 충방전 용량, 사이클 수명 등의 전지 특성을 향상시키는 관점에서는, 탄소질 입자의 002면의 면 간격(d002)는, 0.34 nm~0.37 nm인 것이 바람직하다. d002가 0.34 nm 이상이면, 양호한 첫 회 충방전 효율이 얻어지는 경향이 있고, 0.37 nm 이하이면, 수명 특성 및 입출력 특성이 우수한 경향이 있다. From the viewpoint of improving battery characteristics such as irreversible capacity, charge/discharge capacity, and cycle life, the interplanar spacing (d002) of the 002 plane of the carbonaceous particles is preferably 0.34 nm to 0.37 nm. If d002 is 0.34 nm or more, good first charge/discharge efficiency tends to be obtained, and if d002 is 0.37 nm or less, life characteristics and input/output characteristics tend to be excellent.
탄소질 입자의 002면의 면 간격(d002)는, XRD 측정으로부터 구할 수 있다. 구체적으로는, X선(CuKα선)을 시료에 조사하고, 회절선을 고니오미터에 의해 측정하여 얻어지는 회절 프로파일로부터, 회절각 2θ=24°~26°부근에 나타나는 탄소 002면에 대응한 회절 피크로부터, 브래그(Bragg)의 식을 이용하여 산출할 수 있다. The interplanar spacing (d002) of the 002 plane of the carbonaceous particle can be determined from XRD measurement. Specifically, from the diffraction profile obtained by irradiating the sample with From the peak, it can be calculated using Bragg's equation.
리튬 이온 이차 전지의 불가역 용량, 수명 특성 및 충방전 용량을 높인다는 관점에서는, 탄소질 입자는, 코크스로 제조되는 것이 바람직하다. 탄소질 입자의 제조에 사용하는 코크스의 종류는 특별히 제한되지 않으며, 석탄계 코크스, 석유계 코크스 등을 들 수 있다. 코크스는 결정성이 비교적 낮은 모자이크 코크스와 결정성이 비교적 높은 니들 코크스로 대별되는데, 니들 코크스가 보다 바람직하다. 탄소질 입자의 제조에 사용하는 코크스는, 1종만이거나 2종 이상이어도 된다. From the viewpoint of increasing the irreversible capacity, life characteristics, and charge/discharge capacity of a lithium ion secondary battery, it is preferable that the carbonaceous particles are made of coke. The type of coke used for producing carbonaceous particles is not particularly limited, and examples include coal-based coke and petroleum-based coke. Coke is roughly divided into mosaic coke with relatively low crystallinity and needle coke with relatively high crystallinity, with needle coke being more preferable. The coke used for producing carbonaceous particles may be one type or two or more types.
탄소질 입자는, 핵으로서의 제1 탄소재와, 상기 제1 탄소재 표면의 적어도 일부에 존재하고, 상기 제1 탄소재보다도 결정성이 낮은 제2 탄소재를 갖는 것이어도 된다. 탄소질 입자가 핵으로서의 제1 탄소재와, 상기 제1 탄소재 표면의 적어도 일부에 존재하고, 상기 제1 탄소재보다도 결정성이 낮은 제2 탄소재를 갖는 경우, 핵 표면의 전체에 제2 탄소재가 존재하고 있어도, 일부에만 존재하고 있어도 된다. The carbonaceous particles may have a first carbon material as a nucleus, and a second carbon material that exists on at least a part of the surface of the first carbon material and has a lower crystallinity than the first carbon material. When a carbonaceous particle has a first carbon material as a nucleus and a second carbon material that is present on at least a part of the surface of the first carbon material and has a lower crystallinity than the first carbon material, the second carbon material is spread over the entire surface of the nucleus. Even if a carbon material exists, it may exist only in a part.
탄소질 입자가 핵으로서의 제1 탄소재와, 상기 제1 탄소재 표면의 적어도 일부에 존재하고, 상기 제1 탄소재보다도 결정성이 낮은 제2 탄소재를 갖는 경우, 핵이 되는 제1 탄소재가 코크스로 제조되고, 상기 제1 탄소재 표면의 적어도 일부에 존재하는 제2 탄소재가, 열처리에 의해 탄소질로 변화될 수 있는 재료(제2 탄소재의 전구체)로 제조되는 것이어도 된다. 제2 탄소재의 전구체는, 특별히 제한은 없지만, 열가소성 수지, 나프탈렌, 안트라센, 페난트롤린, 콜타르, 타르, 피치 등을 들 수 있다. When a carbonaceous particle has a first carbon material as a nucleus and a second carbon material that is present on at least a part of the surface of the first carbon material and has a lower crystallinity than the first carbon material, the first carbon material as the nucleus The second carbon material, which is manufactured from coke and exists on at least a portion of the surface of the first carbon material, may be manufactured from a material that can be changed to carbonaceous by heat treatment (precursor of the second carbon material). The precursor of the second carbon material is not particularly limited, and examples include thermoplastic resin, naphthalene, anthracene, phenanthroline, coal tar, tar, and pitch.
탄소질 입자가 핵으로서의 제1 탄소재와, 상기 제1 탄소재 표면의 적어도 일부에 존재하고, 상기 제1 탄소재보다도 결정성이 낮은 제2 탄소재를 갖는 경우, 제2 탄소재의 양은 특별히 제한되지 않는다. 제2 탄소재의 양이 많을수록 R값이 커지고, 제2 탄소재의 양이 적을수록 R값이 작아진다는 관계성이 있다. 또한, 비표면적의 증대를 억제하여 전해액과의 부반응을 일어나기 어렵게 하여, 양호한 입출력 특성을 얻는 관점에서는, 제2 탄소재의 양은 너무 적지 않은 것이 바람직하다. 한편, 제2 탄소재 그 자체의 저항이 높아져, 입출력 특성이 악화되는 것을 억제하는 관점에서는, 제2 탄소재의 양은 너무 많지 않은 것이 바람직하다. When carbonaceous particles have a first carbon material as a nucleus and a second carbon material that exists on at least a part of the surface of the first carbon material and has a lower crystallinity than the first carbon material, the amount of the second carbon material is particularly Not limited. There is a relationship that the larger the amount of the second carbon material, the larger the R value is, and the smaller the amount of the second carbon material is, the smaller the R value is. Additionally, from the viewpoint of suppressing an increase in the specific surface area to prevent side reactions with the electrolyte solution from occurring and obtaining good input/output characteristics, it is preferable that the amount of the second carbon material is not too small. On the other hand, from the viewpoint of suppressing the resistance of the second carbon material itself from increasing and the input/output characteristics from deteriorating, it is preferable that the amount of the second carbon material is not too large.
핵으로서의 제1 탄소재와, 상기 제1 탄소재 표면의 적어도 일부에 존재하고, 상기 제1 탄소재보다도 결정성이 낮은 제2 탄소재를 갖는 탄소질 입자의 제조 방법은, 특별히 제한되지 않는다. 예를 들어, 후술하는 탄소질 입자의 제조 방법에 의해 제조할 수 있다. The method for producing carbonaceous particles having a first carbon material as a nucleus and a second carbon material that is present on at least part of the surface of the first carbon material and has a lower crystallinity than the first carbon material is not particularly limited. For example, it can be manufactured by the carbonaceous particle manufacturing method described later.
리튬 이온 이차 전지의 저저항화의 관점에서는, 탄소질 입자의 셰러(Scherrer)의 식으로 산출되는 c축 방향의 결정자 사이즈(Lc)가 4.5 nm~5.4 nm인 것이 바람직하다. c축 방향의 결정자 사이즈(Lc)가 클수록 결정성이 높은 것을 의미한다. c축 방향의 결정자 사이즈(Lc)가 4.5 nm~5.4 nm인 탄소질 입자로는, 니들 코크스의 입자를 들 수 있다. 탄소질 입자의 c축 방향의 결정자 사이즈(Lc)는, X선 회절 측정에 의해 얻어지는 d002의 회절 피크의 반가폭으로부터 셰러의 식에 의해 산출되는 값으로 한다. From the viewpoint of lowering the resistance of the lithium ion secondary battery, it is preferable that the crystallite size (Lc) of the carbonaceous particles in the c-axis direction calculated by Scherrer's equation is 4.5 nm to 5.4 nm. The larger the crystallite size (Lc) in the c-axis direction, the higher the crystallinity. Carbonaceous particles having a crystallite size (Lc) in the c-axis direction of 4.5 nm to 5.4 nm include needle coke particles. The crystallite size (Lc) in the c-axis direction of the carbonaceous particles is a value calculated by Scherer's equation from the half width of the diffraction peak of d002 obtained by X-ray diffraction measurement.
탄소질 입자의 비표면적은, 2.0 ㎡/g~5.0 ㎡/g인 것이 바람직하며, 2.5 ㎡/g~4.0 ㎡/g 이하인 것이 보다 바람직하며, 2.7 ㎡/g~3.3 ㎡/g인 것이 더욱 바람직하다. 본 개시에 있어서 탄소질 입자의 비표면적은, BET법(질소가스 흡착법)에 의해 얻어지는 값으로 한다. The specific surface area of the carbonaceous particles is preferably 2.0 m2/g to 5.0 m2/g, more preferably 2.5 m2/g to 4.0 m2/g, and even more preferably 2.7 m2/g to 3.3 m2/g. do. In the present disclosure, the specific surface area of the carbonaceous particles is taken as a value obtained by the BET method (nitrogen gas adsorption method).
탄소질 입자의 평균 입경(50%D)는, 5 ㎛~20 ㎛인 것이 바람직하며, 8 ㎛~18㎛인 것이 보다 바람직하며, 9 ㎛~16 ㎛인 것이 더욱 바람직하다. 탄소질 입자의 평균 입경이 5 ㎛ 이상이면, 비표면적이 너무 커지지 않아, 리튬 이온 이차 전지의 첫 회 충방전 효율의 저하가 억제되는 경향이 있다. 또한, 입자끼리의 접촉이 충분히 확보되어 입출력 특성의 저하가 억제되는 경향이 있다. 탄소질 입자의 평균 입경이 20 ㎛ 이하이면, 전극면에 요철이 발생하여 전지의 단락이 발생하는 것이 억제되는 경향이 있다. 또한, 입자 표면에서 내부로의 Li의 확산 거리가 너무 길어지 지 않아, 입출력 특성이 양호하게 유지되는 경향이 있다. The average particle diameter (50%D) of the carbonaceous particles is preferably 5 μm to 20 μm, more preferably 8 μm to 18 μm, and even more preferably 9 μm to 16 μm. If the average particle diameter of the carbonaceous particles is 5 μm or more, the specific surface area does not become too large, and a decrease in the first charge and discharge efficiency of the lithium ion secondary battery tends to be suppressed. Additionally, sufficient contact between particles is ensured, which tends to suppress deterioration of input/output characteristics. If the average particle size of the carbonaceous particles is 20 μm or less, the occurrence of irregularities on the electrode surface and short circuit of the battery tends to be suppressed. In addition, the diffusion distance of Li from the particle surface to the inside does not become too long, so the input/output characteristics tend to be maintained well.
본 개시에 있어서 탄소질 입자의 평균 입경(50%D)는, 레이저 회절·산란법에 의해 얻어지는 체적 기준의 입도 분포에 있어서 소직경측으로부터의 누적이 50%가 될 때의 입경이다. In the present disclosure, the average particle diameter (50%D) of carbonaceous particles is the particle size when the accumulation from the small diameter side is 50% in the volume-based particle size distribution obtained by laser diffraction/scattering method.
본 개시의 탄소질 입자의 제조 방법은, 특별히 제한되지 않는다. 예를 들어, 핵이 되는 제1 탄소재와, 제1 탄소재보다도 결정성이 낮은 제2 탄소재의 전구체를 포함하는 혼합물을 열처리하는 공정을 포함하는 방법에 의해 제조되는 것이어도 된다. The method for producing carbonaceous particles of the present disclosure is not particularly limited. For example, it may be manufactured by a method including a step of heat treating a mixture containing a first carbon material serving as a nucleus and a precursor of a second carbon material whose crystallinity is lower than that of the first carbon material.
상기 방법에 의하면, 핵으로서의 제1 탄소재와, 상기 제1 탄소재 표면의 적어도 일부에 존재하고, 상기 제1 탄소재보다도 결정성이 낮은 제2 탄소재를 갖는 탄소질 입자를 효율적으로 제조할 수 있다. According to the above method, carbonaceous particles having a first carbon material as a nucleus and a second carbon material present on at least a portion of the surface of the first carbon material and having a lower crystallinity than the first carbon material can be efficiently produced. You can.
상기 방법에 있어서, 제1 탄소재 및 제2 탄소재의 상세 그리고 바람직한 양태는, 전술한 리튬 이온 이차 전지용 음극재의 항목에서 설명한 것과 동일하다. In the above method, the details and preferred embodiments of the first carbon material and the second carbon material are the same as those described in the above-mentioned section on the negative electrode material for lithium ion secondary battery.
혼합물을 열처리할 때의 온도는, 리튬 이온 이차 전지에 있어서의 입출력 특성을 향상시키는 점에서, 800℃~1500℃인 것이 바람직하며, 850℃~1100℃인 것이 보다 바람직하며, 900℃~1000℃인 것이 더욱 바람직하다. 혼합물을 열처리할 때의 온도는, 열처리의 개시부터 종료까지 일정해도, 변화되어도 된다. The temperature when heat treating the mixture is preferably 800°C to 1500°C, more preferably 850°C to 1100°C, and 900°C to 1000°C in terms of improving the input/output characteristics of the lithium ion secondary battery. It is more preferable to be The temperature when heat treating the mixture may be constant from the start of the heat treatment to the end or may vary.
열처리 후의 혼합물은, 필요에 따라 분쇄, 해쇄, 입도 조정 등의 처리를 실시해도 된다. The mixture after heat treatment may be subjected to processing such as pulverization, disintegration, or particle size adjustment as necessary.
상기 방법에 있어서, 열처리 전의 혼합물 중의 제1 탄소재 및 제2 탄소재의 전구체 함유율은, 특별히 제한되지 않는다. 리튬 이온 이차 전지에 있어서의 입출력 특성을 향상시키는 점에서, 제1 탄소재의 함유율은, 혼합물의 총 질량에 대해, 85 질량%~99.9 질량%인 것이 바람직하며, 90 질량%~99 질량%인 것이 보다 바람직하며, 95 질량%~99 질량%인 것이 더욱 바람직하다. 한편, 제2 탄소재의 전구체 함유율은, 리튬 이온 이차 전지에 있어서의 입출력 특성을 향상시키는 점에서, 혼합물의 총 질량에 대해, 0.1 질량%~15 질량%인 것이 바람직하며, 1 질량%~10 질량%인 것이 보다 바람직하며, 1 질량%~5 질량%인 것이 더욱 바람직하다. In the above method, the precursor content rates of the first carbon material and the second carbon material in the mixture before heat treatment are not particularly limited. In terms of improving the input/output characteristics in a lithium ion secondary battery, the content rate of the first carbon material is preferably 85% by mass to 99.9% by mass, and is 90% by mass to 99% by mass with respect to the total mass of the mixture. It is more preferable, and it is even more preferable that it is 95 mass% to 99 mass%. On the other hand, the precursor content of the second carbon material is preferably 0.1% by mass to 15% by mass, and 1% by mass to 10% by mass, relative to the total mass of the mixture, from the viewpoint of improving the input/output characteristics in the lithium ion secondary battery. It is more preferable that it is % by mass, and it is still more preferable that it is 1 mass % to 5 mass %.
<리튬 이온 이차 전지용 음극재><Anode materials for lithium ion secondary batteries>
본 개시의 리튬 이온 이차 전지용 음극재(이하, 음극재라고도 칭한다)는, 상술한 탄소질 입자를 포함한다. The negative electrode material (hereinafter also referred to as negative electrode material) for a lithium ion secondary battery of the present disclosure contains the carbonaceous particles described above.
본 개시의 음극재는, 상술한 탄소질 입자만으로 이루어지는 것이어도, 탄소질 입자와 그 밖의 음극재와의 조합이어도 된다. 예를 들어, 흑연 입자에 탄소질 입자를 조합함으로써, 흑연 입자만을 사용한 경우에 비해 리튬 이온 이차 전지의 입출력 특성이 한층 향상되는 경향이 있다. The negative electrode material of the present disclosure may be composed of only the carbonaceous particles described above or may be a combination of carbonaceous particles and other negative electrode materials. For example, by combining carbonaceous particles with graphite particles, the input/output characteristics of a lithium ion secondary battery tend to be further improved compared to the case where only graphite particles are used.
본 개시의 음극재가 탄소질 입자와 흑연 입자를 포함하는 경우, 탄소질 입자와 흑연 입자의 합계에서 차지하는 탄소질 입자의 비율은 5 질량%~50 질량%인 것이 바람직하며, 10 질량%~40 질량%인 것이 보다 바람직하며, 15 질량%~30 질량%인 것이 더욱 바람직하다. When the negative electrode material of the present disclosure includes carbonaceous particles and graphite particles, the proportion of carbonaceous particles in the total of carbonaceous particles and graphite particles is preferably 5% by mass to 50% by mass, and 10% by mass to 40% by mass. It is more preferable that it is %, and it is more preferable that it is 15 mass% to 30 mass%.
<리튬 이온 이차 전지용 음극><Cathode for lithium ion secondary battery>
본 개시의 리튬 이온 이차 전지용 음극(이하, 음극이라고도 칭한다)은, 상술한 음극재를 포함한다. 음극의 구체적인 구성으로는, 예를 들어, 집전체와, 집전체의 적어도 일방의 면에 배치되는 음극재를 포함하는 음극재층으로 이루어지는 구성을 들 수 있다. The negative electrode for a lithium ion secondary battery (hereinafter also referred to as a negative electrode) of the present disclosure includes the negative electrode material described above. A specific configuration of the negative electrode includes, for example, a configuration consisting of a current collector and a negative electrode material layer containing a negative electrode material disposed on at least one surface of the current collector.
음극을 제작하는 방법은, 특별히 제한되지 않는다. 예를 들어, 음극재와 유기계 결착재를 용제와 함께 교반기, 볼밀, 슈퍼 샌드밀, 가압 니더 등의 분산 장치에 의해 혼련하여, 음극재 슬러리를 조제하고, 이것을 집전체에 도포하여 음극층을 형성하는 방법, 페이스트상의 음극재 슬러리를 시트상, 펠릿상 등의 형상으로 성형하고, 이것을 집전체와 일체화하는 방법 등을 들 수 있다. The method of manufacturing the cathode is not particularly limited. For example, the negative electrode material and the organic binder are mixed with a solvent using a dispersing device such as a stirrer, ball mill, super sand mill, or pressure kneader to prepare a negative electrode material slurry, and this is applied to the current collector to form a negative electrode layer. A method of forming a paste-like negative electrode material slurry into a shape such as a sheet or a pellet and integrating it with a current collector can be mentioned.
음극재 슬러리의 조제에 사용하는 유기계 결착재는, 특별히 한정되지 않는다. 유기계 결착제로는, 스티렌-부타디엔 공중합체, 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, 부틸(메타)아크릴레이트, (메타)아크릴로니트릴, 히드록시에틸(메타)아크릴레이트 등의 에틸렌성 불포화 카르복실산에스테르, 아크릴산, 메타크릴산, 이타콘산, 푸마르산, 말레산 등의 에틸렌성 불포화 카르복실산, 폴리불화비닐리덴, 폴리에틸렌옥사이드, 폴리에피클로히드린, 폴리포스파젠, 폴리아크릴로니트릴 등의 이온 도전성이 큰 고분자 화합물 등을 들 수 있다. 음극재 슬러리 중 유기계 결착제의 함유량은, 예를 들어, 본 개시의 음극재와 유기계 결착제의 합계의 1 질량%~20 질량%의 양인 것이 바람직하다. The organic binder used to prepare the negative electrode material slurry is not particularly limited. Organic binders include ethylene such as styrene-butadiene copolymer, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, (meth)acrylonitrile, and hydroxyethyl (meth)acrylate. Ethylenically unsaturated carboxylic acids such as esters of acrylic acid, methacrylic acid, itaconic acid, fumaric acid, and maleic acid, polyvinylidene fluoride, polyethylene oxide, polyepichlorhydrin, polyphosphazene, polyacrylic and polymer compounds with high ionic conductivity such as ronitrile. The content of the organic binder in the negative electrode material slurry is preferably, for example, 1% by mass to 20% by mass of the total of the negative electrode material and the organic binder of the present disclosure.
본 개시에 있어서 "(메타)아크릴레이트"는 아크릴레이트 및 메타크릴레이트 중 적어도 일방을 의미하며, "(메타)아크릴로니트릴"은 아크릴로니트릴 및 메타크릴로니트릴 중 적어도 일방을 의미한다. In the present disclosure, “(meth)acrylate” means at least one of acrylate and methacrylate, and “(meth)acrylonitrile” means at least one of acrylonitrile and methacrylonitrile.
음극재 슬러리에는, 점도를 조정하기 위한 증점제를 첨가해도 된다. 증점제로는, 카르복시메틸셀룰로오스, 메틸셀룰로오스, 히드록시메틸셀룰로오스, 에틸셀룰로오스, 폴리비닐알코올, 폴리아크릴산(염), 산화전분, 인산화전분, 카세인 등을 들 수 있다. A thickener for adjusting viscosity may be added to the negative electrode material slurry. Examples of thickeners include carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, polyacrylic acid (salt), oxidized starch, phosphorylated starch, casein, and the like.
음극재 슬러리에는, 도전 보조재를 혼합해도 된다. 도전 보조재로는, 카본블랙, 그래파이트, 아세틸렌블랙, 도전성을 나타내는 산화물, 도전성을 나타내는 질화물 등을 들 수 있다. 도전 보조제의 사용량은, 예를 들어, 음극재(불휘발분) 전체의 1 질량%~15 질량%이어도 된다. A conductive additive may be mixed into the cathode material slurry. Examples of conductive additives include carbon black, graphite, acetylene black, conductive oxides, and conductive nitrides. The amount of the conductive additive used may be, for example, 1% by mass to 15% by mass of the total negative electrode material (non-volatile matter).
음극의 제작에 사용하는 집전체의 재질 및 형상은, 특별히 한정되지 않는다. 예를 들어, 구리, 니켈, 티탄, 스테인리스강 등을, 박상(箔狀), 천공 박상, 메쉬 상 등으로 한 띠상의 것을 사용해도 된다. 또한, 포러스 메탈(발포 메탈) 등의 다공성 재료, 카본 페이퍼 등을 사용해도 된다. The material and shape of the current collector used to produce the negative electrode are not particularly limited. For example, you may use a strip-shaped material made of copper, nickel, titanium, stainless steel, etc. in the form of foil, perforated foil, mesh, etc. Additionally, porous materials such as porous metal (foamed metal), carbon paper, etc. may be used.
음극재 슬러리를 집전체에 도포하는 방법은 특별히 한정되지 않고, 메탈 마스크 인쇄법, 정전 도장법, 딥 코트법, 스프레이 코트법, 롤 코트법, 독터 블레이드법, 그라비아 코트법, 스크린 인쇄법 등을 들 수 있다. 도포 후에는, 필요에 따라 평판 프레스, 캘린더 롤 등에 의한 압연 처리를 실시해도 된다. The method of applying the negative electrode material slurry to the current collector is not particularly limited, and includes metal mask printing, electrostatic coating, dip coating, spray coating, roll coating, doctor blade method, gravure coating, and screen printing. You can. After application, rolling treatment using a flat press, calendar roll, etc. may be performed as needed.
시트상, 펠릿상 등의 형상으로 성형된 음극재 슬러리와 집전체를 일체화하는 방법은 특별히 한정되지 않고, 롤, 프레스, 이들의 조합 등을 들 수 있다. The method of integrating the negative electrode material slurry molded into a shape such as a sheet or a pellet and the current collector is not particularly limited, and examples include roll, press, and combinations thereof.
<리튬 이온 이차 전지><Lithium ion secondary battery>
본 개시의 리튬 이온 이차 전지는, 상술한 본 개시의 리튬 이온 이차 전지용 음극을 구비한다. 구체적으로는, 본 개시의 음극과, 양극과, 필요에 따라서 세퍼레이터와, 전해액을 적어도 구비한다. The lithium ion secondary battery of the present disclosure includes the negative electrode for a lithium ion secondary battery of the present disclosure described above. Specifically, it is provided with at least the cathode of the present disclosure, the anode, a separator if necessary, and an electrolyte solution.
양극은, 본 개시의 음극과 동일하게, 집전체 상에 양극 재료를 포함하는 양극층을 형성한 것이어도 된다. 집전체로는, 알루미늄, 티탄, 스테인리스강 등의 금속 또는 합금을, 박상, 천공 박상, 메쉬상 등으로 한 띠상의 것을 사용할 수 있다. The positive electrode may be one in which a positive electrode layer containing a positive electrode material is formed on a current collector, similar to the negative electrode of the present disclosure. As the current collector, a strip-shaped material such as a foil, perforated foil, mesh, or other metal or alloy such as aluminum, titanium, or stainless steel can be used.
양극층에 포함되는 양극 재료는 특별히 제한되지 않으며, 리튬 이온을 도핑 또는 인터컬레이션 가능한 금속 화합물, 금속 산화물, 금속 황화물, 도전성 고분자 재료 등에서 선택할 수 있다. 구체적으로는, 코발트산리튬(LiCoO2), 니켈산리튬(LiNiO2), 망간산리튬(LiMnO2), 및 이들의 복산화물(LiCoxNiyMnzO2, x+y+z=1), 리튬망간스피넬(LiMn2O4), 리튬바나듐 화합물, V2O5, V6O13, VO2, MnO2, TiO2, MoV2O8, TiS2, V2S5, VS2, MoS2, MoS3, Cr3O8, Cr2O5, 올리빈형 LiMPO4(M은 Co, Ni, Mn 또는 Fe) 등의 무기 재료, 폴리아세틸렌, 폴리아닐린, 폴리피롤, 폴리티오펜, 폴리아센 등의 도전성 폴리머, 다공질 탄소 등을 들 수 있다. 양극 재료는, 1종을 단독으로 사용해도 2종 이상을 병용해도 된다. The anode material included in the anode layer is not particularly limited, and may be selected from metal compounds capable of doping or intercalating lithium ions, metal oxides, metal sulfides, and conductive polymer materials. Specifically, lithium cobaltate (LiCoO 2 ), lithium nickelate (LiNiO 2 ), lithium manganate (LiMnO 2 ), and their double oxides (LiCoxNiyMnzO 2 , x+y+z=1), lithium manganese spinel ( LiMn 2 O 4 ), lithium vanadium compound, V 2 O 5 , V 6 O 13 , VO 2 , MnO 2 , TiO 2 , MoV 2 O 8 , TiS 2 , V 2 S 5 , VS 2 , MoS 2 , MoS 3 , Cr 3 O 8 , Cr 2 O 5 , inorganic materials such as olivine type LiMPO 4 (M is Co, Ni, Mn or Fe), conductive polymers such as polyacetylene, polyaniline, polypyrrole, polythiophene and polyacene, porous Carbon, etc. can be mentioned. The positive electrode material may be used individually or in combination of two or more types.
세퍼레이터로는, 예를 들어, 폴리에틸렌, 폴리프로필렌 등의 폴리올레핀을 주성분으로 한 부직포, 크로스, 미공 필름 또는 그들을 조합한 것을 사용할 수 있다. 또한, 제작하는 리튬 이온 이차 전지의 양극과 음극이 직접 접촉하지 않는 구조로 한 경우는, 세퍼레이터를 사용할 필요는 없다. As a separator, for example, non-woven fabric, cloth, microporous film, or a combination thereof containing polyolefin such as polyethylene or polypropylene as a main component can be used. In addition, if the lithium ion secondary battery being manufactured has a structure in which the positive and negative electrodes do not directly contact each other, there is no need to use a separator.
전해액으로는, 전해질을 비수계 용제에 용해한, 이른바 유기 전해액을 사용할 수 있다. As the electrolyte solution, a so-called organic electrolyte solution in which an electrolyte is dissolved in a non-aqueous solvent can be used.
전해질로는, LiClO4, LiPF6, LiAsF6, LiBF4, LiSO3CF3 등의 리튬염을 들 수 있다. Examples of the electrolyte include lithium salts such as LiClO 4 , LiPF 6 , LiAsF 6 , LiBF 4 , and LiSO 3 CF 3 .
비수계 용제로는, 에틸렌카보네이트, 프로필렌카보네이트, 부틸렌카보네이트, 비닐렌카보네이트, 시클로펜타논, 술포란, 3-메틸술포란, 2,4-디메틸술포란, 3-메틸-1,3-옥사졸리딘-2-온, γ-부티로락톤, 디메틸카보네이트, 디에틸카보네이트, 에틸메틸카보네이트, 메틸프로필카보네이트, 부틸메틸카보네이트, 에틸프로필카보네이트, 부틸에틸카보네이트, 디프로필카보네이트, 1,2-디메톡시에탄, 테트라히드로푸란, 2-메틸테트라히드로푸란, 1,3-디옥소란, 아세트산메틸, 아세트산에틸, 이들의 혼합물 등을 들 수 있다.Non-aqueous solvents include ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, cyclopentanone, sulfolane, 3-methylsulfolane, 2,4-dimethylsulfolane, and 3-methyl-1,3-oxa. Zolidin-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-dimethoxy Examples include ethane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, methyl acetate, ethyl acetate, and mixtures thereof.
리튬 이온 이차 전지의 구조는, 특별히 한정되지 않는다. 예를 들어, 양극과 음극 사이에 세퍼레이터를 배치한 상태에서, 롤상으로 권회(捲回)하거나, 평판상의 적층체로서 얻은 극판군을 외장체 중에 봉입하여, 전해액으로 외장체 내부를 채운 구조로 하는 것이 일반적이다. The structure of the lithium ion secondary battery is not particularly limited. For example, with a separator disposed between the anode and the cathode, the electrode plate group is wound into a roll or is obtained as a flat laminate and enclosed in an exterior body, and the interior of the exterior body is filled with an electrolyte. It is common.
리튬 이온 이차 전지의 형상은 특별히 한정되지 않고, 페이퍼형 전지, 버튼형 전지, 코인형 전지, 적층형 전지, 원통형 전지 등을 들 수 있다. The shape of the lithium ion secondary battery is not particularly limited, and examples include paper-type batteries, button-type batteries, coin-type batteries, stacked batteries, and cylindrical batteries.
실시예Example
이하, 실시예에 기초하여 본 개시의 실시형태를 보다 구체적으로 설명하지만, 본 개시는 이들 실시예에 제한되는 것은 아니다. Hereinafter, embodiments of the present disclosure will be described in more detail based on examples, but the present disclosure is not limited to these examples.
<실시예 1><Example 1>
d002가 0.346 nm, Lc가 4.6 nm인 시판되는 코크스를, 분급기가 부착된 충격 분쇄기를 사용하여 분쇄하였다. 이 분쇄물 99 질량부에 콜타르 피치(연화점 98℃, 잔탄률(탄화율) 50%) 1 질량부를 첨가하여 혼합물을 얻었다. 이어서 이 혼합물을 질소 유통하, 20 ℃/시간의 승온 속도로 900℃까지 승온하고, 900℃(소성 처리 온도)에서 1시간 유지하여, 열처리물을 얻었다. 얻어진 열처리물을 커터밀로 해쇄한 후, 300메쉬 체로 체 분리를 실시하여 굵은 가루를 제거하고, 코크스에서 유래하는 제1 탄소재(핵)와, 상기 제1 탄소재 표면의 적어도 일부에 존재하는 콜타르 피치에서 유래하는 제2 탄소재를 갖는 탄소질 입자를 얻었다. Commercially available coke with d002 of 0.346 nm and Lc of 4.6 nm was pulverized using an impact mill equipped with a classifier. To 99 parts by mass of this pulverized material, 1 part by mass of coal tar pitch (softening point: 98°C, residual carbon rate (carbonization rate): 50%) was added to obtain a mixture. Next, this mixture was heated to 900°C at a temperature increase rate of 20°C/hour under nitrogen flow and held at 900°C (calcination temperature) for 1 hour to obtain a heat-treated product. The obtained heat-treated product is pulverized with a cutter mill, then sieved through a 300 mesh sieve to remove coarse powder, and the first carbon material (nucleus) derived from coke and coal tar present on at least a portion of the surface of the first carbon material are removed. Carbonaceous particles having a second carbon material derived from pitch were obtained.
(d002 및 Lc의 측정)(measurement of d002 and Lc)
얻어진 탄소질 입자의 d002와 Lc의 측정을, X선 회절 측정에 의해 실시하였다. 구체적으로는, 리가쿠덴키 주식회사의 광각 X선 회절 장치를 이용하여, 모노크로미터로 단색화한 Cu-Kα선을 사용하여, 고순도 실리콘을 표준 물질로서 측정하였다. d002는, 회절각 2θ=24°~26°부근에 나타나는 002면에 대응한 회절 피크로부터, 브래그의 식을 이용하여 산출하였다. Lc는, d002의 회절 피크의 반가폭으로부터 셰러의 식에 의해 산출하였다. 결과를 표 1에 나타낸다. The d002 and Lc of the obtained carbonaceous particles were measured by X-ray diffraction measurement. Specifically, high-purity silicon was measured as a standard material using a wide-angle d002 was calculated using Bragg's equation from the diffraction peak corresponding to the 002 plane that appears around the diffraction angle 2θ = 24° to 26°. Lc was calculated by Scherer's equation from the half width of the diffraction peak of d002. The results are shown in Table 1.
(평균 입경의 측정)(Measurement of average particle size)
얻어진 탄소질 입자의 평균 입경(50%D)의 측정을, 레이저 회절·산란법에 의해 실시하였다. 구체적으로는, 레이저 회절식 입도 분포 측정 장치(주식회사 시마즈 제작소의 SALD-3000J)를 이용하여, 탄소질 입자를 계면 활성제와 함께 정제수 중에 분산시킨 분산액을 장치의 수조에 넣고, 초음파를 가한 상태에서 펌프로 순환시키면서 측정하였다. 얻어진 체적 기준의 입도 분포에 있어서의 누적이 50%일 때의 입경(50%D)를 평균 입경으로 하였다. 결과를 표 1에 나타낸다. The average particle diameter (50%D) of the obtained carbonaceous particles was measured by a laser diffraction/scattering method. Specifically, using a laser diffraction particle size distribution measuring device (SALD-3000J manufactured by Shimadzu Corporation), a dispersion in which carbonaceous particles are dispersed in purified water together with a surfactant is placed in the water tank of the device, and then pumped while applying ultrasonic waves. It was measured while circulating. The particle size (50%D) when the accumulation in the obtained volume-based particle size distribution was 50% was taken as the average particle size. The results are shown in Table 1.
(Rc 및 R50의 측정)(Measurement of Rc and R 50 )
얻어진 탄소질 입자의 Rc와 R50의 측정을, 라만 매핑에 의해 실시하였다. 구체적으로는, 라만 매핑 장치(서모피셔 사이언티픽사의 DXR 현미 레이저 라만)를 이용하여, 대물 렌즈의 배율: 50배, 노광 시간: 2초, 적산 횟수: 4회, 샘플링 범위: 100 ㎛×100 ㎛, 측정 간격: 2 ㎛로 하여 실시하였다. 측정에서 얻어진 흑연의 G밴드(1580 cm-1)와 D밴드(1360 cm-1)의 피크 강도비(G/D)를 R값으로 하고, 그 최빈값(Rc)와 빈도의 누적이 50%가 될 때의 R값(R50)을 산출하였다. 결과를 표 1에 나타낸다. Rc and R 50 of the obtained carbonaceous particles were measured by Raman mapping. Specifically, using a Raman mapping device (DXR Micro Laser Raman from Thermo Fisher Scientific), objective lens magnification: 50 times, exposure time: 2 seconds, number of integrations: 4, sampling range: 100 ㎛ × 100. ㎛, measurement interval: 2 ㎛. The peak intensity ratio (G/D) of the G band (1580 cm -1 ) and D band (1360 cm -1 ) of graphite obtained from the measurement is set as the R value, and the accumulation of the mode (Rc) and frequency is 50%. The R value (R 50 ) was calculated. The results are shown in Table 1.
얻어진 R값의 도수 분포를 나타내는 그래프를 도 1에, 누적 곡선을 도 2에, 후술하는 비교예 1과 비교예 2에서 얻어진 결과와 함께 나타낸다. A graph showing the frequency distribution of the obtained R value is shown in Figure 1, and the cumulative curve is shown in Figure 2, together with the results obtained in Comparative Example 1 and Comparative Example 2, which will be described later.
(비표면적의 측정)(Measurement of specific surface area)
얻어진 탄소질 입자의 비표면적(㎡/g)을, 비표면적계(주식회사 시마즈 제작소의 FlowSorb)를 이용하여 BET법(질소가스 흡착법)에 의해 구하였다. The specific surface area (m2/g) of the obtained carbonaceous particles was determined by the BET method (nitrogen gas adsorption method) using a specific surface area meter (FlowSorb, Shimadzu Corporation).
(충방전 용량의 측정)(Measurement of charge/discharge capacity)
탄소질 입자 98 질량%에 대해, 카르복시메틸셀룰로오스(CMC) 1 질량%, 스티렌·부타디엔고무(SBR) 1 질량%가 되도록 첨가하고, 혼련하여 페이스트상의 음극재 슬러리를 제작하였다. 이 슬러리를 두께 11 ㎛의 전해 구리박에 두께 200 ㎛의 마스크를 사용하여 직경 9.5 mm의 원형이 되도록 도포하였다. 이것을 105℃에서 건조시켜, 단극 시험용의 음극을 제작하였다. For 98% by mass of carbonaceous particles, 1% by mass of carboxymethyl cellulose (CMC) and 1% by mass of styrene-butadiene rubber (SBR) were added and kneaded to produce a paste-like negative electrode material slurry. This slurry was applied to an electrolytic copper foil with a thickness of 11 μm using a mask with a thickness of 200 μm to form a circle with a diameter of 9.5 mm. This was dried at 105°C to produce a cathode for a monopole test.
이어서, 제작한 음극, 세퍼레이터, 양극의 순으로 적층한 것을 코인셀 용기에 넣고, 에틸렌카보네이트(EC) 및 에틸메틸카보네이트(EMC)(EC와 EMC는 체적비로 1:1)의 혼합 용매에 LiPF6을 1.0 몰/리터의 농도가 되도록 용해한 전해액을 주입하여, 코인 전지를 제작하였다. 양극에는 금속 리튬을 사용하고, 세퍼레이터에는 두께 20 ㎛의 폴리에틸렌 미공막을 사용하였다. Next, the manufactured negative electrode, separator, and positive electrode were placed in a coin cell container, and LiPF 6 was added to a mixed solvent of ethylene carbonate (EC) and ethylmethyl carbonate (EMC) (EC and EMC are 1:1 by volume). A coin battery was manufactured by injecting an electrolyte solution dissolved to a concentration of 1.0 mol/liter. Metal lithium was used as the anode, and a polyethylene microporous membrane with a thickness of 20 μm was used as the separator.
얻어진 코인 전지를 사용하여, 음극과 양극 사이에 0.1C의 정전류를 통전하고, 양극에 대한 음극의 전위가 0.005V(Vvs. Li/Li+)에 도달할 때까지 충전(음극에 리튬을 흡장)하고, 이어서 0.005V의 정전압으로 전류가 0.01C로 감쇠될 때까지 충전하였다. 다음에 30분간의 휴지를 설정한 후에, 0.1C의 정전류로 양극에 대한 음극의 전위가 1.5V(Vvs. Li/Li+)에 도달할 때까지 방전(음극으로부터 리튬을 방출)하였다. 이 충방전 시험을 1사이클 실시하고, 첫회 충방전에 있어서의 충전 용량과 방전 용량을 측정하고, 얻어진 값으로부터 첫회 충방전 효율을 구하였다. 결과를 표 1에 나타낸다. Using the obtained coin battery, a constant current of 0.1C is passed between the cathode and the anode, and the battery is charged until the potential of the cathode relative to the anode reaches 0.005 V (Vvs. Li/Li + ) (lithium is stored in the cathode). Then, it was charged at a constant voltage of 0.005V until the current was attenuated to 0.01C. Next, after resting for 30 minutes, discharge was performed (lithium was released from the cathode) at a constant current of 0.1 C until the potential of the cathode relative to the anode reached 1.5 V (Vvs. Li/Li + ). This charge/discharge test was performed for one cycle, the charge capacity and discharge capacity at the first charge/discharge were measured, and the first charge/discharge efficiency was determined from the obtained values. The results are shown in Table 1.
첫회 충방전 효율은, 방전 용량(Ah/kg)/충전 용량(Ah/kg)×100(%)로 하여 산출하였다. The first charge/discharge efficiency was calculated as discharge capacity (Ah/kg)/charge capacity (Ah/kg) x 100 (%).
(직류 저항값의 측정)(Measurement of direct current resistance value)
탄소질 입자 98 질량%에, CMC 1 질량%, SBR 1 질량%가 되도록 첨가하여 혼련하고, 페이스트상의 음극재 슬러리를 제작하였다. 이 슬러리를, 두께 11 ㎛의 전해 구리박에 단위 면적당 도포량이 4.5 mg/c㎡가 되도록 도공기를 사용하여 도포하였다. 그 후, 105℃에서 건조시키고, 또한, 롤 프레스기에 의해 합재 밀도가 1.05 g/㎤가 되도록 압축 성형하여, 음극을 제작하였다. To 98% by mass of carbonaceous particles, 1% by mass of CMC and 1% by mass of SBR were added and kneaded to produce a paste-like negative electrode material slurry. This slurry was applied to an electrolytic copper foil with a thickness of 11 μm using a coating machine so that the application amount per unit area was 4.5 mg/cm 2 . Afterwards, it was dried at 105°C, and compression molded using a roll press machine so that the composite density was 1.05 g/cm3 to produce a negative electrode.
이어서, 음극, 세퍼레이터, 양극(Li 금속)의 순으로 적층한 것을 코인셀 용기에 세트하였다. 이것에 에틸렌카보네이트(EC) 및 에틸메틸카보네이트(EMC)(EC와 EMC는 체적비로 1:1)의 혼합 용매에 LiPF6을 1.0 몰/리터의 농도가 되도록 용해한 전해액 용액을 3 ml 주입하고, 코인셀 용기를 코킹 접합하여, 코인셀형의 리튬 이온 이차 전지를 제작하였다. Next, the cathode, separator, and anode (Li metal) were stacked in that order and set in a coin cell container. To this, 3 ml of an electrolyte solution in which LiPF 6 was dissolved to a concentration of 1.0 mol/liter in a mixed solvent of ethylene carbonate (EC) and ethylmethyl carbonate (EMC) (EC and EMC in a volume ratio of 1:1) was injected, and the coin was injected. The cell container was caulk bonded to produce a coin cell type lithium ion secondary battery.
제작한 리튬 이온 이차 전지를 사용하여, 직류 저항(DCR)을 측정하였다. 구체적으로는, 우선, 25℃ 분위기하에서 0.2C의 정전류, 0V의 정전압으로 전류값이 0.02C가 될 때까지 충전하고, 이어서, 0.2C의 정전류로 1.5V의 전압값까지 방전을 실시하였다. Direct current resistance (DCR) was measured using the manufactured lithium ion secondary battery. Specifically, first, in an atmosphere of 25°C, the battery was charged at a constant current of 0.2C and a constant voltage of 0V until the current value reached 0.02C, and then discharged at a constant current of 0.2C to a voltage value of 1.5V.
상기 조건으로 충방전을 실시한 후, 0.2C의 정전류로 50%의 충전 상태(SOC)가 되도록 충전을 실시하였다. 그 후, 1C로 1분간 정전류 방전하고, 이어서 3C로 1분간 정전류 방전하고, 이어서 5C로 1분간 정전류 방전을 실시하였다. 이상의 시험으로부터, SOC가 50%일 때의 전압값과 각 전류값에서의 방전 10초 후의 전압값의 차(ΔV)를 구하고, 가로축에 전류값, 세로축에 ΔV를 플롯한 도면의 기울기를 25℃에서의 직류 저항(25℃DCR)값(Ω)로 하였다. 결과를 표 1에 나타낸다. After charging and discharging was performed under the above conditions, charging was performed to reach a state of charge (SOC) of 50% at a constant current of 0.2C. After that, constant current discharge was performed at 1 C for 1 minute, followed by constant current discharge at 3 C for 1 minute, and then constant current discharge at 5 C for 1 minute. From the above test, the difference (ΔV) between the voltage value when SOC is 50% and the voltage value after 10 seconds of discharge at each current value was determined, and the slope of the figure plotting the current value on the horizontal axis and ΔV on the vertical axis was calculated at 25°C. The direct current resistance (25°C DCR) value (Ω) was set as . The results are shown in Table 1.
상기 리튬 이온 이차 전지를 25℃로 설정한 항온조 내에 넣고, 하기 조건으로 1사이클 충방전을 실시하였다. The lithium ion secondary battery was placed in a constant temperature bath set at 25°C, and one cycle of charging and discharging was performed under the following conditions.
충전 : CC/CV 0.2C 0V 0.02C CutCharging: CC/CV 0.2C 0V 0.02C Cut
방전 : CC 0.2C 1.5V CutDischarge: CC 0.2C 1.5V Cut
이어서, 전류값 0.2C로, SOC가 50%가 될 때까지 정전류 충전을 실시하였다. 그 후, -30℃로 설정한 항온조에 넣고, 0.1C로 1분간 정전류 방전을 실시하고, 이어서 0.3C로 1분간 정전류 방전을 실시하고, 이어서 0.5C로 1분간 정전류 방전을 실시하였다. 그리고 SOC가 50%일 때의 전압값과 각 전류값에서의 방전 10초 후의 전압값의 차(ΔV)를 구하고, 가로축에 전류값, 세로축에 ΔV를 플롯한 도면의 기울기를 -30℃에서의 직류 저항(-30℃DCR)의 값(Ω)으로 하였다. 결과를 표 1에 나타낸다. Next, constant current charging was performed at a current value of 0.2C until SOC reached 50%. After that, it was placed in a constant temperature bath set at -30°C, and constant current discharge was performed at 0.1 C for 1 minute, followed by constant current discharge at 0.3 C for 1 minute, and then constant current discharge at 0.5 C for 1 minute. Then, the difference (ΔV) between the voltage value when the SOC is 50% and the voltage value after 10 seconds of discharge at each current value is calculated, and the slope of the figure plotting the current value on the horizontal axis and ΔV on the vertical axis is obtained at -30°C. It was set as the value (Ω) of direct current resistance (-30°C DCR). The results are shown in Table 1.
<실시예 2><Example 2>
d002가 0.346 nm, Lc가 5.2 nm인 시판되는 코크스를, 분급기가 부착된 충격 분쇄기를 사용하여 분쇄한 것을 이용한 것 이외는 실시예 1과 동일하게 하여, 탄소질 입자를 얻었다. 이 탄소질 입자에 대해 실시예 1과 동일한 측정을 실시하였다. 또한, 이 탄소질 입자를 사용하여 리튬 이온 이차 전지를 제작하고, 실시예 1과 동일한 측정을 실시하였다. 결과를 표 1에 나타낸다. Carbonaceous particles were obtained in the same manner as in Example 1, except that commercially available coke with d002 of 0.346 nm and Lc of 5.2 nm was pulverized using an impact mill equipped with a classifier. The same measurement as Example 1 was performed on these carbonaceous particles. Additionally, a lithium ion secondary battery was produced using these carbonaceous particles, and the same measurements as in Example 1 were performed. The results are shown in Table 1.
<실시예 3><Example 3>
d002가 0.347 nm, Lc가 5.4 nm인 시판되는 코크스를, 분급기가 부착된 충격 분쇄기를 사용하여 분쇄한 것을 이용한 것 이외는 실시예 1과 동일하게 하여, 탄소질 입자를 얻었다. 이 탄소질 입자에 대해 실시예 1과 동일한 측정을 실시하였다. 또한, 이 탄소질 입자를 사용하여 리튬 이온 이차 전지를 제작하고, 실시예 1과 동일한 측정을 실시하였다. 결과를 표 1에 나타낸다. Carbonaceous particles were obtained in the same manner as in Example 1, except that commercially available coke with d002 of 0.347 nm and Lc of 5.4 nm was pulverized using an impact mill equipped with a classifier. The same measurement as Example 1 was performed on these carbonaceous particles. Additionally, a lithium ion secondary battery was produced using these carbonaceous particles, and the same measurements as in Example 1 were performed. The results are shown in Table 1.
<실시예 4><Example 4>
d002가 0.345 nm, Lc가 4.7 nm인 시판되는 코크스를, 분급기가 부착된 충격 분쇄기를 사용하여 분쇄한 것을 이용한 것 이외는 실시예 1과 동일하게 하여, 탄소질 입자를 얻었다. 이 탄소질 입자에 대해 실시예 1과 동일한 측정을 실시하였다. 또한, 이 탄소질 입자를 사용하여 리튬 이온 이차 전지를 제작하고, 실시예 1과 동일한 측정을 실시하였다. 결과를 표 1에 나타낸다. Carbonaceous particles were obtained in the same manner as in Example 1, except that commercially available coke with d002 of 0.345 nm and Lc of 4.7 nm was pulverized using an impact mill equipped with a classifier. The same measurement as Example 1 was performed on these carbonaceous particles. Additionally, a lithium ion secondary battery was produced using these carbonaceous particles, and the same measurements as in Example 1 were performed. The results are shown in Table 1.
<실시예 5><Example 5>
d002가 0.346 nm, Lc가 5.1 nm인 시판되는 코크스를, 분급기가 부착된 충격 분쇄기를 사용하여 분쇄한 것을 이용한 것 이외는 실시예 1과 동일하게 하여, 탄소질 입자를 얻었다. 이 탄소질 입자에 대해 실시예 1과 동일한 측정을 실시하였다. 또한, 이 탄소질 입자를 사용하여 리튬 이온 이차 전지를 제작하고, 실시예 1과 동일한 측정을 실시하였다. 결과를 표 1에 나타낸다. Carbonaceous particles were obtained in the same manner as in Example 1, except that commercially available coke with d002 of 0.346 nm and Lc of 5.1 nm was pulverized using an impact mill equipped with a classifier. The same measurement as Example 1 was performed on these carbonaceous particles. Additionally, a lithium ion secondary battery was produced using these carbonaceous particles, and the same measurements as in Example 1 were performed. The results are shown in Table 1.
<비교예 1><Comparative Example 1>
d002가 0.347 nm, Lc가 5.2 nm인 시판되는 코크스를, 분급기가 부착된 충격 분쇄기를 사용하여 분쇄한 것을 이용한 것 이외는 실시예 1과 동일하게 하여, 탄소질 입자를 얻었다. 이 탄소질 입자에 대해 실시예 1과 동일한 측정을 실시하였다. 또한, 이 탄소질 입자를 사용하여 리튬 이온 이차 전지를 제작하고, 실시예 1과 동일한 측정을 실시하였다. 결과를 표 1에 나타낸다. Carbonaceous particles were obtained in the same manner as in Example 1, except that commercially available coke with d002 of 0.347 nm and Lc of 5.2 nm was pulverized using an impact mill equipped with a classifier. The same measurement as Example 1 was performed on these carbonaceous particles. Additionally, a lithium ion secondary battery was produced using these carbonaceous particles, and the same measurements as in Example 1 were performed. The results are shown in Table 1.
<비교예 2><Comparative Example 2>
d002가 0.347 nm, Lc가 3.5 nm인 시판되는 코크스를, 분급기가 부착된 충격 분쇄기를 사용하여 분쇄한 것을 이용한 것 이외는 실시예 1과 동일하게 하여, 탄소질 입자를 얻었다. 이 탄소질 입자에 대해 실시예 1과 동일한 측정을 실시하였다. 또한, 이 탄소질 입자를 사용하여 리튬 이온 이차 전지를 제작하고, 실시예 1과 동일한 측정을 실시하였다. 결과를 표 1에 나타낸다. Carbonaceous particles were obtained in the same manner as in Example 1, except that commercially available coke with d002 of 0.347 nm and Lc of 3.5 nm was pulverized using an impact mill equipped with a classifier. The same measurement as Example 1 was performed on these carbonaceous particles. Additionally, a lithium ion secondary battery was produced using these carbonaceous particles, and the same measurements as in Example 1 were performed. The results are shown in Table 1.
<비교예 3><Comparative Example 3>
d002가 0.346 nm, Lc가 5.7 nm인 시판되는 코크스를, 분급기가 부착된 충격 분쇄기를 사용하여 분쇄한 것을 이용한 것 이외는 실시예 1과 동일하게 하여, 탄소질 입자를 얻었다. 이 탄소질 입자에 대해 실시예 1과 동일한 측정을 실시하였다. 또한, 이 탄소질 입자를 사용하여 리튬 이온 이차 전지를 제작하고, 실시예 1과 동일한 측정을 실시하였다. 결과를 표 1에 나타낸다. Carbonaceous particles were obtained in the same manner as in Example 1, except that commercially available coke with d002 of 0.346 nm and Lc of 5.7 nm was pulverized using an impact mill equipped with a classifier. The same measurement as Example 1 was performed on these carbonaceous particles. Additionally, a lithium ion secondary battery was produced using these carbonaceous particles, and the same measurements as in Example 1 were performed. The results are shown in Table 1.
<비교예 4><Comparative Example 4>
d002가 0.346 nm, Lc가 4.7 nm인 시판되는 코크스를, 분급기가 부착된 충격 분쇄기를 사용하여 분쇄한 것을 이용한 것 이외는 실시예 1과 동일하게 하여, 탄소질 입자를 얻었다. 이 탄소질 입자에 대해 실시예 1과 동일한 측정을 실시하였다. 또한, 이 탄소질 입자를 사용하여 리튬 이온 이차 전지를 제작하고, 실시예 1과 동일한 측정을 실시하였다. 결과를 표 1에 나타낸다. Carbonaceous particles were obtained in the same manner as in Example 1, except that commercially available coke with d002 of 0.346 nm and Lc of 4.7 nm was pulverized using an impact mill equipped with a classifier. The same measurement as Example 1 was performed on these carbonaceous particles. Additionally, a lithium ion secondary battery was produced using these carbonaceous particles, and the same measurements as in Example 1 were performed. The results are shown in Table 1.
표 1에 나타내는 바와 같이, 라만 매핑으로 얻어지는 Rc가 0.87~0.96의 범위에 있고, 또한 R50이 0.88~0.92의 범위에 있는 실시예의 탄소질 입자를 사용하여 제작한 리튬 이온 이차 전지는, Rc와 R50 중 적어도 일방이 상기 범위 외인 비교예의 탄소질 입자를 사용하여 제작한 리튬 이온 이차 전지보다도 직류 저항의 값이 작고, 특히 저온(-30℃)에 있어서 직류 저항의 값이 현저히 작은 것을 알 수 있었다. As shown in Table 1, the lithium ion secondary battery produced using the carbonaceous particles of the examples in which Rc obtained by Raman mapping is in the range of 0.87 to 0.96 and R 50 is in the range of 0.88 to 0.92 has Rc and It can be seen that the direct current resistance value is lower than that of the lithium ion secondary battery manufactured using the carbonaceous particles of the comparative example in which at least one of R 50 is outside the above range, and the direct current resistance value is significantly lower, especially at low temperature (-30°C). there was.
이상의 결과로부터, 본 개시의 탄소질 입자를 음극재로서 사용함으로써, 저저항인 리튬 이온 이차 전지가 얻어지는 것을 알 수 있었다. From the above results, it was found that a low-resistance lithium ion secondary battery could be obtained by using the carbonaceous particles of the present disclosure as a negative electrode material.
본 명세서에 기재된 모든 문헌, 특허출원, 및 기술 규격은, 개개의 문헌, 특허출원, 및 기술 규격이 참조에 의해 받아들여지는 것이 구체적이면서 개별적으로 기재된 경우와 동일한 정도로, 본 명세서 중에 원용되어 받아들여진다. All documents, patent applications, and technical standards described in this specification are herein incorporated by reference to the same extent as if each individual document, patent application, or technical standard was specifically and individually indicated to be incorporated by reference. .
Claims (9)
핵으로서의 제1 탄소재와, 상기 제1 탄소재 표면의 적어도 일부에 존재하며, 상기 제1 탄소재보다도 결정성이 낮은 제2 탄소재를 갖는, 리튬 이온 이차 전지의 음극재용 탄소질 입자.
(1) R값의 최빈값(Rc)가 0.87~0.96이다.
(2) R값이 작은 측으로부터의 빈도의 누적이 50%일 때의 R값(R50)이 0.88~0.92이다.In the frequency distribution of the R value representing the peak intensity ratio (G/D) of the G band (1580 cm -1 ) and D band (1360 cm -1) of graphite obtained by Raman mapping measurement, the following conditions (1) and ( 2) is satisfied,
Carbonaceous particles for a negative electrode material of a lithium ion secondary battery, which has a first carbon material as a nucleus, and a second carbon material that exists on at least a part of the surface of the first carbon material and has a lower crystallinity than the first carbon material.
(1) The mode of R value (Rc) is 0.87 to 0.96.
(2) The R value (R 50 ) when the accumulation of frequencies from the side with the smaller R value is 50 % is 0.88 to 0.92.
c축 방향의 결정자 사이즈(Lc)가 4.5 nm~5.2 nm인, 탄소질 입자. According to claim 1,
Carbonaceous particles with a crystallite size (Lc) in the c-axis direction of 4.5 nm to 5.2 nm.
비표면적이 2.0 ㎡/g~5.0 ㎡/g인, 탄소질 입자. According to claim 1 or 3,
Carbonaceous particles with a specific surface area of 2.0 m2/g to 5.0 m2/g.
평균 입경(50%D)가 5 ㎛~20 ㎛인, 탄소질 입자.According to claim 1 or 3,
Carbonaceous particles with an average particle diameter (50%D) of 5 μm to 20 μm.
흑연 입자를 더 포함하는, 리튬 이온 이차 전지용 음극재. According to claim 6,
A negative electrode material for a lithium ion secondary battery further containing graphite particles.
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| JP2016186912A (en) | 2015-03-27 | 2016-10-27 | 三菱化学株式会社 | Composite carbon material for nonaqueous secondary battery, and nonaqueous secondary battery |
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