WO2022060106A1 - 음극 활물질, 이를 포함하는 음극 및 이차전지 - Google Patents
음극 활물질, 이를 포함하는 음극 및 이차전지 Download PDFInfo
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- WO2022060106A1 WO2022060106A1 PCT/KR2021/012632 KR2021012632W WO2022060106A1 WO 2022060106 A1 WO2022060106 A1 WO 2022060106A1 KR 2021012632 W KR2021012632 W KR 2021012632W WO 2022060106 A1 WO2022060106 A1 WO 2022060106A1
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- WIPO (PCT)
- Prior art keywords
- active material
- negative active
- thermal expansion
- coefficient
- negative
- Prior art date
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- 239000011269 tar Substances 0.000 description 2
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- 239000006234 thermal black Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
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- 235000015041 whisky Nutrition 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
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- 229910010238 LiAlCl 4 Inorganic materials 0.000 description 1
- 229910010090 LiAlO 4 Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013372 LiC 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910013733 LiCo Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910015644 LiMn 2 - z Ni Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 1
- 229910017095 Ni0.6Mn0.2Co0.2 Inorganic materials 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- NXPZICSHDHGMGT-UHFFFAOYSA-N [Co].[Mn].[Li] Chemical compound [Co].[Mn].[Li] NXPZICSHDHGMGT-UHFFFAOYSA-N 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
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- 238000003915 air pollution Methods 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- NDPGDHBNXZOBJS-UHFFFAOYSA-N aluminum lithium cobalt(2+) nickel(2+) oxygen(2-) Chemical compound [Li+].[O--].[O--].[O--].[O--].[Al+3].[Co++].[Ni++] NDPGDHBNXZOBJS-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000002579 anti-swelling effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
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- 150000005678 chain carbonates Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 1
- 238000010281 constant-current constant-voltage charging Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 150000004862 dioxolanes Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
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- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
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- 239000003365 glass fiber Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
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- 229920001519 homopolymer Polymers 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
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- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
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- 230000008961 swelling Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- YTWOHSWDLJUCRK-UHFFFAOYSA-N thiolane 1,1-dioxide Chemical compound O=S1(=O)CCCC1.O=S1(=O)CCCC1 YTWOHSWDLJUCRK-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/205—Preparation
-
- 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
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Definitions
- the present invention relates to an anode active material, an anode comprising the same, and a secondary battery.
- lithium metal was conventionally used as the negative electrode, but as the battery short circuit due to the formation of dendrites and the risk of explosion due to this become a problem, reversible intercalation and desorption of lithium ions are possible, The use of carbon-based active materials that maintain structural and electrical properties is emerging.
- the carbon-based active material various types of carbon-based materials such as artificial graphite, natural graphite, and hard carbon have been applied. there is. Since the graphite-based active material has a discharge voltage as low as -0.2V compared to lithium, a battery using the graphite-based active material can exhibit a high discharge voltage of 3.6V, providing many advantages in terms of energy density of a lithium battery.
- artificial graphite has an advantage in that it has an excellent anti-swelling effect and excellent high-temperature characteristics compared to natural graphite.
- artificial graphite has a problem in that the output characteristics are low because there are fewer pores compared to natural graphite. It is known to use
- artificial graphite assembled with secondary particles is highly likely to have an irregular and non-smooth shape depending on the shape of the primary particles and their assembly.
- Such artificial graphite has a problem of poor electrode adhesion when used for an anode, and deterioration of processability due to a decrease in electrode adhesion, and a problem of deterioration of long-term cycle characteristics due to active material desorption when the anode is driven.
- Japanese Patent Registration Publication No. 4403327 discloses a graphite powder for a negative electrode of a lithium ion secondary battery, but does not provide an alternative to the above-mentioned problem.
- One object of the present invention is to provide an anode active material having excellent adhesion and high capacity and initial efficiency in a negative active material containing artificial graphite in the form of secondary particles.
- Another object of the present invention is to provide a negative electrode including the above-described negative electrode active material.
- Another object of the present invention is to provide a secondary battery including the above-described negative electrode.
- the present invention includes artificial graphite particles in the form of secondary particles in which a plurality of primary artificial graphite particles are bonded, and the coefficient of thermal expansion measured by a method comprising the following steps is 108 ⁇ 10 -6 /K to 150 ⁇ 10 - Provided is an anode active material of 6 /K.
- Equation 1 A is the thermal expansion coefficient of the negative active material, B is the thermal expansion coefficient of the pitch binder pellets, C is the thermal expansion coefficient of the mixture pellets.
- the present invention is a negative electrode current collector; and an anode active material layer disposed on the anode current collector, wherein the anode active material layer provides an anode including the anode active material described above.
- the present invention is the above-described negative electrode; an anode opposite to the cathode; a separator interposed between the negative electrode and the positive electrode; and an electrolyte; provides a secondary battery comprising.
- the negative active material of the present invention includes artificial graphite particles in the form of secondary particles, and the coefficient of thermal expansion measured by the above method satisfies a specific range.
- the negative active material satisfying the thermal expansion coefficient range has excellent adhesion in the negative electrode, and at the same time, capacity and initial efficiency can be improved.
- the average particle diameter (D 50 ) may be defined as a particle diameter corresponding to 50% of the cumulative volume in the particle size distribution curve of the particles.
- the average particle diameter (D 50 ) may be measured using, for example, a laser diffraction method.
- the laser diffraction method can measure a particle diameter of several mm from a submicron region, and can obtain high reproducibility and high resolution results.
- the present invention relates to an anode active material, and more particularly, to an anode active material for a lithium secondary battery.
- the negative active material according to the present invention includes artificial graphite in the form of secondary particles to which a plurality of primary artificial graphite particles are bonded, and the coefficient of thermal expansion measured by a method comprising the following steps is 108 ⁇ 10 -6 / K to 150 x 10 -6 /K.
- A is the thermal expansion coefficient of the negative active material
- B is the thermal expansion coefficient of the pitch binder pellet
- C is the thermal expansion coefficient of the mixture pellet
- artificial graphite has less swelling than natural graphite and has excellent storage characteristics, but is known to have inferior output characteristics.
- a method of preparing artificial graphite in the form of secondary particles by aggregating or combining a plurality of primary particles and preparing voids between primary particles is being studied, but these secondary particles
- the artificial graphite assembled in the form has a problem that the electrode adhesion is greatly reduced due to its irregular and complicated shape, and accordingly, the processability is deteriorated, and the active material desorption phenomenon occurs when the negative electrode is driven, thereby reducing the long-term lifespan characteristics.
- the negative active material of the present invention is characterized in that the coefficient of thermal expansion measured by the above method is adjusted to a specific range.
- the negative active material satisfying the thermal expansion coefficient of the above range is evaluated as having a random structure of primary particles in the active material, and secondary particles formed by combining these random primary particles have a smooth surface as a whole, and irregular shape.
- electrode adhesion may be improved, and thus may have high processability and lifespan characteristics.
- the negative active material satisfying the coefficient of thermal expansion in the above range may have improved electrode adhesion and, at the same time, excellent capacity and initial efficiency.
- the negative active material includes artificial graphite particles.
- the artificial graphite particles may be artificial graphite particles in the form of secondary particles in which a plurality of primary artificial graphite particles are combined. Specifically, the artificial graphite particles may be a combination of a plurality of primary artificial graphite particles.
- the artificial graphite particles are artificial graphite particles in the form of secondary particles, since voids are formed between the primary artificial graphite particles, the output characteristics of the artificial graphite particles can be further improved by securing these voids.
- the secondary particles may be a combination of a plurality of primary artificial graphite particles, and specifically, in the artificial graphite particles in the secondary particle form, the primary artificial graphite particles are It may not be bonded to each other by van der Waals force, but a plurality of primary artificial graphite particles may be combined or aggregated by a resin binder such as pitch to form secondary particles.
- the primary artificial graphite particles may be formed after pulverizing a carbon precursor.
- the carbon precursor may be at least one selected from the group consisting of coal-based heavy oil, fiber-based heavy oil, tars, pitches, and cokes.
- the primary artificial graphite particles formed of the powdered carbon precursor may have improved cohesiveness, so that the primary artificial graphite particles having high hardness may be formed.
- the artificial graphite particles in the form of secondary particles are formed by adding a carbon precursor in powder form to a reactor and operating the reactor to combine the powders by centrifugal force to form secondary particles to which primary particles are bonded, 2,500° C. to 3,500 It can be formed by performing graphitization at a temperature of °C, preferably at a temperature of 2,700 °C to 3,200 °C. In the graphitization process, graphitization of the primary particles and the secondary particles may be performed simultaneously. In the process of combining the powders, a resin binder such as pitch may be added to the reactor together, and heat treatment may be performed at a temperature of about 400°C to 800°C.
- the primary artificial graphite particles may have an average particle diameter (D 50 ) of 5 ⁇ m to 15 ⁇ m, preferably 8 ⁇ m to 12 ⁇ m, and more preferably 8.5 ⁇ m to 9.5 ⁇ m.
- D 50 average particle diameter
- the negative active material may include sulfur (S) distributed in the primary artificial graphite particles.
- the sulfur is treated as an impurity, and can be removed in graphitization and de-iron processes when manufacturing artificial graphite. For example, heat treatment at a high temperature of 1,000 ° C. to 1,500 ° C. to remove these impurities.
- the sulfur when included in the raw material in an appropriate content, it may play a role of randomizing the crystal structure of the primary artificial graphite particles prepared by performing a process such as grinding on the raw material, and accordingly, the crushed primary artificial graphite particles The randomness of the graphite particle shape may be improved.
- the sulfur may be included in the negative active material preferably in an amount of 15 ppm to 40 ppm, preferably 18 ppm to 35 ppm, and even more preferably 23 ppm to 25 ppm, and when in the above range, it is easy to implement the coefficient of thermal expansion of the negative active material of the present invention, While electrode adhesion and lifespan characteristics are improved, an increase in electrolyte side reaction due to excessive sulfur content, a decrease in initial efficiency, and a decrease in capacity are prevented, which is preferable.
- the content of the sulfur according to the present invention is to control the heat treatment conditions of graphitization and de-iron process when manufacturing artificial graphite particles, or do not perform a calcination process generally performed when manufacturing artificial graphite, or adjust calcination conditions Or, it may be implemented by a method such as appropriately selecting an artificial graphite raw material.
- the content of sulfur according to the present invention in the manufacturing process of artificial graphite particles, do not perform the calcination process performed before pulverization of the artificial graphite raw material (coke, etc.), or perform the calcination process at 500 ° C. or less, preferably It can be implemented by carrying out at a low temperature of 300 °C or less.
- the content of sulfur may be measured by an inductively coupled plasma (ICP) analysis method.
- ICP inductively coupled plasma
- the negative active material may further include a carbon coating layer positioned on the artificial graphite particles.
- the carbon coating layer may contribute to improving the structural stability of the artificial graphite particles and preventing a side reaction between the negative electrode active material and the electrolyte.
- the carbon coating layer may be included in the negative active material in an amount of 0.1 wt% to 5 wt%, preferably 1 wt% to 4 wt%.
- the presence of the carbon coating layer can improve the structural stability of the anode active material, but excessive formation of the carbon coating layer causes a decrease in initial efficiency due to an increase in specific surface area during rolling of the anode and there is a risk of lowering high temperature storage performance, so the above-mentioned range It is preferable to form a carbon coating layer with a content of.
- the carbon coating layer may include amorphous carbon.
- the carbon coating layer may be formed by heat-treating the artificial graphite particles with one or more carbon coating layer precursors selected from the group consisting of coal-based heavy oil, fiber-based heavy oil, tars, pitches, and cokes. .
- the heat treatment process for forming the carbon coating layer may be performed at 1,000° C. to 1,500° C. in terms of promoting the uniform formation of the carbon coating layer.
- the average particle diameter (D 50 ) of the negative active material may be 10 ⁇ m to 30 ⁇ m, preferably 14 ⁇ m to 25 ⁇ m, more preferably 15 ⁇ m to 20 ⁇ m, and even more preferably 16 ⁇ m to 17 ⁇ m.
- the negative active material includes artificial graphite particles in the form of secondary particles and has an average particle diameter within the above range, it can be evaluated that the secondary particles are assembled smoothly, and further electrode adhesion can be improved, and the negative electrode Fairness of manufacturing can be improved.
- the BET specific surface area of the negative active material may be 0.3 m 2 /g to 2.5 m 2 /g, preferably 0.5 m 2 /g to 1 m 2 /g, and when in the above range, prevent side reactions with the electrolyte to prevent the initial It is preferable in terms of being able to further improve the efficiency.
- the spacing d002 of the crystal planes measured by X-ray diffraction analysis (XRD) of the artificial graphite particles in the secondary particle form may be 0.3357 nm to 0.3361 nm, preferably 0.33575 nm to 0.33585 nm, and in the above range, It is preferable because it is easy to implement a coefficient of thermal expansion within a range, so that electrode adhesion is improved, and the graphite layer and its laminated structure are well crystallized to secure the capacity of the anode active material, and to improve initial efficiency and energy density.
- the crystallite size Lc in the c-axis direction of the artificial graphite particles in the form of secondary particles may be 45 nm to 75 nm, preferably 60 nm to 70 nm.
- the thermal expansion coefficient of the above range is easy to implement, so that the electrode adhesion is improved, and the graphite layer and its laminate structure are well crystallized, so that it is possible to secure the capacity of the negative active material, and to improve the initial efficiency and energy density.
- the negative active material may have a tap density of 0.88 g/cc to 1.20 g/cc, preferably 0.92 g/cc to 1.15 g/cc, more preferably 1.04 g/cc to 1.10 g/cc, and the coefficient of thermal expansion When the tap density range is satisfied together with the range, it is possible to implement a negative active material having a smooth and uniform surface, and thus it is preferable to realize high electrode adhesion.
- the coefficient of thermal expansion of the negative active material measured by a method including the following steps (steps (a) to (d)) is 108 ⁇ 10 -6 /K to 150 ⁇ 10 -6 /K.
- thermomechanical analysis of the mixture pellets to obtain a coefficient of thermal expansion of the mixture pellets
- A is the thermal expansion coefficient of the negative active material
- B is the thermal expansion coefficient of the pitch binder pellets
- C is the thermal expansion coefficient of the mixture pellets
- the negative active material of the present invention has no volatile matter in the artificial graphite particles contained therein, and it is difficult to prepare in the form of pellets because there is no viscosity, so the negative active material and the pitch binder having viscosity It is a step to prepare a mixture pellet by mixing. As will be described later, after measuring the thermal expansion coefficient of the mixture pellet, the thermal expansion coefficient of the negative active material may be evaluated according to Equation 1.
- the mixture pellets may be prepared to have a density of 1.5 g/cc to 2.0 g/cc, specifically 1.8 g/cc, to ensure objectivity of evaluation.
- the diameter of the mixture pellets may be 10mm to 15mm, specifically 13mm.
- step (b) of the method for measuring the coefficient of thermal expansion it is a step of measuring the coefficient of thermal expansion of the mixture pellet through thermomechanical analysis.
- the thermomechanical analysis and measurement of the coefficient of thermal expansion may use a TMA instrument (Thermomechanical analyzer), specifically setting the temperature increase rate to 10 ° C / min, and measuring the coefficient of thermal expansion in a temperature range of 30 ° C to 100 ° C. can
- step (c) of the method for measuring the coefficient of thermal expansion it is a step of manufacturing the pitch binder pellets and measuring the coefficient of thermal expansion of the pitch binder itself.
- the pitch binder may be manufactured to have the same shape, density, and diameter as the mixture pellets.
- the pitch binder pellets may be prepared to have a density of 1.5 g/cc to 2.0 g/cc, specifically 1.8 g/cc, to ensure objectivity of evaluation, specifically the same as the mixture pellets prepared in step (a) It can be manufactured to have a density, shape, and diameter.
- the pitch binder pellets may be manufactured to have a diameter of 10 mm to 15 mm, specifically 13 mm.
- step (d) of the method for measuring the coefficient of thermal expansion it is a step of obtaining the coefficient of thermal expansion of the negative active material itself in consideration of the mixing weight ratio (90:10) of the negative active material and the pitch binder in step (a).
- the negative active material and the pitch binder will have their respective coefficients of thermal expansion, and will contribute to the coefficient of thermal expansion of the mixture pellet according to their weight ratio.
- the relationship between the thermal expansion coefficient (B) of the pellet and the thermal expansion coefficient (A) of the negative active material may be expressed by Equation 2 below.
- Equation 1 If Equation 2 is converted into an expression related to the coefficient of thermal expansion (A) of the negative active material, Equation 1 can be obtained, through which the coefficient of thermal expansion of the negative active material itself can be predicted and evaluated.
- the negative active material has a coefficient of thermal expansion within the above range, high electrode adhesion, processability and lifespan characteristics may be improved through this, and a negative active material having high capacity and initial efficiency may be realized.
- the coefficient of thermal expansion of the negative active material is less than 108 ⁇ 10 -6 /K, it is difficult to see that the primary artificial graphite particles have a random structure, and the secondary particle type artificial graphite particles that are an assembly of the primary artificial graphite particles Since the surface is not smooth, it is difficult to improve electrode adhesion, and there is a possibility that the long-term cycle life characteristics may be deteriorated because the processability is deteriorated and there is a high possibility that the anode active material is detached during the operation of the anode.
- the coefficient of thermal expansion of the anode active material exceeds 150 ⁇ 10 -6 /K, the primary artificial graphite particles have an excessively random structure, so that the graphitization degree is low, the capacity is excessively reduced, and the initial efficiency is lowered It is not recommended because there is a risk of becoming
- the coefficient of thermal expansion of the negative active material may be preferably 110 ⁇ 10 -6 /K to 140 ⁇ 10 -6 /K, more preferably 112 ⁇ 10 -6 /K to 120 ⁇ 10 -6 /K, and in the above range When there is, it is good that the effect of simultaneously improving electrode adhesion, lifespan characteristics, capacity and initial efficiency can be preferably realized.
- the coefficient of thermal expansion of the negative active material may be implemented by appropriately adjusting the randomness of the primary artificial graphite particles and the shape of the secondary particle-type artificial graphite particles.
- the coefficient of thermal expansion of the negative electrode active material may be implemented by appropriately adjusting the content of impurities such as sulfur in the primary artificial graphite particles, the size of the primary artificial graphite particles, the size of the secondary particles, the degree of assembly, etc., but limited thereto it's not going to be
- the present invention provides a negative electrode comprising the above-described negative electrode active material, more specifically, a negative electrode for a lithium secondary battery.
- the negative electrode current collector and an anode active material layer disposed on the anode current collector.
- the negative active material layer includes the above-described negative active material.
- the negative electrode current collector may be used without limitation any negative current collector generally used in the art, for example, as long as it has high conductivity without causing a chemical change in the lithium secondary battery.
- the negative electrode current collector may include at least one selected from copper, stainless steel, aluminum, nickel, titanium, calcined carbon, and an aluminum-cadmium alloy, preferably copper.
- the negative electrode current collector may form fine irregularities on the surface to strengthen the bonding force of the negative electrode active material, and may be used in various forms such as a film, sheet, foil, net, porous body, foam, non-woven body, and the like.
- the negative electrode current collector may generally have a thickness of 3 ⁇ m to 500 ⁇ m.
- the negative electrode active material layer is laminated on the negative electrode current collector, and includes the negative electrode active material described above.
- the negative active material may be included in the anode active material layer in an amount of 80 wt% to 99 wt%, preferably 93 wt% to 98 wt%.
- the anode active material layer may further include a binder, a conductive material, and/or a thickener in addition to the anode active material described above.
- the binder is a component that assists in bonding between the active material and/or the current collector, and may be included in an amount of typically 1 wt% to 30 wt%, preferably 1 wt% to 10 wt% in the anode active material layer.
- the binder is polyvinylidene fluoride (PVDF), polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, polytetrafluoroethylene , polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), sulfonated-EPDM, at least one selected from the group consisting of styrene-butadiene rubber and fluororubber, preferably polyvinylidene fluoride and styrene-butadiene rubber It may include at least one selected from among.
- PVDF polyvinylidene fluoride
- CMC carboxymethyl cellulose
- EPDM ethylene-propylene-diene polymer
- sulfonated-EPDM at least one selected from the group consisting of styrene-butadiene rubber and fluororubber, preferably polyvinylidene fluoride
- any thickener used in conventional lithium secondary batteries may be used, and an example thereof includes carboxymethyl cellulose (CMC).
- CMC carboxymethyl cellulose
- the conductive material is a component for further improving the conductivity of the anode active material, and may be included in the anode active material layer in an amount of 1 wt% to 30 wt%, preferably 1 wt% to 10 wt%.
- the conductive material is not particularly limited as long as it has conductivity without causing a chemical change in the battery.
- graphite such as natural graphite or artificial graphite
- carbon black such as acetylene black, Ketjen black, channel black, furnace black, lamp black, and thermal black
- conductive fibers such as carbon fibers and metal fibers
- metal powders such as carbon fluoride, aluminum, and nickel powder
- conductive whiskeys such as zinc oxide and potassium titanate
- conductive metal oxides such as titanium oxide
- Conductive materials such as polyphenylene derivatives may be used.
- acetylene black-based products such as Chevron Chemical Company, Denka Singapore Private Limited, Gulf Oil Company, etc.
- Ketjenblack EC series (products of the Armak Company)
- Vulcan XC-72 products of the Cabot Company
- Super P products of the Timcal Company
- the anode active material layer may be prepared by mixing the above-described anode active material with at least one selected from a binder, a conductive material and a thickener in a solvent to prepare an anode slurry, and coating, rolling, and drying the anode slurry on the anode current collector there is.
- the solvent may include water or an organic solvent such as N-methyl-2-pyrrolidone (NMP), and may be used in an amount having a desirable viscosity when the negative electrode active material and, optionally, a binder and a conductive material are included.
- NMP N-methyl-2-pyrrolidone
- the negative active material, and optionally the concentration of the solids including at least one selected from a binder, a thickener, and a conductive material may be included to be 50 wt% to 95 wt%, preferably 70 wt% to 90 wt% .
- the area ratio I(004)/I(110) (orientation index) may be 7 to 14, more preferably 7.5 to 9.5.
- the particles may be arranged to minimize the diffusion path of lithium ions, so that the lithium ion diffusion resistance may be reduced.
- the achievement of the orientation index may be realized by using the above-described negative active material for the negative electrode.
- the present invention provides a secondary battery including the above-described negative electrode, more specifically, a lithium secondary battery.
- the secondary battery may include the above-described negative electrode; an anode opposite to the cathode; a separator interposed between the negative electrode and the positive electrode; and electrolytes.
- the positive electrode is a positive electrode current collector; and a positive electrode active material layer disposed on the positive electrode current collector.
- the positive electrode current collector any negative current collector generally used in the art may be used without limitation, for example, as long as it has high conductivity without causing chemical change in the secondary battery.
- the positive electrode current collector may include at least one selected from copper, stainless steel, aluminum, nickel, titanium, calcined carbon, and an aluminum-cadmium alloy, preferably aluminum.
- the positive electrode current collector may form fine irregularities on the surface to strengthen the bonding strength of the positive electrode active material, and may be used in various forms, such as a film, sheet, foil, net, porous body, foam, non-woven body, and the like.
- the positive electrode current collector may generally have a thickness of 3 ⁇ m to 500 ⁇ m.
- the positive active material layer may include a positive active material.
- the positive active material is a compound capable of reversible intercalation and deintercalation of lithium, and specifically, may include a lithium composite metal oxide including lithium and one or more metals such as cobalt, manganese, nickel or aluminum.
- the lithium composite metal oxide is a lithium-manganese-based oxide (eg, LiMnO 2 , LiMn 2 O 4 , etc.), a lithium-cobalt-based oxide (eg, LiCoO 2 etc.), lithium-nickel-based oxide (eg, LiNiO 2 , etc.), lithium-nickel-manganese oxide (eg, LiNi 1-Y Mn Y O 2 (here, 0 ⁇ Y ⁇ 1), LiMn 2-z Ni z O 4 ( Here, 0 ⁇ Z ⁇ 2, etc.), lithium-nickel-cobalt-based oxides (eg, LiNi 1-Y1 Co Y1 O 2 (here, 0 ⁇ Y1 ⁇ 1), etc.), lithium-manganese
- the lithium composite metal oxide is LiCoO 2 , LiMnO 2 , LiNiO 2 , lithium nickel manganese cobalt oxide (eg, Li(Ni 0.6 Mn 0.2 Co 0.2 )O 2 , in that it is possible to increase the capacity characteristics and stability of the battery.
- the lithium composite metal oxide is Li(Ni 0.6 Mn 0.2 Co 0.2 )O 2 , Li (Ni 0.5 Mn 0.3 Co 0.2 )O 2 , Li(Ni 0.7 Mn 0.15 Co 0.15 )O 2 , or Li(Ni 0.8 Mn 0.1 Co 0.1 )O 2 , and the like, and any one or a mixture of two or more thereof may be used .
- the positive active material may be included in the positive active material layer in an amount of 80 wt% to 99 wt%.
- the positive active material layer may further include at least one selected from the group consisting of a binder and a conductive material together with the positive active material.
- the binder is a component that assists in bonding between the active material and the conductive material and bonding to the current collector, and is typically added in an amount of 1 to 30% by weight based on the total weight of the positive electrode mixture.
- binders include polyvinylidene fluoride, polyvinyl alcohol, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, polytetrafluoroethylene , polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene-butadiene rubber, and may include at least one selected from the group consisting of fluororubber.
- the binder may be included in an amount of 1 wt% to 30 wt% in the cathode active material layer.
- the conductive material is not particularly limited as long as it has conductivity without causing a chemical change in the battery.
- graphite carbon-based materials such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, and thermal black
- conductive fibers such as carbon fibers and metal fibers
- metal powders such as carbon fluoride, aluminum, and nickel powder
- conductive whiskeys such as zinc oxide and potassium titanate
- conductive metal oxides such as titanium oxide
- Conductive materials such as polyphenylene derivatives may be used.
- acetylene black-based products such as Chevron Chemical Company, Denka Singapore Private Limited, Gulf Oil Company, etc.
- Ketjenblack EC series (products of the Armak Company)
- Vulcan XC-72 products of the Cabot Company
- Super P products of the Timcal Company
- the conductive material may be added in an amount of 1 wt% to 30 wt% in the cathode active material layer.
- the separator separates the anode and the anode and provides a passage for lithium ions to move, and can be used without any particular limitation as long as it is normally used as a separator in a lithium secondary battery. Excellent is preferred.
- a porous polymer film for example, a porous polymer film made of a polyolefin-based polymer such as ethylene homopolymer, propylene homopolymer, ethylene/butene copolymer, ethylene/hexene copolymer, and ethylene/methacrylate copolymer, or these A laminated structure of two or more layers of may be used.
- a conventional porous nonwoven fabric for example, a nonwoven fabric made of high melting point glass fiber, polyethylene terephthalate fiber, etc. may be used.
- a coated separator including a ceramic component or a polymer material may be used, and may optionally be used in a single-layer or multi-layer structure.
- examples of the electrolyte used in the present invention include organic liquid electrolytes, inorganic liquid electrolytes, solid polymer electrolytes, gel polymer electrolytes, solid inorganic electrolytes, molten inorganic electrolytes, and the like, which can be used in the manufacture of lithium secondary batteries, and are limited to these. it is not going to be
- the electrolyte may include an organic solvent and a lithium salt.
- the organic solvent may be used without any particular limitation as long as it can serve as a medium through which ions involved in the electrochemical reaction of the battery can move.
- ester solvents such as methyl acetate, ethyl acetate, gamma-butyrolactone, ⁇ -caprolactone
- ether solvents such as dibutyl ether or hydrofuran
- ketone solvents such as cyclohexanone
- aromatic hydrocarbon solvents such as benzene and fluorobenzene
- carbonate solvents such as dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC), ethylene carbonate (EC), and propylene carbonate (PC)
- alcohol solvents such as ethyl alcohol and isopropyl alcohol
- nitriles such as R-CN (R is a C2 to C20 linear, branched or cyclic hydrocarbon group, which may include a double bond aromatic ring or an ether
- a carbonate-based solvent is preferable, and a cyclic carbonate (eg, ethylene carbonate or propylene carbonate, etc.) having high ionic conductivity and high dielectric constant capable of increasing the charge/discharge performance of the battery, and a low-viscosity linear carbonate-based compound (for example, a mixture of ethyl methyl carbonate, dimethyl carbonate or diethyl carbonate) is more preferable.
- a cyclic carbonate and the chain carbonate are mixed in a volume ratio of about 1:1 to about 1:9, the performance of the electrolyte may be excellent.
- the lithium salt may be used without particular limitation as long as it is a compound capable of providing lithium ions used in a lithium secondary battery.
- the lithium salt is LiPF 6 , LiClO 4 , LiAsF 6 , LiBF 4 , LiSbF 6 , LiAlO 4 , LiAlCl 4 , LiCF 3 SO 3 , LiC 4 F 9 SO 3 , LiN(C 2 F 5 SO 3 ) 2 , LiN(C 2 F 5 SO 2 ) 2 , LiN(CF 3 SO 2 ) 2 , LiCl, LiI, or LiB(C 2 O 4 ) 2 , etc. may be used.
- the concentration of the lithium salt is preferably used within the range of 0.1 to 2.0M. When the concentration of the lithium salt is included in the above range, since the electrolyte has appropriate conductivity and viscosity, excellent electrolyte performance may be exhibited, and lithium ions may move effectively.
- the lithium secondary battery according to the present invention stably exhibits excellent discharge capacity, rapid charging characteristics and capacity retention rate, portable devices such as mobile phones, notebook computers, digital cameras, and hybrid electric vehicles, HEV), etc., are useful in the field of electric vehicles and the like, and in particular, can be preferably used as a component battery of a medium or large-sized battery module. Accordingly, the present invention also provides a medium and large-sized battery module including the secondary battery as described above as a unit battery.
- These medium and large-sized battery modules can be preferably applied to power sources that require high output and large capacity, such as electric vehicles, hybrid electric vehicles, and power storage devices.
- Petroleum coke having a sulfur content of 2,916 ppm was pulverized using an impact mill to obtain a powder having an average particle diameter (D 50 ) of 10 ⁇ m. A separate calcination process was not performed for pulverizing the coke.
- the powder was heat-treated at 550° C. in an inert gas (N 2 ) atmosphere using a vertical granulator to prepare secondary particles in which a plurality of primary particles were combined.
- the secondary particles were graphitized by heat treatment at 3,000° C. for 20 hours or more in an inert gas atmosphere to prepare artificial graphite particles in the form of secondary particles.
- An amorphous carbon coating layer was formed on the secondary particles by mixing artificial graphite particles in the form of secondary particles and petroleum pitch, and heat-treating them at 1,300° C. in a roller hearth kiln.
- the sulfur content of the prepared negative active material was 29.4 ppm, the average particle diameter (D 50 ) of the primary artificial graphite particles was 11 ⁇ m, and the average particle diameter (D 50 ) of the negative active material was 19.4 ⁇ m, measured by XRD d002 is 0.3360 nm, the crystallite size Lc in the c-axis direction is 63.9 nm, the BET specific surface area is 0.7 m 2 /g, the tap density is 0.95 g/cc, and the content of the amorphous carbon coating layer in the anode active material is 3 wt% it was
- the tap density was obtained by measuring the apparent density by measuring the final volume obtained by vibrating up and down 1,000 times after charging 40 g of the negative active material in a container.
- the BET specific surface area of the negative active material was measured by pretreating the negative active material at 130° C., and using nitrogen gas and BET (Brunauer-Emmett-Teller) measurement method using BELSORP (BET equipment) manufactured by BEL JAPAN.
- the anode active material and the pitch binder prepared above were mixed in a weight ratio of 90:10, and a mixture pellet having a density of 1.8 g/cc and a diameter of 13 mm was prepared.
- the density was 1.8 g / cc, the diameter was 13mm, to prepare a pitch binder pellets of the same shape as the mixture pellets.
- 1 g of the pitch binder pellets were put into a TMA device, and the coefficient of thermal expansion (56 ⁇ 10 -6 /K) of the pitch binder pellets was measured under the same conditions as the measurement conditions for the coefficient of thermal expansion of the mixture pellets.
- Equation 1 the coefficient of thermal expansion (136 ⁇ 10 -6 /K) of the negative active material was calculated by Equation 1 below.
- Petroleum-based coke having a sulfur content of 2,531 ppm was pulverized using an impact mill to obtain powder having an average particle diameter (D 50 ) of 10 ⁇ m, except that the powder was secondarily granulated using a horizontal granulator
- An anode active material was prepared in the same manner as in Example 1.
- the sulfur content of the prepared negative active material was 22.4 ppm, the average particle diameter (D 50 ) of the primary artificial graphite particles was 10 ⁇ m, and the average particle diameter (D 50 ) of the negative electrode active material was 18.1 ⁇ m, measured by XRD d002 is 0.3359 nm, the crystallite size Lc in the c-axis direction is 66.7 nm, the BET specific surface area is 0.7 m 2 /g, the tap density is 1.03 g/cc, and the content of the amorphous carbon coating layer in the anode active material is 3 wt% it was
- the coefficient of thermal expansion of the negative active material was measured in the same manner as in Example 1, except that the negative active material prepared above was used.
- Petroleum-based coke having a sulfur content of 2,008 ppm was pulverized using an impact mill to obtain powder having an average particle diameter (D 50 ) of 10 ⁇ m, the powder was secondarily granulated using a horizontal granulator, anode active material
- An anode active material was prepared in the same manner as in Example 1, except that the mixing weight ratio of the secondary particle type artificial graphite particles and the petroleum pitch was adjusted so that the content of the amorphous carbon coating layer in the inside was 2% by weight.
- the sulfur content of the prepared negative active material was 23.6 ppm, the average particle diameter (D 50 ) of the primary artificial graphite particles was 9 ⁇ m, and the average particle diameter (D 50 ) of the negative active material was 16.5 ⁇ m, measured by XRD d002 is 0.3358 nm, the crystallite size Lc in the c-axis direction is 73.1 nm, the BET specific surface area is 0.6 m 2 /g, the tap density is 1.05 g/cc, and the content of the amorphous carbon coating layer in the anode active material is 2 wt% it was
- the coefficient of thermal expansion of the negative active material was measured in the same manner as in Example 1, except that the negative active material prepared above was used.
- a negative active material was prepared in the same manner as in Example 1, except that a horizontal granulator was used instead of a vertical granulator when the secondary particles to which a plurality of primary particles were combined were prepared using the powder.
- the sulfur content of the prepared negative active material was 26.7 ppm, the average particle diameter (D 50 ) of the primary artificial graphite particles was 11 ⁇ m, and the average particle diameter (D 50 ) of the negative electrode active material was 22.4 ⁇ m, measured by XRD d002 is 0.3360 nm, the crystallite size Lc in the c-axis direction is 64.1 nm, the BET specific surface area is 0.7 m 2 /g, the tap density is 0.89 g/cc, and the content of the amorphous carbon coating layer in the anode active material is 3 wt% it was
- the coefficient of thermal expansion of the negative active material was measured in the same manner as in Example 1, except that the negative active material prepared above was used.
- Petroleum-based needle coke having a sulfur content of 1,671 ppm was heat-treated at a temperature increase rate of 25° C./min to 1,000° C., and then pulverized using an impact mill to obtain a powder having an average particle diameter (D 50 ) of 10 ⁇ m.
- the powder and petroleum pitch are mixed in a weight ratio of 87:13, and heat treatment is performed at 550° C. for 10 hours in an inert gas (N 2 ) atmosphere using a vertical granulator to prepare secondary particles in which a plurality of primary particles are aggregated (average particle size (D 50 ): 22.8 ⁇ m).
- the secondary particles were graphitized by heat treatment at 3,000° C. for 20 hours or more in an inert gas atmosphere to prepare artificial graphite particles in the form of secondary particles.
- the artificial graphite particles in the form of secondary particles and petroleum pitch were mixed, and heat-treated at 1,300° C. in a roller hearth kiln to form an amorphous carbon coating layer on the secondary particles.
- the sulfur content of the prepared negative active material was less than 10 ppm, the average particle diameter (D 50 ) of the primary artificial graphite particles was 10 ⁇ m, and the average particle diameter (D 50 ) of the negative electrode active material was 21.8 ⁇ m, measured by XRD d002 is 0.3361 nm, the crystallite size Lc in the c-axis direction is 67.7 nm, the BET specific surface area is 0.7 m 2 /g, the tap density is 0.86 g/cc, and the content of the amorphous carbon coating layer in the anode active material is 3 wt% it was
- the coefficient of thermal expansion of the negative active material was measured in the same manner as in Example 1, except that the negative active material prepared above was used.
- Petroleum-based needle coke having a sulfur content of 1,513 ppm was pulverized using an impact mill to obtain powder having an average particle diameter (D 50 ) of 9 ⁇ m, a separate calcination process was not performed for pulverizing the coke, An anode active material was prepared in the same manner as in Comparative Example 1, except that the powder and petroleum pitch were mixed in a weight ratio of 90:10, and secondary particles were granulated using a vertical granulator.
- the sulfur content of the prepared negative active material was 12.2 ppm, the average particle diameter (D 50 ) of the primary artificial graphite particles was 9 ⁇ m, and the average particle diameter (D 50 ) of the negative active material was 13.4 ⁇ m, measured by XRD d002 is 0.3359 nm, the crystallite size Lc in the c-axis direction is 69.4 nm, the BET specific surface area is 0.9 m 2 /g, the tap density is 1.00 g/cc, and the content of the amorphous carbon coating layer in the negative electrode active material is 3 wt% it was
- the coefficient of thermal expansion of the negative active material was measured in the same manner as in Example 1, except that the negative active material prepared above was used.
- An anode active material was prepared in the same manner as in Comparative Example 2, except that petroleum-based needle coke having a sulfur content of 1,236 ppm was used.
- the sulfur content of the prepared negative active material was 10.8 ppm, the average particle diameter (D 50 ) of the primary artificial graphite particles was 10 ⁇ m, and the average particle diameter (D 50 ) of the negative electrode active material was 15.6 ⁇ m, measured by XRD d002 is 0.3357 nm, the crystallite size Lc in the c-axis direction is 75.7 nm, the BET specific surface area is 0.8 m 2 /g, the tap density is 1.05 g/cc, and the content of the amorphous carbon coating layer in the anode active material is 3 wt% it was
- the coefficient of thermal expansion of the negative active material was measured in the same manner as in Example 1, except that the negative active material prepared above was used.
- Petroleum coke having a sulfur content of 4,000 ppm or more was pulverized using an impact mill to obtain powder with an average particle diameter (D 50 ) of 10 ⁇ m, except that an amorphous carbon coating layer was not formed on artificial graphite in the form of secondary particles prepared an anode active material in the same manner as in Example 1.
- the sulfur content of the prepared negative active material was 64.0 ppm, the average particle diameter (D 50 ) of the primary artificial graphite particles was 10 ⁇ m, and the average particle diameter (D 50 ) of the negative electrode active material was 15.2 ⁇ m, measured by XRD d002 was 0.3371 nm, the crystallite size Lc in the c-axis direction was 29 nm, the BET specific surface area was 0.9 m 2 /g, and the tap density was 0.86 g/cc.
- the coefficient of thermal expansion of the negative active material was measured in the same manner as in Example 1, except that the negative active material prepared above was used.
- the negative electrode active material prepared in Example 1 carbon black as a conductive material, styrene-butadiene rubber as a binder, and carboxymethyl cellulose as a thickener were mixed in a weight ratio of 95.3: 1.0: 1.2: 2.5, and water was added to prepare a negative electrode slurry did
- the negative electrode slurry was applied to a copper negative electrode current collector (thickness: 15 ⁇ m), vacuum dried and rolled at about 130° C. for 8 hours to form a negative electrode active material layer (thickness: 84 ⁇ m) to prepare the negative electrode of Example 1 .
- the loading of the negative electrode was prepared to be 3.6mAh/cm 2 .
- Anodes of Examples 2 to 4 and Comparative Examples 1 to 4 were prepared in the same manner as in Example 1, except that the negative active materials prepared in Examples 2 to 4 and Comparative Examples 1 to 4 were used, respectively.
- the orientation index of the negative electrode of Examples and Comparative Examples was obtained as an area ratio I(004)/I(110) obtained by measuring the (004) plane and the (110) plane by XRD, and integrating each measured XRD peak.
- the negative electrode of Example 1 was punched out to a size of 20 mm ⁇ 150 mm, fixed using double-sided tape to the center of a 25 mm ⁇ 75 mm slide glass, and then the negative electrode was collected using UTM (manufacturer: LLOYD Instrument LTD., device name: LF Plus) The 90 degree peel strength was measured while peeling off the negative active material layer from the whole. Five identical negative electrodes of Example 1 were prepared, and 90 degree peel strength was measured 5 times in the same manner, and the average value thereof was taken as the adhesive force of the negative electrode of Example 1 (unit: gf/10mm).
- a lithium metal counter electrode was prepared as the positive electrode.
- Secondary batteries of Examples and Comparative Examples were prepared by interposing a polyolefin separator between each of the negative electrodes and the positive electrodes prepared in Examples 1 to 4 and Comparative Examples 1 to 4, and then injecting an electrolyte.
- the electrolyte is a non-aqueous electrolyte solvent in which ethylene carbonate (EC) and ethyl methyl carbonate (EMC) are mixed in a volume ratio of 2:8, vinylene carbonate (VC) is added in an amount of 0.5% by weight based on the solvent, and LiPF 6 is 1M The dissolved one was used.
- the charging capacity and the discharging capacity of the secondary batteries of Examples and Comparative Examples prepared above were measured, and the initial efficiency was calculated by the following formula, and the results are shown in Table 2.
- the charging and discharging conditions are as follows.
- Charging conditions CCCV mode, 0.1C charge, cut-off at 5mV and 1/200C
- the negative electrode and the secondary battery including the negative active material of Examples 1 to 4 have excellent electrode adhesion while improving both initial efficiency and discharge capacity.
- Li[Ni 0.6 Mn 0.2 Co 0.2 ]O 2 as a positive electrode active material, carbon black as a conductive material, and PVdF as a binder in a weight ratio of 94:4:2 were mixed, and N-methylpyrrolidone was added as a solvent to prepare a positive electrode slurry.
- the anode slurry was applied to aluminum foil, and vacuum dried and rolled at about 130° C. for 8 hours to prepare a cathode. At this time, the loading of the positive electrode was prepared to be 3.34mAh/cm 2 .
- Secondary batteries of Examples and Comparative Examples were prepared by interposing a polyolefin separator between each negative electrode and positive electrode prepared in Examples 1 to 4 and Comparative Examples 1 to 2, and then injecting an electrolyte.
- the electrolyte is a non-aqueous electrolyte solvent in which ethylene carbonate (EC) and ethyl methyl carbonate (EMC) are mixed in a volume ratio of 2:8, vinylene carbonate (VC) is added in an amount of 0.5% by weight based on the solvent, and LiPF 6 is 1M The dissolved one was used.
- the secondary batteries of Examples 1 to 4 and Comparative Examples 1 and 2 were charged (CC/CV mode, 1.0C charge, cut-off at 4.2V, 0.05C) and discharged (CC mode, 1.0C discharge, 3.0 Charging and discharging were performed up to the 300th cycle under the cut-off condition at V.
- 300 cycle capacity retention rate (%) ⁇ (discharge capacity at 300th cycle)/(discharge capacity at first cycle) ⁇ ⁇ 100
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Abstract
Description
Claims (14)
- 복수의 1차 인조흑연 입자가 결합된 2차 입자 형태인 인조흑연 입자를 포함하며,하기 단계를 포함하는 방법에 의해 측정된 열팽창 계수가 108 × 10-6/K 내지 150 × 10-6/K인 음극 활물질:(a) 상기 음극 활물질 및 피치 바인더를 90:10의 중량비로 혼합하고, 1.5g/cc 내지 2.0g/cc의 밀도를 갖는 혼합물 펠렛을 제조하는 단계;(b) 상기 혼합물 펠렛을 열기계 분석하여 상기 혼합물 펠렛의 열팽창 계수를 얻는 단계;(c) 상기 피치 바인더를 1.5g/cc 내지 2.0g/cc의 밀도를 갖는 피치 바인더 펠렛으로 제조하고, 열기계 분석하여 상기 피치 바인더 펠렛의 열팽창 계수를 얻는 단계; 및(d) 하기 수학식 1을 통해 상기 음극 활물질의 열팽창 계수를 얻는 단계:[수학식 1]A = {C - (B × 0.1)}/0.9상기 수학식 1에서 A는 음극 활물질의 열팽창 계수이고, B는 피치 바인더 펠렛의 열팽창 계수이고, C는 혼합물 펠렛의 열팽창 계수이다.
- 청구항 1에 있어서, 상기 1차 인조흑연 입자의 평균 입경(D50)은 5㎛ 내지 15㎛인 음극 활물질.
- 청구항 1에 있어서, 상기 2차 입자 형태의 인조흑연 입자의 XRD에 의한 (002) 면의 면각격 d002가 0.3357nm 내지 0.3361nm인 음극 활물질.
- 청구항 1에 있어서, 상기 음극 활물질의 BET 비표면적은 0.3m2/g 내지 2.5m2/g인 음극 활물질.
- 청구항 1에 있어서, 상기 인조흑연 입자의 c축 방향의 결정자 크기 Lc는 45nm 내지 75nm인 음극 활물질.
- 청구항 1에 있어서, 상기 음극 활물질은 상기 1차 인조흑연 입자에 분포된 황을 15ppm 내지 40ppm으로 포함하는 음극 활물질
- 청구항 1에 있어서, 상기 음극 활물질의 탭 밀도는 0.88g/cc 내지 1.20g/cc인 음극 활물질.
- 청구항 1에 있어서, 상기 음극 활물질의 평균 입경(D50)은 10㎛ 내지 30㎛인 음극 활물질.
- 청구항 1에 있어서, 상기 인조흑연 입자 상에 위치하는 탄소 코팅층을 더 포함하는 음극 활물질.
- 청구항 9에 있어서, 상기 탄소 코팅층은 상기 음극 활물질 내에 0.1중량% 내지 5중량%로 포함되는 음극 활물질.
- 청구항 9에 있어서, 상기 탄소 코팅층은 비정질 탄소를 포함하는 음극 활물질.
- 음극 집전체; 및상기 음극 집전체 상에 배치된 음극 활물질층;을 포함하고,상기 음극 활물질층은 청구항 1에 따른 음극 활물질을 포함하는 음극.
- 청구항 12에 있어서, 상기 음극의 X선 회절 분석 시 면적비 I(004)/I(110)는 7 내지 14인 음극.
- 청구항 12에 따른 음극;상기 음극에 대향하는 양극;상기 음극 및 상기 양극 사이에 개재되는 분리막; 및전해질;을 포함하는 이차전지.
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US18/020,894 US20230307640A1 (en) | 2020-09-18 | 2021-09-15 | Negative electrode active material, and negative electrode and secondary battery which include the same |
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JP2023538318A (ja) | 2023-09-07 |
CN116114088A (zh) | 2023-05-12 |
EP4181237A1 (en) | 2023-05-17 |
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