WO2012036372A2 - 음극 활물질, 그를 갖는 비수계 리튬이차전지 및 그의 제조 방법 - Google Patents
음극 활물질, 그를 갖는 비수계 리튬이차전지 및 그의 제조 방법 Download PDFInfo
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- WO2012036372A2 WO2012036372A2 PCT/KR2011/004389 KR2011004389W WO2012036372A2 WO 2012036372 A2 WO2012036372 A2 WO 2012036372A2 KR 2011004389 W KR2011004389 W KR 2011004389W WO 2012036372 A2 WO2012036372 A2 WO 2012036372A2
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- ammonia
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- secondary battery
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a non-aqueous lithium secondary battery and a method for manufacturing the same. More particularly, the surface of the carbon-based material applied as a negative electrode active material of the lithium secondary battery is subjected to a surface treatment by a pyrolysis method of an ammonia-based compound to react with the electrolyte on the surface.
- the present invention relates to a negative electrode active material surface-treated with an ammonia-based compound that suppresses side reactions and improves structural stability, thereby improving lifetime and high rate characteristics of a lithium secondary battery, and a non-aqueous lithium secondary battery having the same.
- a lithium secondary battery is a battery in which metal lithium is used as a negative electrode active material and a nonaqueous solvent is used as an electrolyte. Since lithium is a metal with a high tendency to ionize, development of a battery with high energy density is possible because of high voltage expression. Lithium secondary batteries using lithium metal as a negative electrode active material have been used for a long time as next generation batteries.
- a lithium secondary battery in which metal lithium is used as a negative electrode active material has a short cycle life because lithium is grown as a dendrite from the negative electrode and penetrates the separator as an insulator and short circuit occurs due to repeated charging and discharging. .
- the reaction at the negative electrode during the charging and discharging removes lithium ions into the intercalation layer of carbon.
- electrons are transferred to the carbonaceous material of the negative electrode so that the carbon becomes negatively charged.
- lithium ions inserted into the positive electrode are detached and inserted into the carbonaceous material of the negative electrode.
- lithium ions inserted into the carbonaceous material of the negative electrode are removed and then inserted into the positive electrode.
- Lithium secondary batteries using this carbon-based material as a negative electrode active material have been put to practical use, which is called a lithium ion secondary battery, and has been widely used for power supply of portable electronic and communication devices.
- the carbon-based material is used as the negative electrode active material, the charge and discharge potential of lithium is lower than the stable range of the existing non-aqueous electrolyte, so that the decomposition reaction of the electrolyte occurs during charge and discharge, which is the current lithium secondary battery in which the carbon-based material is applied to the negative electrode. It has been pointed out as the root cause of low initial charge / discharge efficiency, deterioration of life characteristics and degradation of high rate characteristics.
- an object of the present invention is to modify the surface of the carbon-based material without using an electrolyte additive and improve the surface reactivity and structural stability, when applied as a negative electrode active material of a non-aqueous lithium secondary battery, long life without deterioration of charge and discharge efficiency and high rate characteristics
- the present invention provides a negative electrode active material surface-treated with an ammonia-based compound capable of securing characteristics, a non-aqueous lithium secondary battery having the same, and a method of manufacturing the same.
- the present invention provides a negative electrode active material for a non-aqueous lithium secondary battery and a method of manufacturing the surface-treated with ammonia-based compound to the carbon-based material used as the negative electrode active material of the non-aqueous lithium secondary battery. do.
- the present invention provides a negative electrode active material for a non-aqueous lithium secondary battery comprising a carbon material and a coating layer formed by heat treatment with an ammonia compound on the surface of the carbon material.
- the ammonia-based compound is represented by the formula (NH 4 ) x MyNz.
- M is B, P, Al, N, S, Mo, Mn, Pt or Cr.
- N is F, O, Cl or I.
- the coating layer may be formed by heat treatment using a pyrolysis method using an ammonia-based compound of 10% by weight or less relative to the carbon-based material.
- the coating layer may be partially formed on the surface of the carbon-based material.
- the ammonia-based compound is NH 4 F, NH 4 BF 4 , NH 4 PF 6 , NH 4 AlF 6 , NH 4 NO 2 , NH 4 NO 3 , NH 4 ClO 3 , NH 4 ClO 4 , (NH 4 ) 2 SO 3 , (NH 4 ) 2 SO 4 , (NH 4 ) 2 CO 3 , (NH 4 ) 2 MoO 4 , (NH 4 ) 2 PO 4 , NH 4 PO 3 , NH 4 MnO 4 , (NH 4 ) 2 Cr 2 O 7 , NH 4 SO 4 , (NH 4 ) 2 MnSO 4 , (NH 4 ) 2 S 2 O 8 , NH 4 Cl, (NH 4 ) PtCl 6 or NH 4 I.
- the carbonaceous material is at least in artificial graphite, natural graphite, graphitized carbon fiber, graphitized mesocarbon microbead, petroleum coke, resin, carbon fiber and pyrolytic carbon It may include one.
- the present invention also provides a non-aqueous lithium interest battery comprising a negative electrode having the negative electrode active material described above.
- the present invention also provides a negative active material for a non-aqueous lithium secondary battery comprising a preparation step of preparing a carbon-based material and an ammonia-based compound, and forming a coating layer on the surface of the carbon-based material using the ammonia-based compound. It provides a manufacturing method.
- the forming step may include a dissolving step of dissolving the carbonaceous material and the ammonia compound in a solvent to form a solution, and a carbonaceous material of the solution.
- the forming step may include a dissolving step of dissolving the ammonia compound in a solvent to form a solution, and spraying the solution onto the carbonaceous material. And heat-treating the carbon-based material in which the solution is injected to form the coating layer based on the ammonia-based compound on the surface of the carbon-based material.
- the forming step may include a mixing step of mixing the carbonaceous material and the powder of the ammonia compound, and the carbonaceous material and the ammonia compound. And heat-treating the mixed powder to form the coating layer based on the ammonia-based compound on the surface of the carbonaceous material.
- ammonia constituting the ammonia-based compound is removed by heat treatment, and other inorganic substances are formed on the surface of the carbon-based material. Can be formed.
- the heat treatment step may be performed at 200 to 3000 degrees.
- the present invention by treating the carbonaceous material used as the negative electrode active material of the non-aqueous lithium secondary battery by thermally treating the ammonia-based compound in a pyrolysis manner to form a coating layer, side reaction of the surface by the coating layer formed on the surface of the carbonaceous material. This not only reduces, but also ensures structural stability.
- the negative electrode active material according to the present invention has an effect of improving the affinity with the electrolyte solution to improve the life characteristics and high rate characteristics of the non-aqueous lithium secondary battery.
- FIG. 1 is a flowchart illustrating a method of manufacturing a negative active material for a non-aqueous lithium secondary battery, which is surface treated with an ammonia compound according to an embodiment of the present invention.
- FIGS 2 and 3 are graphs showing the life characteristics of the non-aqueous lithium secondary battery according to the surface treatment temperature of the negative electrode active material according to the Examples and Comparative Examples of the present invention.
- Figure 4 is a graph showing the high rate characteristics of the non-aqueous lithium secondary battery according to the Examples and Comparative Examples of the present invention.
- the negative active material for a non-aqueous lithium secondary battery according to the present invention includes a carbon-based material and a coating layer formed by heat treatment with an ammonia-based compound on the surface of the carbon-based material.
- the carbon-based material may be at least one selected from materials consisting of amorphous carbon such as artificial graphite, natural graphite, graphitized carbon fiber, graphitized mesocarbon microbead, petroleum coke, resin plastic, carbon fiber, and pyrolytic carbon.
- amorphous carbon such as artificial graphite, natural graphite, graphitized carbon fiber, graphitized mesocarbon microbead, petroleum coke, resin plastic, carbon fiber, and pyrolytic carbon.
- the coating layer may be formed by heat-treating the surface of the carbon-based material by a pyrolysis method using an ammonia-based compound of 10% by weight or less of the carbon-based material. That is, in the process of thermally thermally treating the ammonia-based compound, ammonia constituting the ammonia-based compound is removed and other inorganic substances form a coating layer on the surface of the carbon-based material.
- the ammonia-based compound may be represented by the formula (1) below.
- M is B, P, Al, N, S, Mo, Mn, Pt or Cr.
- N is F, O, Cl or I.
- the ammonia compound may be NH 4 F, NH 4 BF 4 , NH 4 PF 6 , NH 4 AlF 6 , NH 4 NO 2 , NH 4 NO 3 , NH 4 ClO 3 , NH 4 ClO 4 , (NH 4 ) 2 SO 3 , (NH 4 ) 2 SO 4 , (NH 4 ) 2 CO 3 , (NH 4 ) 2 MoO 4 , (NH 4 ) 2 PO 4 , NH 4 PO 3 , NH 4 MnO 4 , (NH 4 ) 2 Cr 2 O 7 , NH 4 SO 4 , (NH 4 ) 2 MnSO 4 , (NH 4 ) 2 S 2 O 8 , NH 4 Cl, (NH 4 ) PtCl 6 or NH 4 I, including but not limited to no.
- the coating layer may be uniformly formed on the entire surface of the carbon-based material or may be formed only on a part of the surface of the carbon-based material according to the amount of the ammonia-based compound to be heat treated.
- the negative electrode active material according to the present invention heat-treats the surface of the carbon-based material using an ammonia-based compound to form a coating layer, thereby suppressing side reactions with the electrolyte on the surface of the carbon-based material and improving structural stability according to the present invention.
- the lifespan characteristics and high rate characteristics of the lithium secondary battery manufactured using the negative electrode active material can be improved.
- FIG. 1 is a flowchart illustrating a method of manufacturing a negative active material for a non-aqueous lithium secondary battery, which is surface treated with an ammonia compound according to the present invention.
- the method for producing a negative electrode active material according to the present invention is a step of preparing a carbon-based material and ammonia-based compound (S11), and forming a coating layer using ammonia-based compound on the surface of the carbon-based material Steps S13 to S19 are included.
- a carbonaceous material and an ammonia compound are prepared.
- the carbonaceous material an average particle size of 15 ⁇ m or less may be used.
- the ammonia-based compound a compound represented by the formula (1) is used.
- step S13 the carbonaceous material and the ammonia compound are dissolved in water to form an aqueous solution.
- an organic solvent such as alcohol may be used.
- step S15 the carbonaceous material and the ammonia compound of the aqueous solution are uniformly mixed.
- the mixing step according to step S15 may proceed for about 5 minutes.
- step S17 the aqueous solution is vacuum dried in step S17.
- vacuum drying according to step S17 may be performed for about 6 to 12 hours at 120 degrees.
- the dried product dried in step S17 is thermally treated in the step S19 to form a negative electrode active material according to the present invention, which is a carbon-based material surface-treated with an ammonia-based compound. That is, in the process of thermally thermally treating the ammonia-based compound, ammonia constituting the ammonia-based compound is removed and other inorganic substances form a coating layer on the surface of the carbon-based material.
- the heat treatment step according to the step S19 may be performed in an inert atmosphere at 200 to 3000 degrees or more for 1 hour.
- the heat treatment step may be carried out in an elevated temperature of 10 °C / min, Ar or N 2 atmosphere.
- the forming step (S13 ⁇ S19) discloses an example of forming a coating layer on the surface of the carbon-based material by forming a carbon-based material and ammonia-based compound in an aqueous solution, and then heat-treating through vacuum drying It is not limited.
- the ammonia-based compound may be dissolved in a solvent to form a solution, and then the solution may be sprayed on a carbon-based material, followed by heat treatment of the carbon-based material from which the solution is sprayed to form a coating layer on the surface of the carbon-based material.
- the mixed powder may be heat treated to form a coating layer on the surface of the carbon-based material. That is, the coating layer is formed on the surface of the carbon-based material by a dry method, and the heat treatment is disclosed in an inert atmosphere, but may be performed in a vacuum atmosphere or an oxidizing atmosphere.
- a non-aqueous lithium secondary battery was manufactured as follows. In this case, a carbon-based material surface-treated with an ammonia-based compound was used as the negative electrode active material. In the comparative example, a carbon-based material not surface-treated with an ammonia compound was used as the negative electrode active material. And since the manufacturing of the non-aqueous lithium secondary battery according to the Examples and Comparative Examples except for the negative electrode active material proceeds in the same way, will be described with reference to the manufacturing method of the non-aqueous lithium secondary battery according to the embodiment.
- a slurry was prepared using water as a solvent, with 96 wt% of the negative active material, 2 wt% of the Super-P conductive material, 2 wt% of the binder SBR, and the thickener CMC.
- the slurry was applied to a copper foil (Cu foil) having a thickness of 20 ⁇ m, dried, compacted in a press, dried for 16 hours at 120 ° C. in a vacuum, and an electrode was manufactured from a disc having a diameter of 12 mm.
- As the counter electrode a lithium metal foil punched to a diameter of 12 mm was used, and a PP film was used as the separator.
- the electrolyte solution As the electrolyte solution, a mixed solution in which EC / DME of 1M LiPF 6 was mixed at 3: 7 was used. After the electrolyte solution was impregnated into the separator, the separator was sandwiched between the working electrode and the counter electrode, and a case of Sus (SUS) product was manufactured as a test cell for electrode evaluation, that is, a non-aqueous lithium secondary battery.
- SUS Sus
- the carbon-based material may be at least one selected from materials including amorphous carbon such as artificial graphite, natural graphite, graphitized carbon fiber, graphitized mesocarbon microbead, petroleum coke, resin plastic, carbon fiber, and pyrolytic carbon.
- amorphous carbon such as artificial graphite, natural graphite, graphitized carbon fiber, graphitized mesocarbon microbead, petroleum coke, resin plastic, carbon fiber, and pyrolytic carbon.
- the ammonia compound is NH 4 F, NH 4 BF 4 , NH 4 PF 6 , NH 4 AlF 6 , NH 4 NO 2 , NH 4 NO 3 , NH 4 ClO 3 , NH 4 ClO 4 , (NH 4 ) 2 SO 3 , (NH 4 ) 2 SO 4 , (NH 4 ) 2 CO 3 , (NH 4 ) 2 MoO 4 , (NH 4 ) 2 PO 4 , NH 4 PO 3 , NH 4 MnO 4 , (NH 4 ) 2 Cr 2 O 7 , NH 4 SO 4 , (NH 4 ) 2 MnSO 4 , (NH 4 ) 2 S 2 O 8 , NH 4 Cl, (NH 4 ) PtCl 6 or NH 4 I, but is not limited thereto. .
- Carbon-based material surface-treated with an ammonia-based compound can be applied as a negative electrode active material of a non-aqueous lithium secondary battery using a carbonate electrolyte.
- the carbon-based negative active material surface-treated with the ammonia-based compound can be applied to a lithium secondary battery to which a non-aqueous electrolyte driven in a voltage range of 0 V to 5 V or less is applied.
- the production of the negative electrode plate is one or two or more kinds of powders of the negative electrode active material surface-treated with an ammonia-based compound, which are usually used as conductive agents, binders, fillers, dispersants, ion conductive agents, pressure enhancers, etc. Additional components are added to form a slurry or paste with a suitable solvent (organic solvent).
- a suitable solvent organic solvent
- the conductive agent graphite, carbon black, acetylene black, Ketjen Black, carbon fiber, metal powder, or the like may be used. PVdF, polyethylene, etc. can be used as a binder.
- the electrode support substrate also referred to as 'current collector'
- a lithium secondary battery is manufactured by using the negative electrode thus prepared.
- the form of the lithium secondary battery may be any one of a coin, a button, a sheet, a cylinder, a square, and the like.
- the negative electrode, electrolyte, separator, etc. of the lithium secondary battery shall be used for the existing lithium secondary battery.
- the positive electrode active material includes a positive electrode active material capable of reversibly intercalating and deintercalating lithium ions.
- Representative examples of the cathode active material include LiCoO 2 , LiNiO 2 , LiMnO 2 , LiMn 2 O 4 , or LiNi1-x-yCo xMy O 2 (0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, 0 ⁇ x + y ⁇ 1
- M may be a lithium-transition metal oxide, such as metals such as Al, Sr, Mg, La, etc., and may use one or two or more of the above-described positive electrode active material.
- the above-mentioned positive electrode active material is only one example, but is not limited thereto.
- the electrolyte solution may be a non-aqueous electrolyte solution in which lithium salt is dissolved in an organic solvent, an inorganic solid electrolyte, a composite material of an inorganic solid electrolyte, and the like, but is not limited thereto.
- the carbonate may be dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), methylethyl carbonate (MEC) ethylene carbonate (EC), Propylene carbonate (PC), butylene carbonate (BC) and the like can be used.
- DMC dimethyl carbonate
- DEC diethyl carbonate
- DPC dipropyl carbonate
- MPC methylpropyl carbonate
- EPC ethylpropyl carbonate
- MEC methylethyl carbonate
- EC ethylene carbonate
- PC Propylene carbonate
- BC butylene carbonate
- Esters include butyrolactone (BL), decanolide, valerolactone, mevalonolactone, caprolactone, n-methyl acetate, n-ethyl acetate, n- Propyl acetate and the like can be used.
- Dibutyl ether or the like may be used as the ether.
- the ketone polymethylvinyl ketone may be used.
- the non-aqueous electrolyte according to the present invention is not limited to the type of non-aqueous organic solvent.
- lithium salt of the non-aqueous electrolyte solution examples include LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiClO 4 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , LiAlO 4 At least one selected from the group consisting of LiAlCl 4 , LiN (CxF2x + 1SO2) (CyF2x + 1SO2), wherein x and y are natural water, and LiSO 3 CF 3 .
- a porous film made from polyolefin such as PP or PE, or a porous material such as nonwoven fabric may be used.
- Example 1 natural graphite having an average particle size of 15 ⁇ m or less, surface treated at 3 ° C. with NH 4 F at 3 ° C. in an Ar atmosphere, was used as the negative electrode active material.
- Example 2 natural graphite having an average particle size of 15 ⁇ m or less, surface treated with 3 wt% of NH 4 BF 4 at Ar atmosphere and 400 ° C., was used as the negative electrode active material.
- Example 3 natural graphite having an average particle size of 15 ⁇ m or less, surface treated at 3 ° C. with NH 4 PF 6 at 400 ° C. in an Ar atmosphere, was used as the negative electrode active material.
- Example 4 natural graphite having an average particle size of ⁇ 15 ⁇ m, surface treated with 3 wt% of NH 4 SO 4 at 400 ° C. in an Ar atmosphere, was used as the negative electrode active material.
- Example 5 natural graphite having an average particle size of 15 ⁇ m or less, surface treated at 3 ° C. with NH 4 PF 6 at 800 ° C. in an Ar atmosphere, was used as the negative electrode active material.
- Example 6 natural graphite having an average particle size of 15 ⁇ m or less, surface treated with 3 wt% of NH 4 SO 4 at 800 ° C in an Ar atmosphere, was used as the negative electrode active material.
- Table 1 summarizes the negative electrode active materials according to Comparative Examples and Examples 1 to 6.
- the non-aqueous lithium secondary battery to which the negative electrode active materials of Comparative Examples and Examples 1 to 6 were applied was subjected to 3 cycle charging and discharging at a current of 0.2 C (72 mA / g), followed by 0.5 C (180 mA / g) Charging and discharging was performed for 50 cycles with current, and the results are shown in FIGS. 2 and 3.
- Examples 1 to 6 the surface treatment of the ammonia-based compound has improved life characteristics compared to the comparative example.
- Charging was then fixed at a current of 0.5C (180 mA / g), 0.2C (72 mA / g), 0.5C (180 mA / g), 1C (360 mA / g), 2C (720 mA / g) , 3C (1080 mA / g), 5C (1800 mAh / g) to perform the discharge for 3 seconds each. Then, charging and discharging were performed for 2 cycles each at a current of 0.2C (72 mA / g), and the results are shown in FIG. 4. As can be seen in Figure 4, after the surface treatment it was confirmed that the high rate characteristics were also improved.
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Abstract
Description
탄소계 재료 | 표면처리소스 | 표면처리 양(wt%) | 표면처리 온도(℃) | |
비교예 | 천연흑연 (~15㎛) | - | 0 | - |
실시예 1 | 천연흑연 (~15㎛) | NH4F | 3 | 300 |
실시예 2 | 천연흑연 (~15㎛) | NH4BF4 | 3 | 400 |
실시예 3 | 천연흑연 (~15㎛) | NH4PF6 | 3 | 400 |
실시예 4 | 천연흑연 (~15㎛) | NH4SO4 | 3 | 400 |
실시예 5 | 천연흑연 (~15㎛) | NH4PF6 | 3 | 800 |
실시예 6 | 천연흑연 (~15㎛) | NH4SO4 | 3 | 800 |
Claims (12)
- 탄소계 재료;상기 탄소계 재료의 표면에 암모니아계 화합물로 열처리하여 형성된 코팅층;을 포함하며,상기 암모니아계 화합물은,(NH4)xMyNz의 화학식으로 표시되고,상기 화학식에서 M은 B, P, Al, N, S, Mo, Mn, Pt 또는 Cr이고,N은 F, O, Cl 또는 I 이고,1≤x≤3, 0≤y≤2, 1≤z≤8(x, y, z는 정수)인 것을 특징으로 하는 비수계 리튬이차전지용 음극 활물질.
- 제1항에 있어서, 상기 코팅층은,상기 탄소계 재료 대비 10 중량% 이하의 암모니아계 화합물을 이용한 열분해 방식으로 열처리하여 형성하는 것을 특징으로 하는 비수계 리튬이차전지용 음극 활물질.
- 제2항에 있어서,상기 코팅층은 상기 탄소계 재료의 표면에 균일하게 또는 부분적으로 형성되는 것을 특징으로 하는 비수계 리튬이차전지용 음극 활물질.
- 제1항에 있어서, 상기 암모니아계 화합물은,NH4F, NH4BF4, NH4PF6, NH4AlF6, NH4NO2, NH4NO3, NH4ClO3, NH4ClO4, (NH4)2SO3, (NH4)2SO4, (NH4)2CO3, (NH4)2MoO4, (NH4)2PO4, NH4PO3, NH4MnO4, (NH4)2Cr2O7, NH4SO4, (NH4)2MnSO4, (NH4)2S2O8, NH4Cl, (NH4)PtCl6 또는 NH4I인 것을 특징으로 하는 비수계 리튬이차전지용 음극 활물질.
- 제1항에 있어서, 상기 탄소계 재료는,인조흑연, 천연흑연, 흑연화탄소 섬유, 흑연화 메조카본마이크로비드, 석유코크스, 수지소성체, 탄소섬유 및 열분해 탄소 중에 적어도 하나를 포함하는 것을 특징으로 하는 비수계 리튬이차전지용 음극 활물질.
- 제1항 내지 제5항 중 어느 한 항에 따른 음극 활물질을 갖는 음극을 포함하는 것을 특징으로 하는 비수계 리튬이차전지.
- 탄소계 재료와 암모니아계 화합물을 준비하는 준비 단계;상기 암모니아계 화합물을 이용하여 상기 탄소계 재료의 표면에 코팅층을 형성하는 형성 단계;를 포함하며,상기 암모니아계 화합물은,(NH4)xMyNz의 화학식으로 표시되고,상기 화학식에서 M은 B, P, Al, N, S, Mo, Mn, Pt 또는 Cr이고,N은 F, O, Cl 또는 I 이고,1≤x≤3, 0≤y≤2, 1≤z≤8(x, y, z는 정수)인 것을 특징으로 하는 비수계 리튬이차전지용 음극 활물질의 제조 방법.
- 제7항에 있어서, 상기 형성 단계는,상기 탄소계 재료와 상기 암모니아계 화합물을 용매에 용해시켜 용액을 형성하는 용해 단계;상기 용액의 탄소계 재료와 상기 암모니아계 화합물을 균일하게 혼합하는 혼합 단계;상기 용액을 진공 건조시키는 건조 단계;상기 건조 단계에서 건조된 건조물을 열분해 방식으로 열처리하여 상기 암모니아계 화합물을 기반으로 한 상기 코팅층을 상기 탄소계 재료의 표면에 형성하는 열처리 단계;를 포함하는 것을 특징으로 하는 비수계 리튬이차전지용 음극 활물질의 제조 방법.
- 제7항에 있어서, 상기 형성 단계는,상기 암모니아계 화합물을 용매에 용해시켜 용액을 형성하는 용해 단계;상기 용액을 상기 탄소계 재료에 분사하는 분사 단계;상기 용액이 분사된 상기 탄소계 재료를 열처리하여 상기 탄소계 재료의 표면에 상기 암모니아계 화합물을 기반으로 한 상기 코팅층을 형성하는 열처리 단계;를 포함하는 것을 특징으로 하는 비수계 리튬이차전지용 음극 활물질의 제조 방법.
- 제7항에 있어서, 상기 형성 단계는,상기 탄소계 재료와 상기 암모니아계 화합물의 분말을 혼합하는 혼합 단계;상기 탄소계 재료와 상기 암모니아계 화합물이 혼합된 분말을 열처리하여 상기 탄소계 재료의 표면에 상기 암모니아계 화합물을 기반으로 한 코팅층을 형성하는 열처리 단계;를 포함하는 것을 특징으로 하는 비수계 리튬이차전지용 음극 활물질의 제조 방법.
- 제8항 내지 제10항 중 어느 한 항에 있어서, 상기 열처리 단계에서,상기 암모니아계 화합물을 구성하는 암모니아는 열처리에 의해 제거되고 그 외 무기물이 상기 탄소계 재료의 표면에 상기 코팅층을 형성하는 것을 특징으로 하는 비수계 리튬이차전지용 음극 활물질의 제조 방법.
- 제11항에 있어서, 상기 열처리 단계는,200 내지 3000도에서 1시간 이상 수행하는 것을 특징으로 하는 비수계 리튬이차전지용 음극 활물질의 제조 방법.
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CN201180044312.7A CN103109403B (zh) | 2010-09-16 | 2011-06-15 | 阳极活性材料、包括该阳极活性材料的非水性锂二次电池及其制备方法 |
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