WO2012036385A2 - Matériau actif d'anode, batterie secondaire au lithium non aqueuse contenant celui-ci, et procédé de préparation de celui-ci - Google Patents

Matériau actif d'anode, batterie secondaire au lithium non aqueuse contenant celui-ci, et procédé de préparation de celui-ci Download PDF

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WO2012036385A2
WO2012036385A2 PCT/KR2011/006110 KR2011006110W WO2012036385A2 WO 2012036385 A2 WO2012036385 A2 WO 2012036385A2 KR 2011006110 W KR2011006110 W KR 2011006110W WO 2012036385 A2 WO2012036385 A2 WO 2012036385A2
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lithium secondary
secondary battery
active material
carbon
aqueous lithium
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PCT/KR2011/006110
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English (en)
Korean (ko)
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WO2012036385A3 (fr
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김영준
조용남
박민식
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전자부품연구원
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Priority claimed from KR1020110077357A external-priority patent/KR101316638B1/ko
Application filed by 전자부품연구원 filed Critical 전자부품연구원
Priority to US13/822,383 priority Critical patent/US20130177815A1/en
Priority to CN201180044303.8A priority patent/CN103140968B/zh
Publication of WO2012036385A2 publication Critical patent/WO2012036385A2/fr
Publication of WO2012036385A3 publication Critical patent/WO2012036385A3/fr

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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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, and more particularly, to perform a side treatment of the carbon-based material applied as a negative electrode active material of the lithium secondary battery through heterogeneous element substitution to perform side reactions with the electrolyte on the surface.
  • the present invention relates to a negative active material, a non-aqueous lithium secondary battery having the same, and a method of manufacturing the same, which suppresses and improves structural stability, thereby improving life and rate characteristics of a lithium secondary battery.
  • 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.
  • the lithium secondary battery in which metal lithium is used as the negative electrode active material, grows and discharges from the negative electrode to dendrite as the charge and discharge are repeated, and penetrates the separator which is an insulator. There was a short disadvantage.
  • 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 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.
  • the low initial charge and discharge efficiency, the degradation of life characteristics and the rate characteristics are pointed as the root cause.
  • 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 rate characteristics
  • the present invention provides a negative electrode active material, a non-aqueous lithium secondary battery, and a method for manufacturing the same, which are surface-treated through heterogeneous element substitution capable of securing characteristics.
  • the present invention includes a carbon-based material, and a coating layer formed on the surface of the carbon-based material through heterogeneous substitution, the hetero-element is a negative electrode for a non-aqueous lithium secondary battery containing phosphorus (P) It provides an active material.
  • the hetero element may include sulfur (S).
  • 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 carbonaceous material is L a (110) > 10 nm, L c (002) > 10 nm.
  • L a (110) 0.89 ⁇ / [B 110 cos ( ⁇ 110 )]
  • L c (002) 0.89 ⁇ / [B 002 cos ( ⁇ 002 )]
  • FWHM full width at half-maximum
  • the carbon-based material may have a d 002 value of 0.344 nm or less with respect to the (002) peak.
  • the carbon-based material may have a specific surface area of 10 m 2 / g or less.
  • the carbon-based material may have a degree of graphitization value of 0.4 to 1.0.
  • the graphitization degree can be calculated as (3.44-d 002 ) / (0.086).
  • the coating layer may be 10% by weight or less compared to the carbonaceous material.
  • the coating layer may be formed uniformly or partially on the surface of the carbonaceous material.
  • the present invention also provides a non-aqueous lithium secondary battery comprising a negative electrode having the negative electrode active material described above.
  • the present invention also includes a preparation step of preparing a carbon-based material and a heterogeneous material, and forming a coating layer through heterogeneous element substitution on the surface of the carbon-based material by using the heterogeneous material.
  • the elemental material contains phosphorus (P).
  • the hetero element material may include sulfur (S).
  • the hetero element material is NH 4 PF 6 , (NH 4 ) 2 PO 4 , NH 4 PO 3 , (NH 4 ) 2 SO 3 , (NH 4 ) 2 SO 4 , NH 4 SO 4 And (NH 4 ) 2 S 2 O 8 At least one of the.
  • the forming step the step of dissolving the hetero-element material in a solvent to form a solution, the carbon-based material in the solution and uniformly mixed
  • the present invention by forming a coating layer on the surface of the carbon-based material used as a negative electrode active material of the non-aqueous lithium secondary battery through the substitution of heterogeneous elements such as phosphorous or sulfur, the surface of the surface of the carbon-based material by the coating layer formed In addition to reducing side reactions, structural stability can be achieved.
  • 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 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 through dissimilar element substitution according to an embodiment of the present invention.
  • FIG. 2 is a photograph showing a negative electrode active material according to an embodiment of the present invention and a comparative example.
  • Example 3 is a view showing the results of EDS (Energy Dispersive Spectroscopy) analysis of the negative electrode active material according to Example 1 of the present invention.
  • Example 4 is a view showing an EDS analysis result of a negative active material according to Example 2 of the present invention.
  • FIG. 5 is a graph showing XPS (X-ray Photoelectron Spectroscopy) analysis results of the anode active material according to Example 1 of the present invention.
  • Example 6 is a graph showing the XPS analysis result of the negative electrode active material according to Example 2 of the present invention.
  • FIG. 7 is a graph showing the results of X-ray diffraction (XRD) analysis of the negative electrode active material according to the Examples and Comparative Examples of the present invention.
  • FIG. 8 is a graph 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 embodiment and the comparative example of the present invention.
  • FIG. 9 is a graph showing the 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 through heterogeneous element substitution on the surface of the carbon-based material.
  • the heterologous element includes phosphorus (P) or sulfur (S).
  • 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 through heterogeneous element substitution on the carbon-based material, it is preferable to use the following carbon-based material in order to improve the life characteristics and rate characteristics of the non-aqueous lithium secondary battery to which the negative electrode active material is applied.
  • B is the full width at half for the (110) or (002) peak according to the Bragg diffraction angle -maximum) value.
  • As the carbonaceous material it is preferable to use a d 002 value of 0.344 nm or less with respect to the (002) peak.
  • carbon-based material those having a degree of graphitization value of 0.4 to 1.0 are preferably used.
  • Graphitization degree (3.44- d002 ) / (0.086) can be calculated here.
  • a carbonaceous material having a specific surface area of 10 m 2 / g or less.
  • the coating layer may be formed by heat-treating the surface of the carbon-based material by a pyrolysis method using a heterogenous material of 10 wt% or less of the carbon-based material. That is, in the process of thermally dissociating the hetero element material, the components except the hetero element in the hetero element material are removed and the hetero element forms a coating layer on the surface of the carbon-based material.
  • the coating layer may be uniformly formed on the entire surface of the carbonaceous material or may be formed only on a part of the surface of the carbonaceous material depending on the amount of the dissimilar element material to be heat treated.
  • Heteroelement materials can exist in various compound forms, including heteroatoms, such as NH 4 PF 6 , (NH 4 ) 2 PO 4 , NH 4 PO 3 , (NH 4 ) 2 SO 3 , (NH 4 ) 2 SO 4 , NH 4 SO 4 , (NH 4 ) 2 S 2 O 8 And the like, but are not limited thereto.
  • the negative electrode active material according to the present invention can improve the affinity with the electrolyte solution to improve the life characteristics and rate characteristics of the non-aqueous lithium secondary battery.
  • the production efficiency of the negative electrode active material may be improved due to a simple surface treatment process.
  • 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 through heterogeneous element substitution according to an embodiment of 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 hetero-element material (S11), and forming a coating layer using the hetero-element material on the surface of the carbon-based material Steps S13 to S19 are included.
  • a carbonaceous material and a heterogeneous material are prepared.
  • the carbonaceous material an average particle size of 15 ⁇ m or less may be used.
  • Heterogeneous element is NH 4 PF 6 , (NH 4 ) 2 PO 4 , NH 4 PO 3 , (NH 4 ) 2 SO 3 , (NH 4 ) 2 SO 4 , NH 4 SO 4 , (NH 4 ) 2 S 2 O 8 And the like can be used.
  • step S13 the dissimilar element material is dissolved in deionized water to form an aqueous solution.
  • deionized water an organic solvent such as alcohol may be used.
  • step S15 the carbon-based material is mixed with the aqueous solution in step S15 to form a mixture.
  • the mixing step according to step S15 may be performed for about 5 minutes so that the carbon-based material is uniformly mixed in the aqueous solution.
  • step S17 the mixture is vacuum dried in step S17.
  • vacuum drying according to step S17 may be performed for about 1 to 5 hours at 80 to 150 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 a dissimilar element material. That is, in the process of thermally dissociating the hetero element material, the components except the hetero element in the hetero element material are removed and the hetero element forms 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 a heterogeneous material in an aqueous solution, and then heat-treated through vacuum drying It is not limited.
  • a dissimilar element material 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 a hetero element material was used as the negative electrode active material. In the comparative example, a carbon-based material that was not surface treated with a heteroelement material 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, the binder SBR, and the thickener CMC as 2 wt%, respectively.
  • 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 14 mm was used, and a PE film was used as the separator.
  • As the electrolyte solution a mixed solution in which EC / DMC of 1M LiPF 6 was mixed at 3: 7 was used.
  • 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.
  • Heterogeneous material is NH 4 PF 6 , (NH 4 ) 2 PO 4 , NH 4 PO 3 , (NH 4 ) 2 SO 3 , (NH 4 ) 2 SO 4 , NH 4 SO 4 , (NH 4 ) 2 S 2 O 8 It includes, but is not limited to this.
  • the carbon-based material surface-treated with a heterogeneous material may 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 a heterogeneous material may 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 a dissimilar element material, which are usually used as conductive agents, binders, fillers, dispersants, ion conductive agents, pressure enhancers, etc.
  • the additive component is added to form a slurry or paste with a suitable solvent (organic solvent).
  • the slurry or paste thus obtained is coated and dried on an electrode support substrate using a doctor blade method or the like, and then pressed using a rolling roll or the like is used as the negative electrode plate.
  • 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 positive 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.
  • carbonate As the solvent of the non-aqueous electrolyte, carbonate, ester, ether or ketone can be used.
  • the carbonate is 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 in order to introduce phosphorus (P) into the hetero element, natural graphite having an average particle size of 15 ⁇ m or less, which was surface treated using NH 4 PF 6 as the hetero element material, was used as the negative electrode active material.
  • Example 2 in order to introduce sulfur (S) into the hetero element, natural graphite having an average particle size of 15 ⁇ m or less, which was surface-treated with (NH 4 ) 2 SO 4 as the hetero element material, was used as the negative electrode active material.
  • the negative electrode active materials according to Example 1 and Example 2 were prepared as follows. In order to introduce phosphorus (P) and sulfur (S) on the surface of natural graphite among carbon materials, 3 wt% of NH 4 PF 6 and (NH 4 ) 2 SO 4 were dissolved in DI water, respectively. The surface of the natural graphite was uniformly coated, and finally, a negative active material for a non-aqueous lithium secondary battery including phosphorus or sulfur on the surface was prepared by heat treatment at 800 ° C.
  • Example 1 XPS analysis was performed for surface structure analysis of the anode active materials according to Examples 1 and 2, and the results are shown in FIGS. 5 and 6.
  • P 2p peaks 131 to 135eV
  • S 2p peak 161 ⁇ 168eV
  • Table 2 shows the d 002 values and FWHM (full-width at half maximum) values of Comparative Examples, Examples 1 and 2 through the obtained XRD data. After introduction of the heterogeneous element, the change of d 002 value was insignificant and the FWHM was increased. This is judged to be because a part of P or S introduced into the surface is substituted on the surface.
  • Comparative Example was 2.7845 m 2 / g
  • Example 1 was 2.7461 m 2 / g
  • Example 2 was 2.7199 m 2 / g.
  • Example 1 and Example 2 were applied The same test was performed. That is, the non-aqueous lithium secondary battery to which the comparative examples and the negative electrode active materials of Examples 1 and 2 were applied was subjected to 3 cycle charging and discharging at a current of 0.2C (72 mA / g), followed by 0.5C (180 mA / g). Charging and discharging was performed for 50 cycles with the current of), and the results are shown in FIG. As can be seen in Figure 8, Example 1 and Example 2, the surface treatment of the hetero-element material is improved compared to the comparative example.
  • the non-aqueous lithium secondary battery to which the negative electrode active materials of Comparative Examples, Examples 1 and 2 are applied The following test was carried out using. That is, the non-aqueous lithium secondary battery to which the negative electrode active materials of Comparative Example, Example 1 and Example 2 were applied is subjected to 1 cycle charging and discharging at a current of 0.2C (72 mA / g).
  • 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. 9. As can be seen in Figure 9, it was confirmed that the rate characteristic after surface treatment was also improved.

Abstract

La présente invention concerne un matériau actif d'anode, une batterie secondaire au lithium non aqueuse, et un procédé de préparation de celui-ci. La surface d'un matériau carboné est modifiée sans utiliser un additif d'électrolyte, et la réactivité et la stabilité structurale de la surface sont améliorées, de manière à obtenir des caractéristiques de durée de vie longue sans dégrader l'efficacité de charge/décharge et les caractéristiques de régime lorsqu'il est appliqué en tant que matériau actif d'anode d'une batterie secondaire au lithium non aqueuse. Selon la présente invention, le matériau d'anode actif comprend un matériau carboné, et une couche de revêtement formée sur la surface du matériau carboné par substitution d'hétéroatome, l'hétéroatome pouvant être le phosphore (P) ou le soufre (S). Une réaction secondaire avec une électrolyte sur la surface du matériau carboné est inhibée et la stabilité structurale de la surface est améliorée en formant une couche de revêtement sur la surface du matériau carboné avec un hétéroatome tel que le phosphore (P) ou le soufre (S), de manière à améliorer les caractéristiques de durée de vie et les caractéristiques de régime d'une batterie secondaire au lithium.
PCT/KR2011/006110 2010-09-16 2011-08-19 Matériau actif d'anode, batterie secondaire au lithium non aqueuse contenant celui-ci, et procédé de préparation de celui-ci WO2012036385A2 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US13/822,383 US20130177815A1 (en) 2010-09-16 2011-08-19 Negative active material, lithium secondary battery comprising the negative active material and manufacturing method thereof
CN201180044303.8A CN103140968B (zh) 2010-09-16 2011-08-19 阳极活性材料、含有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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Application Number Priority Date Filing Date Title
KR10-2010-0091296 2010-09-16
KR20100091296 2010-09-16
KR10-2011-0077357 2011-08-03
KR1020110077357A KR101316638B1 (ko) 2010-09-16 2011-08-03 음극 활물질, 그를 갖는 비수계 리튬이차전지 및 그의 제조 방법

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WO2012036385A2 true WO2012036385A2 (fr) 2012-03-22
WO2012036385A3 WO2012036385A3 (fr) 2012-05-10

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KR20050115480A (ko) * 2004-06-03 2005-12-08 한국과학기술연구원 이차전지의 전극활물질용 탄소복합체 및 그 제조방법,이를 이용한 이차전지
KR20070059389A (ko) * 2005-12-06 2007-06-12 주식회사 엘지화학 이차 전지용 고용량 음극활물질
KR20080099132A (ko) * 2007-05-07 2008-11-12 한양대학교 산학협력단 리튬 이차 전지용 양극 활물질의 제조방법, 이 방법으로제조된 리튬 이차 전지용 양극 활물질 및 이를 포함하는리튬 이차 전지
KR20090028986A (ko) * 2007-09-17 2009-03-20 삼성에스디아이 주식회사 리튬 이차 전지용 음극 활물질 및 이의 제조 방법
KR20100073506A (ko) * 2008-12-23 2010-07-01 삼성전자주식회사 음극 활물질, 이를 포함하는 음극, 음극의 제조 방법 및 리튬 전지

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20050115480A (ko) * 2004-06-03 2005-12-08 한국과학기술연구원 이차전지의 전극활물질용 탄소복합체 및 그 제조방법,이를 이용한 이차전지
KR20070059389A (ko) * 2005-12-06 2007-06-12 주식회사 엘지화학 이차 전지용 고용량 음극활물질
KR20080099132A (ko) * 2007-05-07 2008-11-12 한양대학교 산학협력단 리튬 이차 전지용 양극 활물질의 제조방법, 이 방법으로제조된 리튬 이차 전지용 양극 활물질 및 이를 포함하는리튬 이차 전지
KR20090028986A (ko) * 2007-09-17 2009-03-20 삼성에스디아이 주식회사 리튬 이차 전지용 음극 활물질 및 이의 제조 방법
KR20100073506A (ko) * 2008-12-23 2010-07-01 삼성전자주식회사 음극 활물질, 이를 포함하는 음극, 음극의 제조 방법 및 리튬 전지

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