WO2012091515A2 - Matériau actif d'électrode négative pour une batterie secondaire au lithium, procédé pour sa fabrication et batterie secondaire au lithium l'utilisant - Google Patents

Matériau actif d'électrode négative pour une batterie secondaire au lithium, procédé pour sa fabrication et batterie secondaire au lithium l'utilisant Download PDF

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WO2012091515A2
WO2012091515A2 PCT/KR2011/010374 KR2011010374W WO2012091515A2 WO 2012091515 A2 WO2012091515 A2 WO 2012091515A2 KR 2011010374 W KR2011010374 W KR 2011010374W WO 2012091515 A2 WO2012091515 A2 WO 2012091515A2
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secondary battery
active material
lithium secondary
negative electrode
electrode active
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PCT/KR2011/010374
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English (en)
Korean (ko)
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WO2012091515A3 (fr
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이종혁
최정우
김선아
이종민
이정무
김정곤
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애경유화 주식회사
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Priority to JP2013547363A priority Critical patent/JP5886875B2/ja
Priority to CN201180043190.XA priority patent/CN103250283B/zh
Priority claimed from KR1020110146964A external-priority patent/KR101375688B1/ko
Publication of WO2012091515A2 publication Critical patent/WO2012091515A2/fr
Publication of WO2012091515A3 publication Critical patent/WO2012091515A3/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
    • H01M4/13—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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a negative electrode active material for a lithium secondary battery, a method for manufacturing the same, and a lithium secondary battery using the same, and more particularly, by preparing a negative electrode active material including a carbonized carbide obtained by heat treatment of a polyurethane resin under an active gas atmosphere.
  • the specific surface area reduces the problem of water adsorption, improves the initial charge and discharge efficiency of the secondary battery, improves the energy density of the battery, and improves battery characteristics such as excellent life characteristics, charge and discharge output, and high temperature storage characteristics.
  • the present invention relates to a negative electrode active material for a lithium secondary battery, a method of manufacturing the same, and a lithium secondary battery using the same.
  • the type of vehicle driven by an electric motor may be classified into an electric vehicle (EV), a hybrid electric vehicle (HEV), a plug-in hybrid electric vehicle (PHEV), and the like.
  • the secondary battery is responsible for a power source for driving the motor.
  • automotive secondary batteries require very large output characteristics and lifetime characteristics.
  • lithium secondary batteries have higher energy density to weight and superior output characteristics than nickel-hydrogen batteries, and thus, they are widely used as power sources for driving motors of electric vehicles.
  • Graphite is mostly used as a negative electrode active material of automotive lithium secondary batteries, and exhibits a high discharge voltage of 3.6 V, which is the most widely used for ensuring high energy density of lithium secondary batteries and high life characteristics of secondary batteries with excellent reversibility. .
  • graphite has a problem in that energy input / output characteristics are inferior, and in particular, low temperature output characteristics are insufficient.
  • about 10% of the volume change of graphite occurs during charging and discharging, thereby adversely affecting the bonding strength between the current collector and the mixture layer, thereby degrading the lifespan of the battery.
  • non-graphitizable carbon having fine pores has been proposed and partially used.
  • the non-graphitizable carbon is a structure in which lithium ions are stored and released in numerous pores, and there is almost no volume expansion during charging and discharging of lithium ions, so the battery has excellent life characteristics, and fine lithium pores are present in all directions of particles. It is known to be excellent in output characteristics because it can be stored and released.
  • non-graphitizable carbon has a large specific surface area, the amount of solvents and binders must be increased when manufacturing electrode slurries, and the energy density of the battery is lowered as the amount of binder increases. When the secondary battery is increased, moisture reacts with the electrolyte to form hydrofluoric acid (HF), thereby increasing irreversible capacity and lowering durability.
  • HF hydrofluoric acid
  • Patent Document 1 relates to nano-sized spherical non-graphitizable carbon and a method for manufacturing the same and a lithium secondary battery containing the carbon as a negative electrode active material, nano-sized non-graphite including a surfactant Chemical carbon was prepared, and Korean Unexamined Patent Publication No. 2011-0042840 (Patent Document 2) discloses a negative active material for a lithium secondary battery including spherical graphite and plate-like graphite obtained by coating amorphous carbon on natural graphite and firing the same. A secondary battery was manufactured.
  • the conventional anode active material for lithium secondary batteries using the non-graphitizable carbon and graphite as described above has a small specific surface area and is insufficient to be used as a negative electrode active material by satisfying the requirements of a carbon material having excellent output characteristics.
  • the present invention is to solve the conventional problems, by producing a negative electrode active material comprising a carbonized carbide by heat-treating the polyurethane resin in an active gas atmosphere, the problem of water adsorption is reduced due to the low specific surface area, 2
  • the purpose of the present invention is to provide a negative electrode active material for a lithium secondary battery and a method of manufacturing the same, which improves the energy density of the battery by improving the initial charge and discharge efficiency of the secondary battery and improves battery characteristics such as excellent life characteristics, charge and discharge output, and high temperature storage characteristics. It is done.
  • another object of the present invention is to provide a negative electrode for a lithium secondary battery including the negative electrode active material and a lithium secondary battery comprising the same.
  • the polyurethane resin is heat treated and carbonized under an inert gas atmosphere to smooth out the gas so as not to contaminate the surface of the product due to the tar component, and further carbon coating after carbonization. It is possible to achieve the desired surface properties only by the carbonization process of the present invention so that no post-treatment is required.
  • the polyurethane resin which is a precursor of the negative electrode active material for a lithium secondary battery according to the present invention, may be prepared by the reaction of a polyol and an isocyanate.
  • the polyol is a conventional one used for preparing a polyurethane resin, but is not particularly limited, but specifically, a polyether polyol, a polyester polyol, a polytetramethylene ether glycol polyol, a Polyharnstoff Dispersion (PHD) polyol, Any one or two or more selected from amine-modified polyols, Manmich polyols, and mixtures thereof are preferred, more preferably polyester polyols, amine-modified polyols, Manmich polyols Or mixtures thereof.
  • PLD Polyharnstoff Dispersion
  • the molecular weight of the said polyol is 300-3000, More preferably, it is effective that it is 400-1500. If the molecular weight of the polyol is less than 300, there is a disadvantage in that the thermal stability of the polyurethane resin synthesized by the formation of a monool is reduced and melting occurs in the carbonization process. If the molecular weight of the polyol exceeds 3000, it is amorphous in the polyol structure. Carbon chains increase and the thermal stability of polyurethane resin falls.
  • the number of hydroxyl groups of the polyol is preferably 1.5 to 6.0, more preferably 2.0 to 4.0, and it is effective that the hydroxyl group content present in the polyol is 3 to 15% by weight.
  • the specific surface area becomes excessively large when the polyurethane resin is carbonized, thereby increasing water adsorption, thereby reducing battery efficiency.
  • the isocyanate reacting with the polyol is a conventional one used for preparing a polyurethane resin, but is not particularly limited. Specifically, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 4,4'-dicyclo Hexylmethane diisocyanate (H12MDI), polyethylene polyphenyl isocyanate, toluene diisocyanate (TDI), 2,2'-diphenylmethane diisocyanate (2,2'-MDI), 2,4'-diphenylmethane diisocyanate ( 2,4'-MDI), 4,4'-diphenylmethane diisocyanate (4,4'-MDI, monomeric MDI), polymeric diphenylmethane diisocyanate (polymeric MDI), orthotoluidine diisocyanate (TODI), Any one or two or more selected from naphthalene diosocyanate (NDI), is
  • 4,4'-diphenylmethane diisocyanate (4,4'-MDI, monomeric MDI), polymeric diphenylmethane diisocyanate (polymeric MDI) or polyethylene polyphenyl isocyanate is effective.
  • the mixing ratio of the polyol and isocyanate is effective to include 150 to 240 parts by weight of the isocyanate based on 100 parts by weight of the polyol. If the content of isocyanate is less than 150 parts by weight, the formation of isocyanurate bonds that enhance thermal stability is not sufficient, resulting in a problem that the resin is melted similarly to digraphitizable carbon during the carbonization process, and the content of isocyanate is If it is more than 240 parts by weight, isocyanurate bonds are excessively generated, and the specific surface area is increased after the carbonization process, thereby increasing the water adsorption rate, and the element ratio of oxygen to the resulting polyurethane resin is increased to produce a secondary battery. When the problem occurs that the electrical characteristics are deteriorated.
  • a catalyst may be added to induce the reaction of the polyol and the isocyanate to prepare the polyurethane resin.
  • the catalyst is pentamethyldiethylene triamine, dimethyl cyclohexyl amine, bis- (2-dimethyl aminoethyl) ether, triethylene diamine ( (triethylene diamine) potassium octoate (potassium octoate), tris (dimethylaminomethyl) phenol (tris (dimethylaminomethyl) phenol), potassium acetate (potassium acetate) or any one or more selected from them may be used, and
  • the content of the catalyst is preferably added in an amount of 0.1 to 5 parts by weight based on the polyol, and more preferably in an amount of 0.5 to 3 parts by weight, and when the content of the catalyst is 0.1 parts by weight or less, the reaction between the polyol and the isocyanate is too slow.
  • the problem occurs that the production efficiency of the negative electrode active material decreases, and when the content of the catalyst exceeds 5 parts by weight It proceeds too fast and the formed non-uniformly is a polyurethane resin, so that there arises a problem that the physical properties of the negative electrode active material decreases.
  • a foaming agent may be included in order to facilitate the pulverization of the polyurethane resin, and a foam stabilizer may be further added to improve the quality of the polyurethane resin.
  • flame retardants such as Tris (2-ChloroPropyl) Phosphate (TCPP), Tris (2-Chroroethyl) Phosphate (TCEP), Triethyl phosphate (TEP), and Trimethyl phosphate (TMP) are further added to improve the thermal stability of the polyurethane resin. More may be added.
  • the mixing ratio of the polyol and isocyanate may vary depending on the amount of additives such as catalysts, foam stabilizers, blowing agents, flame retardants, etc., but is not limited thereto.
  • the isocyanate contains a large amount of NCO group, as the addition rate of the isocyanate increases, the content of nitrogen and oxygen increases. It is effective that the preferred nitrogen content ranges from 7 to 9% by weight of the total polyurethane resin.
  • the content of nitrogen is more than 9% by weight, the specific surface area of carbon after the carbonization process increases to increase the moisture adsorption in the air to reduce the efficiency of the battery, when the content of nitrogen is less than 7% by weight It is not preferable because the amount of isocyanurate bond is insufficient, so that the thermal stability of the polyurethane resin is reduced and the resin melts like carbonaceous carbon when carbonized.
  • the content of hydrogen is preferably 4 to 6% by weight of the total polyurethane resin
  • the oxygen content is preferably 15 to 22% by weight of the total polyurethane resin.
  • the manufacturing method of the negative electrode active material for lithium secondary batteries is demonstrated in detail.
  • the above-mentioned polyol and isocyanate are reacted to prepare a polyurethane resin, and the carbonized step of heat-treating the prepared polyurethane resin under an inert gas atmosphere.
  • the polyurethane resin may be obtained by exothermic reaction by uniformly mixing the polyol and isocyanate at a constant ratio.
  • a conventional polymer resin mixing method may be used.
  • mixing by an impeller or in-line mixing by high pressure extrusion is effective.
  • the obtained polyurethane resin is in the form of agglomerates, and is preferably pulverized to a suitable size to perform a carbonization step because the density is low due to foaming and the processing yield per hour is lowered.
  • the process is not necessarily performed, and a process of pulverizing the bulk polyurethane resin after the carbonization process is also possible.
  • the cumulative volume of the particles analyzed by the particle size analyzer is 50% after the first crushing through a crusher using a mechanical crushing method.
  • the secondary grinding process is performed such that the average particle size (D50) of the spot is about 100 to 200 ⁇ m.
  • the carbonization step includes a pre-carbonization step and the main carbonization step, the pre-carbonization step is heat-treated for 30 to 120 minutes at 600 to 1000 °C temperature, the main carbonization step is 1000 to 1400 °C temperature It is effective to heat treatment for 30 to 120 minutes at.
  • the pre-carbonization step and the main carbonation step is preferably performed sequentially.
  • the precarbonization step is carried out under an inert gas atmosphere, the inert gas is preferably used helium, nitrogen, argon or a mixture thereof.
  • the precarbonization step is preferably performed at 600 to 1000 ° C, more preferably at 700 to 900 ° C. If the preliminary carbonization is carried out below 600 ° C., the low molecular weight gases are less volatilized and thus remain inside the material, which may reduce the yield of the product, and due to the residual gas generated in the main carbonization step, There is a problem of contaminating the inside of the furnace and the surface of the product.
  • the pre-carbonization step, after the pre-carbonization step or after the main carbonization step may include a fine grinding step of adjusting the particle size to a size suitable for manufacturing as an electrode for a lithium secondary battery.
  • the pulverizing step may be pulverized using a conventional pulverizer using a mechanical pulverization method, and in particular, various pulverizers such as ball mills, pin mills, rotor mills, and jet mills may be used.
  • the jet mill grinding process which is easy to pulverize, has a problem in that it is difficult to reduce the particle size to 60 ⁇ m or less since the specific gravity of the polyurethane resin is low when the pre-carbonization step is performed, thereby limiting the impact between particles.
  • Pin mill and rotor mill processes also have a limit in the rotational force, it is difficult to reduce the particle size due to the low specific gravity of the particles. Therefore, when the fine grinding step is performed using a jet mill, a pin mill and a rotor mill, it is preferable to carry out after the precarbonization step or after the main carbonization step.
  • the fine-pulverization step is performed after the pre-carbonization step because the fine-pulverized particles may aggregate with each other after the pre-carbonization step. Is more effective. Jet mills are most effective when the milling step is carried out after the preliminary carbonization step.
  • the average particle size (D50) of the particles pulverized by the jet mill is preferably 3 to 50 ⁇ m, more preferably 3 to 20 ⁇ m, and most preferably 6 to 15 ⁇ m.
  • the average particle size (D50) is less than 3 ⁇ m, the amount of fine particles generated less than 1 ⁇ m increases, the specific surface area of the particles increases, and the property of adsorbing moisture in the air increases, causing lithium ions and water to react in the battery reaction.
  • the capacity can be increased, and the fine powder increases, the porosity between the particles increases, the filling density of the particles is lowered, and lithium ions inserted into the carbon particles are easily eluted at a high temperature of 65 ° C. or higher during the battery reaction.
  • a problem occurs that the high temperature storage characteristics of the deteriorate.
  • the main carbonization step of heat treatment for 30 to 120 minutes at a temperature of 1000 to 1500 °C.
  • This carbonization step improves the conductivity of carbon after removing the low molecular weight gases generated in the precarbonization step, and optimizes the characteristics as a negative electrode material for secondary batteries by reducing the element ratio (H / C%) of hydrogen and carbon. It is a step for.
  • the main carbonization step is carried out under an inert gas atmosphere, and the inert gas is preferably helium, nitrogen, argon or a mixture thereof.
  • the heat treatment temperature of the carbonization step is preferably 1000 to 1500 ° C, more preferably 1200 to 1400 ° C.
  • the element ratio (H / C%) of hydrogen and carbon is increased to decrease the output characteristics of the battery, and the remaining hydrogen in carbon reacts irreversibly with lithium ions for the first 5 cycles.
  • the carbonization temperature is higher than 1400 ° C, the reversible capacity, which is the storage capacity of lithium ions, decreases, the energy density of the battery is greatly reduced, and the specific surface area increases.
  • the commercial furnace in order to withstand the heat treatment temperature of more than 1500 °C because the material and configuration of the electric furnace must be changed to a heat-resistant material, there arises a problem that the manufacturing cost and process cost increases.
  • the negative active material for a lithium secondary battery that has undergone the preliminary carbonization step, the fine grinding step and the carbonization step according to the present invention has a specific surface area of 2.0 to 5.0 m 2 / g, and as shown in FIG. 6, an average pore size of 1 It is preferable that it is-5 nm.
  • the (002) mean layer spacing (d002) obtained by the X-ray diffraction method (XRD) was 3.7 to 4.0 kPa
  • the crystallite diameter Lc (002) in the C-axis direction was 0.8 to 2 nm
  • the R value was 1.3 to It is preferable that it is 2, and it is preferable that the peak intensity ratio (5 degree peak / 002 peak) is 2-4
  • required by elemental analysis is 0.1 or less, oxygen and It is preferable that the element ratio (O / C%) of carbon is 1.0 or less.
  • the negative electrode active material for a lithium secondary battery manufactured by the manufacturing method of the present invention has physical properties in the above range, the water adsorption rate is reduced, it is formed in a structure that is easy to charge and discharge lithium ions to improve the initial charge and discharge efficiency of the secondary battery You can.
  • the structure of the negative electrode active material for a lithium secondary battery is formed by uniformly and appropriately combining the urethane reaction, urea reaction, and isocyanurate reaction of the polyurethane resin in the structure, and the microstructure close to amorphous is fine and uniform pores. It was confirmed that including the formed.
  • the specific surface area of the negative electrode active material is prepared by preparing a negative electrode active material including a carbonized carbide by heat-treating a polyurethane resin under an active gas atmosphere. It is lowered, prevents the adsorption of water by forming a surface in which the mesopores are not developed, and it is easy to remove moisture in the electrode drying process, thereby improving the initial efficiency, output and life characteristics of the secondary battery.
  • the lithium secondary battery including the negative electrode active material has an advantage that the initial charge and discharge efficiency of the battery is significantly improved.
  • 1 is a graph showing a change in the nitrogen content according to the isocyanate content of the negative electrode active material of the lithium secondary battery according to the present invention.
  • FIG. 2 is a graph showing the change in specific surface area according to the isocyanate content of the negative electrode active material of the lithium secondary battery according to the present invention.
  • FIG 3 is a graph showing a change in the initial charge and discharge efficiency according to the isocyanate content of the negative electrode active material of the lithium secondary battery according to the present invention.
  • FIG 4 is a graph showing a change in the initial charge and discharge efficiency according to the carbonization temperature of the negative electrode active material of the lithium secondary battery according to the present invention.
  • FIG. 5 is a graph analyzing mesopores on the surface of the negative electrode active material of the lithium secondary battery according to the present invention.
  • FIG. 6 is a graph analyzing micropores on the surface of the negative electrode active material of the lithium secondary battery according to the present invention.
  • the R value is defined as the ratio of the intensities of (A) and (B) in 2 ⁇ representing the (002) peak.
  • (A) is the background established by drawing a straight line based on the baselines on both sides of the (002) peak
  • (B) is the intensity at the junction where the background meets the (002) peak in parallel with the (002) peak.
  • Samples were collected according to KS A 0094, KS L ISO 18757 standards, and degassed at 300 ° C for 3 hours through a pretreatment device, followed by nitrogen gas adsorption BET method through surface area and pore size analyzer devices (P / P0) The specific surface area of the sample was measured at 0.05 to 0.3.
  • pores on the surface of the sample were analyzed by nitrogen gas adsorption through a Pore Size Analyzer (Bellsorp mini II).
  • the analysis shows the total volume distribution of the pores (Micropore) having a diameter of 2 nm or less by the HK method, and the total volume distribution of the pores (Mesopore) having a diameter of 2-50 nm by the BJH method. .
  • the prepared carbon was left at a relative humidity of 70% and a temperature of 25 ° C. for 24 hours, and then maintained at 200 ° C. for 5 minutes using Karl fischer moisture measurement equipment to measure the amount of moisture adsorbed on the sample.
  • a slurry was prepared in a ratio of 97: 3 to a negative electrode active material and a binder, coated to a thickness of 100 ⁇ m, dried, perforated in the form of a circular disc of 1 cm 2, and then measured by Karl Fischer for measuring the moisture content of the electrode after 120 hours vacuum drying for 6 hours. The instrument was held at 200 ° C. for 5 minutes to measure the residual moisture content of the electrode.
  • the measuring cell is a coin-type half-cell with lithium metal foil as an electrode and a counter electrode prepared with a cathode active material and a binder in a ratio of 97: 3, and EC / DEC is mixed in a 1: 1 ratio with an organic electrolyte with a separator therebetween. It was prepared in 2016 type coin cell by impregnating 1M LiPF6 dissolved electrolyte solution.
  • Charging was performed by inserting lithium ions into the carbon electrode with a constant current method up to 0.005V at 0.1 C rate, and then inserting lithium ions with a constant current method from 0.005V. When the current reached 0.01 mA, the lithium ion insertion was terminated. In the discharge, lithium ion was detached from the carbon electrode at a constant current method at a rate of 0.1 C with a final voltage of 1.5 V.
  • the output characteristic evaluation is a measure of the output characteristics at the time of lithium ion discharge. After 5 cycles of charging and discharging to 0.1 C at the initial stage, the discharge (lithium ion desorption) C rate is increased step by step and 5 C-rate compared to 0.1 C rate reversible capacity. The retention rate of the reversible capacity was measured.
  • the polyurethane resin was pulverized using a crusher to have a particle diameter of 0.1 to 2 mm, and then the pulverized product was heated to 700 ° C. in a nitrogen gas atmosphere, and maintained at 700 ° C. for 1 hour to carry out preliminary carbonization. A yield of 38% lithium secondary battery negative electrode active material precursor was obtained.
  • the obtained negative electrode active material precursor was pulverized with an average particle size of about 6 ⁇ 12 ⁇ m using a jet mill, the maximum particle size was not to exceed 50 ⁇ m.
  • the pulverized negative electrode active material precursor is placed in a ceramic crucible and heated to 1200 ° C. at a temperature rising rate of 5 ° C./min. Under a nitrogen gas atmosphere, and maintained at 1200 ° C. for 1 hour to undergo a carbonization process.
  • Table 1 below shows the composition ratio and carbonization temperature of the polyol and isocyanate, and the ⁇ evaluation test items> of the anode active material for the lithium secondary battery prepared in Example 1 were measured, and the results are shown in Tables 2 and 3 below. And in Table 4.
  • Example 2 was carried out in the same manner as in Example 1 except that the carbonization temperature was carried out at 1300 °C.
  • Example 2 was carried out in the same manner as in Example 1 except that the carbonization temperature was carried out at 1400 °C.
  • Example 4 was carried out in the same manner as in Example 1 except that the isocyanate content was performed at 194 g.
  • Example 5 was carried out in the same manner as in Example 4 except that the carbonization temperature was carried out at 1300 °C.
  • Example 5 was carried out in the same manner as in Example 4 except that the carbonization temperature was carried out at 1400 °C.
  • Example 7 was carried out in the same manner as in Example 1 except that the isocyanate content was carried out at 210 g.
  • Example 8 was carried out similarly to Example 7, except that the carbonization temperature was performed at 1300 ° C.
  • Example 9 was carried out in the same manner as in Example 7, except that the carbonization temperature was performed at 1400 ° C.
  • Example 10 was carried out in the same manner as in Example 1 except that the isocyanate content was carried out at 225 g.
  • Example 11 was carried out in the same manner as in Example 10 except that the carbonization temperature was performed at 1300 ° C.
  • Example 12 was carried out in the same manner as in Example 10 except that the carbonization temperature was performed at 1400 ° C.
  • Sucrose as a precursor was heated to 1200 °C at a temperature increase rate of 5 °C / min in a nitrogen atmosphere and maintained for 1 hour and carbonized, and then pulverized into particles of an average particle diameter of 12 ⁇ m with a rotary blade cutter mill to prepare carbon.
  • Comparative Example 2 was carried out in the same manner as in Comparative Example 1 except that the carbonization temperature was 1300 °C.
  • the petroleum pitch was melted at 150 ° C. using a precursor, extruded to form granules, and then maintained at 300 ° C. in air for 6 hours to insolubilize. Thereafter, the temperature was raised to 700 ° C. under a nitrogen atmosphere, and preliminary carbonization was performed for 1 hour to obtain a cathode active material precursor having a yield of 68% of carbonization.
  • the obtained negative electrode active material precursor was pulverized with an average particle size of about 6-12 ⁇ m using a jet mill, placed in a crucible made of ceramic material, heated to 1200 ° C. at a temperature increase rate of 5 ° C./min under a nitrogen atmosphere, and maintained for 1 hour.
  • a carbon material usable as a negative electrode active material for a lithium secondary battery was prepared.
  • Comparative Example 4 was carried out in the same manner as in Comparative Example 3 except that the carbonization temperature was 1300 ° C.
  • Comparative Example 5 was carried out in the same manner as in Example 1 except that the carbonization temperature was 900 ° C.
  • Comparative Example 6 was carried out in the same manner as in Example 2, except that the isocyanate content was carried out at 350 g.
  • the negative electrode active materials prepared in Examples and Comparative Examples were used in the negative electrode of the aqueous electrolyte secondary battery, and the charge (lithium insertion) capacity and the discharge (lithium detachment) capacity of the negative electrode active material were precisely independent without being affected by the performance of the counter electrode.
  • a lithium secondary battery was constructed using lithium metal as a counter electrode, and characteristics were evaluated.
  • the lithium secondary battery is a 2016-sized (20 mm diameter, 16 mm thick) coin-type battery assembled in a glove box under an argon atmosphere. A 1 mm thick metal lithium is pressed onto the bottom of a coin-type battery can, and a polypropylene separator is placed thereon. Was formed and the negative electrode was faced with lithium.
  • the electrolyte used was prepared by adding 1.2 M of LiPF6 salt to a solvent prepared by mixing EC (Ethylene Carbonate), DMC (Dimethyl Carbonate) and EMC (Ethyl Methyl Carbonate) in a volume ratio of 1: 1: 1.
  • the lithium secondary battery was assembled by putting it in a doll battery, touching the can cover, and pressing.
  • the amount of electricity supplied at this time divided by the weight of the negative electrode active material of the electrode was called the charging capacity per unit weight of the negative electrode active material (mAh / g).
  • the battery was stopped for 10 minutes and discharged.
  • the discharge was carried out at a constant current until the voltage of the coin-type battery became 1.5V.
  • the value of the discharged electricity divided by the weight of the negative electrode active material of the electrode was the discharge capacity per unit weight of the negative electrode active material (mAh / g). It was.
  • the reversible capacity was defined as the discharge capacity, the irreversible capacity was calculated by subtracting the discharge capacity from the charging capacity, and the efficiency was calculated as the percentage (%) of the discharge capacity.
  • the characteristic value of a basic coin-type battery was shown by averaging the characteristic value of three or more of the same batteries made from the same sample.
  • High rate charge / discharge characteristics analysis of the assembled lithium secondary battery was performed at 25 ° C. by the constant current-constant voltage method (CCCV) as in (c).
  • the high rate charge / discharge characteristics change the current density during charge and discharge, increase the constant current density supplied or discharged by cycle, and represent the capacity (mAh / g) measured and charged at the current density.
  • the specific surface area is reduced, such as reversible capacity and initial charge and discharge efficiency It was confirmed that the characteristic was remarkably improved.
  • the active material for a lithium secondary battery of the present invention does not develop mesopores on the carbon surface, so that the water content is low, and the adsorption amount of the water is also reduced, thereby reducing irreversible capacity and initial charging and discharging efficiency. It can be seen that the electrochemical properties such as increased significantly.

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Abstract

La présente invention porte sur un matériau actif d'électrode négative pour une batterie secondaire au lithium, sur un procédé pour sa fabrication, et sur une batterie secondaire au lithium l'utilisant, dans lesquels le matériau actif d'électrode négative comprend des carbures obtenus par traitement thermique d'une résine de polyuréthane dans une atmosphère de gaz actif, et carbonisation de la résine traitée thermiquement, de façon à réduire ainsi la surface spécifique et à remédier ainsi aux problèmes d'adsorption de l'humidité, d'amélioration de l'efficacité de charge/décharge initiale d'une batterie secondaire, et, par conséquent, d'amélioration de la densité d'énergie de la batterie secondaire et d'amélioration des caractéristiques de la batterie, comme, par exemple, le fait de communiquer une durée de vie prolongée et des propriétés de sortie de charge/décharge améliorées, des caractéristiques de stockage à haute température, etc., à celle-ci.
PCT/KR2011/010374 2010-12-31 2011-12-30 Matériau actif d'électrode négative pour une batterie secondaire au lithium, procédé pour sa fabrication et batterie secondaire au lithium l'utilisant WO2012091515A2 (fr)

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JP2013547363A JP5886875B2 (ja) 2010-12-31 2011-12-30 リチウム二次電池用負極活物質及びその製造方法、これを利用したリチウム二次電池
CN201180043190.XA CN103250283B (zh) 2010-12-31 2011-12-30 用于锂二次电池的阴极活性物质及其制备方法，以及利用其的锂二次电池

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KR20100139741 2010-12-31
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KR1020110146964A KR101375688B1 (ko) 2010-12-31 2011-12-30 리튬이차전지용 음극 활물질 및 그 제조방법, 이를 이용한 리튬이차전지

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015062157A (ja) * 2013-01-25 2015-04-02 住友ベークライト株式会社 負極材料、負極活物質、負極およびアルカリ金属イオン二次電池
JP2017505517A (ja) * 2014-01-24 2017-02-16 エキョンペトロケミカル シーオー., エルティーディー.Aekyungpetrochemical Co., Ltd. リチウム二次電池用負極活物質およびその製造方法、これを用いたリチウム二次電池
US9905848B2 (en) 2015-11-10 2018-02-27 Samsung Sdi Co., Ltd. Negative active material for rechargeable lithium battery, negative electrode for rechargeable lithium battery including same and rechargeable lithium battery including same
US10128504B2 (en) 2015-10-27 2018-11-13 Samsung Sdi Co., Ltd. Negative active material for rechargeable lithium battery, and rechargeable lithium battery including same
WO2018212374A1 (fr) * 2017-05-17 2018-11-22 서울과학기술대학교 산학협력단 Matériau actif d'électrode, son procédé de fabrication et batterie secondaire au lithium le comprenant
CN111837269A (zh) * 2019-02-15 2020-10-27 爱敬油化株式会社 用于锂二次电池的负极活性材料添加剂的碳质材料
CN114824165A (zh) * 2022-06-30 2022-07-29 宁德新能源科技有限公司 负极极片、电化学装置及电子设备

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4067956A (en) * 1976-10-08 1978-01-10 Chemotronics International, Inc. Reticulated anisotropic porous vitreous carbon
US5510212A (en) * 1993-01-13 1996-04-23 Delnick; Frank M. Structural micro-porous carbon anode for rechargeable lithium ion batteries
US20080254296A1 (en) * 2005-03-22 2008-10-16 Bussan Nanotech Research Institute Inc. Carbon Fibrous Conjunct and Composite Material Using Thereof
US20090136809A1 (en) * 2004-08-16 2009-05-28 Jing Wang Porous carbon foam composites, applications, and processes of making
EP2221841A1 (fr) * 2007-11-16 2010-08-25 Osaka Gas Company Limited Matériau d'électrode positive pour élément de stockage de type lithium

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4067956A (en) * 1976-10-08 1978-01-10 Chemotronics International, Inc. Reticulated anisotropic porous vitreous carbon
US5510212A (en) * 1993-01-13 1996-04-23 Delnick; Frank M. Structural micro-porous carbon anode for rechargeable lithium ion batteries
US20090136809A1 (en) * 2004-08-16 2009-05-28 Jing Wang Porous carbon foam composites, applications, and processes of making
US20080254296A1 (en) * 2005-03-22 2008-10-16 Bussan Nanotech Research Institute Inc. Carbon Fibrous Conjunct and Composite Material Using Thereof
EP2221841A1 (fr) * 2007-11-16 2010-08-25 Osaka Gas Company Limited Matériau d'électrode positive pour élément de stockage de type lithium

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015062157A (ja) * 2013-01-25 2015-04-02 住友ベークライト株式会社 負極材料、負極活物質、負極およびアルカリ金属イオン二次電池
JP2017505517A (ja) * 2014-01-24 2017-02-16 エキョンペトロケミカル シーオー., エルティーディー.Aekyungpetrochemical Co., Ltd. リチウム二次電池用負極活物質およびその製造方法、これを用いたリチウム二次電池
US10128504B2 (en) 2015-10-27 2018-11-13 Samsung Sdi Co., Ltd. Negative active material for rechargeable lithium battery, and rechargeable lithium battery including same
US9905848B2 (en) 2015-11-10 2018-02-27 Samsung Sdi Co., Ltd. Negative active material for rechargeable lithium battery, negative electrode for rechargeable lithium battery including same and rechargeable lithium battery including same
WO2018212374A1 (fr) * 2017-05-17 2018-11-22 서울과학기술대학교 산학협력단 Matériau actif d'électrode, son procédé de fabrication et batterie secondaire au lithium le comprenant
US11440802B2 (en) 2017-05-17 2022-09-13 Foundation For Research And Business Seoul National University Of Science And Technology Electrode active material, method for manufacturing same, and lithium secondary battery comprising same
CN111837269A (zh) * 2019-02-15 2020-10-27 爱敬油化株式会社 用于锂二次电池的负极活性材料添加剂的碳质材料
US20210214234A1 (en) * 2019-02-15 2021-07-15 Aekyungpetrochemicalco.,Ltd Carbonaceous Material for Negative Electrode Active Material Additive for Lithium Secondary Battery
CN114824165A (zh) * 2022-06-30 2022-07-29 宁德新能源科技有限公司 负极极片、电化学装置及电子设备
CN114824165B (zh) * 2022-06-30 2022-10-14 宁德新能源科技有限公司 负极极片、电化学装置及电子设备

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