WO2017164650A1 - Matériau actif d'anode pour accumulateur, et accumulateur le comprenant - Google Patents

Matériau actif d'anode pour accumulateur, et accumulateur le comprenant Download PDF

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WO2017164650A1
WO2017164650A1 PCT/KR2017/003088 KR2017003088W WO2017164650A1 WO 2017164650 A1 WO2017164650 A1 WO 2017164650A1 KR 2017003088 W KR2017003088 W KR 2017003088W WO 2017164650 A1 WO2017164650 A1 WO 2017164650A1
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active material
negative electrode
lithium
electrode active
secondary battery
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PCT/KR2017/003088
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English (en)
Korean (ko)
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박성빈
이동훈
전혜림
정왕모
강성훈
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주식회사 엘지화학
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Priority to EP17770620.7A priority Critical patent/EP3312914B1/fr
Priority to PL17770620T priority patent/PL3312914T3/pl
Priority to US15/746,910 priority patent/US10665859B2/en
Priority to CN201780002684.0A priority patent/CN107925069B/zh
Priority claimed from KR1020170036235A external-priority patent/KR101908222B1/ko
Publication of WO2017164650A1 publication Critical patent/WO2017164650A1/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
    • 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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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 secondary battery and a lithium secondary battery including the same, which exhibits an output characteristic together with an excellent capacity recovery rate when applied to a battery, can prevent the decomposition of an electrolyte and reduce gas generation.
  • lithium secondary batteries having high energy density and voltage, long cycle life, and low self discharge rate have been commercialized and widely used.
  • high capacity and high output technology of negative electrode active materials is required.
  • a carbon-based material especially graphite, which is capable of reversible intercalation and desorption of lithium ions while maintaining structural and electrical properties, is mainly used as a negative electrode active material, but in recent years, there is a demand for a high capacity battery.
  • lithium oxide-based negative electrode materials such as a lithium alloy (alloy) anode material using silicon (Si), tin (Sn), and lithium titanium oxide, which have a larger theoretical capacity than graphite, have been conducted.
  • lithium titanium oxide is a zero-strain material having extremely low structural changes during charging and discharging.
  • the lithium titanium oxide has excellent life characteristics, forms a relatively high voltage band, and does not generate dendrite.
  • the safety and stability are very good.
  • lithium titanium oxide does not form a solid electrolyte interface (SEI) layer because the operating voltage is higher than the electrolyte decomposition voltage. Therefore, in the case of a lithium secondary battery to which lithium titanium oxide is applied, electrolyte decomposition is continuously generated as charging and discharging proceeds, which causes a problem of depletion of electrolyte and deterioration of life characteristics. In addition, in the case of a lithium secondary battery to which lithium titanium oxide is applied, a large amount of gas is generated when left at a high temperature.
  • SEI solid electrolyte interface
  • the first technical problem to be solved by the present invention is to provide an anode active material for a secondary battery and a method of manufacturing the same, which exhibit an output characteristic with excellent capacity recovery rate when applied to a battery, and can prevent the decomposition of electrolyte and reduce the generation of gas. .
  • a second technical problem to be solved by the present invention is to provide a secondary battery negative electrode, a lithium secondary battery, a battery module and a battery pack including the negative electrode active material.
  • the surface treatment layer is boron-containing Lithium oxide is contained in an amount such that the boron content is in a molar ratio of 0.002 to 0.02 per 1 mol of lithium titanium oxide, and a titration amount of 0.9 to 1.5 ml when titrating 2 g of the negative electrode active material to pH 5 or less using 0.1 M HCl
  • a negative electrode active material for phosphorus secondary batteries is provided.
  • the boron-containing lithium oxide on the surface of the core Provided is a method for producing a negative electrode active material for a secondary battery, comprising the step of forming a surface treatment layer comprising an amount such that the boron content is a molar ratio of 0.002 to 0.02 with respect to 1 mol of lithium titanium oxide.
  • a negative electrode for a secondary battery and a lithium secondary battery including the negative electrode active material are provided.
  • the negative electrode active material for a secondary battery according to the present invention may exhibit excellent capacity recovery.
  • the negative electrode active material can improve the output characteristics by preventing a decrease in resistance caused by lithium by-products generated in the manufacturing process of the core, the surface treatment layer can reduce the generation of gas by preventing the decomposition of the electrolyte, in particular low SOC In the state of charge, electrolyte decomposition and gas generation due to elution of titanium ions (Ti 4 + ) may be reduced.
  • FIG. 1 is a schematic diagram schematically showing a mechanism of generating a lithium ion mobile energy barrier.
  • FIG. 2 is a schematic diagram schematically showing a migration path of lithium ions in the crystal structure of Li 2 B 4 O 7.
  • FIG. 2 is a schematic diagram schematically showing a migration path of lithium ions in the crystal structure of Li 2 B 4 O 7.
  • FIG 3 is a schematic diagram schematically showing a migration path of lithium ions in the crystal structure of Al 2 O 3 .
  • Figure 4 is a photograph of the negative electrode active material prepared in Example 1 observed with a scanning electron microscope.
  • Example 7 is a graph measuring the initial discharge capacity at 0.2C for the negative electrode active materials of Example 1 and Comparative Example 1.
  • Example 8 is a graph measuring the discharge capacity at 10C for the negative electrode active materials of Example 1 and Comparative Example 1.
  • Example 9 is a graph measuring the amount of gas generated in the lithium secondary battery including the negative electrode active material of Example 1 and Comparative Example 1, respectively.
  • Example 10 is a graph measuring the amount of gas generation in a lithium secondary battery including the negative electrode active materials of Example 4, Comparative Examples 9 and 10.
  • Example 11 is a graph showing the normal capacity of the lithium secondary battery including the negative electrode active material of Example 1 and Comparative Example 11.
  • the electrical conductivity in the surface treatment layer is related to the surface resistance of the negative electrode active material and the side reactivity with the electrolyte solution. Specifically, when the electrical conductivity in the surface treatment layer is low, the surface resistance is increased while the side reaction with the electrolyte may be reduced. Boron (B) usually has a low electrical conductivity as an insulator. Accordingly, it is preferable to appropriately control the content of boron included in the surface treatment layer in order to reduce the surface resistance of the negative electrode active material and thereby improve output characteristics and to prevent side reactions with the electrolyte.
  • a surface treatment layer of boron-containing lithium oxide is formed on the core surface containing lithium titanium oxide, but in consideration of the electrical conductivity in the surface treatment layer and the suppression of side reaction with the electrolyte solution.
  • the negative electrode active material for a secondary battery including a lithium titanium oxide, and a surface treatment layer located on the surface of the core, the surface treatment layer is boron-containing lithium oxide To 1 mol of lithium titanium oxide, the boron content is contained in an amount such that the molar ratio of 0.002 to 0.02, the titration amount is 0.9 to 1.5ml when titrating 2g of the negative electrode active material to pH 5 or less using 0.1M HCl.
  • the surface treatment layer including the boron-containing lithium oxide is formed through reaction with a lithium impurity in which a precursor of boron-containing lithium oxide such as boric acid is present on the core surface, and a lithium raw material additionally added in the manufacturing process,
  • a lithium impurity in which a precursor of boron-containing lithium oxide such as boric acid is present on the core surface, and a lithium raw material additionally added in the manufacturing process.
  • the content of lithium impurities in the core may be reduced, and at the same time, the lithium ion conductivity and the electrical conductivity in the surface treatment layer may be improved by optimizing the boron content.
  • electrolyte decomposition may be prevented from the core surface including lithium titanium oxide, thereby exhibiting excellent capacity recovery.
  • the decomposition of the electrolyte may be prevented by the surface treatment layer, so that the amount of gas generated may be reduced, and in particular, electrolyte decomposition and gas generation due to the dissolution of titanium ions (Ti 4 + ) may be reduced at low SOC (state of charge).
  • the surface treatment layer uniformly covers the entire surface of the core without recrystallization, thereby preventing a decrease in resistance caused by lithium by-products generated in the manufacturing process of the core, thereby improving output characteristics.
  • the capacity recovery rate means the average discharge capacity during two and three cycles except for the initial discharge capacity when the battery is stored for one week at 80 ° C. after full charge, discharged, and charged and discharged under the same charge and discharge conditions. do.
  • the surface treatment layer containing boron-containing lithium oxide is an amount such that the boron content is a molar ratio of 0.002 to 0.02 with respect to 1 mol of lithium titanium oxide constituting the core. It may include a boron-containing lithium oxide as described above. If the content of boron is less than 0.002 molar ratio compared to lithium titanium oxide, the improvement effect due to the formation of the surface treatment layer is insignificant. If the content of boron exceeds 0.02 molar ratio, the surface resistance is increased due to the decrease in the electrical conductivity in the surface treatment layer and the output characteristics of the battery. May cause degradation. More specifically, the surface treatment layer may include boron-containing lithium oxide in an amount of 5000 to 7000 ppm with respect to the total weight of lithium titanium oxide.
  • the content of boron included in the surface treatment layer may be analyzed using an inductively coupled plasma optical emission spectrometer (ICP).
  • ICP inductively coupled plasma optical emission spectrometer
  • the lithium ion migration energy barrier (E barrier ) can be predicted from the diffusion path of lithium ions in the material forming the surface treatment layer.
  • FIG. 1 is a schematic diagram showing a mechanism of generating a lithium ion mobile energy barrier
  • FIGS. 2 and 3 are schematic diagrams showing crystal structures of Li 2 B 4 O 7 and Al 2 O 3 , respectively. 1 to 3 are only examples for describing the present invention, but the present invention is not limited thereto.
  • both boron and aluminum have low electrical conductivity as an insulator, and as a result, side reaction with the electrolyte solution can be suppressed, and the resistance at the negative electrode interface can be increased to improve the safety of the active material, thereby providing a surface treatment agent for the active material.
  • Mainly used Li 2 B 4 O 7 is a representative example of the boron-containing lithium oxide, and the movement path of lithium ions in the crystal structure is lower than that of Al 2 O 3 , which is usually used for forming a surface treatment layer. long. Accordingly, relatively large lithium ion is Al 2 O 3 the movement of lithium ions between the crystal and easier than, as a result, can exhibit a lower lithium ion migration barrier energy values and more excellent lithium ion conductivity.
  • the E barrier value of boron-containing lithium oxide is usually about 0.05 eV to 0.45 eV.
  • the value of the E barrier of the boron-containing lithium oxide is due to the difference in the lithium ion migration path in the crystal structure, which can be controlled according to the heat treatment temperature during manufacture. In this case, when the heat treatment temperature is too high and the E barrier value is too large, the gas reduction effect and the output characteristic improvement effect may be reduced due to the decrease in the surface coverage ratio due to the recrystallization of the boron-containing lithium oxide.
  • the E barrier value is increased as the heat treatment is performed at a high temperature when forming the surface treatment layer. At this time, the recrystallization occurs, and as a result, the surface coverage is decreased, thereby decreasing the output characteristics and reducing the gas generation effect.
  • the surface treatment layer may be made of a single boron-containing lithium oxide, or may be made of a mixture of two or more boron-containing lithium oxides.
  • the present invention by controlling the type or mixing ratio of the boron-containing lithium oxide forming the surface treatment layer under the conditions that satisfy the above content range of boron in the surface treatment layer, it is possible to improve the lithium ion conductivity in the surface treatment layer. .
  • the surface treatment layer may have an E barrier value of 0.05 eV to 0.3 eV, more specifically 0.05 eV to 0.2 eV. If the E barrier value in the surface treatment layer is less than 0.05 eV, it is difficult to manufacture itself, and if it exceeds 0.3 eV, gas reduction effect and output characteristic improvement effect may be deteriorated due to the decrease of the surface coverage due to the recrystallization of boron-containing lithium oxide. have.
  • the E barrier value can be obtained through first principle calculation using the VIenna Ab initio simulation package (VASP) program.
  • VASP VIenna Ab initio simulation package
  • the boron-containing lithium oxide constituting the surface treatment layer may be a compound of Formula 1 below:
  • Li 2 B 4 O 7 LiB 3 O 5 , LiB 8 O 13 , Li 4 B 2 O 5 , Li 3 BO 3 , Li 2 B 2 O 4 , or Li 2 B 6 O 10 . And any one or a mixture of two or more thereof.
  • the boron-containing lithium oxide may have an E barrier value of 0.05 eV to 0.3 eV, and more specifically, may satisfy the above E barrier value and at the same time, a band gap of 8.5 eV to 10.5 eV. .
  • the band gap may be 8.9 eV to 10.1 eV.
  • the band gap of the boron-containing lithium oxide can be measured using cyclic voltammetry.
  • the surface treatment layer is preferably formed to an appropriate thickness in consideration of the particle diameter of the core for determining the capacity of the negative electrode active material. Specifically, it may be formed in an average thickness ratio of 0.01 to 0.1 with respect to the radius of the core under the conditions satisfying the boron content. If the thickness ratio of the surface treatment layer is less than 0.01, the thickness of the surface treatment layer may be too thin, so that the effect of suppressing side reactions between the negative electrode active material and the electrolyte during charging and discharging may be insignificant. If the thickness ratio of the surface treatment layer exceeds 0.1, the surface treatment layer may be too thick. Due to this, there is a risk of deterioration of output characteristics due to an increase in resistance.
  • the particle diameter of the core and the thickness of the surface treatment layer can be measured through particle cross-sectional analysis using a focused ion beam (fib).
  • the surface treatment layer may be formed on the entire surface of the core, or may be partially formed. More specifically, the surface treatment layer may be formed at least 80% of the total surface area of the core under the conditions satisfying the above-described boron content range, and more specifically, the surface treatment when considering the effect of preventing electrolyte decomposition at the core surface
  • the layer can be formed over 100% of the total surface area of the core, ie over the core surface.
  • the core includes lithium titanium oxide.
  • the lithium titanium oxide may be a compound of Formula 2 below:
  • M includes at least one element selected from the group consisting of metals of Groups 2 to 13 on the periodic table, specifically, Al, Ni, Co, Fe, Mn, V, Cr, Ti, W, Ta, Mg and May be one or more selected from the group consisting of Mo,
  • A is a nonmetallic element having a -monovalent oxidation number, and specifically, may be at least one selected from the group consisting of F, Cl, Br, and I.
  • composition of lithium titanium oxide of Formula 2 is the average composition of the entire core.
  • the lithium titanium oxide is Li 4 Ti 5 O 12 , Li 0 . 8 Ti 2 . 2 O 4 , Li 2.67 Ti 1.33 O 4 , LiTi 2 O 4 , Li 1 . 33 Ti 1 . 67 O 4 or Li 1 . 14 Ti 1 . 71 O 4 , and any one or a mixture of two or more thereof may be used.
  • the lithium titanium oxide may be a single particle having an average particle diameter (D 50 ) of 0.1 ⁇ m to 5 ⁇ m, or fine primary particles having an average particle diameter of 200 nm to 1000 nm are aggregated, and an average particle diameter (D 50 )
  • the secondary particles may be 3 ⁇ m to 20 ⁇ m.
  • the lithium titanium oxide is a single particle, if the average particle diameter is less than 0.1 ⁇ m, there is a fear of lowering structural stability and capacity characteristics. If the average particle diameter exceeds 5 ⁇ m, output characteristics of the secondary battery may be reduced. .
  • the average particle diameter (D 50 ) of the core particles can be defined as the particle size at 50% of the particle size distribution.
  • the average particle diameter (D 50 ) of the core particles can be measured using, for example, a laser diffraction method. More specifically, when measured by the laser diffraction method, the core particles were dispersed in a solvent, and then introduced into a commercially available laser diffraction particle size measuring apparatus (for example, Microtrac MT 3000) to irradiate an ultrasonic wave of about 28 kHz at an output of 60 W. after that, it is possible to calculate the average particle diameter (D 50) of from 50% based on the particle size distribution of the measuring device.
  • a laser diffraction particle size measuring apparatus for example, Microtrac MT 3000
  • the core is from the surface side of the particle, specifically the interface in contact with the surface treatment layer, and from the interface in contact with the surface treatment layer from more than 0% to less than 100% with respect to the core particle radius in the direction of the core particle center.
  • Some boron (B) elements of the boron-containing lithium oxide may be doped in an area corresponding to a distance of 0% to 30%.
  • the content of the B element may have a concentration gradient that decreases from the surface of the core toward the core center.
  • the negative electrode active material according to an embodiment of the present invention having the structure and configuration as described above is much lower than the prior art due to the decrease in the lithium impurity content, such as lithium carbonate, lithium hydroxide, and the increase of boron content on the surface of the active material Initial pH value is shown.
  • the lithium impurity content such as lithium carbonate, lithium hydroxide
  • the increase of boron content on the surface of the active material Initial pH value is shown.
  • side reactions between the negative electrode active material and the electrolyte can be suppressed, and at the same time, the lithium ion conductivity and the electrical conductivity in the surface treatment layer can be improved with good balance.
  • the negative electrode active material has an initial pH value of 9 to 10, more specifically, 9.3 to 9.7, and the appropriate amount when titrating 2 g of the negative electrode active material to pH 5 or less, specifically pH 5 using 0.1M HCl, is 0.9 To 1.5 ml, and more specifically 0.9 to 1.4 ml. As the titration amount is smaller, side reactions between the negative electrode active material and the electrolyte are suppressed, and at the same time, an effect of improving the balance of the lithium ion conductivity and the electrical conductivity in the surface treatment layer can be achieved.
  • the pH of the negative electrode active material may be measured by mixing 2 g of the negative electrode active material in 100 ml of distilled water, stirring for 5 to 10 minutes, filtration, and titrating to pH 5 or less with an acid such as HCl. At this time, by-products such as lithium carbonate and lithium hydroxide included in the active material may be repeatedly soaked and decanted to be included in distilled water. At this time, it is not particularly affected by variables such as time to add the negative electrode active material to distilled water.
  • the negative electrode active material may be one having a BET specific surface area of 0.5m 2 / g to 10.0m 2 / g.
  • the BET specific surface area of the negative electrode active material exceeds 10.0 m 2 / g, the dispersibility of the negative electrode active material in the active material layer and the resistance in the electrode may increase due to aggregation between the negative electrode active materials, and the BET specific surface area is 0.5 m 2 / g.
  • the negative electrode active material according to an embodiment of the present invention may exhibit excellent capacity and charge / discharge characteristics by accelerating the BET specific surface conditions. More specifically, the negative electrode active material may have a BET specific surface area of 3.0m 2 / g to 6.0m 2 / g.
  • the specific surface area of the negative electrode active material is measured by the Brunauer-Emmett-Teller (BET) method, specifically, nitrogen gas at liquid nitrogen temperature (77K) using BELSORP-mino II manufactured by BEL Japan It can calculate from adsorption amount.
  • BET Brunauer-Emmett-Teller
  • the negative electrode active material according to the embodiment of the present invention having the structure as described above, after the surface treatment of the precursor of the boron-containing lithium oxide to the core containing lithium titanium oxide, heat treatment at 350 °C to 450 °C, the core It can be prepared by a manufacturing method comprising the step of forming a surface treatment layer comprising a boron-containing lithium oxide on the surface of the amount of boron content relative to 1 mol of lithium titanium oxide in a molar ratio of 0.002 to 0.02. Accordingly, according to another embodiment of the present invention is provided a method for producing the negative electrode active material.
  • the core including the lithium titanium oxide is the same as described above, and may be manufactured according to a conventional manufacturing method.
  • the precursor of the boron-containing lithium oxide may be a material capable of forming boron-containing lithium oxide by reacting by boron-containing lithium oxide or a subsequent heat treatment process.
  • the precursor of the boron-containing lithium oxide is boric acid of H 3 BO 3 ; Boron oxides such as B 2 O 3 or B 2 O 5 ; LiBO 3, Li 2 B 4 O 7, LiB 3 O 5, LiB 8 O 13, Li 4 B 2 O 5, Li 3 BO 3, Li 2 B 2 O 4, or Li 2 lithium borate such as B 6 O 10 And boron-containing lithium oxides such as salts. Any one or a mixture of two or more thereof may be used.
  • the surface treatment step for the lithium titanium oxide may be a dry mixing of the core containing the lithium titanium oxide and the precursor of the boron-containing lithium oxide, or the boron-containing lithium to the core containing the lithium titanium oxide.
  • the composition for forming a surface treatment layer including a precursor of an oxide may be performed according to a conventional surface treatment process such as spraying, coating, or dipping.
  • a precursor of boron-containing lithium oxide is dissolved or dispersed in a solvent to prepare a composition for forming a surface treatment layer, and then includes lithium titanium oxide using a conventional spraying apparatus.
  • a polar solvent may be used as the solvent, and specifically, water or an alcohol having 1 to 8 carbon atoms (for example, methanol, ethanol, or isopropyl alcohol), or dimethyl sulfoxide (DMSO), N- Polar organic solvents such as methylpyrrolidone (NMP), acetone, and the like, and any one or a mixture of two or more thereof may be used.
  • the solvent may be included in an amount that can exhibit a suitable coating property when the surface treatment of the composition, and can be easily removed during the subsequent heat treatment.
  • the mixing ratio of the core containing the lithium titanium oxide and the precursor of the boron-containing lithium oxide, the execution time of the surface treatment process, and the like, the content of boron in the final negative electrode active material It can be mutually adjusted as appropriate within the range to satisfy the range.
  • a lithium raw material capable of reacting with the precursor of the boron-containing lithium oxide in the surface treatment process to form a boron-containing lithium oxide may optionally be further used.
  • the lithium raw material is specifically lithium hydroxide such as LiOH; Carbonates such as Li 2 CO 3 , etc., and any one or a mixture of two or more thereof may be used.
  • the lithium raw material may be used so that the boron-containing lithium oxide in the surface treatment layer is formed in an amount such that the boron content is a molar ratio of 0.002 to 0.02 with respect to 1 mol of lithium titanium oxide.
  • a heat treatment process is performed at 350 ° C to 450 ° C for the cores surface-treated by the surface treatment process.
  • the E barrier value of the boron-containing lithium oxide forming the surface treatment layer may be controlled by the heat treatment temperature for the surface-treated core.
  • the heat treatment temperature for the surface-treated core When the heat treatment is performed within the above temperature range, boron-containing lithium oxide that satisfies the above E barrier value condition may be formed, and at the same time, the coverage of the core surface may be improved. If the temperature during the heat treatment is less than 350 °C, the formation of boron-containing lithium oxide that satisfies the above E barrier value conditions and the control of the E barrier value is not easy, and the side reaction occurs due to the unreacted precursor material and the residual solvent component There is a fear of deterioration of the characteristics of the active material and battery characteristics.
  • the heat treatment process may be performed at 400 °C to 450 °C.
  • the heat treatment process may be carried out in a multi-step within the above temperature range, in this case it may be carried out by increasing the temperature according to the progress of each step.
  • the heat treatment process may be performed in an air atmosphere or an oxygen atmosphere (for example, O 2 ), and more specifically, may be performed in an oxygen atmosphere having an oxygen partial pressure of 20% by volume or more.
  • the heat treatment process may be performed for 5 hours to 48 hours, or 10 hours to 20 hours under the above conditions.
  • a surface treatment layer including boron-containing lithium oxide satisfying the above E barrier value range is formed on the core including lithium titanium oxide in an optimal content.
  • the prepared negative electrode active material may exhibit excellent capacity recovery due to its unique structure and constituent characteristics.
  • the negative electrode active material can improve the output characteristics by preventing a decrease in resistance caused by lithium by-products generated in the manufacturing process of the core, and can also reduce the generation of gas by preventing the decomposition of the electrolyte solution by the surface treatment layer, especially low In the SOC (state of charge), it is possible to reduce electrolyte decomposition and gas generation due to elution of titanium ions Ti 4+ .
  • a negative electrode and a lithium secondary battery including the negative electrode active material provide a negative electrode and a lithium secondary battery including the negative electrode active material.
  • the negative electrode includes a negative electrode current collector and a negative electrode active material layer positioned on the negative electrode current collector.
  • the negative electrode current collector is not particularly limited as long as it has high conductivity without causing chemical change in the battery.
  • copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper or stainless steel Surface-treated with carbon, nickel, titanium, silver, and the like on the surface of the steel, aluminum-cadmium alloy and the like can be used.
  • the negative electrode current collector may have a thickness of about 3 to 500 ⁇ m, and like the positive electrode current collector, fine concavities and convexities may be formed on the surface of the current collector to enhance the bonding force of the negative electrode active material.
  • it can be used in various forms, such as a film, a sheet, a foil, a net, a porous body, a foam, a nonwoven body.
  • the negative electrode active material layer may further include a binder and a conductive material optionally together with the negative electrode active material, and may be prepared according to a conventional negative electrode manufacturing method except using the negative electrode active material. Can be.
  • the negative electrode is coated with a negative electrode active material, and optionally a composition for forming a negative electrode comprising a binder and a conductive material on the negative electrode current collector and dried, or casting the negative electrode forming composition on a separate support,
  • a composition for forming a negative electrode comprising a binder and a conductive material on the negative electrode current collector and dried, or casting the negative electrode forming composition on a separate support,
  • the film obtained by peeling from this support may be produced by laminating on a negative electrode current collector.
  • the conductive material is used to impart conductivity to the electrode.
  • the conductive material may be used without particular limitation as long as it has electronic conductivity without causing chemical change. Specific examples thereof include graphite such as natural graphite and artificial graphite; Carbon-based materials such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, summer black and carbon fiber; Metal powder or metal fibers such as copper, nickel, aluminum, and silver; Conductive whiskeys such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Or conductive polymers such as polyphenylene derivatives, and the like, or a mixture of two or more kinds thereof may be used.
  • the conductive material may be included in an amount of 1 to 30% by weight based on the total weight of the negative electrode active material layer.
  • the binder serves to improve adhesion between the negative electrode active material particles and the adhesion between the negative electrode active material and the current collector.
  • specific examples include polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinyl alcohol, polyacrylonitrile, carboxymethyl cellulose (CMC).
  • the binder may be included in an amount of 1 to 30% by weight based on the total weight of the negative electrode active material layer.
  • the solvent usable in the preparation of the negative electrode composition may include a solvent generally used in the art, dimethyl sulfoxide (DMSO), isopropyl alcohol, N- Methyl pyrrolidone (NMP), acetone (acetone) or water, and the like, and one of these alone or a mixture of two or more thereof may be used.
  • the amount of the solvent is sufficient to dissolve or disperse the negative electrode active material, the conductive material and the binder in consideration of the coating thickness and the production yield of the slurry, and to have a viscosity that can exhibit excellent thickness uniformity during the coating for the negative electrode production. Do.
  • the coating of the composition for forming a negative electrode on the negative electrode current collector may be performed by a conventional slurry coating method.
  • the slurry coating method may include bar coating, spin coating, roll coating, slot die coating, or spray coating, and any one or two or more of these methods may be mixed.
  • it may be preferable to apply the composition for forming the negative electrode to an appropriate thickness in consideration of the loading amount and the thickness of the active material in the negative electrode active material layer to be finally prepared.
  • the drying process for the coating film of the composition for forming a negative electrode formed on the negative electrode current collector carried out after the coating process, as well as the evaporation of the solvent in the composition for forming a negative electrode to remove the moisture contained in the negative electrode to the maximum, and at the same time can increase the binding strength of the binder It may be carried out by a method such as heat treatment at a temperature, hot air injection and the like. Specifically, the drying process may be carried out at a temperature below the boiling point of the solvent or less than the melting point of the binder, more specifically, may be carried out at 100 °C to 150 °C. More preferably, it may be carried out for 1 to 50 hours at a temperature of 100 °C to 120 °C and a pressure of 10torr or less.
  • the negative electrode as described above may exhibit excellent output characteristics by including the negative electrode active material in the negative electrode active material layer, and gas generation may be reduced by preventing decomposition of the electrolyte.
  • an electrochemical device including the cathode is provided.
  • the electrochemical device may be specifically a battery, a capacitor, or the like, and more specifically, a lithium secondary battery.
  • the lithium secondary battery specifically includes a positive electrode, a negative electrode positioned to face the positive electrode, a separator and an electrolyte interposed between the positive electrode and the negative electrode, and the negative electrode is as described above.
  • the lithium secondary battery may further include a battery container for accommodating the electrode assembly of the positive electrode, the negative electrode, and the separator, and a sealing member for sealing the battery container.
  • the positive electrode is formed on the positive electrode current collector and the positive electrode current collector, and includes a positive electrode active material layer containing the positive electrode active material.
  • the positive electrode current collector is not particularly limited as long as it has conductivity without causing chemical changes in the battery.
  • carbon, nickel, titanium on a surface of aluminum or stainless steel Surface treated with silver, silver or the like can be used.
  • the positive electrode current collector may have a thickness of about 3 to 500 ⁇ m, and may form fine irregularities on the surface of the current collector to increase adhesion of the positive electrode active material.
  • it can be used in various forms, such as a film, a sheet, a foil, a net, a porous body, a foam, a nonwoven body.
  • a compound capable of reversible intercalation and deintercalation of lithium may be used as the cathode active material.
  • the lithium transition metal oxide may be a lithium transition metal oxide including lithium and a transition metal such as cobalt, manganese, nickel or aluminum.
  • the lithium transition metal oxide is specifically a lithium-manganese oxide (eg, LiMnO 2 , LiMn 2 O Etc.), lithium-cobalt-based oxides (e.g., LiCoO 2, etc.), lithium-nickel-based oxides (e.g., LiNiO 2, etc.), lithium-nickel-manganese-based oxides (e.g., LiNi 1 - Y Mn Y O 2 (where, 0 ⁇ Y ⁇ 1), LiMn 2-z Ni z O 4 (where, 0 ⁇ Z ⁇ 2) and the like), lithium-nickel-cobalt-based oxide (for example, LiNi 1 - Y Co Y O 2 (where, 0 ⁇ Y ⁇ 1) and the like), lithium-manganese-cobalt oxide (e.g., LiCo 1-Y M
  • LiNi 0.8 Mn 0.1 Co 0.1 O 2 or the like, or lithium nickel cobalt aluminum oxide (eg, LiNi 0.8 Co 0.15 Al 0.05 O 2, etc.), and any one or a mixture of two or more thereof may be used. Can be used.
  • the positive electrode as described above may be manufactured according to a conventional positive electrode manufacturing method. Specifically, the composition for forming a cathode prepared by dissolving a conductive material and a binder in a solvent together with the cathode active material may be coated on a cathode current collector, followed by drying and rolling.
  • the separator is to separate the negative electrode and the positive electrode and to provide a passage for the movement of lithium ions, if it is usually used as a separator in a lithium secondary battery can be used without particular limitation, in particular for ion transfer of the electrolyte It is desirable to have a low resistance against the electrolyte and excellent electrolytic solution-moisture capability.
  • a porous polymer film for example, a porous polymer film made of a polyolefin-based polymer such as ethylene homopolymer, propylene homopolymer, ethylene / butene copolymer, ethylene / hexene copolymer and ethylene / methacrylate copolymer or the like Laminate structures of two or more layers may be used.
  • a porous nonwoven fabrics such as nonwoven fabrics made of high melting point glass fibers, polyethylene terephthalate fibers and the like may be used.
  • a coated separator containing a ceramic component or a polymer material may be used to secure heat resistance or mechanical strength, and may be optionally used as a single layer or a multilayer structure.
  • examples of the electrolyte used in the present invention include an organic liquid electrolyte, an inorganic liquid electrolyte, a solid polymer electrolyte, a gel polymer electrolyte, a solid inorganic electrolyte, a molten inorganic electrolyte, and the like, which can be used in manufacturing a lithium secondary battery. It doesn't happen.
  • the electrolyte may include an organic solvent and a lithium salt.
  • the organic solvent may be used without particular limitation as long as it can serve as a medium through which ions involved in the electrochemical reaction of the battery can move.
  • the organic solvent may be an ester solvent such as methyl acetate, ethyl acetate, ⁇ -butyrolactone or ⁇ -caprolactone; Ether solvents such as dibutyl ether or tetrahydrofuran; Ketone solvents such as cyclohexanone; Aromatic hydrocarbon solvents such as benzene and fluorobenzene; Dimethylcarbonate (DMC), diethylcarbonate (DEC), methylethylcarbonate (MEC), ethylmethylcarbonate (EMC), ethylene carbonate (EC), propylene carbonate, Carbonate solvents such as PC); Alcohol solvents such as ethyl alcohol and isopropyl alcohol; Nitriles such as R-CN (R is a C2 to C20 linear, branched or cyclic hydrocarbon group, which may include a
  • carbonate-based solvents are preferable, and cyclic carbonates having high ionic conductivity and high dielectric constant (for example, ethylene carbonate or propylene carbonate) that can improve the charge and discharge performance of a battery, and low viscosity linear carbonate compounds (for example, a mixture of ethyl methyl carbonate, dimethyl carbonate or diethyl carbonate and the like is more preferable.
  • the cyclic carbonate and the chain carbonate may be mixed and used in a volume ratio of about 1: 1 to about 1: 9, so that the performance of the electrolyte may be excellent.
  • the lithium salt may be used without particular limitation as long as it is a compound capable of providing lithium ions used in a lithium secondary battery.
  • the lithium salt is LiPF 6 , LiClO 4 , LiAsF 6 , LiBF 4 , LiSbF 6 , LiAl0 4 , LiAlCl 4 , LiCF 3 SO 3 , LiC 4 F 9 SO 3 , LiN (C 2 F 5 SO 3 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , LiN (CF 3 SO 2 ) 2 .
  • LiCl, LiI, or LiB (C 2 O 4 ) 2 and the like can be used.
  • the concentration of the lithium salt is preferably used within the range of 0.1 to 2.0M. When the concentration of the lithium salt is included in the above range, since the electrolyte has an appropriate conductivity and viscosity, it can exhibit excellent electrolyte performance, and lithium ions can move effectively.
  • the electrolyte includes, for example, haloalkylene carbonate-based compounds such as difluoro ethylene carbonate, pyridine, tri, etc. for the purpose of improving battery life characteristics, reducing battery capacity, and improving discharge capacity of the battery.
  • haloalkylene carbonate-based compounds such as difluoro ethylene carbonate, pyridine, tri, etc.
  • Ethyl phosphite triethanolamine, cyclic ether, ethylene diamine, n-glyme, hexaphosphate triamide, nitrobenzene derivative, sulfur, quinone imine dye, N-substituted oxazolidinone, N, N-substituted imida
  • One or more additives such as zolidine, ethylene glycol dialkyl ether, ammonium salt, pyrrole, 2-methoxy ethanol or aluminum trichloride may be included. In this case, the additive may be included in 0.1 to 5% by weight based on the total weight of the electrolyte.
  • the lithium secondary battery including the cathode active material according to the present invention stably exhibits excellent discharge capacity, output characteristics, and capacity retention rate
  • portable devices such as mobile phones, notebook computers, digital cameras, and hybrid electric vehicles ( It is useful for electric vehicle fields such as hybrid electric vehicle (HEV).
  • HEV hybrid electric vehicle
  • a battery module including the lithium secondary battery as a unit cell and a battery pack including the same are provided.
  • the battery module or the battery pack is a power tool (Power Tool); Electric vehicles including electric vehicles (EVs), hybrid electric vehicles, and plug-in hybrid electric vehicles (PHEVs); Or it can be used as a power source for any one or more of the system for power storage.
  • Power Tool Electric vehicles including electric vehicles (EVs), hybrid electric vehicles, and plug-in hybrid electric vehicles (PHEVs); Or it can be used as a power source for any one or more of the system for power storage.
  • Li 2 B 4 O 7 isopropyl alcohol for Li 4 Ti 5 O 12 (primary particle average particle diameter (D 50 ): 500 nm, secondary particle average particle diameter (D 50 ): 8 ⁇ m) on secondary particles.
  • Surface treatment using a composition prepared by mixing in, and heat treatment was performed for 5 hours at 400 °C under an atmosphere (wherein Li 2 B 4 O 7 is Li 4 Ti 5 O 12 Used in such a way that the molar ratio of B per mole is 0.005).
  • a negative electrode active material having a surface treatment layer including LiBO 2 and Li 2 B 4 O 7 formed on the surface of Li 4 Ti 5 O 12 was prepared.
  • An anode active material having a treatment layer was prepared.
  • Li 4 Ti 5 O 12 was carried out in the same manner as in Example 1, except that Li 2 B 4 O 7 was used in an amount such that the molar ratio of B was 0.01 with respect to 1 mol of Li 4 Ti 5 O 12.
  • a negative electrode active material having a surface treatment layer including LiBO 2 and Li 2 B 4 O 7 formed on its surface was prepared.
  • Li 2 B 4 O 7 5000 ppm isotropic to Li 4 Ti 5 O 12 (primary particle average particle diameter (D 50 ): 500 nm, secondary particle average particle diameter (D 50 ): 8 ⁇ m) on secondary particles.
  • Surface treatment was carried out using a composition prepared by mixing in propyl alcohol, and heat treatment was performed at 400 ° C. for 5 hours under an atmospheric atmosphere.
  • a negative electrode active material including 5,000 ppm of B was added to the total weight of Li 4 Ti 5 O 12 on the surface of Li 4 Ti 5 O 12 .
  • Li 4 Ti 5 O 12 (primary particle average particle diameter (D 50 ): 500 nm, secondary particle average particle diameter (D 50 ): 8 ⁇ m) on secondary particles without surface treatment was used as a negative electrode active material.
  • the Li 2 B 4 O Al 2 O 3 to 7 instead of the Li 4 Ti 5 O 12 A surface treatment layer including Al 2 O 3 on the surface of Li 4 Ti 5 O 12 by the same method as in Example 1, except that the molar ratio of Al to 0.005 was used per 1 mole. This formed negative electrode active material was prepared.
  • AlF 3 is Li 4 Ti 5 O 12 instead of Li 2 B 4 O 7
  • a surface treatment layer including AlF 3 was formed on the surface of Li 4 Ti 5 O 12 in the same manner as in Example 1 except that the molar ratio of Al was set to 0.005 per 1 mole.
  • a negative electrode active material was prepared.
  • Li 2 B 4 O 7 to Li 4 Ti 5 O 12 LiBO 2 and Li 2 B 4 O 7 were applied to the surface of Li 4 Ti 5 O 12 in the same manner as in Example 1, except that the molar ratio of B to 0.001 per mole was used.
  • a negative electrode active material including a surface treatment layer was prepared.
  • the Li 2 B 4 O Al 2 O 3 to 7 instead of the Li 4 Ti 5 O 12 A surface treatment layer including Al 2 O 3 on the surface of Li 4 Ti 5 O 12 by performing the same method as in Example 1 except that the molar ratio of Al was set to 0.003 per 1 mole. This formed negative electrode active material was prepared.
  • the Li 2 B 4 O Al 2 O 3 to 7 instead of the Li 4 Ti 5 O 12 A surface treatment layer including Al 2 O 3 on the surface of Li 4 Ti 5 O 12 by the same method as in Example 1, except that the molar ratio of Al was set to 0.004 per 1 mole. This formed negative electrode active material was prepared.
  • the negative electrode active material prepared in Comparative Example 1 was put into 100 ml of water, washed by stirring for 5 minutes, and used as a negative electrode active material.
  • Li 2 B 4 O 7 for Li 4 Ti 5 O 12 (primary particle average particle diameter (D 50 ): 500 nm, secondary particle average particle diameter (D 50 ): 8 ⁇ m) on secondary particles.
  • Surface treatment was carried out using a composition prepared by mixing 300 ppm in isopropyl alcohol, and heat treatment was performed at 400 ° C. for 5 hours under an atmospheric atmosphere.
  • a negative electrode active material comprising a.
  • Li 2 B 4 O 7 for Li 4 Ti 5 O 12 (primary particle average particle diameter (D 50 ): 500 nm, secondary particle average particle diameter (D 50 ): 8 ⁇ m) on secondary particles.
  • the surface treatment was carried out using a composition prepared by adding 500 ppm of the mixture to isopropyl alcohol and performing heat treatment at 400 ° C. for 5 hours under an atmospheric atmosphere.
  • the negative electrode active material having a surface treatment layer including LiBO 2 and Li 2 B 4 O 7 was formed on the surface of Li 4 Ti 5 O 12 by the above method, and 500 ppm of B was added based on the total weight of Li 4 Ti 5 O 12.
  • a negative electrode active material comprising a.
  • Example 2 Li 0. In the same manner as in Example 1 except that the heat treatment was performed at 500 ° C. for 5 hours . 8 Ti 2 . An anode active material having a surface treatment layer including LiBO 2 and LiB 4 O 7 formed on the surface of 2 O 4 was prepared.
  • a lithium secondary battery was prepared using the negative electrode active materials prepared in Examples 1 to 4, respectively.
  • the negative electrode active material, the carbon black conductive material, and the PVdF binder prepared in Examples 1 to 4 were mixed in a ratio of 85: 10: 5 by weight in an N-methylpyrrolidone solvent in a composition for forming a negative electrode.
  • Viscosity: 5000 mPa ⁇ s was prepared, coated on Cu foil with a loading amount of 2.6 mAh / cm 3 , dried by heat treatment at 120 ° C., and rolled to prepare a negative electrode.
  • Li (Ni 0.6 Mn 0.2 Co 0.2 ) O 2 A positive electrode active material, a carbon black conductive material, and a PVdF binder were mixed in an N-methylpyrrolidone solvent in a weight ratio of 90: 5: 5 to prepare a composition for forming a positive electrode (viscosity: 5000 cps), which was applied to an aluminum current collector. After that, dry rolling was performed to prepare a positive electrode.
  • An electrode assembly was manufactured by interposing a separator of porous polyethylene between the positive electrode and the negative electrode prepared as described above, the electrode assembly was placed in a case, and an electrolyte solution was injected into the case to prepare a lithium secondary battery.
  • the negative electrode active material of Comparative Examples 1 to 11 was carried out in the same manner as above to prepare a negative electrode and a lithium secondary battery including the same.
  • the E barrier value was obtained by first principle calculation using The vienna Ab initio simulation package (VASP) program.
  • the band gap was measured using cyclic voltammetry.
  • the content of element B contained in the surface treatment layer of the negative electrode active material was analyzed by the ICP-AES method (Inductively Coupled Plasma-Atomic Emission Spectroscophy).
  • ICP-AES Inductively Coupled Plasma-Atomic Emission Spectroscometer
  • the surface treatment layer of the cathode active materials of Examples 1 and 2 had a significantly lower E barrier value than the surface treatment layers of Comparative Examples 2 to 5 and 11, and from this it was confirmed that it has a better lithium ion conductivity. Can be.
  • Example 1 The negative electrode active materials prepared in Example 1 and Comparative Example 2 were processed using ion milling, and then observed by scanning electron microscopy (SEM). The results are shown in FIGS. 4 and 5, respectively.
  • the surface treatment layer containing B was uniformly formed on the core surface, whereas in the negative electrode active material prepared in Comparative Example 2, the Al-containing coating layer was partially formed on the core surface. It can be confirmed that the formed.
  • pH titration was performed to determine the change in the amount of lithium impurities according to the amount of B contained in the surface treatment layer.
  • the pH meter (metrohm 794) for 2g of the negative electrode active material of Examples 1 and 3 varying in the molar ratio of B contained in the surface treatment layer with respect to 1 mol of Li 4 Ti 5 O 12 was 0.005 and 0.01, respectively.
  • 0.1M HCl was titrated in 0.02ml increments and the pH change was recorded.
  • the pH was recorded by performing the same method for the negative active material of Comparative Examples 1 and 5-8 for comparison. The results are shown in FIG.
  • the negative electrode active materials of Examples 1 and 3 had a pH of 9 to 10, and the initial pH was lower than that of Comparative Examples 1 and 5-8.
  • the coin cell (using a negative electrode of Li metal) prepared using the negative electrode active material prepared in Example 1 was charged at 25 ° C. until a constant current (CC) of 4.25V was reached, followed by a constant voltage of 4.25V (CV). ), And the first charge was performed until the charging current became 0.05 mAh. After 20 minutes, the battery was discharged to a constant current of 0.2C until 3.0V, and the initial discharge capacity of the first cycle was measured. After that, the charge and discharge capacity, charge and discharge efficiency and rate characteristics were evaluated by varying the discharge conditions at 10C. The results are shown in Table 3 below and FIGS. 7 and 8.
  • Example 1 having a surface treatment layer of boron-containing lithium oxide was better in initial discharge capacity and rate characteristics than Comparative Example 1, which is a negative electrode active material of lithium titanium oxide having no surface treatment layer. The effect was shown.
  • the resultant was stored at 80 ° C. for 1 week to measure the type of gas and the amount of gas generated.
  • the negative electrode active material of Example 1 compared with the negative electrode active material of Comparative Example 1 having no surface treatment layer, the amount of gas generated in the case of H 2 , CH 4 , while CO, CO 2 and C 2 H In the case of 4 , gas generation was significantly reduced.
  • the lithium secondary battery containing the negative electrode active material of Example 4 and Comparative Examples 9, 10 was also impregnated with the electrolyte in the same manner as described above, and stored for one week at 80 °C to measure the type of gas and the amount of gas generated. The results are shown in FIG.
  • the negative electrode active material of Example 4 is less than 10 to 20 times the content of boron in comparison with the negative electrode active material of Comparative Examples 9, 10, CH 4 and C 2 H 4 showed the same level of gas generation, while H 2 , In the case of CO and CO 2 , the amount of gas generated was significantly reduced.
  • the B content is 300 ppm and 500 ppm, respectively, with respect to the total weight of the negative electrode active material, so that the content of B is less than the total weight of the negative electrode active material, and lithium is formed according to the formation of the surface treatment layer including B. It is considered that the effect of preventing the decomposition of the electrolyte on the surface of the titanium oxide has not been achieved.
  • Example 4 After charging the lithium secondary battery each containing the negative electrode active material in Example 1 and Comparative Example 1 to 2.5V at a constant current of 0.1C, and stored at 80 °C for 21 days, two and three cycles excluding the initial discharge capacity The average discharge capacity of the first was measured. The results are shown in Table 4 below.
  • Example 1 having a surface treatment layer of boron-containing lithium oxide showed a significantly better capacity recovery than Comparative Example 1.
  • C-rate of Figure 11 shows the amount of current required when charging and discharging for 1 hour at 1C conditions, it was confirmed that the resistance is also increased as the current amount is increased, and as a result, the normal capacity is also lowered.
  • the capacity decreases as the C-rate increases, and the gap widens to charge at 20C.
  • the lithium secondary battery containing the negative electrode active material prepared in Example 1 during discharge showed a capacity of 85% or more, and the lithium secondary battery containing the negative electrode active material prepared in Comparative Example 11 showed a capacity of less than 80%.
  • the boron source includes LiBO 2 and Li 2 B 4 O 7 generated by reacting with lithium by-products such as Li 2 CO 3 , LiOH at 400 °C E barrier value of the surface treatment layer is adjusted to about 0.3 eV, Li 4 Ti 5 O 12 The conductivity of Li ions at the surface is improved, resulting in improved output characteristics.
  • the heat treatment at 500 °C Li 4 Ti 5 O 12 The higher the E barrier value for Li ion transport of the LiBO 2 and LiB 4 O 7 surface treatment layers formed on the surface, the lower the Li ion conductivity and the higher the resistance. .
  • due to the heat treatment at a high temperature it is difficult to cover the entire surface of Li 4 Ti 5 O 12 due to the recrystallization of the boron-containing lithium oxide, thereby increasing the amount of gas generated.

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Abstract

La présente invention concerne un matériau actif d'anode pour accumulateur et un accumulateur le comprenant, le matériau actif d'anode comprenant : un noyau contenant de l'oxyde de lithium-titane (LTO); et une couche de traitement de surface située sur la surface du noyau, la couche de traitement de surface comprenant de l'oxyde de lithium contenant du bore en une quantité telle que la teneur en bore corresponde à un rapport molaire de 0,002 à 0,02 pour 1 mole d'oxyde de lithium-titane, et lors du titrage de 2 g du matériau actif d'anode avec du HCl 0,1 M à un pH de 5 ou moins, une quantité de titrage est de 0,9 à 1,5 ml. Le matériau actif d'anode peut présenter un excellent taux de récupération de capacité et d'excellentes caractéristiques de sortie lorsqu'il est appliqué à un accumulateur, et peut empêcher la décomposition d'un électrolyte, ce qui permet de réduire la génération de gaz.
PCT/KR2017/003088 2016-03-22 2017-03-22 Matériau actif d'anode pour accumulateur, et accumulateur le comprenant WO2017164650A1 (fr)

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EP17770620.7A EP3312914B1 (fr) 2016-03-22 2017-03-22 Matériau actif d'anode pour accumulateur, et accumulateur le comprenant
PL17770620T PL3312914T3 (pl) 2016-03-22 2017-03-22 Masa czynna anody do akumulatora i zawierający ją akumulator
US15/746,910 US10665859B2 (en) 2016-03-22 2017-03-22 Negative electrode active material for secondary battery and secondary battery including the same
CN201780002684.0A CN107925069B (zh) 2016-03-22 2017-03-22 二次电池用负极活性材料和包含它的二次电池

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