WO2016036091A1 - Additif de mélange de matériau d'électrode pour batterie rechargeable, son procédé de préparation, électrode pour batterie rechargeable le comprenant, et batterie rechargeable - Google Patents

Additif de mélange de matériau d'électrode pour batterie rechargeable, son procédé de préparation, électrode pour batterie rechargeable le comprenant, et batterie rechargeable Download PDF

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WO2016036091A1
WO2016036091A1 PCT/KR2015/009144 KR2015009144W WO2016036091A1 WO 2016036091 A1 WO2016036091 A1 WO 2016036091A1 KR 2015009144 W KR2015009144 W KR 2015009144W WO 2016036091 A1 WO2016036091 A1 WO 2016036091A1
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electrode
additive
secondary battery
electrode mixture
secondary batteries
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PCT/KR2015/009144
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English (en)
Korean (ko)
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WO2016036091A8 (fr
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이규태
권미숙
최아람
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서울대학교 산학협력단
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Priority claimed from KR1020150122058A external-priority patent/KR101746188B1/ko
Application filed by 서울대학교 산학협력단 filed Critical 서울대학교 산학협력단
Publication of WO2016036091A1 publication Critical patent/WO2016036091A1/fr
Publication of WO2016036091A8 publication Critical patent/WO2016036091A8/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • Electrode mixture additive for a secondary battery a method of manufacturing the same, an electrode for a secondary battery and the secondary battery comprising the same
  • Electrode additive for a secondary battery a method of manufacturing the same, and a secondary battery electrode and a secondary battery comprising the same.
  • the electrode mixture of the secondary battery is generally manufactured by including various compositions in addition to the active material powder for storing energy.
  • the solid composition including the active material in the binder solution is prepared by dispersing the solid composition including the active material in the binder solution and mixed in the form of a slurry, it can be produced in the form of a thick film of a micron thickness by applying this to a metal foil.
  • the electrode may be manufactured using only a combination of the active material and the binder, but since the binder acts as a non-conductor to prevent electron transfer inside the electrode, a conductive material for providing an electron path in the electrode is required.
  • the conductive material a carbon material having a particle size of several tens of nanometers is widely used, but various problems occur due to the characteristics of the carbon material.
  • the energy density of the total electrode mixture decreases as the amount of the input increases, and the secondary battery including the same occurs due to the high specific surface area of the carbon material.
  • the present inventors in addition to the active material, the binder, and the conductive material, in order to solve the above-mentioned problems, developed a material that is additionally introduced into the electrode mixture. Details of this are as follows.
  • an electrode mixture additive for a secondary battery which is a compound powder of the ABX 3 type perovskite structure.
  • a secondary battery including the electrode mixture additive for a secondary battery having the above structure may be provided.
  • an electrode mixture additive for a secondary battery which is a compound powder having a perovskite structure represented by Formula 1 below, is provided.
  • A is at least one element selected from the group of alkaline earth metals including barium (Ba), calcium (Ca), magnesium (Mg) and strontium (Sr),
  • B is at least one element selected from the group of titanium metals including titanium (Ti) and zirconium (Zr).
  • the formula (1) may be at least one from the group comprising titanium barium (BaTi0 3), titanium calcium (CaTi0 3), titanate magnesium thoracic (MgTi0 3), and titanium strontium (SrTi0 3) selected have. More specifically, Chemical Formula 1 may be barium titanate (BaTi0 3 ).
  • the average particle diameter of the compound powder may be 10 nm to 20 // m, specifically 300 Pa to 20 im, 300 nm to 10, 50 nm to 10, more specifically 50 nm to 5.
  • the surface area of the compound powder by adsorption of nitrogen gas may be 0.5 to 300 m 2 / g, specifically 0.6 to 50 m 2 / g.
  • preparing a precursor solution comprising an alkaline earth metal raw material and a titanium group metal raw material Stirring the precursor solution to obtain an intermediate compound in a gel state; And heat treating the intermediate compound to obtain a compound having a perovskite structure. It provides a method for producing an electrode mixture additive for a secondary battery.
  • the compound of the perovskite structure may be represented by the following formula (1).
  • A is at least one element selected from the group of alkaline earth metals including barium (Ba), calcium (Ca), magnesium (Mg) and strontium (Sr),
  • B is at least one element selected from the group of titanium metals including titanium (Ti) and zirconium (Zr).
  • preparing a precursor solution comprising an alkaline earth metal raw material and a titanium group metal raw material;
  • the molar ratio of the alkaline earth metal raw material to the titanium group metal raw material is 0.9: 1 to 1.1: It may be to prepare a precursor solution of 1.
  • an electrode In another embodiment of the present invention, an electrode; And an electrode mixture coated on the electrode, wherein the electrode mixture includes an active material, a conductive material, a binder, and an electrode additive for a secondary battery, and the additive has a perovskite structure represented by the following Chemical Formula 1.
  • a compound powder of an electrode for secondary batteries is provided.
  • A is at least one element selected from the group of alkaline earth metals including barium (Ba), calum (Ca), magnesium (Mg) and strontium (Sr),
  • B is at least one element selected from the group of titanium metals including titanium (Ti) and zirconium (Zr).
  • the content of the additive in the electrode mixture with respect to 100 parts by weight of the solid component of the electrode mixture, the additive may be contained in 0.1 to 20 parts by weight, 0.1 to more than 16 parts by weight
  • the additive may be contained in 0.1 to 20 parts by weight, 0.1 to more than 16 parts by weight
  • each content of the active material, the conductive material, and the binder in the electrode mixture is 70 to 95 parts by weight of the active material, 2 to 15 parts by weight of the conductive material, based on 100 parts by weight of the solid component of the electrode mixture. It may be included in 2 to 15 parts by weight.
  • the active material may be one or more of metals containing cobalt, manganese, nickel, or a combination thereof forming a complex oxide or phosphide with lithium.
  • the conductive material may be at least one selected from the group consisting of carbon black, carbon, hard carbon.
  • the binder is polyvinylidene fluoride (PVdF, Poly Vinylidene Fluoride), carboxymethyl cellulose (CMC 'Carboxymethyl Cel lulose), polyacrylic acid (PM, PolyAcrylic Ac id) and styrene-butadiene rubber ( SBR, Styrene-Butadi ene Rubber) may be one or more selected from the group containing.
  • PVdF Polyvinylidene fluoride
  • CMC 'Carboxymethyl Cel lulose carboxymethyl cellulose
  • PM PolyAcrylic Ac id
  • SBR Styrene-Butadi ene Rubber
  • the thickness of the electrode may be 10 to 300.
  • the electrode may be an anode.
  • the anode In another embodiment of the present invention, the anode; cathode; Electrolyte; And a separator; wherein at least one or more of the positive electrode to the negative electrode includes any one of the above-described electrode mixture additives for a secondary battery.
  • the ferroelectric structure of the ferroelectric ternary oxide, the perovskite structure to improve the charge transfer (charge t rans fer) resistance of the secondary battery, and ultimately contribute to the high rate charge and discharge characteristics
  • the electrode mixture additive for secondary batteries can be provided.
  • the additive is included in the optimum ratio, it is possible to provide a secondary battery electrode that improves the high rate characteristics, minimize side effects of the secondary battery, and contribute to improve the cycle characteristics have.
  • La is a SEM photograph of the additive according to an embodiment of the present invention.
  • Lb is an X-ray diffraction analysis result of the additive according to an embodiment of the present invention.
  • 2A is a constant current charge / discharge test result of a secondary battery according to one embodiment and a comparative example of the present invention.
  • 2C is an electrochemical impedance spectroscopy (EIS) test result of secondary batteries according to one embodiment and a comparative example of the present invention.
  • EIS electrochemical impedance spectroscopy
  • 3A to 3D are results of constant current layer discharge experiments according to embodiments and comparative examples of the present invention, performed by different kinds of active materials.
  • 4A to 4B are results of constant current charge and discharge experiments according to embodiments and comparative examples of the present invention, performed by different types of additives.
  • 5 is a result of a constant current charge and discharge experiment according to embodiments of the present invention, performed by varying the thickness of the electrode.
  • 6A to 6B are results of constant current layer discharge experiments according to embodiments and comparative examples of the present invention, performed by varying the ratio of the conductive material and the electrode additive.
  • 7A is a SEM photograph of an additive according to one embodiment of the present invention.
  • 7B is a result of a constant current charge / discharge test according to embodiments of the present invention, which is performed by changing particle diameters of an electrode additive.
  • an electrode mixture additive for a secondary battery which is a compound powder having a perovskite structure represented by the following Chemical Formula 1.
  • A is at least one element selected from the group of alkaline earth metals including barium (Ba), calcium (Ca), magnesium (Mg) and strontium (Sr),
  • B is at least one element selected from the group of titanium metals including titanium (Ti and zirconium (Zr).
  • the mass-transfer resistance associated with the diffusion of lithium ions in the electrode material particles, at the interface between the electrolyte and the electrode material It is characterized by the charge transfer resistance that occurs and the electrical conductivity between particles in the electrode.
  • the material transfer resistance or the electrical conductivity by improving the active material or the conductive material among the materials constituting the electrode mixture in order to achieve the high rate characteristics of the secondary battery. Limit Pointed out.
  • active materials capable of reducing the diffusion length of lithium have been studied, which are nanoparticle-sized spherical or one-dimensional rod-shaped primary particles, or such primary particles. Secondary particles and the like are collected and used as the active material.
  • the present inventors deviated from the conventional research direction and have developed an additive for a secondary battery that is additionally added to an electrode mixture composed only of an active material, a conductive material, and a binder.
  • the ferroelectric ternary oxide which is a compound powder having a perovskite structure represented by Chemical Formula 1, is provided as an electrode mixture additive for a secondary battery, which may contribute to improving charge transfer resistance among the aforementioned factors.
  • the dielectric properties of the additive As a result, ion dissociation of the electrolyte salt may be more easily performed.
  • this is not a material for coating the surface of the active material, and the ferroelectric oxide powder is a solid additive that is additionally added during the electrode manufacturing process.
  • the ferroelectric oxide powder is a solid additive that is additionally added during the electrode manufacturing process.
  • Formula 1 may be one or more selected from the group consisting of barium titanate (BaTi3 ⁇ 4 calcium titanate (CaTi0 3 ), magnesium titanate (MgTi), and strontium titanate (SrTi0 3 ), specifically barium titanate (BaTi0 3 ).
  • barium titanate BaTi3 ⁇ 4 calcium titanate (CaTi0 3 ), magnesium titanate (MgTi), and strontium titanate (SrTi0 3 ), specifically barium titanate (BaTi0 3 ).
  • the average particle diameter of the compound powder is 10 nm to 20, specifically
  • 300 nm to 20 ⁇ m, 300 nm to 10, 300 nm to 10 m, 50 nm to 10, and more specifically 50 nm to 5 may be.
  • the surface area is small so that the contribution to the dissociation of the salt is not large, there is a limit in improving the speed characteristics, and if less than 10 nm, the difficulty of the synthesis process to be described later may occur In this range, the average particle diameter of the compound powder is defined.
  • the surface area of the compound powder by adsorption of nitrogen gas may be 0.5 to 300 m 2 / g, specifically 0.6 to 50 mVg.
  • the particles having an average particle diameter of 10 nm or less should be synthesized. Accordingly, the above-mentioned problem may occur, and in the case of less than 0.5 m 2 / g, Since the surface area may be too small to cause a problem in that the contribution to the dissociation of the salt is not large, this range is limited to the surface area by nitrogen gas adsorption of the compound powder.
  • preparing a precursor solution comprising an alkaline earth metal raw material and a titanium group metal raw material; Stirring the precursor solution to obtain an intermediate compound in a gel state; And heat-treating the intermediate compound to obtain a compound having a perovskite structure. It provides a method for producing an electrode mixture additive for a secondary battery.
  • the compound of the perovskite structure may be represented by the following formula (1), the description thereof is as described above.
  • A is at least one element selected from the group of alkaline earth metals including barium (Ba), calcium (Ca), magnesium (Mg) and strontium (Sr),
  • B is at least one element selected from the group of titanium metals including titanium (Ti and zirconium (Zr).
  • preparing a precursor solution comprising an alkaline earth metal raw material and a titanium group metal raw material;
  • the molar ratio of the alkaline earth metal raw material to the titanium group metal raw material is 0.9: 1 to 1.1: 1 It may be to prepare a precursor solution.
  • the alkaline earth metal raw materials are barium nitrate (Ba (N0 3 ) 2 ), calcium nitrate hydrate (Ca (N0 3 ) 2 .4H 2 0), magnesium nitrate hydrate (Mg (N0 3 ) 2 .63 ⁇ 40), And strontium nitrate It may be one or more selected from the group containing (Sr (N0 3 ) 2 ).
  • This is a raw material capable of providing elements of the alkaline earth metal group represented by A in Chemical Formula 1.
  • the titanium group metal raw material may be titanium isopropoxide (t i anium i sopropoxi de), and may provide an element of the titanium group metal group represented by B in Chemical Formula 1.
  • an intermediate compound in a gel (gel) state may be performed at 100 to 140.
  • the step of heat-treating the intermediate compound, to obtain a compound having a perovskite structure may be performed in an oxidizing atmosphere, thereby providing an element represented by X in the formula (1).
  • X may be oxygen (0).
  • heat treating the intermediate compound to obtain a compound having a perovskite structure may be included.
  • A is at least one element selected from the group of alkaline earth metals including barium (Ba), calcium (Ca), magnesium (Mg) and strontium (Sr), and B is titanium (Ti) and zirconium (Zr). At least one element selected from the group of titanium metals containing metal.
  • the secondary battery electrode additive is further included, and thus the charge generated at the interface between the electrolyte and the electrode material. It is meaningful to improve the charge transfer resistance and ultimately achieve the high rate characteristics of the secondary battery including the same.
  • the conventional research focused on the active material or conductive material, which is the basic material of the electrode mixture, and attempted to improve the mass transfer resistance or the electrical conductivity, but the present inventors pay attention to the additives added to the electrode mixture. It contributes to improving the charge transfer resistance of the electrode comprising.
  • the properties of the additives are as described in detail above, it is important to formulate each component of the electrode mixture including the same in the optimum ratio, in particular to minimize the ratio of components that do not participate in direct energy expression.
  • the amount of the additive in the electrode mixture may be that the additive is contained in 0.1 to 20 parts by weight, specifically 100 parts by weight to 16 parts by weight based on 100 parts by weight of the solid component of the electrode mixture. Less than 0.4 parts by weight or more and less than 8 parts by weight, more specifically, 0.4 parts by weight or more and less than 4 parts by weight.
  • each content of the active material, the conductive material, and the binder in the electrode mixture is 70 to 95 parts by weight of the active material, 2 to 15 parts by weight of the conductive material with respect to 100 parts by weight of the solid component of the electrode mixture, the binder It may be included in 2 to 15 parts by weight.
  • the active material may be one or more of metals containing cobalt, manganese, nickel, or a combination thereof forming lithium, a composite oxide, and a phosphide.
  • Specific examples thereof may be a compound represented by any one of the following formulas. LiaAi-bRbl wherein 0.90 ⁇ a ⁇ 1.8 and 0 ⁇ .b ⁇ 0.5); LiaE R b C c D c (wherein 0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5, and 0 ⁇ c ⁇ 0.05) .; LiE 2 — b R b 0 4 - c D c (where 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05); Li a Nh— b — c Co b R c D a (wherein 0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05 and 0 ⁇ ⁇ 2); Li a N —bc Co b R c
  • A is Ni, Co, Mn or a combination thereof;
  • R is A1 , Ni, Co, Mn, Cr, Fe, Mg, Sr, V, rare earth elements or combinations thereof;
  • D is 0, F, S, P or a combination thereof;
  • E is Co, Mn or a combination thereof;
  • Z is F, S, P or a combination thereof;
  • G is Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V or a combination thereof;
  • Q is Ti, Mo, Mn or a combination thereof;
  • T is Cr, V, Fe, Sc, Y or a combination thereof;
  • J is V, Cr, Mn, Co, Ni, Cu or a combination thereof;
  • K is Fe, Mn Co, Mg, Ca, Ti or a combination thereof.
  • the coating layer may include an oxide of a coating element, a hydroxide of a coating element, an oxyhydroxide of a coating element, an oxycarbonate of a coating element, or a hydroxycarbonate of a coating element.
  • the compounds constituting these coating layers may be amorphous or crystalline.
  • As the coating element included in the coating layer Mg, Al, Co, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, Zr or a combination thereof may be used.
  • the coating layer forming process may be any method that does not adversely affect the physical properties of the positive electrode active material by using such elements in the compound (for example, any coating method may be used as long as it can be coated by spray coating, precipitation method, etc. Details that will be well understood by those in the field will be omitted.
  • the conductive material may be at least one selected from the group consisting of carbon black, abyss, and hard carbon.
  • the binder is polyvinylidene fluoride (PVdF, Poly Vinylidene Fluoride), carboxymethyl cellulose (CMC, Carboxymethyl Cellulose), polyacrylic acid (PM, PolyAcrylic Acid) and styrene-butadiene rubber (SBR, Styrene-Butadiene Rubber) may be one or more selected from the group containing.
  • PVdF Poly Vinylidene Fluoride
  • CMC Carboxymethyl Cellulose
  • PM PolyAcrylic Acid
  • SBR Styrene-Butadiene Rubber
  • the conductive material is necessary because it acts as an obstacle to the transfer.
  • the thickness of the electrode may be 10 to 300 kPa.
  • the high rate property is improved by the additive, and the high rate property is improved even in the electrode thickness in the range of 10 to 100, which is conventionally used. It can be secured. However, in consideration of the above side effects are limited to less than 300 urn.
  • the electrode may be a positive electrode.
  • This, as described above, includes an electrode made of an electrode mixture further contains the additive than in the conventional case, and means a secondary battery of excellent performance that the high rate characteristic is improved through this, and the energy density is secured.
  • a compound powder of perovskite structure was prepared by using a sol-gel synthesis method.
  • a specific manufacturing method will be described in detail.
  • Barium nitrate Ba (N0 3 ) 2 , barium nitrate
  • titanium isopropoxide was used as the titanium group metal raw material.
  • barium nitrate Ba (N0 3 ) 2 , barium nitrate
  • a complexing agent a complexing agent
  • a solution of 2.8 g of titanium isopropoxide dissolved in 2 ml of l-hexanol was added.
  • the precursor solution thus prepared was stirred again at 120 to obtain an intermediate compound in a gel state.
  • the intermediate compound was heat-treated at 300 to 15 hours, followed by 900 to 15 hours, in an oxidizing atmosphere to prepare a final product, BaTi0 3 compound.
  • the particle diameter of the prepared compound powder is 0.5 to 5.
  • the particle diameter of the prepared compound powder is 0.3 to 1.
  • magnesium hydrate Mg (N0 3) 2 .6H 2 0, magnesium nitrate hexahydrate
  • MgTi0 magnesium nitrate hexahydrate
  • the particle diameter of the prepared compound powder is 0.5 to 2.
  • SrTi0 3 compounds were prepared in the same manner, except that 2.1 g of strontium nitrate (Sr (N0 3 ) 2 , strontium nitrate) was used instead of barium nitrate as the alkaline earth metal raw material.
  • the particle diameter of the prepared compound powder is 0.1 to 1.
  • the particle diameter of the prepared compound powder is 50 to 100 ran.
  • the particle size of each additive powder is found in the range of about 100 ran to 5 according to Fig. La, and according to Fig. 7a is found to be about 300 ⁇ or less.
  • these XRD peaks are all compared to the powder diffraction file (PDF) of the XRD database provided by the International Center for diffraction data (ICDD), all of which form a perovskite crystal structure Can be.
  • PDF powder diffraction file
  • ICDD International Center for diffraction data
  • the electrode mixture was selected as an active material of lithium cobalt oxide (LiCo0 2 , lithium cobalt oxide), a representative cathode material of a lithium battery, carbon black (conductive material) and polyvinylidene fluoride (PVdF) as a binder.
  • LiCo0 2 lithium cobalt oxide
  • carbon black conductive material
  • PVdF polyvinylidene fluoride
  • an active material, a conductive material, an electrode additive, and a binder selected as described above are prepared, and each of 76, 10, 4, and 10 parts by weight per 100 parts by weight of the solid component of the electrode is N-methylpyridone ( ⁇ P). It was put in a solvent, and the paste mixture obtained by mixing and stirring was applied onto an aluminum foil current collector.
  • the mixture was pressed with a roll press to adjust the porosity in the mixture to 25% by volume, and then punched out in the size (diameter 16 s) and shape (circle) required for assembling the secondary battery.
  • the electrode thickness at this time is 20-30 ⁇ (except an electrical power collector).
  • Example 1 all of the secondary battery electrodes were prepared in the same manner except that the active material, the conductive material, and the binder were 80, 10, and 10 parts by weight, respectively, per 100 parts by weight of the solid component, and the electrode additive was not included.
  • Example 2 Fabrication of Secondary Battery Including Secondary Battery Electrode of Example 1 Using a electrode prepared in Example 1, a coin-type 2016 lithium secondary battery in a dry box filled with inert argon gas was used. Assembled.
  • a lithium metal foil was punched out as a counter electrode, and a solution in which LiPF 6 was dissolved in EC / DEC (volume ratio 3: 7) at a 1.3 molar concentration was used as an electrolyte.
  • a polypropylene film was punched out with a diameter of 19 mm as a separator.
  • Comparative Example 2 Fabrication of Secondary Battery Comprising Secondary Battery Electrode of Comparative Example 1
  • a lithium secondary battery was assembled in the same manner as in Example 2, except that the electrode prepared in Comparative Example 1 was used. '
  • the additive according to the embodiment of the present invention is further included in the electrode mixture, it can be seen that the rate characteristic of the secondary battery manufactured by using the improved.
  • the capacity recovers when it returns to low current after charging and discharging of high current, it is an electrode material that shows stable cycle characteristics. Therefore, the rate characteristic is not affected by the capacity decrease as the cycle progresses. can do.
  • the difference in the rate property is not due to the degradation of the electrode, it can be seen that the result of the improvement of the high rate property by the additive.
  • Example 2 which shows a constant current charge / discharge curve of 0.2 cycles under the above experimental conditions
  • polarization was remarkably reduced in Example 2 (electrode of Example 1) compared to Comparative Example 2 (electrode of Comparative Example 1). You can check it.
  • the charge transfer resistance (R ct ) value of the temperature was directly determined by electrochemical impedance spectroscopy (EIS), and the Arenius plot ( arrhenius plot) to obtain the activation energy.
  • EIS electrochemical impedance spectroscopy
  • Arenius plot arrhenius plot
  • the relationship between the charge transfer resistance with temperature is related to the inverse of the temperature according to the Arrhenius law, which is based on the charge transfer resistance values obtained from the EIS data measured at various experimental temperatures. Shown. Linearity was satisfied when each charge transfer resistance was expressed on a logarithmic scale with respect to the inverse of silver.
  • the activation energy was calculated from the slope of the trend line, it was found to be 0.70 eV in Example 2 (the electrode of Example 1) and 0.77 eV in Comparative Example 2 (the electrode of Comparative Example 1).
  • Example 2 the electrode of Example 1 including the additive has a lower activation energy than Comparative Example 2 (the electrode of Comparative Example 1) that does not include the same. It can be inferred that the electrode additive played a positive role in reducing charge transfer resistance in the insertion and desorption process of lithium ions.
  • a nickel-cobalt-manganese oxide lithium (... LiNi 0 6 Co 0 2 Mn 0 2 0 2) to use, and the active material, the conductive material, the electrode additive, the proportion of the binding agent, each per 100 parts by weight of solid component 88,
  • a secondary battery electrode was manufactured in the same manner as in Example 1, except that 4, 4, and 4 parts by weight were prepared, and the secondary battery was assembled in the same manner as in Example 2.
  • a secondary battery electrode was manufactured in the same manner as in Example 3, except that the active material, the conductive material, and the binder were 92, 4, and 4 parts by weight, respectively, per 100 parts by weight of the solid component, and the electrode additive was not included. It was.
  • a nickel-cobalt-manganese oxide lithium (... LiNi 0 5 Co 0 2 Mn 0 3 0 2) for use, the active material, the conductive material, the electrode additive, the proportion of the binding agent, each per 100 parts by weight of solid component 88,
  • the active material As active material, a nickel-cobalt-manganese oxide lithium (... LiNi 0 5 Co 0 2 Mn 0 3 0 2) for use, the active material, the conductive material, the electrode additive, the proportion of the binding agent, each per 100 parts by weight of solid component 88,
  • 4 parts by weight were prepared, and secondary batteries were assembled in the same manner as in Example 2.
  • a secondary battery electrode was manufactured in the same manner as in Example 4 except that the active material, the conductive material, and the binder were 92, 4, and 4 parts by weight, respectively, per 100 parts by weight of the solid component, and the electrode additive was not included. It was.
  • Example 5 When BaTi of Preparation Example 1 was used as an additive and lithium iron phosphate (LiFeP0 4 , l ithium iron phosphate) was used as the active material
  • Lithium iron phosphate LiFeP0 4 , li thium i ron phosphate
  • the secondary battery electrode was manufactured in the same manner as in Example 1, and the secondary battery was assembled in the same manner as in Example 2.
  • a secondary battery electrode was manufactured in the same manner as in Example 5, except that the active material, the conductive material, and the binder were 70, 20, and 10 parts by weight, respectively, per 100 parts by weight of the solid component, and the electrode additive was not included. It was.
  • Nickel-cobalt-manganese manganese (L.sNio.aCocuMno. + A) is used as the active material, and the ratio of the active material, the conductive material, the electrode additive, and the binder is 76, 4, 10, 10 weights per 100 parts by weight of the solid component, respectively.
  • a secondary battery electrode was manufactured in the same manner as in Example 1, except that the secondary battery was prepared, and a secondary battery was assembled in the same manner as in Example 2.
  • a secondary battery electrode was manufactured in the same manner as in Example 6, except that the active material, the conductive material, and the binder were 80, 10, and 10 parts by weight, respectively, per 100 parts by weight of the solid component, and the electrode additive was not included. It was.
  • LiCo0 2 cathode active material used in Example 1 except for the LiCo0 2 cathode active material used in Example 1, in Examples 3 to 6 (LiNio.6Coo.2Mno.2O2, LiNio.5Coo.2Mno.3O2, LiFeP0 4 , Li i. 3 Nio .2Coo.iMno.70 2+ a) BaTi0 3 electrode additives were also introduced into the positive electrode active material, respectively.
  • 3A to 3D show the results of the experiments of Examples 3 to 6 and Comparative Examples 3 to 6, and for the same active material, the effect of the presence or absence of an additive can be confirmed.
  • the electrode mixture additive is not only exert the effect when using a specific positive electrode active material, but can be applied regardless of the type of the positive electrode active material.
  • Example 7 Fabrication of Secondary Battery Containing CaTi0 3 of Preparation Example 2 As an Additive Cobalt acid was used as a cathode active material, except that the CaTi0 3 material prepared in Preparation Example (2) was used as an electrode additive.
  • lithium LiCo0 2, li thium cobal t oxi de
  • nickel-cobalt-manganese oxide lithium ... LiNi 0 6 Co 0 2 Mn 0 2 0 2 0 2
  • a secondary battery electrode was manufactured by the method, and secondary batteries were assembled in the same manner as in Example 2.
  • Example 8 Fabrication of Secondary Battery Containing MgTi0 3 of Manufacturing Example 3 as an Additive Cobalt acid was used as a positive electrode active material except that the MgTi0 3 material prepared according to Manufacturing Example (3) was used as an electrode additive.
  • Example 9 Fabrication of Secondary Battery Containing SrTi3 ⁇ 4 in Preparation Example 4 As an Additive
  • SrTi material prepared in Preparation Example 4 as an electrode additive
  • a cathode active material is lithium cobalt oxide (LiCo0 2, li thium cobal t oxide) or nickel-cobalt-using the lithium manganese oxide (... LiNi 0 6 Co 0 2 Mn 0 2 0 2)
  • each A secondary battery electrode was manufactured in the same manner as in Example 1 with respect to the active material, and secondary batteries were assembled in the same manner as in Example 2.
  • Example 10 Preparation of a Secondary Battery with an Electrode Thickness of 20 ⁇ 2 / ⁇ (Except Current Collector) Except that the thickness of the manufactured electrode after drying was 20 ⁇ 2 im (without current collector), A secondary battery electrode was manufactured in the same manner as in Example 1, and a secondary battery was assembled in the same manner as in Example 2.
  • Example 11 Fabrication of a Secondary Battery having an Electrode Thickness of 30 ⁇ 2 (Current Collector) Except that the electrode manufactured after the drying process had a thickness of 30 ⁇ 2 (Current collector excluded), A secondary battery electrode was manufactured in the same manner, and a secondary battery was assembled in the same manner as in Example 2.
  • Example 12 Fabrication of a Secondary Battery with an Electrode Thickness of 50 ⁇ 2 (Current Collector) Example 1 except that the electrode manufactured after the drying process had a thickness of 50 ⁇ 2 im (excluding current collector).
  • a secondary battery electrode was manufactured in the same manner as described above, and a secondary battery was assembled in the same manner as in Example 2.
  • Example 12 in case of using LiCo0 2 positive electrode active material and BaTi0 3 as an additive, even in Example 12 having a relatively thick thickness (50 ⁇ 2), better rate-rate characteristics were obtained than electrodes using LiCoC as a positive electrode active material.
  • the charge transfer resistance is reduced due to the additive, it can be seen that the high rate characteristics of the secondary battery can be maintained despite the change in the electrode thickness. Through this, it can be confirmed that the charge transfer resistance is a factor that greatly affects the rate characteristic.
  • the other components are kept the same, and the electrode is manufactured by varying the ratio of the electrode additive and the conductive material, and the secondary battery is assembled and its electric The chemical properties were confirmed.
  • Example 13 When LiFePO 4 was used as the active material, and the ratio of the conductive material and the electrode additive was 19, 1 part by weight per 100 parts by weight of the solid component
  • An electrode mixture and a secondary battery were manufactured in the same ratio and method as in Example 5, except that LiFePO 4 was used as the active material, and the ratio of the conductive material and the electrode additive was 19 and 1 part by weight, respectively, per 100 parts by weight of the solid component. .
  • Example 14 When LiFePO 4 was used as the active material and the ratio of the conductive material and the electrode additive was 16 and 4 parts by weight, respectively, per 100 parts by weight of the solid component.
  • the electrode mixture and the secondary battery were manufactured in the same ratio and method as in Example 5, except that the ratio of the conductive material and the electrode additive was 16 to 4 parts by weight, respectively, per 100 parts by weight of the solid component.
  • Example 15 When LiFePO 4 was used as the active material, and the ratio of the conductive material and the electrode additive was 12 and 8 parts by weight for 100 parts by weight of the solid component, respectively.
  • a secondary battery was prepared.
  • Comparative Example 7 When LiFePO 4 was used as the active material, and the ratio of the conductive material and the electrode additive was 4 and 16 parts by weight for 100 parts by weight of the solid component, respectively.
  • the electrode mixture and the secondary battery were manufactured in the same ratio and method as in Example 5, except that the ratio of the conductive material and the electrode additive was 4 and 16 parts by weight, respectively, per 100 parts by weight of the solid component.
  • Example 16 to the active material nickel-cobalt-lithium manganese oxide (LiNi 0 6 Co 0 .2Mno 2 0 2..)
  • An electrode mixture and a secondary battery were prepared in the same manner as in Example 3, except that the active material, the conductive material, and the binder were 96.6, 4, and 0.4 parts by weight, respectively, per 100 parts by weight of the solid component, and the electrode additive was not included.
  • Example 17 Preparation of Secondary Battery Containing BaTi0 3 of Preparation Example 5 as an Additive Example, except that BaTi0 3 of Manufacturing Example 5 was used as an electrode additive.
  • a secondary battery electrode was manufactured in the same manner as in Example 3, and a secondary battery was assembled in the same manner as in Example 2.
  • the graph located at the bottom relates to Example 17 (when the average particle diameter of the additive is 50 to 100 nm), and the graph located at the top is Example 12 (average particle diameter of the additive). Is 0.5 to 5).
  • the high rate characteristic of the secondary battery including the same is improved. This is understood to be due to an increase in dielectricity as the particle size of the additive increases, and to facilitate dissociation of the electrolyte salt into ions.
  • the present invention is not limited to the above embodiments, but may be manufactured in various forms, and a person of ordinary skill in the art to which the present invention pertains does not change the technical spirit or essential features of the present invention. It will be appreciated that the present invention may be practiced as. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive.

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  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
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Abstract

La présente invention concerne : un additif de mélange de matériau d'électrode pour batterie rechargeable ; son procédé de préparation ; une électrode pour batterie rechargeable le comprenant ; et une batterie rechargeable. Spécifiquement, la présente invention peut porter sur : un additif de mélange de matériau d'électrode pour batterie rechargeable, qui est une poudre d'un composé à structure pérovskite représenté par la formule chimique 1 suivante ; son procédé de préparation ; une électrode pour batterie rechargeable le comprenant ; et une batterie rechargeable. [Formule chimique 1] ABX3, dans laquelle A est au moins un élément choisi dans le groupe des métaux alcalino-terreux comprenant le baryum (Ba), le calcium (Ca), le magnésium (Mg) et le strontium (Sr), et B est au moins un élément choisi dans le groupe des métaux du groupe du titane comprenant le titane (Ti) et le zirconium (Zr).
PCT/KR2015/009144 2014-09-02 2015-08-31 Additif de mélange de matériau d'électrode pour batterie rechargeable, son procédé de préparation, électrode pour batterie rechargeable le comprenant, et batterie rechargeable WO2016036091A1 (fr)

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KR20140116418 2014-09-02
KR10-2014-0116418 2014-09-02
KR1020150122058A KR101746188B1 (ko) 2014-09-02 2015-08-28 이차 전지용 전극 합제 첨가제, 이의 제조 방법, 이를 포함하는 이차 전지용 전극 및 이차 전지
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CN114784288B (zh) * 2022-04-08 2023-08-18 哈尔滨工业大学 一种用于无锂负极锂电池的复合集流体及其制备方法

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