US20050208380A1 - Electrode additives coated with electro conductive material and lithium secondary comprising the same - Google Patents

Electrode additives coated with electro conductive material and lithium secondary comprising the same Download PDF

Info

Publication number
US20050208380A1
US20050208380A1 US11/050,973 US5097305A US2005208380A1 US 20050208380 A1 US20050208380 A1 US 20050208380A1 US 5097305 A US5097305 A US 5097305A US 2005208380 A1 US2005208380 A1 US 2005208380A1
Authority
US
United States
Prior art keywords
electrode
battery
electro
electrode additive
coating material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US11/050,973
Inventor
Hong-Kyu Park
Kwang Kim
Sun Kim
Seung Yoo
Jae-Up Jang
Yong Kwon
Kyungmin Chun
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LG Chem Ltd
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Assigned to LG CHEM, LTD. reassignment LG CHEM, LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CHUN, KYUNGMIN, JANG, JAE-UP, KIM, KWANG HOON, KIM, SUN KYU, KWON, YONG HOON, PARK, HONG-KYU, YOO, SEUNG IL
Publication of US20050208380A1 publication Critical patent/US20050208380A1/en
Priority to US13/473,415 priority Critical patent/US9252429B2/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
    • A47L13/00—Implements for cleaning floors, carpets, furniture, walls, or wall coverings
    • A47L13/10—Scrubbing; Scouring; Cleaning; Polishing
    • A47L13/20—Mops
    • A47L13/22—Mops with liquid-feeding devices
    • 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
    • H01M4/624—Electric conductive fillers
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
    • A47L13/00—Implements for cleaning floors, carpets, furniture, walls, or wall coverings
    • A47L13/10—Scrubbing; Scouring; Cleaning; Polishing
    • A47L13/20—Mops
    • A47L13/24—Frames for mops; Mop heads
    • A47L13/254—Plate frames
    • 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
    • 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
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/626—Metals
    • 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
    • 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 an electrode additive that is capable of improving battery performance and high temperature storage characteristics when it is added to an electrode of a lithium secondary battery, and an electrode and lithium secondary battery comprising the same.
  • lithium secondary batteries are increasingly in demand.
  • environmental conditions to which batteries are applied become more severe such that maintenance of initial performance without degradation in battery performance even when being maintained at higher temperatures of more than 80° C. for a prolonged period of time is required.
  • reaction between electrolyte and electrode surface leads to poor high-temperature characteristics, such as swelling and bulking in storage at a higher temperature of more than 80° C.
  • charge/discharge cycles are repeatedly performed at the higher temperature, the electrochemical reaction continuously occurring at a cathode or anode surface contributes to production of decomposed by-products of the electrolyte and gas in the battery, thereby severely swelling the battery.
  • Korean Patent Laid-open Publication No. 2003-0057321 discloses a technique of forming a protective coating film using electrolyte additives such as vinylene carbonate, alkenylethylene carbonate and the like, wherein the electrolyte additives are used to inhibit electrolyte decomposition reaction of the cathode at higher temperatures, such that these additives are first decomposed at cathode potential, thereby forming the protective film.
  • electrolyte additives such as vinylene carbonate, alkenylethylene carbonate and the like
  • the electrolyte additives are used to inhibit electrolyte decomposition reaction of the cathode at higher temperatures, such that these additives are first decomposed at cathode potential, thereby forming the protective film.
  • electrolyte additives such as vinylene carbonate, alkenylethylene carbonate and the like
  • Korean Patent Laid-open Publication No. 2001-35700 and Japanese Patent Laid-Open Publication No. 1998-255389 disclose techniques of improving battery life characteristics and high temperature storage characteristics by addition of metal oxides or metal hydroxides to an electrode (cathode).
  • metal oxides or metal hydroxides are electrically non-conductive and thus, when they are used as additives, interfere with electrical flow in the electrodes, thereby resulting in decreased high rate discharge characteristics of the battery, as well as increased resistance thereof leading to lowering of battery life characteristics.
  • Japanese Patent Laid-Open Publication Nos. 2003-86174 and 1997-22733 disclose a method of coating the cathode active material with an electro-conductive material such as conductive material using a mechanofusion apparatus and a binder.
  • an electro-conductive material such as conductive material
  • the present invention has been made to solve the above problems, and other technical problems that have yet to be resolved.
  • the present inventors have surprisingly found that battery performance and high temperature storage characteristics can be improved by preparing an electrode additive having core particles such as metal hydroxides, metal oxides or metal carbonates coated with electro-conductive material and adding the electrode additive to a cathode and/or anode of a lithium secondary battery.
  • an object of the present invention to provide an electrode additive that is capable of improving battery performance and high temperature storage characteristics, and an electrode for a lithium secondary battery and lithium secondary battery comprising the same.
  • an electrode additive for a secondary battery electrode in which electro-conductive material is coated on the surface of a material that is added to the electrode material so as to improve battery characteristics.
  • electrode additive refers to materials that are added to electrodes for various purposes such as improving high temperature characteristics and charge/discharge cycle characteristics of the battery. Since, among those materials, there are various kinds of low conductivity materials, as described above, such materials generally interfere with electron migration due to their high resistivity, when added to electrodes, and thereby lower battery performance.
  • an electrode additive that can exert original effects without causing deterioration of battery performance, by coating the surface of the electrode additive with electro-conductive materials.
  • additive material which is coated with electro-conductive materials, is added to electrodes for improvement of high temperature storage characteristics, and is exemplified as compounds represented by Formula 1 below: M x A y Formula 1 wherein, M is a metal, A is selected from the group consisting of OH, O and CO 3 , and x represents the valence of M and y represents the oxidation number of A.
  • Metal hydroxides, metal oxides, and metal carbonates of Formula 1 may be used alone or in any combination thereof.
  • Electro-conductive materials which are coated on core particles, are not particularly limited, so long as they exhibit excellent conductivity without causing chemical changes in the battery of interest.
  • coating materials there may be preferably used at least one selected from the group consisting of carbon that has been used as conductive material for a conventional lithium secondary battery, electro-conductive materials, electro-conductive metals, electro-conductive inorganic materials and electro-conductive polymers.
  • an electrode fabricated by preparing an electrode slurry using electrode material containing the electrode additive and electrode active material and then applying the thus-prepared electrode slurry to a current collector, and a lithium secondary battery comprising the same.
  • FIG. 1 schematically shows a cross-sectional view of an electrode additive in accordance with the present invention
  • FIG. 2 is a micrograph showing carbon-coated Mg(OH) 2 particles in accordance with the present invention.
  • FIG. 3 graphically shows battery life characteristics, i.e. changes in cell capacity with respect to charge/discharge cycles, for bicells in which the electrode additive of the present invention is added to cathodes thereof (Examples) and bicells in which the electrode additive of the present invention is not added to cathodes thereof (Comparative Examples); and
  • FIG. 4 graphically shows battery life characteristics, i.e. changes in cell capacity with respect to charge/discharge cycles, for bicells in which the electrode additive of the present invention is added to anodes thereof (Examples) and bicells in which the electrode additive of the present invention is not added to anodes thereof (Comparative Examples).
  • an electrode additive to a cathode and/or anode of a battery, it is possible to inhibit battery swelling due to formation of decomposition by-products or gas production even when the battery is stored at high temperatures for a prolonged period of time, and also to improve battery performance such as life characteristics and charge/discharge rate at room temperature.
  • materials such as metal hydroxides, metal oxides and metal carbonate were used per se as cathode additives, but these materials are coated on the surface of the cathode active material and then impede migration of cathode active material and electrons, thereby deteriorating high rate discharge characteristics of the battery.
  • core particles such as metal hydroxides, metal oxides or metal carbonates
  • the coating material preferably has high electronic conductivity and small particle size to the maximum extent possible. Where electronic conductivity is lower, this may disadvantageously result in increase of electrode resistance thereby degrading battery performance. In addition, where the particle size of the coating material is too large, it may be difficult to coat the surface of core particles. On the other hand, the smaller the particle size of the coating material the denser and more uniform the coating on the core particles.
  • electrical conductivity of the coating material is preferably more than 2.0 ⁇ 10 2 /cm ⁇ and the particle size thereof is preferably within the range of 10 to 1000 nm.
  • Electro-conductive metals may be selected from the group consisting of Cu, Ag, Pt and Ni.
  • Electro-conductive inorganic materials may be selected from the group consisting of indium tin oxide (In 2 O 3 SnO 2 ), tin oxide (SnO 2 ), zinc oxide (ZnO), ruthenium oxide (RuO 2 ) and TiB 2 .
  • Electro-conductive polymers may be selected from the group consisting of polypyrrole and polyaniline.
  • acetylene black preferably has a particle size of 100 nm and electrical conductivity of more than 6.1 ⁇ 10 2 /cm ⁇ .
  • Ni preferably has a particle size of 1000 nm and electrical conductivity of more than 9.17 ⁇ 10 4 /cm ⁇ .
  • Polypyrrole preferably has a particle size of 200 nm and electrical conductivity of more than 2.0 ⁇ 10 2 /cm ⁇ .
  • metal elements which are contained in metal hydroxides, metal oxides or metal carbonates, those being described as preferred examples of the core particles.
  • metals may be preferably selected from the group consisting of Al, B, Mg, K, Be, Ca, Sr, Ba, Na, Cr, Sn, Ga, Bi, Ni, Co, Fe, Cr, Y and Zr. More preferably, metals may be selected from the group consisting of Al, B, Mg, Ba, Y and Zr.
  • a process for preparing an electrode additive in accordance with the present invention will be exemplified as follows.
  • Core particles to be coated are mixed with the coating material to prepare a mixture.
  • the amount of the coating material is preferably within the range of 0.01 to 20% by weight, relative to that of the core particles. Where the amount of the coating material exceeds the above-mentioned range, the resulting coating layer is too thick. On the other hand, where the amount of the coating material is less than the above range, core particles may be incompletely and partially coated.
  • the mixture thus obtained was fused using a mechanofusion apparatus, for example, so as to coat core particles with the coating material.
  • a mechanofusion apparatus for example, so as to coat core particles with the coating material.
  • rotation speed and treatment time of the mechanofusion apparatus can be controlled as desired.
  • the rotation speed of the mechanofusion apparatus is between 1500 and 3000 rpm, and treatment time is in the range of 0.1 to 10 hours.
  • FIG. 1 schematically shows a coating material-coated core particle.
  • FIG. 2 is a micrograph showing carbon-coated Mg(OH) 2 particles. As can be seen from FIG. 2 , carbon, which is coating material, uniformly surrounded core particles.
  • an electrode fabricated by adding the thus-prepared electrode additive of the present invention to an electrode material including electrode active material so as to prepare an electrode slurry and coating a current collector with the thus-prepared electrode slurry.
  • an electrode material including electrode active material so as to prepare an electrode slurry and coating a current collector with the thus-prepared electrode slurry.
  • the electrode additive may be included in the range of 0.05 to 10% by weight in the electrode, relative to the electrode active material.
  • a lithium secondary battery comprising the above-prepared electrode.
  • the lithium secondary battery of the present invention may be prepared by conventional methods known in the art, for example disposing a porous separator between the cathode and anode, followed by introduction of a non-aqueous electrolyte.
  • LiCoO 2 LiNiO 2 , LiMnO 2 , LiMn 2 O 4 , LiFePO 4 .
  • anode active materials that can be used in fabricating the electrode of the present invention, mention may be made of graphite, carbon, lithium metals, alloys and complexes thereof, which are capable of occluding and releasing lithium ions.
  • the porous separator may be preferably used as the separator.
  • the separator may include, but is not limited to, polypropylene-based, polyethylene-based, and other polyolefin-based porous separators.
  • the non-aqueous electrolyte of the lithium secondary battery that can be utilized in the present invention may contain cyclic carbonates and linear carbonates.
  • the cyclic carbonates include, for example ethylene carbonate (EC), propylene carbonate (PC) and gamma-butyro lactone (GBL).
  • the linear carbonate may be at least one selected from the group consisting of diethylcarbonate (DEC), dimethylcarbonate (DMC), ethylmethylcarbonate (EMC) and methylpropylcarbonate (MPC).
  • the non-aqueous electrolyte of the lithium secondary battery in accordance with the present invention may contain lithium salts, in addition to carbonate compounds.
  • lithium salts may be selected from the group consisting of LiClO 4 , LiCF 3 SO 3 , LiPF 6 , LiBF 4 , LiAsF 6 and LiN(CF 3 SO 2 ) 2 .
  • Acetylene black which is a carbon material, as a coating material and Mg(OH) 2 , which is a metal hydroxide, as a core particle, were used to prepare an electrode additive.
  • the content of acetylene black was 5% by weight, relative to that of the core particle, Mg(OH) 2 .
  • a mixture of acetylene black and Mg(OH) 2 was loaded on a mechanofusion apparatus, and subjected to low speed rotation at 250 rpm for 3 min and subsequently to high speed rotation at 1400 rpm for 20 min so as to coat carbon on the surface of the metal hydroxide, thereby preparing the electrode additive (C 0.05 Mg(OH) 2 ).
  • LiCoO 2 was used as a cathode active material, and 0.5% by weight of the above-prepared electrode additive (C 0.05 Mg(OH) 2 ) was added thereto, relative to the cathode active material. Then, together with 2.5% Super-P(conductive material) and 2.5% polyvinylidene difluoride (PVdF) as a binding agent, a cathode active material powder (LiCoO 2 ) and the electrode additive were dispersed in an n-methylpyrolidone (NMP) solvent to obtain a slurry. The slurry thus obtained was coated on aluminum foil and heated to evaporate the NMP solvent to dryness, followed by compression at a pressure of about 500 kg/cm 2 to prepare a cathode.
  • NMP n-methylpyrolidone
  • a conventional pouch-type bicell was prepared using the above-prepared cathode and anode, and as an electrolyte, a solution in which 1M LiPF 6 was dissolved in a 1:2 (v/v) mixed solvent of ethylene carbonate (EC) and ethyl methyl carbonate (EMC).
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • An electrode and a battery were prepared and evaluated using the same procedure as in Example 1, except that 10% by weight of acetylene black as a coating material was added, relative to core particles, when preparing an electrode additive.
  • An electrode and a battery were prepared and evaluated using the same procedure as in Example 1, except that, relative to an anode active material, there was added 1.0% by weight of an electrode additive, which was prepared in a manner that an electrode additive was not added to a cathode and 10% by weight of acetylene black as a coating material was added to an anode, relative to core particles (Mg(OH) 2 ).
  • An electrode and a battery were prepared and evaluated using the same procedure as in Example 1, except that 10% by weight of acetylene black as a coating material was added, relative to core particles and LiMn 2 O 4 powder was used as a cathode active material, when preparing an electrode additive.
  • An electrode and a battery were prepared and evaluated using the same procedure as in Example 1, except that 10% by weight of acetylene black as a coating material was added, relative to core particles and LiNi 1/3 Mn 1/3 Co 1/3 O 2 powder was used as a cathode active material, when preparing an electrode additive.
  • An electrode and a battery were prepared and evaluated using the same procedure as in Example 1, except that 10% by weight of acetylene black as a coating material was added, relative to core particles and BaCO 3 was used as core particles, when preparing an electrode additive.
  • An electrode and a battery were prepared and evaluated using the same procedure as in Example 1, except that 10% by weight of acetylene black as a coating material was added, relative to core particles and MgO was used as core particles, when preparing an electrode additive.
  • An electrode and a battery were prepared and evaluated using the same procedure as in Example 1, except that 10% by weight of acetylene black as a coating material was added, relative to core particles and Al 2 O 3 was used as core particles, when preparing an electrode additive.
  • An electrode and a battery were prepared and evaluated using the same procedure as in Example 1, except that 10% by weight of acetylene black as a coating material was added, relative to core particles and Y(OH) 3 was used as core particles, when preparing an electrode additive.
  • An electrode and a battery were prepared and evaluated using the same procedure as in Example 1, except that 10% by weight of acetylene black as a coating material was added, relative to core particles and Al(OH) 3 was used as core particles, when preparing an electrode additive.
  • An electrode and a battery were prepared and evaluated using the same procedure as in Example 1, except that Ag metal powder was used as a coating material and 10% by weight of the coating material was added, relative to core particles, when preparing an electrode additive.
  • An electrode and a battery were prepared and evaluated using the same procedure as in Example 1, except that Al metal powder was used as a coating material and the coating material was added in an amount of 10% by weight, relative to core particles, when preparing an electrode additive.
  • An electrode and a battery were prepared and evaluated using the same procedure as in Example 1, except that TiB 2 powder was used as a coating material and the coating material was added in an amount of 10% by weight, relative to core particles, when preparing an electrode additive.
  • An electrode and a battery were prepared and evaluated using the same procedure as in Example 1, except that a conductive polymer, polypyrrole powder was used as a coating material and the coating material was added in an amount of 10% by weight, relative to core particles, when preparing an electrode additive.
  • An electrode and a battery were prepared and evaluated using the same procedure as in Example 1, except that a coating material was added in an amount of 10% by weight, relative to core particles, when preparing an electrode additive, and an electrode additive was added in an amount of 10% by weight, relative to a cathode active material, when preparing an electrode.
  • An electrode and a battery were prepared and evaluated using the same procedure as in Example 1, except that a coating material was added in an amount of 10% by weight, relative to core particles, and an electrode additive was added to a cathode and anode, in amounts of 1% by weight and 2% by weight, respectively, relative to a cathode active material and an anode active material, when preparing an electrode additive.
  • An electrode and a battery were prepared and evaluated using the same procedure as in Example 3, except that metal Si was used as an anode active material.
  • An electrode and a battery were prepared and evaluated using the same procedure as in Example 3, except that Al metal powder was used as a coating material, the coating material was added in an amount of 10% by weight, relative to core particles and metal Si was used as an anode active material, when preparing an electrode additive.
  • An electrode and a battery were prepared and evaluated using the same procedure as in Example 1, except that an electrode additive was not used
  • An electrode and a battery were prepared and evaluated using the same procedure as in Example 1, except that pure Mg(OH) 2 was added as a cathode additive.
  • An electrode and a battery were prepared and evaluated using the same procedure as in Example 3, except that pure Mg(OH) 2 was added as an anode additive.
  • batteries prepared in Examples 1, 2 and 4 through 16 exhibited less changes in thickness under high temperature storage, compared to batteries prepared in Comparative Examples 1 and 2.
  • TABLE 2 Changes in thickness of bicell, with or without addition of electrode additive to anode, and with time Comp. Comp. Ex. 1 Ex. 3 Ex. 3 Ex. 16 Ex. 17 Ex. 18 1 day 3.08 3.09 3.10 3.10 3.11 3.10 3 days 3.20 3.26 3.12 3.14 3.19 3.18 5 days 3.42 3.41 3.16 3.19 3.21 3.32 7 days 3.91 3.87 3.38 3.37 3.45 3.50 9 days 4.43 4.11 3.42 3.42 3.55 3.56 11 days 4.87 4.22 3.57 3.64 3.66 3.2
  • batteries prepared in Examples 1 through 18, to which the electrode additive in accordance with the present invention was added exhibited relatively little drop in high rate discharge, compared to batteries of Comparative Examples 1 through 3.
  • batteries prepared in Examples 1 through 18 exhibited relatively less changes in battery capacity with respect to charge/discharge cycles, compared to batteries prepared in Comparative Examples 1 through 3.
  • the electrode additive in accordance with the present invention when introduced to a cathode and/or anode of a lithium secondary battery, can exert characteristics intrinsic to the additive such as improvement of high temperature storage characteristics, without deteriorating battery performance.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

Provided are an electrode additive coated with a coating material made of electrically conductive materials such as metal hydroxides, metal oxides or metal carbonates, and an electrode and a lithium secondary battery comprising the same. The electrode additive in accordance with the present invention can improve high temperature storage characteristics of the battery, without deterioration of performance thereof.

Description

    FIELD OF THE INVENTION
  • The present invention relates to an electrode additive that is capable of improving battery performance and high temperature storage characteristics when it is added to an electrode of a lithium secondary battery, and an electrode and lithium secondary battery comprising the same.
    • BACKGROUND OF THE INVENTION
  • In order to keep pace with the continuing trend towards portabilization, miniaturization, and higher functionalization of a variety of electronic devices and instruments with development of the Information-Electronic Industry, higher capacity, smaller and lighter lithium secondary batteries are increasingly in demand. Recently, with diversification of functions of the electronic devices and instruments, there is also a strong need for realization of higher capacity, functionality, and performance of lithium secondary batteries, as a main power source. In addition, as the temperature range of lithium secondary batteries in use is also further extended, environmental conditions to which batteries are applied become more severe such that maintenance of initial performance without degradation in battery performance even when being maintained at higher temperatures of more than 80° C. for a prolonged period of time is required.
  • However, when material such as LiCoO2, LiMn2O4 or the like is used as a cathode active material for the lithium secondary battery, reaction between electrolyte and electrode surface leads to poor high-temperature characteristics, such as swelling and bulking in storage at a higher temperature of more than 80° C. Additionally, when charge/discharge cycles are repeatedly performed at the higher temperature, the electrochemical reaction continuously occurring at a cathode or anode surface contributes to production of decomposed by-products of the electrolyte and gas in the battery, thereby severely swelling the battery.
  • A variety of study and research has been made to solve those problems. Korean Patent Laid-open Publication No. 2003-0057321 discloses a technique of forming a protective coating film using electrolyte additives such as vinylene carbonate, alkenylethylene carbonate and the like, wherein the electrolyte additives are used to inhibit electrolyte decomposition reaction of the cathode at higher temperatures, such that these additives are first decomposed at cathode potential, thereby forming the protective film. However, although such additives may effectively inhibit battery swelling at higher temperatures, the additives may result in reduction of battery capacity or deterioration of battery life characteristics. For these reasons, various kinds of additives should be utilized to improve one functionality of the battery, when such electrolyte additives are used.
  • In addition, Korean Patent Laid-open Publication No. 2001-35700 and Japanese Patent Laid-Open Publication No. 1998-255389 disclose techniques of improving battery life characteristics and high temperature storage characteristics by addition of metal oxides or metal hydroxides to an electrode (cathode). However, metal oxides or metal hydroxides are electrically non-conductive and thus, when they are used as additives, interfere with electrical flow in the electrodes, thereby resulting in decreased high rate discharge characteristics of the battery, as well as increased resistance thereof leading to lowering of battery life characteristics.
  • Japanese Patent Laid-Open Publication Nos. 2003-86174 and 1997-22733 disclose a method of coating the cathode active material with an electro-conductive material such as conductive material using a mechanofusion apparatus and a binder. However, due to integration between the cathode active material and the conductive material in this method, it may be possible to improve battery capacity or diminish electrical resistance, thereby improving high rate discharge characteristics, but the conductive material coated on the surface of the cathode active material rather hampers migration of lithium ions, resulting in deterioration of battery performance.
  • Therefore, there is a strong need for an electrode additive that facilitates excellent high temperature storage performance of the lithium secondary battery and simultaneously does not inhibit high rate discharge and other battery performance characteristics.
    • SUMMARY OF THE INVENTION
  • Therefore, the present invention has been made to solve the above problems, and other technical problems that have yet to be resolved.
  • The present inventors have surprisingly found that battery performance and high temperature storage characteristics can be improved by preparing an electrode additive having core particles such as metal hydroxides, metal oxides or metal carbonates coated with electro-conductive material and adding the electrode additive to a cathode and/or anode of a lithium secondary battery.
  • On the basis of this finding, it is an object of the present invention to provide an electrode additive that is capable of improving battery performance and high temperature storage characteristics, and an electrode for a lithium secondary battery and lithium secondary battery comprising the same.
  • In accordance with an aspect of the present invention, the above and other objects can be accomplished by the provision of an electrode additive for a secondary battery electrode in which electro-conductive material is coated on the surface of a material that is added to the electrode material so as to improve battery characteristics.
  • As used herein, the term “electrode additive” refers to materials that are added to electrodes for various purposes such as improving high temperature characteristics and charge/discharge cycle characteristics of the battery. Since, among those materials, there are various kinds of low conductivity materials, as described above, such materials generally interfere with electron migration due to their high resistivity, when added to electrodes, and thereby lower battery performance. In accordance with the present invention, there is provided an electrode additive that can exert original effects without causing deterioration of battery performance, by coating the surface of the electrode additive with electro-conductive materials.
  • In accordance with the present invention, additive material (hereinafter, referred to as “core particle”), which is coated with electro-conductive materials, is added to electrodes for improvement of high temperature storage characteristics, and is exemplified as compounds represented by Formula 1 below:
    MxAy   Formula 1
    wherein, M is a metal, A is selected from the group consisting of OH, O and CO3, and x represents the valence of M and y represents the oxidation number of A.
  • Metal hydroxides, metal oxides, and metal carbonates of Formula 1 may be used alone or in any combination thereof.
  • Electro-conductive materials (hereinafter, referred to as “coating materials”), which are coated on core particles, are not particularly limited, so long as they exhibit excellent conductivity without causing chemical changes in the battery of interest. For example, there may be preferably used at least one selected from the group consisting of carbon that has been used as conductive material for a conventional lithium secondary battery, electro-conductive materials, electro-conductive metals, electro-conductive inorganic materials and electro-conductive polymers.
  • In accordance with another aspect of the present invention, there are provided an electrode fabricated by preparing an electrode slurry using electrode material containing the electrode additive and electrode active material and then applying the thus-prepared electrode slurry to a current collector, and a lithium secondary battery comprising the same.
    • BRIEF DESCRIPTION OF THE DRAWINGS
  • The above and other objects, features and other advantages of the present invention will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings, in which:
  • FIG. 1 schematically shows a cross-sectional view of an electrode additive in accordance with the present invention;
  • FIG. 2 is a micrograph showing carbon-coated Mg(OH)2 particles in accordance with the present invention;
  • FIG. 3 graphically shows battery life characteristics, i.e. changes in cell capacity with respect to charge/discharge cycles, for bicells in which the electrode additive of the present invention is added to cathodes thereof (Examples) and bicells in which the electrode additive of the present invention is not added to cathodes thereof (Comparative Examples); and
  • FIG. 4 graphically shows battery life characteristics, i.e. changes in cell capacity with respect to charge/discharge cycles, for bicells in which the electrode additive of the present invention is added to anodes thereof (Examples) and bicells in which the electrode additive of the present invention is not added to anodes thereof (Comparative Examples).
    • DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
  • Now, the present invention will be described in more detail.
  • In accordance with the present invention, by addition of an electrode additive to a cathode and/or anode of a battery, it is possible to inhibit battery swelling due to formation of decomposition by-products or gas production even when the battery is stored at high temperatures for a prolonged period of time, and also to improve battery performance such as life characteristics and charge/discharge rate at room temperature.
  • Conventionally, materials such as metal hydroxides, metal oxides and metal carbonate were used per se as cathode additives, but these materials are coated on the surface of the cathode active material and then impede migration of cathode active material and electrons, thereby deteriorating high rate discharge characteristics of the battery. In the present invention, via use of core particles, such as metal hydroxides, metal oxides or metal carbonates, coated with the coating material, it was possible to solve the problem associated with lowering of high rate discharge characteristics.
  • In accordance with the present invention, the coating material preferably has high electronic conductivity and small particle size to the maximum extent possible. Where electronic conductivity is lower, this may disadvantageously result in increase of electrode resistance thereby degrading battery performance. In addition, where the particle size of the coating material is too large, it may be difficult to coat the surface of core particles. On the other hand, the smaller the particle size of the coating material the denser and more uniform the coating on the core particles.
  • In the present invention, electrical conductivity of the coating material is preferably more than 2.0×102/cmΩ and the particle size thereof is preferably within the range of 10 to 1000 nm.
  • There is no particular limit to kinds of carbon, electro-conductive metals, electro-conductive inorganic materials and electro-conductive polymers, as described above as being preferred examples of the coat materials. Preferably, for example, carbon may be selected from the group consisting of carbon black, acetylene black and Super-P. Electro-conductive metals may be selected from the group consisting of Cu, Ag, Pt and Ni. Electro-conductive inorganic materials may be selected from the group consisting of indium tin oxide (In2O3SnO2), tin oxide (SnO2), zinc oxide (ZnO), ruthenium oxide (RuO2) and TiB2. Electro-conductive polymers may be selected from the group consisting of polypyrrole and polyaniline. Among the above-mentioned coating materials, acetylene black preferably has a particle size of 100 nm and electrical conductivity of more than 6.1×102/cmΩ. Ni preferably has a particle size of 1000 nm and electrical conductivity of more than 9.17×104/cmΩ. Polypyrrole preferably has a particle size of 200 nm and electrical conductivity of more than 2.0×102/cmΩ.
  • There is no particular limit to kinds of metal elements (M), which are contained in metal hydroxides, metal oxides or metal carbonates, those being described as preferred examples of the core particles. For example, metals may be preferably selected from the group consisting of Al, B, Mg, K, Be, Ca, Sr, Ba, Na, Cr, Sn, Ga, Bi, Ni, Co, Fe, Cr, Y and Zr. More preferably, metals may be selected from the group consisting of Al, B, Mg, Ba, Y and Zr.
  • A process for preparing an electrode additive in accordance with the present invention will be exemplified as follows.
  • Core particles to be coated are mixed with the coating material to prepare a mixture. In preparing the mixture, the amount of the coating material is preferably within the range of 0.01 to 20% by weight, relative to that of the core particles. Where the amount of the coating material exceeds the above-mentioned range, the resulting coating layer is too thick. On the other hand, where the amount of the coating material is less than the above range, core particles may be incompletely and partially coated.
  • Next, the mixture thus obtained was fused using a mechanofusion apparatus, for example, so as to coat core particles with the coating material. During such a fusion process, rotation speed and treatment time of the mechanofusion apparatus can be controlled as desired. Preferably, the rotation speed of the mechanofusion apparatus is between 1500 and 3000 rpm, and treatment time is in the range of 0.1 to 10 hours.
  • The extent that core particles are coated by the coating material may vary depending on the amount of the coating material added. Core particles need not necessarily be completely coated by the coating material to effect desired effects of the present invention. FIG. 1 schematically shows a coating material-coated core particle. FIG. 2 is a micrograph showing carbon-coated Mg(OH)2 particles. As can be seen from FIG. 2, carbon, which is coating material, uniformly surrounded core particles.
  • In accordance with the present invention, there is provided an electrode fabricated by adding the thus-prepared electrode additive of the present invention to an electrode material including electrode active material so as to prepare an electrode slurry and coating a current collector with the thus-prepared electrode slurry. There is no limit to a method for fabricating an electrode, and well-known conventional methods in the art may be employed.
  • Preferably, the electrode additive may be included in the range of 0.05 to 10% by weight in the electrode, relative to the electrode active material.
  • Further, in accordance with the present invention, there is provided a lithium secondary battery comprising the above-prepared electrode. The lithium secondary battery of the present invention may be prepared by conventional methods known in the art, for example disposing a porous separator between the cathode and anode, followed by introduction of a non-aqueous electrolyte.
  • There is no limit to shapes of the lithium secondary battery in accordance with the present invention, and for example, mention may be made of can-shaped cylinders, squares or pouches.
  • As cathode active materials that can be used in fabricating the electrode of the present invention, lithium-containing transition metal oxides may be preferably used. For example, the cathode active material may be at least one selected from the group consisting of LiCoO2, LiNiO2, LiMnO2, LiMn2O4, Li(NiaCobMnc)O2 (0<a<1, 0<b<1, 0<c<1, a+b+c=1), LiNi1-YCoYO2, LiCo1-YMnYO2, LiNi1-YMnYO2 (0≦Y<1), Li(NiaCobMnc)O4 (0<a<2, 0<b<2, 0<c<2, a+b+c=2, LiMn2-zNizO4, LiMn2-zCozO4 (0<Z<2), LiCoPO4 and LiFePO4. Among those materials, more preferred is LiCoO2.
  • As anode active materials that can be used in fabricating the electrode of the present invention, mention may be made of graphite, carbon, lithium metals, alloys and complexes thereof, which are capable of occluding and releasing lithium ions.
  • In addition, in preparing the battery in accordance with the present invention, the porous separator may be preferably used as the separator. For example, the separator may include, but is not limited to, polypropylene-based, polyethylene-based, and other polyolefin-based porous separators.
  • The non-aqueous electrolyte of the lithium secondary battery that can be utilized in the present invention may contain cyclic carbonates and linear carbonates. The cyclic carbonates include, for example ethylene carbonate (EC), propylene carbonate (PC) and gamma-butyro lactone (GBL). The linear carbonate may be at least one selected from the group consisting of diethylcarbonate (DEC), dimethylcarbonate (DMC), ethylmethylcarbonate (EMC) and methylpropylcarbonate (MPC). Further, the non-aqueous electrolyte of the lithium secondary battery in accordance with the present invention may contain lithium salts, in addition to carbonate compounds. As specific examples, preferably, lithium salts may be selected from the group consisting of LiClO4, LiCF3SO3, LiPF6, LiBF4, LiAsF6 and LiN(CF3SO2)2.
    • EXAMPLES
  • Now, the present invention will be described in more detail with reference to the following Examples and Comparative Examples. These examples are provided only for illustrating the present invention and should not be construed as limiting the scope and spirit of the present invention.
    • Example
  • 1.1. Preparation of Electrode Additive
  • Acetylene black, which is a carbon material, as a coating material and Mg(OH)2, which is a metal hydroxide, as a core particle, were used to prepare an electrode additive. The content of acetylene black was 5% by weight, relative to that of the core particle, Mg(OH)2. A mixture of acetylene black and Mg(OH)2 was loaded on a mechanofusion apparatus, and subjected to low speed rotation at 250 rpm for 3 min and subsequently to high speed rotation at 1400 rpm for 20 min so as to coat carbon on the surface of the metal hydroxide, thereby preparing the electrode additive (C0.05Mg(OH)2).
  • 1.2. Preparation of Cathode
  • LiCoO2 was used as a cathode active material, and 0.5% by weight of the above-prepared electrode additive (C0.05Mg(OH)2) was added thereto, relative to the cathode active material. Then, together with 2.5% Super-P(conductive material) and 2.5% polyvinylidene difluoride (PVdF) as a binding agent, a cathode active material powder (LiCoO2) and the electrode additive were dispersed in an n-methylpyrolidone (NMP) solvent to obtain a slurry. The slurry thus obtained was coated on aluminum foil and heated to evaporate the NMP solvent to dryness, followed by compression at a pressure of about 500 kg/cm2 to prepare a cathode.
  • 1.3. Preparation of Anode
  • Artificial graphite was used as an anode active material, and was dispersed, together with 0.8% acetylene black (conductive material), 3.9% PVdF as a binding agent and 0.2% oxalic acid, relative to the anode active material, in an NMP solvent to obtain slurry. The slurry thus obtained was coated on copper foil and heated to evaporate the NMP solvent to dryness, followed by compression at a pressure of about 500 kg/cm2 to prepare an anode.
  • 1.4. Battery Preparation and Evaluation
  • A conventional pouch-type bicell was prepared using the above-prepared cathode and anode, and as an electrolyte, a solution in which 1M LiPF6 was dissolved in a 1:2 (v/v) mixed solvent of ethylene carbonate (EC) and ethyl methyl carbonate (EMC).
  • For the above-prepared battery, voltage of charge and discharge was established in the range of 3.0 to 4.2 V. Evaluation of battery life characteristics was made by 1 C/1 C charge/discharge. Evaluation of high rate discharge characteristics was carried out by charging the battery to 0.5 C, followed by measurement of capacity of 0.2 C, 0.5 C, 1 C, 1.5 C and 2 C and calculation of percentage of respective capacity thus measured, relative to capacity of 0.2 C. In addition, in order to evaluate high temperature storage characteristics, the battery was charged/discharged to 0.5 C/0.5 C two times and then charged to 0.2 C. This was followed by placement of the battery in an oven at 80° C. and determination of thickness changes with respect to the passage of time.
    • Example 2
  • An electrode and a battery were prepared and evaluated using the same procedure as in Example 1, except that 10% by weight of acetylene black as a coating material was added, relative to core particles, when preparing an electrode additive.
    • Example 3
  • An electrode and a battery were prepared and evaluated using the same procedure as in Example 1, except that, relative to an anode active material, there was added 1.0% by weight of an electrode additive, which was prepared in a manner that an electrode additive was not added to a cathode and 10% by weight of acetylene black as a coating material was added to an anode, relative to core particles (Mg(OH)2).
    • Example 4
  • An electrode and a battery were prepared and evaluated using the same procedure as in Example 1, except that 10% by weight of acetylene black as a coating material was added, relative to core particles and LiMn2O4 powder was used as a cathode active material, when preparing an electrode additive.
    • Example 5
  • An electrode and a battery were prepared and evaluated using the same procedure as in Example 1, except that 10% by weight of acetylene black as a coating material was added, relative to core particles and LiNi1/3Mn1/3Co1/3O2 powder was used as a cathode active material, when preparing an electrode additive.
    • Example 6
  • An electrode and a battery were prepared and evaluated using the same procedure as in Example 1, except that 10% by weight of acetylene black as a coating material was added, relative to core particles and BaCO3 was used as core particles, when preparing an electrode additive.
    • Example 7
  • An electrode and a battery were prepared and evaluated using the same procedure as in Example 1, except that 10% by weight of acetylene black as a coating material was added, relative to core particles and MgO was used as core particles, when preparing an electrode additive.
    • Example 8
  • An electrode and a battery were prepared and evaluated using the same procedure as in Example 1, except that 10% by weight of acetylene black as a coating material was added, relative to core particles and Al2O3 was used as core particles, when preparing an electrode additive.
    • Example 9
  • An electrode and a battery were prepared and evaluated using the same procedure as in Example 1, except that 10% by weight of acetylene black as a coating material was added, relative to core particles and Y(OH)3 was used as core particles, when preparing an electrode additive.
    • Example 10
  • An electrode and a battery were prepared and evaluated using the same procedure as in Example 1, except that 10% by weight of acetylene black as a coating material was added, relative to core particles and Al(OH)3 was used as core particles, when preparing an electrode additive.
    • Example 11
  • An electrode and a battery were prepared and evaluated using the same procedure as in Example 1, except that Ag metal powder was used as a coating material and 10% by weight of the coating material was added, relative to core particles, when preparing an electrode additive.
    • Example 12
  • An electrode and a battery were prepared and evaluated using the same procedure as in Example 1, except that Al metal powder was used as a coating material and the coating material was added in an amount of 10% by weight, relative to core particles, when preparing an electrode additive.
    • Example 13
  • An electrode and a battery were prepared and evaluated using the same procedure as in Example 1, except that TiB2 powder was used as a coating material and the coating material was added in an amount of 10% by weight, relative to core particles, when preparing an electrode additive.
    • Example 14
  • An electrode and a battery were prepared and evaluated using the same procedure as in Example 1, except that a conductive polymer, polypyrrole powder was used as a coating material and the coating material was added in an amount of 10% by weight, relative to core particles, when preparing an electrode additive.
    • Example 15
  • An electrode and a battery were prepared and evaluated using the same procedure as in Example 1, except that a coating material was added in an amount of 10% by weight, relative to core particles, when preparing an electrode additive, and an electrode additive was added in an amount of 10% by weight, relative to a cathode active material, when preparing an electrode.
    • Example 16
  • An electrode and a battery were prepared and evaluated using the same procedure as in Example 1, except that a coating material was added in an amount of 10% by weight, relative to core particles, and an electrode additive was added to a cathode and anode, in amounts of 1% by weight and 2% by weight, respectively, relative to a cathode active material and an anode active material, when preparing an electrode additive.
    • Example 17
  • An electrode and a battery were prepared and evaluated using the same procedure as in Example 3, except that metal Si was used as an anode active material.
    • Example 18
  • An electrode and a battery were prepared and evaluated using the same procedure as in Example 3, except that Al metal powder was used as a coating material, the coating material was added in an amount of 10% by weight, relative to core particles and metal Si was used as an anode active material, when preparing an electrode additive.
    • Comparative Example 1
  • An electrode and a battery were prepared and evaluated using the same procedure as in Example 1, except that an electrode additive was not used
    • Comparative Example 2
  • An electrode and a battery were prepared and evaluated using the same procedure as in Example 1, except that pure Mg(OH)2 was added as a cathode additive.
    • Comparative Example 3
  • An electrode and a battery were prepared and evaluated using the same procedure as in Example 3, except that pure Mg(OH)2 was added as an anode additive.
  • Evaluation results of batteries prepared in Examples 1 through 18 and Comparative Examples 1 through 3 are shown in FIGS. 3 and 4, and Tables 1 through 3.
    TABLE 1
    Changes in thickness of bicell, with or without addition of electrode
    additive to cathode, and with time
    Comp. Comp.
    Ex. 1 Ex. 2 Ex. 1 Ex. 2 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8
     1 day 3.08 3.09 3.10 3.08 3.09 3.08 3.10 3.09 3.08
     3 days 3.20 3.24 3.11 3.08 3.10 3.11 3.13 3.12 3.09
     5 days 3.42 3.42 3.15 3.15 3.16 3.17 3.19 3.18 3.11
     7 days 3.91 3.62 3.31 3.31 3.37 3.35 3.33 3.37 3.35
     9 days 4.43 3.97 3.48 3.44 3.43 3.46 3.49 3.48 3.45
    11 days 4.87 4.31 3.57 3.52 3.61 3.57 3.58 3.60 3.56
    Ex. 9 Ex. 10 Ex. 11 Ex. 12 Ex. 13 Ex. 14 Ex. 15 Ex. 16
     1 day 3.09 3.10 3.10 3.09 3.09 3.09 3.10 3.10
     3 days 3.11 3.10 3.12 3.11 3.12 3.13 3.13 3.14
     5 days 3.15 3.17 3.30 3.31 3.18 3.20 3.17 3.19
     7 days 3.32 3.35 3.39 3.38 3.39 3.38 3.32 3.37
     9 days 3.44 3.49 3.49 3.48 3.51 3.52 3.50 3.42
    11 days 3.59 3.55 3.54 3.59 3.58 3.59 3.59 3.64
  • As can be seen from Table 1, batteries prepared in Examples 1, 2 and 4 through 16 exhibited less changes in thickness under high temperature storage, compared to batteries prepared in Comparative Examples 1 and 2.
    TABLE 2
    Changes in thickness of bicell, with or without addition of electrode
    additive to anode, and with time
    Comp. Comp.
    Ex. 1 Ex. 3 Ex. 3 Ex. 16 Ex. 17 Ex. 18
     1 day 3.08 3.09 3.10 3.10 3.11 3.10
     3 days 3.20 3.26 3.12 3.14 3.19 3.18
     5 days 3.42 3.41 3.16 3.19 3.21 3.32
     7 days 3.91 3.87 3.38 3.37 3.45 3.50
     9 days 4.43 4.11 3.42 3.42 3.55 3.56
    11 days 4.87 4.22 3.57 3.64 3.66 3.2
  • As can be seen from Table 2, batteries prepared in Examples 3, 16, 17 and 18 exhibited less changes in thickness under high temperature storage, compared to batteries prepared in Comparative Examples 1 and 3.
    TABLE 3
    Changes in battery capacity with respect to discharge rate
    Discharge Comp. Comp. Comp.
    rate (C) Ex. 1 Ex. 2 Ex. 3 Ex. 1 Ex. 2 Ex. 3 Ex. 4
    0.2 100 100 100 100 100 100 100
    0.5 99.61 99.61 99.45 99.64 99.51 99.88 99.78
    1 99.36 99.38 99.29 99.52 99.40 99.62 99.63
    1.5 99.86 99.85 99.75 99.89 94.92 99.61 99.67
    2 99.56 99.78 99.58 99.87 99.06 99.41 99.78
    Ex. 5 Ex. 6 Ex. 7 Ex. 8 Ex. 9 Ex. 10 Ex. 11
    0.2 100 100 100 100 100 100 100
    0.5 99.51 99.71 99.44 99.58 99.51 99.47 99.46
    1 99.42 99.48 99.35 99.32 99.34 99.35 99.31
    1.5 99.66 99.55 99.54 99.77 99.76 99.71 99.75
    2 99.56 99.48 99.52 99.59 99.54 99.50 99.56
    Ex. 12 Ex. 13 Ex. 14 Ex. 15 Ex. 16 Ex. 17 Ex. 18
    0.2 100 100 100 100 100 100 100
    0.5 99.54 99.53 99.88 99.81 99.53 99.71 99.49
    1 99.50 99.47 99.65 99.73 99.52 99.58 99.32
    1.5 99.81 94.82 99.71 99.70 99.65 99.65 99.69
    2 99.86 99.36 99.49 99.78 99.66 99.58 99.48
  • As can be seen from Table 3, batteries prepared in Examples 1 through 18, to which the electrode additive in accordance with the present invention was added, exhibited relatively little drop in high rate discharge, compared to batteries of Comparative Examples 1 through 3.
  • Further, as shown in FIGS. 3 and 4, batteries prepared in Examples 1 through 18 exhibited relatively less changes in battery capacity with respect to charge/discharge cycles, compared to batteries prepared in Comparative Examples 1 through 3.
    • INDUSTRIAL APPLICABILITY
  • As described above, the electrode additive in accordance with the present invention, when introduced to a cathode and/or anode of a lithium secondary battery, can exert characteristics intrinsic to the additive such as improvement of high temperature storage characteristics, without deteriorating battery performance.
  • Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.

Claims (11)

1. An electrode additive for a secondary battery electrode in which electro-conductive material (“coating material”) is coated on the surface of material (“core particle”) that is added to electrode material so as to improve battery characteristics.
2. The electrode additive according to claim 1, wherein the core particle is a material of Formula 1 that is added to battery electrodes for improving high temperature storage characteristics:

MxAy   (1)
wherein, M is a metal, A is selected from the group consisting of OH, O and CO3, and x represents the valence of M and y represents the oxidation number of A.
3. The electrode additive according to claim 1, wherein the coating material is composed of one or more materials selected from the group consisting of carbon, an electro-conductive metal, an electro-conductive inorganic material and an electro-conductive polymer.
4. The electrode additive according to claim 3, wherein the carbon is selected from the group consisting of carbon black, acetylene black and Super-P, the electro-conductive metal is selected from the group consisting of Cu, Ag, Pt and Ni, the electro-conductive inorganic material is selected from the group consisting of indium tin oxide (In2O3SnO2), tin oxide (SnO2), zinc oxide (ZnO), ruthenium oxide (RuO2) and TiB2, and the electro-conductive polymer is selected from the group consisting of polypyrrole and polyaniline.
5. The electrode additive according to claim 1, wherein the coating material has an electrical conductivity of more than 2.0×102/cmΩ.
6. The electrode additive according to claim 1, wherein the coating material has a particle size of 10 nm to 1000 nm.
7. The electrode additive according to claim 2, wherein M in Formula 1 is one or more elements selected from the group consisting of Al, B, Mg, K, Be, Ca, Sr, Ba, Na, Cr, Sn, Ga, Bi, Ni, Co, Fe, Cr, Y and Zr.
8. The electrode additive according to claim 1, wherein the amount of the coating material is within the range of 0.01 to 20% by weight, relative to the core particle.
9. An electrode fabricated by preparing an electrode slurry using electrode material containing the electrode additive according to claims 1 and electrode active material and applying the thus-prepared electrode slurry to a current collector.
10. The electrode according to claim 9, wherein the electrode additive is included in the range of 0.05 to 10% by weight, relative to the electrode active material.
11. A lithium secondary battery comprising the electrode of claim 9.
US11/050,973 2004-02-07 2005-02-04 Electrode additives coated with electro conductive material and lithium secondary comprising the same Abandoned US20050208380A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US13/473,415 US9252429B2 (en) 2004-02-07 2012-05-16 Electrode additives coated with electro conductive material and lithium secondary comprising the same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2004-0008135 2004-02-07
KR20040008135 2004-02-07

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US13/473,415 Continuation US9252429B2 (en) 2004-02-07 2012-05-16 Electrode additives coated with electro conductive material and lithium secondary comprising the same

Publications (1)

Publication Number Publication Date
US20050208380A1 true US20050208380A1 (en) 2005-09-22

Family

ID=36968329

Family Applications (2)

Application Number Title Priority Date Filing Date
US11/050,973 Abandoned US20050208380A1 (en) 2004-02-07 2005-02-04 Electrode additives coated with electro conductive material and lithium secondary comprising the same
US13/473,415 Expired - Lifetime US9252429B2 (en) 2004-02-07 2012-05-16 Electrode additives coated with electro conductive material and lithium secondary comprising the same

Family Applications After (1)

Application Number Title Priority Date Filing Date
US13/473,415 Expired - Lifetime US9252429B2 (en) 2004-02-07 2012-05-16 Electrode additives coated with electro conductive material and lithium secondary comprising the same

Country Status (7)

Country Link
US (2) US20050208380A1 (en)
EP (1) EP1711971B1 (en)
JP (1) JP5132941B2 (en)
KR (1) KR100674011B1 (en)
CN (1) CN1918731B (en)
TW (1) TWI269477B (en)
WO (1) WO2005076391A1 (en)

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060024582A1 (en) * 2004-03-16 2006-02-02 Wen Li Battery and method of manufacturing the same
US20070112243A1 (en) * 2005-08-11 2007-05-17 United States Of America As Represented By The Administrator Of The National Aeronautics And Spac Bimetallic Treatment System and its Application for Removal and Remediation of Polychlorinated Biphenyls (PCBs)
US20070287628A1 (en) * 2006-05-19 2007-12-13 Usa As Represented By The Administrator Of The National Aeronautics And Space Adm Mechanical Alloying of a Hydrogenation Catalyst Used for the Remediation of Contaminated Compounds
US20080070122A1 (en) * 2006-09-20 2008-03-20 Park Kyu-Sung Cathode active material and lithium battery employing the same
US20090155694A1 (en) * 2007-12-18 2009-06-18 Samsung Sdi Co., Ltd. Cathode and lithium battery using the same
US20100217063A1 (en) * 2005-08-11 2010-08-26 Usa As Represented By The Administrator Of The National Aeronautics And Space Administration Zero-Valent Metallic Treatment System and its Application for Removal and Remediation of Polychlorinated Biphenyls (PCBs)
US20110133131A1 (en) * 2008-08-06 2011-06-09 Haoshen Zhou Method of Producing Electrode Material Precursor and Electrode Material Using the Electrode Material Precursor
US20110159172A1 (en) * 2009-12-25 2011-06-30 Sanyo Electric Co., Ltd. Method for manufacturing positive electrode of nonaqueous electrolyte secondary battery
CN102237509A (en) * 2010-05-06 2011-11-09 三星Sdi株式会社 Negative electrode for energy storage device and energy storage device
US8854012B2 (en) 2011-08-25 2014-10-07 Apple Inc. Management of high-voltage lithium-polymer batteries in portable electronic devices
US20150064556A1 (en) * 2013-09-03 2015-03-05 Samsung Sdi Co., Ltd. Electrode for rechargeable lithium battery and rechargeable lithium battery including the same
US9054376B2 (en) 2010-12-20 2015-06-09 Industrial Technology Research Institute Cathode material structure and method for preparing the same
US9318745B2 (en) 2010-11-30 2016-04-19 Sanyo Electric Co., Ltd. Conductive agent for nonaqueous electrolyte secondary battery, positive electrode for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery
US9406980B2 (en) 2013-09-24 2016-08-02 Blackberry Limited System and method of mitigating high-temperature, high-charge gas swelling of battery of portable electronic device
US9525175B2 (en) 2010-05-25 2016-12-20 Samsung Sdi Co., Ltd. Negative electrode for secondary lithium battery, and secondary lithium battery
JP2017079206A (en) * 2015-10-21 2017-04-27 日亜化学工業株式会社 Non-aqueous secondary battery positive electrode composition and method for producing the same
US9972841B2 (en) 2014-09-30 2018-05-15 Lg Chem, Ltd. Positive electrode active material and preparation method thereof
CN110034292A (en) * 2019-04-30 2019-07-19 河北工业大学 A kind of 3-D ordered multiporous polypyrrole/zinc oxide lithium ion battery negative material and preparation method
WO2020086310A1 (en) * 2018-10-22 2020-04-30 A123 Systems Llc Electrode with flame retardant additives and method and systems for preparation and use
US10749209B2 (en) 2015-02-27 2020-08-18 Murata Manufacturing Co., Ltd. Electrolyte, battery, battery pack, electronic apparatus, electric vehicle, power storage apparatus, and power system
US11031600B2 (en) 2014-12-17 2021-06-08 Lg Energy Solution, Ltd. Lithium ion secondary battery including aluminum silicate
US20220359864A1 (en) * 2021-05-10 2022-11-10 Sk On Co., Ltd. Anode active material for secondary battery, method of preparing the same and secondary battery including the same

Families Citing this family (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008053220A (en) * 2006-07-25 2008-03-06 Gs Yuasa Corporation:Kk Non-aqueous electrolyte battery and its manufacturing method
EP1972267A1 (en) 2007-03-20 2008-09-24 Roche Diagnostics GmbH System for in vivo measurement of an analyte concentration
JP5374851B2 (en) 2007-10-15 2013-12-25 ソニー株式会社 Negative electrode for lithium ion secondary battery and lithium ion secondary battery
JP5407471B2 (en) * 2009-03-25 2014-02-05 Ｔｄｋ株式会社 Lithium ion secondary battery
CN102568840B (en) * 2011-12-23 2014-02-12 彩虹集团公司 Preparation method of counter electrode of dye sensitization battery
CN102623697A (en) * 2012-03-30 2012-08-01 天津巴莫科技股份有限公司 Lithium iron phosphate/titanium diboride composite cathode material for lithium ion battery and preparation method of lithium iron phosphate/titanium diboride composite cathode material
JP6315258B2 (en) * 2014-06-04 2018-04-25 日立化成株式会社 Conductive material for lithium ion secondary battery, composition for forming negative electrode of lithium ion secondary battery, composition for forming positive electrode of lithium ion secondary battery, negative electrode for lithium ion secondary battery, positive electrode for lithium ion secondary battery and lithium ion secondary Secondary battery
JP2015230793A (en) * 2014-06-04 2015-12-21 日立化成株式会社 Electrically conductive material
JP2015230794A (en) * 2014-06-04 2015-12-21 日立化成株式会社 Conductive material for lithium ion secondary battery, composition for forming lithium ion secondary battery negative electrode, composition for forming lithium ion secondary battery positive electrode, negative electrode for lithium ion secondary battery, positive electrode for lithium ion secondary battery, and lithium ion secondary battery
JP6379694B2 (en) * 2014-06-04 2018-08-29 日立化成株式会社 Magnesium aluminum oxide composite
CN104124452B (en) * 2014-07-24 2016-05-18 四川大学 A kind of coated lithium iron phosphate positive material of titanium compound and preparation method thereof that conducts electricity
CN104218217A (en) * 2014-07-29 2014-12-17 江西世纪长河新电源有限公司 Power battery lithium ion secondary battery pole piece
CN104201326A (en) * 2014-07-29 2014-12-10 江西世纪长河新电源有限公司 Pole piece of lithium ion secondary battery
JP6597167B2 (en) * 2015-10-21 2019-10-30 日亜化学工業株式会社 Positive electrode composition for non-aqueous secondary battery
CN106299514B (en) * 2016-08-31 2019-04-26 浙江超威创元实业有限公司 A kind of compound method for lithium ion battery
CN106299494B (en) * 2016-08-31 2018-12-14 浙江超威创元实业有限公司 A kind of water base lithium ion secondary battery
JP2018060604A (en) * 2016-09-30 2018-04-12 日立オートモティブシステムズ株式会社 Lithium ion secondary battery
JP6778385B2 (en) * 2019-02-05 2020-11-04 昭和電工マテリアルズ株式会社 Conductive material for lithium ion secondary battery, composition for forming negative electrode of lithium ion secondary battery, composition for forming positive electrode of lithium ion secondary battery, negative electrode for lithium ion secondary battery, positive electrode for lithium ion secondary battery and lithium ion secondary Next battery
WO2021055939A1 (en) * 2019-09-19 2021-03-25 Ohio State Innovation Foundation Nanofiber- and nanowhisker-based transfection platforms
CN111900377A (en) * 2020-08-04 2020-11-06 中国科学院物理研究所 A kind of magnesium compound material and its preparation method and application
CN116891643A (en) * 2022-03-30 2023-10-17 三星Sdi株式会社 Endothermic Particles and Nonaqueous Electrolytes Rechargeable Batteries
EP4276932A1 (en) * 2022-03-30 2023-11-15 Samsung SDI Co., Ltd. Endothermic particles for non-aqueous electrolyte rechargeable battery and non-aqueous electrolyte rechargeable battery
US20230352659A1 (en) * 2022-03-31 2023-11-02 Samsung Sdi Co., Ltd. Composite particles for non-aqueous electrolyte rechargeable battery, producing method, positive and negative electrodes, and non-aqueous electrolyte rechargeable battery
JP7644731B2 (en) * 2022-03-31 2025-03-12 三星エスディアイ株式会社 Composite particles for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020168574A1 (en) * 1997-06-27 2002-11-14 Soon-Ho Ahn Lithium ion secondary battery and manufacturing method of the same
US20030129494A1 (en) * 1999-02-23 2003-07-10 Junya Kaneda Lithium secondary battery having oxide particles embedded in particles of carbonaceous material as a negative electrode-active material
US20030162100A1 (en) * 2002-02-26 2003-08-28 Yasufumi Takahashi Lithium secondary battery for mounting on substrate
US20040029014A1 (en) * 2002-08-07 2004-02-12 Samsung Sdi Co., Ltd. Positive electrode for lithium-sulfur battery, method of producing same, and lithium-sulfur battery

Family Cites Families (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56130080A (en) * 1980-03-18 1981-10-12 Matsushita Electric Ind Co Ltd Alkaline manganese battery
US4450214A (en) * 1982-06-14 1984-05-22 Union Carbide Corporation Lithium halide additives for nonaqueous cell systems
EP0110344A1 (en) * 1982-12-06 1984-06-13 Eveready Battery Company, Inc. Nonaqueous cells
JP3291803B2 (en) * 1992-11-06 2002-06-17 ダイキン工業株式会社 Carbon fluoride particles and their production and use
JP3197763B2 (en) * 1993-11-18 2001-08-13 三洋電機株式会社 Non-aqueous battery
JP3396696B2 (en) * 1993-11-26 2003-04-14 エヌイーシートーキン栃木株式会社 Rechargeable battery
US5721065A (en) * 1995-05-05 1998-02-24 Rayovac Corporation Low mercury, high discharge rate electrochemical cell
JPH0922733A (en) 1995-07-06 1997-01-21 Toshiba Battery Co Ltd Polymer electrolyte secondary battery
US5707460A (en) * 1995-07-11 1998-01-13 Porter-Cable Corporation Method of producing parts having improved wear, fatigue and corrosion resistance from medium alloy, low carbon steel and parts obtained therefrom
JP3702318B2 (en) * 1996-02-09 2005-10-05 日本電池株式会社 Non-aqueous electrolyte battery electrode and non-aqueous electrolyte battery using the electrode
US6514640B1 (en) 1996-04-23 2003-02-04 Board Of Regents, The University Of Texas System Cathode materials for secondary (rechargeable) lithium batteries
JP3772442B2 (en) 1997-03-11 2006-05-10 松下電器産業株式会社 Disk rotating apparatus and disk recording apparatus provided with the same
JPH10255839A (en) * 1997-03-12 1998-09-25 Matsushita Electric Ind Co Ltd Non-aqueous electrolyte secondary battery
CA2215756C (en) * 1997-09-18 2006-04-04 Moli Energy (1990) Limited Additives for improving cycle life of non-aqueous rechargeable lithium batteries
JP3525710B2 (en) 1997-11-19 2004-05-10 株式会社デンソー Secondary battery and its positive electrode active material
JP3244227B2 (en) * 1999-04-26 2002-01-07 日本電気株式会社 Non-aqueous electrolyte secondary battery
KR100346546B1 (en) 1999-10-01 2002-07-26 삼성에스디아이 주식회사 A positive electrode plate for a lithium secondary battery
JP2001110454A (en) * 1999-10-08 2001-04-20 Matsushita Electric Ind Co Ltd Lithium ion secondary battery
JP4649691B2 (en) 1999-10-20 2011-03-16 株式会社豊田中央研究所 Positive electrode for lithium secondary battery
KR100347882B1 (en) 2000-07-11 2002-08-10 학교법인 서강대학교 Conducting Polymer/Manganese Oxide Composite Cathode Material for Lithium Secondary Batteries and Method for Making Same
JP4581196B2 (en) * 2000-08-03 2010-11-17 株式会社豊田中央研究所 Positive electrode for lithium secondary battery
US6753112B2 (en) * 2000-12-27 2004-06-22 Kabushiki Kaisha Toshiba Positive electrode active material and non-aqueous secondary battery using the same
JP4055368B2 (en) * 2001-02-27 2008-03-05 日本電気株式会社 Secondary battery
US6821677B2 (en) * 2001-03-29 2004-11-23 Kabushiki Kaisha Toshiba Negative electrode active material and nonaqueous electrolyte battery
JP2003086174A (en) 2001-06-25 2003-03-20 Hosokawa Micron Corp Composite particle material for electrode, electrode plate and method for producing them
KR100509968B1 (en) 2001-12-28 2005-08-24 미쓰이 가가쿠 가부시키가이샤 Non-aqueous electrolytic solutions and lithium secondary battery containing the same
JP4761239B2 (en) 2003-10-31 2011-08-31 日立マクセルエナジー株式会社 Non-aqueous secondary battery electrode material, method for producing the same, and non-aqueous secondary battery using the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020168574A1 (en) * 1997-06-27 2002-11-14 Soon-Ho Ahn Lithium ion secondary battery and manufacturing method of the same
US20030129494A1 (en) * 1999-02-23 2003-07-10 Junya Kaneda Lithium secondary battery having oxide particles embedded in particles of carbonaceous material as a negative electrode-active material
US20030162100A1 (en) * 2002-02-26 2003-08-28 Yasufumi Takahashi Lithium secondary battery for mounting on substrate
US20040029014A1 (en) * 2002-08-07 2004-02-12 Samsung Sdi Co., Ltd. Positive electrode for lithium-sulfur battery, method of producing same, and lithium-sulfur battery

Cited By (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7468224B2 (en) * 2004-03-16 2008-12-23 Toyota Motor Engineering & Manufacturing North America, Inc. Battery having improved positive electrode and method of manufacturing the same
US20060024582A1 (en) * 2004-03-16 2006-02-02 Wen Li Battery and method of manufacturing the same
US20070112243A1 (en) * 2005-08-11 2007-05-17 United States Of America As Represented By The Administrator Of The National Aeronautics And Spac Bimetallic Treatment System and its Application for Removal and Remediation of Polychlorinated Biphenyls (PCBs)
US8163972B2 (en) 2005-08-11 2012-04-24 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Zero-valent metallic treatment system and its application for removal and remediation of polychlorinated biphenyls (PCBs)
US20100217063A1 (en) * 2005-08-11 2010-08-26 Usa As Represented By The Administrator Of The National Aeronautics And Space Administration Zero-Valent Metallic Treatment System and its Application for Removal and Remediation of Polychlorinated Biphenyls (PCBs)
US7842639B2 (en) 2006-05-19 2010-11-30 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Mechanical alloying of a hydrogenation catalyst used for the remediation of contaminated compounds
US20110172082A1 (en) * 2006-05-19 2011-07-14 United States of America as represented by the Administrator of the National Aeronautics and Mechanical Alloying of a Hydrogenation Catalyst Used for the Remediation of Contaminated Compounds
WO2007136757A3 (en) * 2006-05-19 2008-01-10 Usa As Represented By The Admi Mechanical alloying of a hydrogenation catalyst used for the remediation of contaminated compounds
US20070287628A1 (en) * 2006-05-19 2007-12-13 Usa As Represented By The Administrator Of The National Aeronautics And Space Adm Mechanical Alloying of a Hydrogenation Catalyst Used for the Remediation of Contaminated Compounds
US8288307B2 (en) 2006-05-19 2012-10-16 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Mechanical alloying of a hydrogenation catalyst used for the remediation of contaminated compounds
US20080070122A1 (en) * 2006-09-20 2008-03-20 Park Kyu-Sung Cathode active material and lithium battery employing the same
US20090155694A1 (en) * 2007-12-18 2009-06-18 Samsung Sdi Co., Ltd. Cathode and lithium battery using the same
US8568617B2 (en) 2008-08-06 2013-10-29 National Institute Of Advanced Industrial Science And Technology Method of producing electrode material precursor and electrode material using the electrode material precursor
US20110133131A1 (en) * 2008-08-06 2011-06-09 Haoshen Zhou Method of Producing Electrode Material Precursor and Electrode Material Using the Electrode Material Precursor
US20110159172A1 (en) * 2009-12-25 2011-06-30 Sanyo Electric Co., Ltd. Method for manufacturing positive electrode of nonaqueous electrolyte secondary battery
US8313796B2 (en) * 2009-12-25 2012-11-20 Sanyo Electric Co., Ltd. Method for manufacturing positive electrode of nonaqueous electrolyte secondary battery
EP2385573A3 (en) * 2010-05-06 2014-04-09 Samsung SDI Co., Ltd. Negative electrode for energy storage device and energy storage device including same
CN102237509A (en) * 2010-05-06 2011-11-09 三星Sdi株式会社 Negative electrode for energy storage device and energy storage device
US8592086B2 (en) 2010-05-06 2013-11-26 Samsung Sdi Co., Ltd. Negative electrode comprising an additive with a ceramic core and carbon disposed on the core for energy storage device and energy storage device including same
US9525175B2 (en) 2010-05-25 2016-12-20 Samsung Sdi Co., Ltd. Negative electrode for secondary lithium battery, and secondary lithium battery
US9318745B2 (en) 2010-11-30 2016-04-19 Sanyo Electric Co., Ltd. Conductive agent for nonaqueous electrolyte secondary battery, positive electrode for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery
US9054376B2 (en) 2010-12-20 2015-06-09 Industrial Technology Research Institute Cathode material structure and method for preparing the same
US10468900B2 (en) 2011-08-25 2019-11-05 Apple Inc. Management of high-voltage lithium-polymer batteries in portable electronic devices
US9450443B2 (en) 2011-08-25 2016-09-20 Apple Inc. Management of high-voltage lithium-polymer batteries in portable electronic devices
US8854012B2 (en) 2011-08-25 2014-10-07 Apple Inc. Management of high-voltage lithium-polymer batteries in portable electronic devices
US9912186B2 (en) 2011-08-25 2018-03-06 Apple Inc. Management of high-voltage lithium-polymer batteries in portable electronic devices
US20150064556A1 (en) * 2013-09-03 2015-03-05 Samsung Sdi Co., Ltd. Electrode for rechargeable lithium battery and rechargeable lithium battery including the same
US9905854B2 (en) * 2013-09-03 2018-02-27 Samsung Sdi Co., Ltd. Electrode for rechargeable lithium battery and rechargeable lithium battery including the same
US9406980B2 (en) 2013-09-24 2016-08-02 Blackberry Limited System and method of mitigating high-temperature, high-charge gas swelling of battery of portable electronic device
US9972841B2 (en) 2014-09-30 2018-05-15 Lg Chem, Ltd. Positive electrode active material and preparation method thereof
TWI630750B (en) * 2014-09-30 2018-07-21 Ｌｇ化學股份有限公司 Positive electrode active material and preparation method thereof
US11031600B2 (en) 2014-12-17 2021-06-08 Lg Energy Solution, Ltd. Lithium ion secondary battery including aluminum silicate
US10749209B2 (en) 2015-02-27 2020-08-18 Murata Manufacturing Co., Ltd. Electrolyte, battery, battery pack, electronic apparatus, electric vehicle, power storage apparatus, and power system
JP2017079206A (en) * 2015-10-21 2017-04-27 日亜化学工業株式会社 Non-aqueous secondary battery positive electrode composition and method for producing the same
WO2020086310A1 (en) * 2018-10-22 2020-04-30 A123 Systems Llc Electrode with flame retardant additives and method and systems for preparation and use
CN110034292A (en) * 2019-04-30 2019-07-19 河北工业大学 A kind of 3-D ordered multiporous polypyrrole/zinc oxide lithium ion battery negative material and preparation method
US20220359864A1 (en) * 2021-05-10 2022-11-10 Sk On Co., Ltd. Anode active material for secondary battery, method of preparing the same and secondary battery including the same

Also Published As

Publication number Publication date
CN1918731A (en) 2007-02-21
KR20050079899A (en) 2005-08-11
EP1711971A1 (en) 2006-10-18
KR100674011B1 (en) 2007-01-24
US9252429B2 (en) 2016-02-02
EP1711971B1 (en) 2017-04-19
JP2007522619A (en) 2007-08-09
TW200532974A (en) 2005-10-01
JP5132941B2 (en) 2013-01-30
US20120288761A1 (en) 2012-11-15
WO2005076391A1 (en) 2005-08-18
TWI269477B (en) 2006-12-21
EP1711971A4 (en) 2010-03-10
CN1918731B (en) 2011-03-09

Similar Documents

Publication Publication Date Title
US9252429B2 (en) Electrode additives coated with electro conductive material and lithium secondary comprising the same
KR102633527B1 (en) Non-aqueous electrolyte for lithium secondary battery and lithium secondary battery comprising the same
CN110998959B (en) Lithium secondary battery having improved high-temperature storage characteristics
KR102258082B1 (en) Negative electrode for rechargeable lithium battery and rechargeable lithium battery including the same
JP4629027B2 (en) High capacity anode material for lithium secondary battery
EP2158635B1 (en) Non-aqueous electrolyte and secondary battery comprising the same
CN111052488B (en) Lithium secondary battery with improved high-temperature storage characteristics
KR20190008100A (en) Additive for nonaqueous electrolyte, nonaqueous electrolyte for lithium secondary battery comprising the same, and lithium secondary battery
US10862108B2 (en) Positive electrode for a lithium electrochemical cell
KR102231209B1 (en) Negative electrode for rechargeable lithium battery and rechargeable lithium battery including the same
JP7301449B2 (en) Non-aqueous electrolyte for lithium secondary battery and lithium secondary battery containing the same
KR102631720B1 (en) Manufacturing method of lithium secondary battery
US12155029B2 (en) Material, negative electrode comprising same and methods for manufacturing same
KR20140032229A (en) Positive active material composition for rechargeable lithium battery, and positive electrode and rechargeable lithium battery including the same
KR20200080170A (en) Electrolyte for lithium secondary battery and lithium secondary battery comprising the same
KR20220009894A (en) Non-aqueous electrolyte solution for lithium secondary battery and lithium secondary battery comprising the same
KR20190123137A (en) Lithium rechargeable battery
US20190260080A1 (en) Non-aqueous Electrolyte and Lithium Secondary Battery Including the Same
KR100873578B1 (en) High Capacity Cathode Active Materials for Secondary Batteries
KR102777175B1 (en) Electrolyte additives for secondary battery, non-aqueous electrolyte for secondary battery comprising the same and secondary battery
KR102735774B1 (en) Non-aqueous electrolyte for lithium secondary battery and lithium secondary battery comprising the same
KR100614368B1 (en) Lithium secondary battery
KR102210219B1 (en) Negative electrode for rechargeable lithium battery and rechargeable lithium battery including the same
JP2001202999A (en) Charge / discharge method for non-aqueous electrolyte secondary battery
EP3982460A1 (en) Manufacturing method of lithium secondary battery

Legal Events

Date Code Title Description
AS Assignment

Owner name: LG CHEM, LTD., KOREA, REPUBLIC OF

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:PARK, HONG-KYU;KIM, KWANG HOON;KIM, SUN KYU;AND OTHERS;REEL/FRAME:016285/0316

Effective date: 20050411

STCB Information on status: application discontinuation

Free format text: ABANDONED -- AFTER EXAMINER'S ANSWER OR BOARD OF APPEALS DECISION