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WO2008146995A1 - Matériau d'anode pour une batterie secondaire et batterie secondaire utilisant ce matériau - Google Patents

Matériau d'anode pour une batterie secondaire et batterie secondaire utilisant ce matériau Download PDF

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Publication number
WO2008146995A1
WO2008146995A1 PCT/KR2007/005450 KR2007005450W WO2008146995A1 WO 2008146995 A1 WO2008146995 A1 WO 2008146995A1 KR 2007005450 W KR2007005450 W KR 2007005450W WO 2008146995 A1 WO2008146995 A1 WO 2008146995A1
Authority
WO
WIPO (PCT)
Prior art keywords
secondary battery
anode material
anode
specific surface
surface area
Prior art date
Application number
PCT/KR2007/005450
Other languages
English (en)
Inventor
Jong-Sung Kim
Jeong-Hun Oh
Chul Youm
Kyung-Hee Han
Jeong-Min Han
Original Assignee
Ls Mtron, Ltd.
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 Ls Mtron, Ltd. filed Critical Ls Mtron, Ltd.
Priority to JP2009516413A priority Critical patent/JP2009533835A/ja
Publication of WO2008146995A1 publication Critical patent/WO2008146995A1/fr

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • 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
    • H01M10/02—Details
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • 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
    • 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 anode material for a secondary battery and a secondary battery using the same, and in particular, to an anode material for a secondary battery, of which a specific surface area ratio is adjusted to 1.4 or less to improve a protection function against a decomposition reaction of an electrolyte liquid on its surface, thereby improving efficiency and cycleability of the secondary battery, and a secondary battery using the same.
  • Background Art
  • the lithium secondary battery includes basically a cathode, an anode and an electrolyte, and accordingly research and development of the lithium secondary battery includes largely studies about a cathode material, an anode material and an electrolyte.
  • a natural graphite used as an anode material of the lithium secondary battery has an excellent initial capacity, however it has low efficiency and cycleability. It is known that this phenomenon is caused by a decomposition reaction of an electrolyte liquid occurring at an edge portion of the natural graphite of high crystallinity.
  • Japanese Patent Application No. 2002-084836 discloses characteristics of a graphite, in which an edge portion of a crystal of a core carbon material is partially or wholly coated with a carbon material for coating.
  • the coating carbide is broken when a resultant anode active material is coated on an electrode collector such as a copper foil and compressed for use as an electrode. And, an edge portion of a natural graphite of high crystallinity is reacted with an electrolyte liquid through the broken portion of the carbide, and in practice, a carbide coating effect is reduced.
  • An object of the present invention is to provide an anode material for a secondary battery, which can prevent a decomposition reaction of an electrolyte liquid at an edge portion of a natural graphite, caused by breakage of a coating carbide during a compression process in a practical application to an electrode, and a secondary battery using the same.
  • an anode material for a secondary battery is prepared by coating a core carbon material with a low crystallinity carbon material and sintering the materials, wherein the anode material has a specific surface area ratio of 1.4 or less.
  • a secondary battery comprises an anode made of the above-mentioned anode material.
  • an extent that a coating of the anode material used practically to the secondary battery is maintained to an electrode state varies depending on a specific surface area ratio obtained by measuring specific surface areas before and after compression when manufacturing an electrode using a coated natural graphite, and charge/discharge characteristics of the battery is influenced accordingly.
  • the specific surface area ratio of the anode material is obtained by measuring specific surface areas before and after compression of a core carbon material coated with a low crystallinity carbon material and applying the measured specific surface areas to the following Math Figure 1.
  • the specific surface area ratio of the anode material for the secondary battery as obtained above is 1.4 or less.
  • the anode material of the secondary battery according to the present invention may be prepared by coating a core carbon material with a low crystallinity carbon material and sintering the materials using a typical method used in the prior art.
  • the core carbon material may be a natural graphite, an artificial graphite or a mixture thereof, and it is preferable to use a natural graphite.
  • the low crystallinity carbon material may be pitch, tar, a phenol resin a furan resin or furfuryl alcohol.
  • the present invention adjusts the specific surface area ratio of the anode material prepared by partially or wholly coating an edge portion of the core carbon material with the low crystallinity carbon material to 1.4 or less.
  • the specific surface area ratio may be adjusted by selecting the kind and process conditions of the low crystallinity carbon material.
  • a conductive agent or binder may be selectively added with a small amount to a slurry for manufacturing an electrode plate including the above-mentioned anode material according to necessity.
  • the content of the conductive agent or binder may be adjusted properly to a typical level used in the prior art, and the content range does not influence the present inv ention.
  • the conductive agent is not limited to a specific material if it is an electronically conductive material that does not bring about a chemical change in the resultant battery.
  • the conductive agent may be carbon black such as acetylene black, Ketjen black, furnace black or thermal black; a natural graphite; an artificial graphite; or a conductive carbon fiber, and in particular, it is preferable to use carbon black, graphite powder or carbon fiber.
  • the binder may be a thermoplastic resin, a thermosetting resin or a mixture thereof.
  • the binder may be polyvinylidene fluoride (PVDF) or polyte- trafluoroethylene (PTFE), more preferably polyvinylidene fluoride.
  • PVDF polyvinylidene fluoride
  • PTFE polyte- trafluoroethylene
  • the slurry for manufacturing an electrode plate including the anode active material and selectively at least one of the conductive agent and the binder is coated on an electrode collector, and dried to remove a solvent or dispersion medium, so that active materials are stuck to the electrode collector and the active materials are stuck together.
  • the electrode collector is not limited to a specific material if it is made of a conductive material, however in particular, it is preferable to use a foil made of copper, gold, nickel, a copper alloy or combination thereof.
  • the anode is made of the anode material prepared by the above-mentioned preparing method.
  • the secondary battery of the present invention may be manufactured by a typical method used in the prior art, for example interposing a porous separator between a cathode and an anode, and a ⁇ frng an electrolyte.
  • the electrolyte is a non-aqueous electrolyte liquid including a lithium salt and an electrolyte liquid compound, and the lithium salt may be at least one compound selected from the group consisting of LiClO , LiCF SO , LiPF , LiBF , LiAsF and
  • the electrolyte liquid compound may be at least one compound
  • the separator of the present invention is a porous separator, for example polypropylene-based, polyethylene-based or polyolefin-based porous separator.
  • the secondary battery of the present invention is not limited to a specific shape, however may be manufactured in various shapes without limitation, for example cylindrical, angular, pouch-shaped or coin-shaped using a can.
  • the secondary battery of the present invention has a charge/discharge efficiency of
  • the pitch dissolved in tetrahydrofuran was added to the spherical natural graphite with a content of 3 weight% based on weight of the natural graphite, wet- mixed at an atmospheric pressure for 2 hours or more, and dried to produce a mixture.
  • the mixture was sintered at 1,100 0 C for 1 hour with temperature being increased with a temperature increase rate of 1 °C/min, and classified to remove fine powder, thereby preparing an anode active material.
  • An anode material having a specific surface area ratio of 1.38 was prepared in the same method as that of the Example 1, except that pitch was 5 weight% based on weight of a natural graphite and a temperature increase rate is 3 °C/min.
  • An anode material having a specific surface area ratio of 1.45 was prepared in the same method as that of the Example 1, except that pitch was 10 weight% based on weight of a natural graphite and a temperature increase rate is 3 °C/min.
  • An anode material having a specific surface area ratio of 1.53 was prepared in the same method as that of the Example 1, except that pitch was 10 weight% based on weight of a natural graphite and a temperature increase rate is 5 °C/min.
  • An anode material having a specific surface area ratio of 1.61 was prepared in the same method as that of the Example 1, except that pitch was 10 weight% based on weight of a natural graphite and a temperature increase rate is 10 °C/min.
  • An anode material having a specific surface area ratio of 1.67 was prepared in the same method as that of the Example 1, except that pitch was 10 weight% based on weight of a natural graphite and a temperature increase rate is 15 °C/min.
  • the present invention improves a protection function against a decomposition reaction of an electrolyte liquid on the surface of an anode material to improve efficiency and cycleability of a secondary battery so as to solve a problem that a coating carbide is broken during a compression process in a practical application to an electrode.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

La présente invention concerne un matériau d'anode pour une batterie secondaire et une batterie secondaire utilisant ce matériau. Le matériau d'anode pour une batterie secondaire selon la présente invention est préparé en revêtant un matériau de carbone de noyau d'un matériau de carbone à faible cristallinité et en frittant les matériaux, le matériau d'anode ayant un rapport d'aire de surface spécifique de 1,4 ou moins. La présente invention peut améliorer une fonction de protection contre une réaction de décomposition d'un électrolyte liquide sur sa surface pour améliorer le rendement et la capacité de recyclage de la batterie secondaire.
PCT/KR2007/005450 2007-05-29 2007-10-31 Matériau d'anode pour une batterie secondaire et batterie secondaire utilisant ce matériau WO2008146995A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2009516413A JP2009533835A (ja) 2007-05-29 2007-10-31 二次電池用負極材及びこれを用いた二次電池

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020070052190A KR100884431B1 (ko) 2007-05-29 2007-05-29 2차 전지용 음극재 및 이를 이용한 2차 전지
KR10-2007-0052190 2007-05-29

Publications (1)

Publication Number Publication Date
WO2008146995A1 true WO2008146995A1 (fr) 2008-12-04

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2007/005450 WO2008146995A1 (fr) 2007-05-29 2007-10-31 Matériau d'anode pour une batterie secondaire et batterie secondaire utilisant ce matériau

Country Status (3)

Country Link
JP (1) JP2009533835A (fr)
KR (1) KR100884431B1 (fr)
WO (1) WO2008146995A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114586193A (zh) * 2019-11-18 2022-06-03 株式会社Lg新能源 制造负极的方法、由此获得的负极和包含所述负极的二次电池

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011243567A (ja) * 2010-04-20 2011-12-01 Jfe Chemical Corp リチウムイオン二次電池用負極材料およびその製造方法、リチウムイオン二次電池用負極ならびにリチウムイオン二次電池
KR102674173B1 (ko) 2023-10-31 2024-06-12 주식회사 태성 수평 이송방식의 2차 전지용 음극재 도금장치 및 그 도금방법

Citations (4)

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US6294291B1 (en) * 1990-09-03 2001-09-25 Matsushita Electric Industrial Co., Ltd. Secondary battery or cell with a non-aqueous electrolyte
US6420070B1 (en) * 1997-09-19 2002-07-16 Matsushita Electric Industrial Co., Ltd. Nonaqueous electrolyte secondary battery and its anode
US6623888B1 (en) * 1994-04-08 2003-09-23 Sony Corporation Non-aqueous electrolyte secondary cell
US7150944B2 (en) * 2000-05-03 2006-12-19 Samsung Sdi Co., Ltd. Non-aqueous electrolyte compositions and lithium secondary batteries made thereof

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JPH07201357A (ja) * 1994-01-06 1995-08-04 Asahi Chem Ind Co Ltd リチウム電池
JP4045438B2 (ja) * 1995-11-14 2008-02-13 大阪瓦斯株式会社 二次電池用の二層炭素材料及びそれを用いたリチウム二次電池
KR100722071B1 (ko) * 1995-11-14 2007-08-16 오사까 가스 가부시키가이샤 리튬이차전지용음극재료,그의제조방법및그를이용한이차전지
JP2001332263A (ja) * 2000-03-16 2001-11-30 Sony Corp 二次電池および炭素系負極材料の製造方法
JP4415241B2 (ja) * 2001-07-31 2010-02-17 日本電気株式会社 二次電池用負極およびそれを用いた二次電池、および負極の製造方法
JP2003100292A (ja) * 2001-09-21 2003-04-04 Osaka Gas Chem Kk 負極用炭素材料及びその製造方法、並びにこれを用いたリチウムイオン二次電池
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JP2003272630A (ja) * 2002-03-19 2003-09-26 Denso Corp 負極活物質の製造方法
JP4215633B2 (ja) * 2002-12-19 2009-01-28 Ｊｆｅケミカル株式会社 複合黒鉛粒子の製造方法

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Publication number Priority date Publication date Assignee Title
US6294291B1 (en) * 1990-09-03 2001-09-25 Matsushita Electric Industrial Co., Ltd. Secondary battery or cell with a non-aqueous electrolyte
US6623888B1 (en) * 1994-04-08 2003-09-23 Sony Corporation Non-aqueous electrolyte secondary cell
US6420070B1 (en) * 1997-09-19 2002-07-16 Matsushita Electric Industrial Co., Ltd. Nonaqueous electrolyte secondary battery and its anode
US7150944B2 (en) * 2000-05-03 2006-12-19 Samsung Sdi Co., Ltd. Non-aqueous electrolyte compositions and lithium secondary batteries made thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114586193A (zh) * 2019-11-18 2022-06-03 株式会社Lg新能源 制造负极的方法、由此获得的负极和包含所述负极的二次电池

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Publication number Publication date
JP2009533835A (ja) 2009-09-17
KR20080104833A (ko) 2008-12-03
KR100884431B1 (ko) 2009-02-19

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