TWI233231B - Cathode material with nano-oxide layer on the surface and the produce method - Google Patents

Cathode material with nano-oxide layer on the surface and the produce method Download PDF

Info

Publication number
TWI233231B
TWI233231B TW092136842A TW92136842A TWI233231B TW I233231 B TWI233231 B TW I233231B TW 092136842 A TW092136842 A TW 092136842A TW 92136842 A TW92136842 A TW 92136842A TW I233231 B TWI233231 B TW I233231B
Authority
TW
Taiwan
Prior art keywords
oxide layer
battery
manufacturing
item
nano
Prior art date
Application number
TW092136842A
Other languages
English (en)
Other versions
TW200522422A (en
Inventor
Mau-Huang Liou
Jin-Ming Chen
Tz-Hua Jeng
Original Assignee
Ind Tech Res Inst
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 Ind Tech Res Inst filed Critical Ind Tech Res Inst
Priority to TW092136842A priority Critical patent/TWI233231B/zh
Priority to US10/866,840 priority patent/US20080299392A1/en
Application granted granted Critical
Publication of TWI233231B publication Critical patent/TWI233231B/zh
Publication of TW200522422A publication Critical patent/TW200522422A/zh

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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Complex oxides containing manganese and at least one other metal element
    • C01G45/1221—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Complex oxides containing cobalt and at least one other metal element
    • C01G51/42—Complex oxides containing cobalt and at least one other metal element containing alkali metals, e.g. LiCoO2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/628—Coating the powders or the macroscopic reinforcing agents
    • C04B35/62802—Powder coating materials
    • C04B35/62805—Oxide ceramics
    • C04B35/6281—Alkaline earth metal oxides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/628—Coating the powders or the macroscopic reinforcing agents
    • C04B35/62886—Coating the powders or the macroscopic reinforcing agents by wet chemical techniques
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/628—Coating the powders or the macroscopic reinforcing agents
    • C04B35/62897—Coatings characterised by their thickness
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/049—Manufacturing of an active layer by chemical means
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
    • C04B2235/3203—Lithium oxide or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3275—Cobalt oxides, cobaltates or cobaltites or oxide forming salts thereof, e.g. bismuth cobaltate, zinc cobaltite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3279—Nickel oxides, nickalates, or oxide-forming salts thereof
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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
    • 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
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Electrochemistry (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Composite Materials (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Description

1233231 玖、發明說明： 【發明所屬之技術領域】 •本發明係關於一種表面具奈米氧化層之電池正極材料 及製法，尤其係指一種可有效提昇鋰電池安全性之表面具 奈米氧化層質之電池正極材料及製法。 【先前技術】 鋰電池之咼容量正極材料不僅會影響電池性能之優劣 ，亦為決定電池安全性之重要因素。因此，優異的鋰電池 正極材料除了克電容量要高之外，其材料的熱穩定性亦十 为重要。亦即，材料的安全性優異，始可用做為正極材’料 。被視為未來新的正極材料短錄氧化物（LiNi〇2 )雖然具 有间克電容置，但其安全性差，因此短期之内很難被加以 應用。而鋰錳氧化物（LiMn2〇4)雖然安全性佳，但其克 電容量較低，約為1 1 〇 m A h/g，較另一正極材料之 魏始鎳氧化物（LiCoNi〇2 )低上4 0%〜4 5%之克電容 量。另外，雖鋰鈷氧化物（LiCo〇2 )為目前市場之主流， 但其價格昂貴，雖電量適中，其性能提昇已達極限，而未 來的行動通訊電子產品所需之鋰離子電池的體極能量密度 需求大於4 0 〇Wh/L，而鋰鈷氧化物之體積能量密度 僅達3 2 0 W h/L〜3 5 0 W h/L，故已無性能提昇 空間。 鐘始鎳氧化物（LiCoNi〇2)正極材料是目前全世界尚 未商品化之材料，其主要關鍵仍在於其安全性問題尚未解 決，一般國際研究單位或材料製造商主要是將含有鋁或鎮 1233231 之金屬離子植入鋰鈷鎳氧化物材料的結構中（ UComO2)，此法雖可提升材料的安全性，但卻會降低材 料的克電容量，並使内阻提高，因此大電流充放電能力不 佳。亦有學者將燒結好的鋰鈷鎳氧化物表面覆蓋一層微米 尺寸的金屬氧化物，但由於其是利用二次燒結方法，使表 面形成有微米級之金屬氧化層，因此會有明顯的界面阻2 及大的非儲電活性區域，故同樣會有電容量降低、内阻提 高及壽命、大電流充放電能力變差之問題。 綜上所述，鋰鈷鎳氧化物（LicoN102)將為未來可;實 用之電池正極材料主流，僅是其安全性及内阻問題仍有待 ㈣，即可取代目前既有之鋰電池正極㈣，而成為一種 具南克電容量及體積能量密度之電池正極材料。 【發明内容】 本發明人有鑑於此，乃積極著手從事研究，以期可提 供二種能提昇正極材料安全性之電池正極材料，經過不斷 的試驗及努力，終於開發出本發明。 本發明的主要目的在於提供一種可有效提昇鋰電池安 全性之表面改質之電池正極材料及製法。 為了達到上述發明目的，本發明乃採取以下之技術手 段予以達成中本發明包含有正極材料及形成於正極材 料表面奈米層大小為i Q nmH Q ◦ nm之金屬氧化物 Ο 本發明之製法包括有： 含浸步冑：該含浸步驟是將正極材料先驅#置入含有 1233231 金屬離子之表面改質劑中； :乂驟該除水步驟是將表面改質劑之水分以加熱 屬離=方式除去，使得正極材料先驅物表面均勻覆蓋有金 雜乂驟該燒結步驟係以氫氧化鐘與上述附有金屬 之正極材料先驅物—同置入燒結爐中，以7 〇 〇〜 屬=進行燒結6〜24小時，以生成表面含有奈米金 屬虱化層之正極材料。 ^由上述之結構及方法，本發明能在正極材料表面形 成:層，米金屬氧化層’利用此—奈米金屬氧化層可以增 ^ ，女全性，且由於奈米金屬氧化層之非館電活性區域 放：：六因此可具有高克電容量、循環壽命長及大電流充 放電施力佳之特性。 【實施方式】 本發明包含有正極材料及形成於正極材料表面，奈米 層大小為10nm〜1〇〇nm之金屬氧化物。 ^ 請參看第一圖所示，本發明之製法包括有·· 含浸步驟（10) ··該含浸步驟（1〇)是將正極材 枓先驅物置入含有金屬離子之表面改質劑中； •除水步驟（1 1):該除水步驟（1 1)是將表面改 貝劑之水分除去，使得正極材料先驅物表面 屬離子； 復盍有金 燒結步驟（1 2 ):該燒結步驟（工2 )係以氣氧化 鐘與上述附有金屬離子之正極材料先驅物一同置入燒結爐 1233231 中進行燒結，以生成表面含有奈米金屬之正極材料。 上述先驅物為C〇xNii-x(〇H)，其中X為〇 =1 ;上述之表面改質劑可以為氫氧化鎂、氫氧化認、氯 氧化鋁、硝酸錳、氣化鈦、硝酸鎵等金屬塩類。 【實施例】 1、 鋰鈷鎳氧化物（LiCoNi02)的製作： 使用粒徑大小約為9 之c〇〇 2N i 〇 8 (〇H) 2 為反應先驅物，在含浸步驟（i 〇 )時，將其加入表面改 質劑的氫氧化鎂（Mg (OH) 2)之水溶液中，在於，除 水步驟（1 1 )中以加熱、蒸發之方式將水分去除，使得 反應先驅物表面均勻覆蓋有氫氧化鎂，於燒結步驟（丄2 )寸將氫氧化鐘（Li〇H.H2〇）與該反應先驅物 混合，其中鋰：鎂：鈷：鎳的比例為1 · 〇 5 : 〇 · 〇 1 : 〇 · 2 : 0 . 8，將該混合物於氧氣氣氛之燒結爐中以7 5 〇°C燒結1 6小時即可得到表面含有約丄5 nm2鎂金屬 氧化層的本發明之鋰鈷鎳氧化物材料。 比較例之純鋰鈷鎳氧化物（LicoNi〇2)的製作〔使用 粒徑大小約為9 之co〇 2N i 〇 8 (〇H) 2為反應 先驅物，將其與氫氧化鋰（L i〇η · Η 2〇）混合，其 中鐘··始··鎳的比例為1 · 0 5 : 0 · 2 : 〇 · 8，將該混 合物於氧氣或大氣氣氛之燒結爐中以7 5 〇 °c燒結1 6小 時即可得到純鎳鈷鋰氧化物材料 2、 錢幣電池的製作及測試： 首先製作陰極板，將本發明之鋰鈷鎳氧化物、石墨及 1233231 ’導電物為KS —6 (Timcai公司生產），黏著劑 為P V D F ’上述鋰鈷鎳粉體、導電物及黏著劑之比例為 8 5 : 1 〇 : 5 ;負極材料為M c M b ( _咖。 ππ⑽bead)，黏著劑為”Df，兩者比例為 。將上述混合粉體以混漿程序製成聚料，將正極聚料塗布 在紹fl基材上’負㈣料塗布在㈣基材上，經過烘乾、 礙壓後製成正、負極極板。方形電池組裝程序乃是以手動 捲繞機將極板捲成電極卷後，在其側面及底部貼上膠帶， 將其裝罐加絕緣片，經過焊柄、雷射焊接端蓋、抽真空後 灌入電解液、文全閥封焊、清洗後即成為方形電池。電池 壓碎安全測試是將電池充電至4.2 V，以圓棒平面（直 徑為25mm)壓注電池’施以l7.2Mpa之壓力後 立刻放鬆夾頭。電池鑽孔安全測試是將電池充電至4. 2 V ’以直徑2mm之鑽頭、snn ” 貝 bUOrpmi轉速鑽穿電池 所述 傳統純錄聽氧化物材料之方形電池製作及測試如上 結果· 請參看第二B圖所示，本發明之鋰鈷鎳氧化物材料的 粉體表面TEM圖可觀察到粉體表面有—層丄5nm〜2 5 n m不同於晶粒結構之金屬氧化層，局部元素分析該奈 米金屬氧化層是含有鎂元素；而第二A圖所示之習用結構 則無法觀察到晶粒表面之金屬氧化層。 請參看第三圖所示，鐘钻鎳氧化物/鐘的錢幣電池以 1233231 〇· 1 C放電具有1 9 6mAh / g (充電至4.2V)的 克電容量，若以5 C放電仍具有1 5 5mAh/g (充電 至4· 2 V)的克電容量，因此可證明奈米表面改質之本 發明的鈹鈷鎳氧化物材料具有大電流放電能力。 請參看第四圖所示，以0.5C放電經過200次的 充電循環後’本發明較有較高之電容量。 請參看第五圖所示，比較本發明及習用結構之D S C 放熱，除了以分解溫度作參考外，最重要的是比較分解時 所釋放的熱量，習用結構所釋放的熱量大於3 5 0焦耳，/ 克’相對於本發明而言為三倍的熱量釋放，因此就安全性 上，本發明較習用結構安全。 經過電池壓碎及鑽孔測試，習用結構之電池會產生火 花及煙霧’無法通過安全測試，而本發明之電池在測試中 並無火彳匕及煙霧產生，更無爆炸現象，而電池表面最高溫 亦僅有1 0 〇 °c左右，因此可通過安全測試。關於本發明 及習用結構比較如下表所示： 分解 溫度（°c) 釋放 熱量 (焦耳 /克） 壓碎 測試 鑽孔 測試 習用 結構 206 大於 350 失敗 失敗 1233231 最大溫 最大 度大於300 溫度大於 °C 300。。 本發 小於 通過 通過 明 208 100 隶大溫 最大 度 liot 溫度90°C 另外’本發明不僅可利用在鋰鈷鎳氧化物材料，其他 關於鋰鈷氧化物（LixCo〇2)、鋰錳氧化物（LixMny〇4)、或含 其他金屬成分之鋰鈷鎳氧化物、鋰鈷氧化物、鋰錳氧化物 等適用於電池之正極材料者均可利用本發提昇其安全性。 【圖式簡單說明】 (一） 圖式部分 第一圖為本發明之流程圖。 第二圖為粉體表面TEM圖；其中A為習用結構，B 為本發明’ C為另一個本發明實施例。 第二圖為本發明不同電流放電能力測試圖。 第四圖為本發明及習用結構之電池壽命比較圖。 第五圖為本發明及習用結構之D S C放熱圖。 第六圖為二個本發明實施例及習用結構之D S C放熱 圖。 (二） 元件代表符號 (1 0 )含浸步驟 (1 1 )除水步驟 (1 2 )燒結步驟 12

Claims (1)

1233231 鋁0 =、如巾請專利範圍第142或3或4項所述之表 有鎵…化層之電池正極材料…該金屬氧化層中含 之電池正極材料的製法 丄1、一種表面具奈米氧化層 ，其包括有： 含浸步驟： 金屬離子之表面 垓合次步驟是將正極材料先驅物置入含有 改質劑中； ::步驟：該除水步驟是將表面改質劑之水分除去， 仟亟材料先驅物表面均勻覆蓋有金屬離子； 燒結步驟：該燒結步驟係以氫氧化鐘與上述 離子之正崎料先㈣—„人燒結爐tit行燒結，以= 成表面含有奈米金屬氧化層之正極材料。 、如申請專利範圍第11項所述之表面具奈米氧化 層之電池正極材料的製法…表面改質劑為氫氧化鎂。 13、 如中請專利範圍第11項所述之表面具奈米氧化 層之電池正極材料的製法，纟中表面改質劑為氫氧化銷。 14、 如申請專利範圍第11項所述之表面具奈米氧化 層之電池正極材料的製法，纟中表面改質劑為氫氧化銘。 15、 如中請專利範圍第11項所述之表面具奈米氧化 層之電池正極材料的製法，其中表面改質劑為硝酸猛。 16如申°月專利範圍第11項所述之表面具奈米氧化 層之電池正極材料的製法，其中表面改質劑為氣化欽。 17、如申請專利範圍第1 1項所述之表面具奈米氧化 14 1233231 層 層 燒 之電池正極材料的製法，其中表面改質劑為硝酸鎵。 18、如中請專利範圍第！ i項所述之表面具奈米氧化 之電池正極材料的製法，其巾燒結步驟是在氧氣氣氛之 結爐中以7 0 〇 t〜8 5 0 °C燒結6〜2 4小時。 19、如申請專利範圍第1 i項所述之表面具奈米氧化 層之電池正極材料的製法，其中燒結步驟是在大氣或氧氣 氣氛之燒結爐中以7 〇 〇 °C〜8 5 CTC燒結6〜2 4小時 拾壹、圖式： 如次頁
15
TW092136842A 2003-12-25 2003-12-25 Cathode material with nano-oxide layer on the surface and the produce method TWI233231B (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
TW092136842A TWI233231B (en) 2003-12-25 2003-12-25 Cathode material with nano-oxide layer on the surface and the produce method
US10/866,840 US20080299392A1 (en) 2003-12-25 2004-06-14 Cathode material particles with nano-metal oxide layers on the surface and a method for manufacturing the cathode material particles

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
TW092136842A TWI233231B (en) 2003-12-25 2003-12-25 Cathode material with nano-oxide layer on the surface and the produce method

Publications (2)

Publication Number Publication Date
TWI233231B true TWI233231B (en) 2005-05-21
TW200522422A TW200522422A (en) 2005-07-01

Family

ID=36480841

Family Applications (1)

Application Number Title Priority Date Filing Date
TW092136842A TWI233231B (en) 2003-12-25 2003-12-25 Cathode material with nano-oxide layer on the surface and the produce method

Country Status (2)

Country Link
US (1) US20080299392A1 (zh)
TW (1) TWI233231B (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8282855B2 (en) * 2009-10-16 2012-10-09 Vista Advance Technology Co., Ltd. Composite positive active material of lithium battery and method for manufacturing the same

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7709149B2 (en) * 2004-09-24 2010-05-04 Lg Chem, Ltd. Composite precursor for aluminum-containing lithium transition metal oxide and process for preparation of the same
US20090181305A1 (en) * 2005-06-14 2009-07-16 Masatoshi Nagayama Non-Aqueous Electrolyte Secondary Battery
US9074296B2 (en) * 2009-08-21 2015-07-07 Cornell University Mesoporous Co3O4 nanoparticles, associated methods and applications

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US621083A (en) * 1899-03-14 Vehicle
JPH07130367A (ja) * 1993-10-29 1995-05-19 Sony Corp リチウム二次電池用正極活物質の製造方法
DE69706592T2 (de) * 1996-03-26 2002-05-29 Sharp K.K., Osaka Verfahren zur Herstellung von positivelektrode-aktivem Material, sowie diese verwendende nichtwässerige Sekundärbatterie
JP3702353B2 (ja) * 1996-05-24 2005-10-05 日本電池株式会社 リチウム電池用正極活物質の製造方法およびリチウム電池
US6218052B1 (en) * 1996-06-19 2001-04-17 Wanxi Wang Electrolyte solution of high-capacity storage battery and producing method thereof
JPH1032005A (ja) * 1996-07-16 1998-02-03 Japan Storage Battery Co Ltd ニッケル酸リチウム正極活物質およびその製造方法ならびに前記活物質を備えたリチウム電池
US5955051A (en) * 1996-08-02 1999-09-21 Westaim Technologies Inc. Synthesis of lithium nickel cobalt dioxide
EP0824087B1 (en) * 1996-08-13 1999-10-27 Murata Manufacturing Co., Ltd. Manufacturing method of lithium complex oxide comprising cobalt or nickel
US5993998A (en) * 1996-12-20 1999-11-30 Japan Storage Battery Co., Ltd. Positive active material for lithium battery, lithium battery having the same and method for producing the same
US6040089A (en) * 1997-02-28 2000-03-21 Fmc Corporation Multiple-doped oxide cathode material for secondary lithium and lithium-ion batteries
US6207325B1 (en) * 1997-05-19 2001-03-27 Showa Denko K.K. Lithium-containing complex metal oxide, preparation methods thereof, and cathode electroactive material using the same and lithium secondary cells
KR100324624B1 (ko) * 2000-02-26 2002-02-27 박호군 다공성 금속, 금속산화물 또는 탄소 박막이 피복된금속산화물전극 및 그 제조방법, 이를 이용한 리튬 이차전지
US6921609B2 (en) * 2001-06-15 2005-07-26 Kureha Chemical Industry Co., Ltd. Gradient cathode material for lithium rechargeable batteries
WO2003076338A1 (en) * 2002-03-08 2003-09-18 Altair Nanomaterials Inc. Process for making nono-sized and sub-micron-sized lithium-transition metal oxides
KR20030083476A (ko) * 2002-04-23 2003-10-30 주식회사 엘지화학 수명 특성과 안전성이 우수한 리튬 금속 복합 산화물 및이의 제조 방법
TWI261045B (en) * 2002-12-30 2006-09-01 Ind Tech Res Inst Composite nanofibers and their fabrications
US7709149B2 (en) * 2004-09-24 2010-05-04 Lg Chem, Ltd. Composite precursor for aluminum-containing lithium transition metal oxide and process for preparation of the same

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8282855B2 (en) * 2009-10-16 2012-10-09 Vista Advance Technology Co., Ltd. Composite positive active material of lithium battery and method for manufacturing the same

Also Published As

Publication number Publication date
TW200522422A (en) 2005-07-01
US20080299392A1 (en) 2008-12-04

Similar Documents

Publication Publication Date Title
WO2022105259A1 (zh) 正极补锂剂及其制备方法和应用
JP5079951B2 (ja) 非水電解液２次電池用正極活物質、その製造方法、非水電解液２次電池、並びに正極の製造方法
CN114975980A (zh) 负极材料及使用其的电化学装置和电子装置
CN101901907B (zh) 锂离子二次电池及其正极材料
JPWO2010150513A1 (ja) 電極構造体及び蓄電デバイス
CN112768688B (zh) 一种磷酸铁锂材料及其制备方法和锂离子电池
CN115332532A (zh) 一种硬碳材料及其制备方法
CN115207304B (zh) 一种石墨负极复合材料及其制备方法和锂离子电池
CN111564612B (zh) 一种高导热导电性锂电正极材料及其制备方法
CN115832224B (zh) 正极片及其制备方法、电极组件、储能设备及用电设备
JP7507434B2 (ja) リチウム含有複合酸化物の製造方法
WO2021212392A1 (zh) 三维复合金属锂负极和金属锂电池与装置
CN114094060B (zh) 一种核壳结构的高电压正极材料的制备方法
TW385565B (en) Cathode for lithium secondary battery
JP2019016484A (ja) 全固体電池用負極およびそれを備える全固体電池
CN100399608C (zh) 一种橄榄石碳绒球复合材料及其用途
WO2025016367A1 (zh) 磷酸锰铁锂复合电极极片及其制备方法与应用
CN114824218B (zh) 锂金属复合材料及其改性材料以及它们的制法和电池
CN103003988A (zh) 负极材料的制造方法、负极材料、锂二次电池的制造方法、锂二次电池
CN116014072A (zh) 一种电池
CN108807904B (zh) 一种锂电池用改性磷酸铁锂正极材料的制备方法
CN117174857A (zh) 硅基复合材料及其制备方法
TWI233231B (en) Cathode material with nano-oxide layer on the surface and the produce method
CN119092690B (zh) 一种负极材料及电池
CN1979929A (zh) 一种表面包覆碳的层状结构含锂复合金属氧化物及其应用

Legal Events

Date Code Title Description
MK4A Expiration of patent term of an invention patent