TW455566B - Lithium manganese oxy-fluorides for li-ion rechargeable battery electrodes - Google Patents
Lithium manganese oxy-fluorides for li-ion rechargeable battery electrodes Download PDFInfo
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- TW455566B TW455566B TW086112903A TW86112903A TW455566B TW 455566 B TW455566 B TW 455566B TW 086112903 A TW086112903 A TW 086112903A TW 86112903 A TW86112903 A TW 86112903A TW 455566 B TW455566 B TW 455566B
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- 229910001416 lithium ion Inorganic materials 0.000 title abstract description 5
- PJPWPNYVKVGFBH-UHFFFAOYSA-N O(F)F.[Mn].[Li] Chemical class O(F)F.[Mn].[Li] PJPWPNYVKVGFBH-UHFFFAOYSA-N 0.000 title abstract 2
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 4
- 150000003624 transition metals Chemical class 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 35
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- 238000011049 filling Methods 0.000 claims description 8
- -1 lithium-fluorene oxyfluoride Chemical compound 0.000 claims description 3
- 238000009434 installation Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 7
- 230000001351 cycling effect Effects 0.000 abstract description 6
- 230000002687 intercalation Effects 0.000 abstract 1
- 238000009830 intercalation Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 14
- 238000012360 testing method Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 239000011737 fluorine Substances 0.000 description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 239000000523 sample Substances 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000002079 cooperative effect Effects 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 150000001768 cations Chemical group 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 2
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000004313 potentiometry Methods 0.000 description 1
- 229910052704 radon Inorganic materials 0.000 description 1
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon atom Chemical compound [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 0.000 description 1
- 235000015170 shellfish Nutrition 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- 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
-
- 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
- C01G45/1242—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof of the type (Mn2O4)-, e.g. LiMn2O4 or Li(MxMn2-x)O4
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/009—Compounds containing iron, with or without oxygen or hydrogen, and containing two or more other elements
-
- 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
- C01G51/44—Complex oxides containing cobalt and at least one other metal element containing alkali metals, e.g. LiCoO2 containing manganese
- C01G51/54—Complex oxides containing cobalt and at least one other metal element containing alkali metals, e.g. LiCoO2 containing manganese of the type (Mn2O4)-, e.g. Li(CoxMn2-x)O4 or Li(MyCoxMn2-x-y)O4
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- 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
- H01M4/582—Halogenides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
- C01P2002/54—Solid solutions containing elements as dopants one element only
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
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- C01P2006/40—Electric properties
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- 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
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- 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
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- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Description
455566 A7 B7 五、發明説明（ t明背景 f請先閒讀背面之注意事項再填寫本頁} 本發明係關於用作_子可再充“池中活化電極材科 之氧化錳鋰夾入化合物，特別是關於這些化合物氟氡化錯 合物，及其使用改良這類電池之循環能力與容量。 3 氧化錳鋰夾入化合物（標稱式爲以?4112〇4)已逐漸證實爲二 次、可充電鋰離子電池及合成電池製造有效與經濟之材 料。美國專利编號5,296,318與5,460,904描述此形式成功之 私池。這些電池在寬廣之電壓範圍内表現極佳水準之電儲 存谷量與充電循環旎力β無論如何，這些性質已被視爲無 法芫全滿足處理現代電子裝備與應用逐漸嚴格之要求。 現已著手廣泛之研究以改良此受注意之性質，而這些工 作已確足LiMhO4尖晶石結構因數之變化（例如化合物a軸晶 格尺寸）對最後電池表現有明顯之影響。依次發現這些結構 大大地隨夹入化合物之構造及其合成情形而變。就這一 點，通常已被認可：例如：a軸參數少於8·23人促進在長期 循環中良好之充電能力。 達到此有利參數範圍之方法已包括精細控制之合成狀 況’例如泰拉康（Tarascon)在美國專利5,425,932號所描 經濟部中央標準局買工消費合作社印策 述’經由較高價數之錳得到小3軸尺寸之優點；及陽離子取 代物’例如泰拉康等在 j. Electrochem. Sol Vol. 138, No. 1〇, ΡΡ· 2859-2864，1991年l〇月所提出，或以c〇、Cr或Fe置換 ~部分錳原子’例如歐洲專利390，1δ5中所建議來表現。— 些其他研究建議根據代表結構之化學式U]〇ct〇4，增 加經崁入物之水準以得到與置換錳類似之效應，如同增進 本紙張尺度通用中圉國家標準（CNS } A4規格（210X297公釐） 經濟部中央標準局員工消费合作社印m 4 5 5 5 6 6 第S6112903號專利申請案 88. J2. 3 η
中文說明書修正頁(88年12月） AT 立、發明説明（2) ―― 猶環能力之有效方法；但是已發現這實際上造成犧牲電池 容量’如同先前Μ η置換方法所觀察到。 比較這些前面實行之方法’本發明利用陽離子取代物， 以提供達到同時改良循環能力與電池容量二者之方法，且 能製造可以長而耐久與高功率工作之電池β 發明概述 我們已發現先前實施上之不適當，可藉由以氟作一部分 標稱為LiMr^O4氧原十之陰離子取代物來補救，雖然最初觀 察到單獨取代物造成a軸參數膨脹超過較佳之範圍，而這明 顯由於錳價數之減少。在進一步研究中，我們發現同時增 加經之鋰取代物意外達到a軸尺寸戲劇性也移至少於8 23入 之理想缸圍内。電解電池槽包含這些氟取代電極材料，其 後表現驚人之電池容量，如同其循環能力。 製備這些有利之氧氟化物尖晶石衍生物可最簡單地根據 平常之習慣，例如泰拉康在美國專利5,425,932提出，在800 °C退火適當前身化合物（典型為Li2C03、LiF及Μη02)之計量 混合物。這些衍生物也可包括陽離予取代物之前身物，如 同早先在EP390,185中提出之。產生之夾入材料可有效運用 以完成在先前電解電池之改良，其以通式表示為 Lii-xMyMn2-Tt-y〇4-zFz ’此處Μ為過渡金屬，例如c〇 ' Cr或 Fe，而 x'S〇.4’y<〇.3&0.05<zSl.〇。 數系列之電池正電極組合物以主要改變氧氟化物之x及z 式組份（即鋰與氟）來製備；以X線繞射分析測定其最終a軸 晶格參數’之後以如同前述專利所述之普通方法组合為測 -5- 本紙伕尺度適用中國國家梯準（CNS ) A4規格（210X297公釐） --------—餐-----.—11:-----▲ {請先閱读背面之注意事項再填寫本莧) 455566 經濟部中央標準局貝工消費合作社印裳 A7 --:~~~~~ -----B7 五、發明説明（3 ) ~~ ——' 試電池°該電池受重覆充電/放電循環，以測定化合物構成 在電池表現之電儲存容量水準之影響，通常以毫安培小時/ 克電極化合物表示’如同循環能力—般，即在長期循環下 維持最初容量水準之能力。 圖之簡述 本發明以關於下列伴隨圖形來描述： 圖I爲本發明化合物之x線繞射模型，Li1+xMyMn2.x.y04.z Fz， 此處 X = 0.1、y = 〇 且 2 = 0」； 圖2爲a軸晶格尺寸對本發明化合物Lii+xMyMn2 之z之圖形，此處x = 〇.〇5、y = 〇且2： <〇5； 圖3爲比較容量及循環能力對包含圖2之正電極化合物之 電池充電循環數之圖形； 圖4爲比較容量及循環能力對包含先前Li|+xivln2〇4電極化 合物之電池及本發明化合物之充電循環數之圖形； 圖5爲比較a軸晶格尺寸對本發明化合物Lii+xMyMii2_x.y04.zFz 中2之圖形，此處\幺〇.2、又=〇且2;£〇.4: 圖6爲比較容量及循環能力對包含本發明化合物 U]_xMyMn2-x.y04.zFz電池之充電循環數之圖形，此處x = 〇、 y = 0且ζ < 0.4 ; 圖7爲比較容量及循環能力對包含本發明化合物 Lii+xMyMri2-XnTy〇4-zFz電池之充電循環數之圖形，此處 X = 0,1、y = 0 且 z S 0.4 ; 圖8爲比較容量及循環能力對包含本發明化合物 Li1+xMyMn2.x.y04.zFz電池之充電循環數之圖形，此處χ = 〇.2、 -6 - 本紙張尺度適用中國國家標率（CNS ) Α4現格（210X297公釐) ----------裳------訂------泉 f請先閑^背面之注意事免再填寫本頁} . Α7 ------Β7 五、發明説明（4 ) --- y = 0且z < 0.4 :以及 {請先閎讀背面之注意事項再填專本頁) .圖9爲比較容量及循環能力對包含本發明化合物
Lli+xMyMn2-x_y〇4_2Fz電池之充電循環數之圖形，此處χ = 〇、 y = 0.2且z s 0.1。 ' 本發明之描Μ “製備先前實行中使用之Lii+xMn2〇4夾人化合物（依據本式 設计：Lll+xMyMn2-x-y〇4-2Fz，此處7 = 〇且2 = 〇)作爲前述 美國專利5,425,932號描述方法之表現控制樣品，使用主要 瓦身化合物之計量混合物，例如以重量計9.23份之U2C〇3 至43.46份之^111〇2以達到標稱之1^1^112〇4。這些控制樣品之 測試電池’如同後面描述之本發明材料樣品同樣地製備， 且在電動勢學及電位學研究下測試，通常如同專利説明書 上描述。這些試驗電池包含鋰箔負電極作爲實用之方法， 因爲已s忍可之經驗在此方法完成之表現結果，可客觀地與 其他上面提及之專利説明書所述之链離子電池組合物比 較。下面簡述之另外試驗’仍然以包含該材料之鋰離子组 合物傳導，以得到此結果修正之進一步確認。 實例1 經濟部中央標隼局員工消費合作社印裝 本發明夾入材料之典型製備中，計量.比例之前身物： 〆>_ 1
Mn02(EMD型式）、Li2C03及LiF在瑪瑙臼與杵中充分混 合，其重量比例爲60.94:12.82 : 1，混合物用控制樣品之方 法以鋁坩堝在空氣中退火，以得到Li1+xMyMn2_x-y〇4-zFz之試 驗組合物，此處X = 0.1、y = 0且z = O.KLiuMnuOs.sFD.i)。特 別地，將混合物在固定速率加熱約1 2小時至溫度爲800°C， 本紙張尺度逋用中國國家標準（CNS ) A4規格（21 OX297公釐） 56 6 A7 B7 五、發明説明（5 請 I 先I 閔 I 讀 背I 面 f 之丨 i主I 意 事I 項 ί 再 f I 寫 本衣 頁 並在這溫度維持約12小時。之後將樣品以固定速率在約“ 小時之期間冷却至室溫。在混合/磨碎後，將樣品再以約5 小時之期間加熱至800。(： ’在此保持12小時，最後以約24 』時之期間冷却至罜溫。產生之氧氟化物以銅& χ線繞射 (XRD)檢驗其特性，得到之圖形模型於圖1。清晰界定之峯 模型確認合成之產物爲完全結晶、單相產物。 實例2 一系列本發明氧氟化物以適當結合前身化合物製備，產 生 Lit+xMyMn2.x.y04.zFz，此處 x = 〇 〇5、y = 〇且 2 = 〇、 0.05 〇·1〇、〇·ΐ5、〇.20、0.35及 0.50。產生之樣品以狀〇記 錄其特性並分別計算a軸晶格參數。這些參數所作之圖形如 訂 圖2所示，顯示規則之增加，其探知並指示氟化取代物之增 加。 % 經濟部中央標準局員工消費合作社印聚 相同樣品數份分別與約1 0 %導電石墨及5 %聚偏氟乙烯結 合劑結合，並在鋁箔基板上形成層以提供正試驗電池電 極。以平常方法排列鋰箔電極與介於其間之玻璃纖維隔離 板，其以溶於2:1混合之碳酸乙二醇與二曱基碳酸中之ιΜ LiPF6電解質溶液充滿’樣品電極形成之試驗電池以n 4.5伏特電麼·範圍在C/5之速率（整個循環爲5小時）下充電/ 放電。每一電池之容量在多至35循環之期間下追腙，得到 此性質改變速率之指示（見圖3)，即長期充電之電池循環能 力。記錄31至36反應上述增加之氟取代物之等級，z，由 0·05至0·5。結果之比較描繪於圖2及3，以圖形確認通常隨 a軸尺寸之增加高於約8.23人之較佳限制時，傾向朝同時損 本纸張尺度適用中國國家標隼（CNS ) Α4規格（2丨0Χ297公釐） 4 5 5 5 6 6
經濟部中央標準局Λ工消費合作社印5L A7 B7 五、發明説明（6 ) 失容量與循環能力二者。 實例3 —系列先前技藝之未取代夾入化合物僅改變鋰之量，即 LM+xMyMn2-x.y04.zFz，此處 X = 〇.〇5、0.075 及 0.1，y = 〇 且Z = 0，以類似方法製備及試驗，得到此變數在產生電池 之容量與循環能力之影響=> 如圖4所見，記錄4丨-43依次增 加ϋ含量，此變化單獨改良循環能力，但明顯減少電池容 量。另外以實例1之氧氟化物（X = 〇，1、Ζ == 〇 · I )製備之電池 表現表示在圖4之記綠44，反應經本發明完成之驚人效 應。特別地’比較記錄43與44具有相似之鋰含量透露出在 谷量及循環能力一者上之傑出改進是結合氟取代物之故。 實例4 改變裡和氟二者製備數系列之氧氟化物，即 LikMyMn2-x.yO4.zFz，此處X s 〇、0.1 及 0.2，y = 〇且2 = 〇、 〇_〇5 ' 0.1、0.2及0‘4。a軸晶格參數對各系列之變化表示於 圖5，s己知52-56依次增加裡含1 ’其顯示在完成這參數之 理想範圍結合鋰及氟含量之驚人效應。 實例5 用實例4 X = 0之一系列化合物製備電池，以上述方法試 驗。結果顯示於圖6，記錄61-65依次增加氟含量，顯示化 合物Li : F比例中F對其容量及循環能力之影響。 實例6 用實例4 X = 0.1之一系列化合物製備電池，以上述方法試 驗8結果顯示於圖7，記綠71-75依次增加氣含量，顯示 •9- 1_________ 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨0X297公釐） I---------裝------訂------良 (請先閲讀背面之注$項再填寫本頁〕 . 455566 A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明（
Li : F比例中接近平衡之F在容量及循環能力之改良。 實例7 用實例4 X = 〇.2之一系列化合物製備電池，以上述方法試 驗。結果顯示於圖8 ’記錄81-85依次增加氟含量，顯示在 Li : F比例中仍接近平衡之F之近一步影響，特別是在循環 能力上。 實例9 含陽離子（C r)及陰離子取代物二者之一系列本發明化合 物 ’ Li|+xMyMn2-x-y〇4-zF；j，此處 X = 0、y = 0.2且 z = 0、0 〇5 及0.1，以上述方法經由結合適當計量之前身物製備，例如 10.3:2.3 1:1.〇:〇.〇86重量比之1^11〇2、1^2(：03、（：1'203及
LiFaiCruMnnOwFow)。用產生之材料製備試驗電池， 其表現之改良和前面之結果相比較如圖9所示，記綠92_96 依次增加氟含量。陽離子Co及以取代物可得到相似之結 果。. 實例1 0 以實例6足正電極材料製備一系列鋰離子電池，並使石油 焦碳負電極與偏二由乙烯共聚物基質電解f/分隔板元素， 3同上美國專利5,460,904號所描述。重覆充電循環試驗 顯示電池容量及循環能力，與實例6相比較。 I預期本發明（其他具體實施對熟練之王匠將成爲 二前又所述見解中，且這些改變預定包括在本發明範固 内，如砰述於附加申請專利範圍中。 H--I---- i n - - I I n -- I τ ^^-9 (諳先閲讀背面之注意事項再填寫本頁)
Claims (1)
- 5 5 5 6 6 第86112903號牟利申請案 中文中請專利範团修正本(88年12月）ce A8 B8 D8:··牟沁労經濟部中央樣準局員工消費合作社印製 1 . 一種鋰鉦氧氟化物，其具有通式LihxMyMn2.x.y04.zFz， 其中Μ為過渡金屬而χ<〇·4，y幺0,3且〇.〇5<zS 1.0。 2 _根據申請專利範固第i項之化合物，其中M為c〇、Cr或 F e 3 ·根據申請專利範圍第2項之化合物，其中x $ 0.2，y = 〇 且 0.0 5 s ζ $ 0 · 4。 4‘根據申請專利範園第2項之化合物，其中〇,丨$ χ $ 0ι2 , y = 0且0.05 < ζ< 0,4。 5·根據申請專利範圍第2項之化合物，其中〇」s x s 〇·2， y = 〇且0.05 2 z S 0.2。 6. 根據申請專利範圍第2項之化合物，其中0.05 < x s 0.2， y S 0.3且 0·〇5 S z S 0_2。 7. —種可再充電電池，其包含正電極，負電極及配置於其 間之分隔板，其特徵為 該正電極包含具有通式為LiuxMyMi^+yOkFz之夾入 化合物’其中Μ為過渡金屬’而X < 0.4，y S 0.3 且0.05 < 1.0 。 8_根據申請專利範圍第7項之可再充電電池，其中Μ為 Co、Cr*Fe。 9.根據申請專利範圍第8項之可再充電電池，其中X S 〇·2， y = 0且0.05 < z S 0·4。 1 〇根據申請專利範圍第8項之可再充電電池，其中 0.1 s X S 0.2，y = 0且0.05 S z S 0.4 ° 11.根據申請專利範圍第8項之可再充電電池，其中 本紙張尺>1ΐΑ用巾u SI家標準（CNS ) A4j^ ( 2丨D χ 297公董） ---------裝---- I - "* >πV - I--- - IT (請先聞讀背面之注意事項再填寫本頁) ο 5 6 6 Α8 Β3 C8 D8 申請專利範圍 0.1 S X < 0·2 * y =.0且 0.05 S z S 0.2。 12.根據申請專利範圍第8項之可再充電電池，其中 0.05 S X 5 0.2，y = 0.3且 0.05 < z S 0.2。 --------—裝-----·丨訂--------線 (請先閱讀背面之注意事項再填寫本頁) 經漭部中央標皂局員工消費合作社印^ -2- 本纸掁尺度通用中國國家標丰（CNS ) A4iUM 210X297公釐）
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Families Citing this family (54)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6087042A (en) * | 1996-10-18 | 2000-07-11 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Positive electrode material for secondary lithium battery |
| US6040089A (en) * | 1997-02-28 | 2000-03-21 | Fmc Corporation | Multiple-doped oxide cathode material for secondary lithium and lithium-ion batteries |
| US6037095A (en) * | 1997-03-28 | 2000-03-14 | Fuji Photo Film Co., Ltd. | Non-aqueous lithium ion secondary battery |
| JP3045998B2 (ja) | 1997-05-15 | 2000-05-29 | エフエムシー・コーポレイション | 層間化合物およびその作製方法 |
| US6277521B1 (en) | 1997-05-15 | 2001-08-21 | Fmc Corporation | Lithium metal oxide containing multiple dopants and method of preparing same |
| US5759720A (en) * | 1997-06-04 | 1998-06-02 | Bell Communications Research, Inc. | Lithium aluminum manganese oxy-fluorides for Li-ion rechargeable battery electrodes |
| US5932374A (en) * | 1997-12-04 | 1999-08-03 | Telcordia Technologies, Inc. | Lithium magnesium manganese oxy-fluorides for Li-ion rechargeable battery electrodes |
| US6004697A (en) * | 1997-12-05 | 1999-12-21 | Minnesota Mining & Manufacturing Co. | Modified lithium vanadium oxide electrode materials products and methods |
| JP3928231B2 (ja) * | 1997-12-15 | 2007-06-13 | 株式会社日立製作所 | リチウム２次電池 |
| US5916516A (en) * | 1998-02-18 | 1999-06-29 | Mitsubishi Chemical Corporation | Fluoridated electrode materials and associated process for fabrication |
| AU3987499A (en) * | 1998-05-15 | 1999-12-06 | Duracell Inc. | Battery cathode materials |
| US5939043A (en) * | 1998-06-26 | 1999-08-17 | Ga-Tek Inc. | Process for preparing Lix Mn2 O4 intercalation compounds |
| US6267943B1 (en) | 1998-10-15 | 2001-07-31 | Fmc Corporation | Lithium manganese oxide spinel compound and method of preparing same |
| DK1137598T3 (da) | 1998-11-13 | 2003-08-18 | Fmc Corp | Lagdelte lithiummetaloxider, der er fri for lokale kubiske spinellignende struktuelle faser, og fremgangsmåder til fremstilling af samme |
| EP1135334B1 (en) | 1998-11-20 | 2002-10-09 | Fmc Corporation | Multiple doped lithium manganese oxide compounds and methods of preparing same |
| US6136476A (en) * | 1999-01-29 | 2000-10-24 | Hydro-Quebec Corporation | Methods for making lithium vanadium oxide electrode materials |
| KR100307160B1 (ko) * | 1999-03-06 | 2001-09-26 | 김순택 | 리튬 이차 전지용 양극 활물질 및 그 제조 방법 |
| US6153333A (en) * | 1999-03-23 | 2000-11-28 | Valence Technology, Inc. | Lithium-containing phosphate active materials |
| KR100296877B1 (ko) * | 1999-05-27 | 2001-07-12 | 김순택 | 리튬 이차 전지용 양극 활물질 및 그를 이용한 리튬 이차 전지 |
| US6322928B1 (en) | 1999-09-23 | 2001-11-27 | 3M Innovative Properties Company | Modified lithium vanadium oxide electrode materials and products |
| JP3913941B2 (ja) * | 1999-10-14 | 2007-05-09 | 株式会社日立製作所 | リチウム二次電池用正極活物質およびリチウム二次電池 |
| AU1951601A (en) | 1999-12-10 | 2001-06-18 | Fmc Corporation | Lithium cobalt oxides and methods of making same |
| CN100342579C (zh) * | 2000-01-27 | 2007-10-10 | 雷天绿色电动源（深圳）有限公司 | 可再充电的固体铬－氟－锂电池 |
| JP2002075366A (ja) * | 2000-08-31 | 2002-03-15 | Kyushu Ceramics Kogyo Kk | リチウム二次電池正極用リチウムマンガン酸化物及びその製造方法 |
| CN100344543C (zh) * | 2002-02-21 | 2007-10-24 | 东曹株式会社 | 锂－锰复合氧化物的粒状二级颗粒、其制备方法和其用途 |
| US7556655B2 (en) * | 2003-03-14 | 2009-07-07 | 3M Innovative Properties Company | Method of producing lithium ion cathode materials |
| US7754111B1 (en) | 2006-06-09 | 2010-07-13 | Greatbatch Ltd. | Method of making silver vanadium oxyfluorides for nonaqueous lithium electrochemical cells |
| US7718319B2 (en) | 2006-09-25 | 2010-05-18 | Board Of Regents, The University Of Texas System | Cation-substituted spinel oxide and oxyfluoride cathodes for lithium ion batteries |
| US8062791B1 (en) * | 2007-06-11 | 2011-11-22 | Northwestern University | Battery cathode |
| KR20110076955A (ko) * | 2008-09-30 | 2011-07-06 | 엔비아 시스템즈 인코포레이티드 | 비용량이 높은 불소 도핑된 리튬 풍부 금속 산화물 양극 배터리 재료 및 상당하는 배터리 |
| US8389160B2 (en) * | 2008-10-07 | 2013-03-05 | Envia Systems, Inc. | Positive electrode materials for lithium ion batteries having a high specific discharge capacity and processes for the synthesis of these materials |
| US8465873B2 (en) | 2008-12-11 | 2013-06-18 | Envia Systems, Inc. | Positive electrode materials for high discharge capacity lithium ion batteries |
| CN101986441B (zh) * | 2009-07-29 | 2013-06-19 | 比亚迪股份有限公司 | 一种锂离子电池正极材料的制备方法 |
| CN102484249A (zh) | 2009-08-27 | 2012-05-30 | 安维亚系统公司 | 具有高比容量和优异循环的层层富含锂的复合金属氧化物 |
| EP2471133A4 (en) * | 2009-08-27 | 2014-02-12 | Envia Systems Inc | METAL OXIDE-COATED POSITIVE ELECTRODE MATERIAL FOR LITHIUM BATTERIES |
| US9843041B2 (en) * | 2009-11-11 | 2017-12-12 | Zenlabs Energy, Inc. | Coated positive electrode materials for lithium ion batteries |
| WO2011084003A2 (ko) | 2010-01-07 | 2011-07-14 | 주식회사 엘지화학 | 4v 영역과 3v 영역에서 우수한 충방전 특성을 발휘할 수 있는 리튬 망간 산화물을 포함하는 양극 활물질 |
| US8741484B2 (en) | 2010-04-02 | 2014-06-03 | Envia Systems, Inc. | Doped positive electrode active materials and lithium ion secondary battery constructed therefrom |
| US8928286B2 (en) | 2010-09-03 | 2015-01-06 | Envia Systems, Inc. | Very long cycling of lithium ion batteries with lithium rich cathode materials |
| US8663849B2 (en) | 2010-09-22 | 2014-03-04 | Envia Systems, Inc. | Metal halide coatings on lithium ion battery positive electrode materials and corresponding batteries |
| FR2972442B1 (fr) * | 2011-03-08 | 2013-03-29 | Accumulateurs Fixes | Materiau d'electrode positive pour accumulateur lithium-ion |
| FR2978137A1 (fr) * | 2011-07-21 | 2013-01-25 | Saint Gobain Ct Recherches | Produit fondu a base de lithium |
| US10170762B2 (en) | 2011-12-12 | 2019-01-01 | Zenlabs Energy, Inc. | Lithium metal oxides with multiple phases and stable high energy electrochemical cycling |
| US9070489B2 (en) | 2012-02-07 | 2015-06-30 | Envia Systems, Inc. | Mixed phase lithium metal oxide compositions with desirable battery performance |
| DE102012102831A1 (de) * | 2012-04-02 | 2013-10-02 | Karlsruher Institut für Technologie | Dotierter Spinell, Verfahren zu seiner Herstellung, seine Verwendung und Lithium-Ionen Batterie |
| US9552901B2 (en) | 2012-08-17 | 2017-01-24 | Envia Systems, Inc. | Lithium ion batteries with high energy density, excellent cycling capability and low internal impedance |
| US10115962B2 (en) | 2012-12-20 | 2018-10-30 | Envia Systems, Inc. | High capacity cathode material with stabilizing nanocoatings |
| CN105050960A (zh) | 2013-02-01 | 2015-11-11 | 特罗诺克斯有限公司 | 改善的锂锰氧化物组合物 |
| US10573885B2 (en) * | 2017-01-24 | 2020-02-25 | Farasis Energy (Ganzhou) Co., Ltd. | Lithium source material and preparation method thereof and use in Li-ion cells |
| EP3399013B1 (en) | 2017-05-05 | 2022-08-03 | The Procter & Gamble Company | Laundry detergent compositions with improved grease removal |
| EP3399012A1 (en) | 2017-05-05 | 2018-11-07 | The Procter & Gamble Company | Liquid detergent compositions with improved rheology |
| JP7138353B2 (ja) | 2017-06-12 | 2022-09-16 | カリフォルニア大学 | リチウムイオン電池のカソード用としての金属および酸素のレドックスの組合せによる高容量のリチウム金属オキシフッ化物 |
| WO2019207065A1 (en) | 2018-04-26 | 2019-10-31 | Rhodia Operations | Fluorinated oxide based on li and mn |
| CN114072356A (zh) * | 2019-07-15 | 2022-02-18 | 加利福尼亚大学董事会 | 锂过量过渡金属缺乏的尖晶石用于快速充电/放电锂离子电池材料 |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2098953A5 (zh) * | 1970-07-31 | 1972-03-10 | Anvar | |
| EP0390185B1 (en) * | 1989-03-30 | 1994-06-22 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary cell |
| US5296318A (en) * | 1993-03-05 | 1994-03-22 | Bell Communications Research, Inc. | Rechargeable lithium intercalation battery with hybrid polymeric electrolyte |
| US5460904A (en) * | 1993-08-23 | 1995-10-24 | Bell Communications Research, Inc. | Electrolyte activatable lithium-ion rechargeable battery cell |
| US5425932A (en) * | 1993-05-19 | 1995-06-20 | Bell Communications Research, Inc. | Method for synthesis of high capacity Lix Mn2 O4 secondary battery electrode compounds |
| US5370949A (en) * | 1993-07-09 | 1994-12-06 | National Research Council Of Canada | Materials for use as cathodes in lithium electrochemical cells |
| JPH07240200A (ja) * | 1994-02-28 | 1995-09-12 | Fuji Photo Film Co Ltd | 非水二次電池 |
-
1996
- 1996-09-06 US US08/706,546 patent/US5674645A/en not_active Expired - Lifetime
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1997
- 1997-09-04 IL IL12839297A patent/IL128392A0/xx unknown
- 1997-09-04 CN CN97197718A patent/CN1229528A/zh active Pending
- 1997-09-06 TW TW086112903A patent/TW455566B/zh not_active IP Right Cessation
- 1997-09-08 ID IDP973116A patent/ID17374A/id unknown
Also Published As
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|---|---|
| CN1229528A (zh) | 1999-09-22 |
| IL128392A0 (en) | 2000-01-31 |
| US5674645A (en) | 1997-10-07 |
| ID17374A (id) | 1997-12-24 |
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