TW558849B - Improved lithium-ion batteries - Google Patents

Improved lithium-ion batteries Download PDF

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TW558849B
TW558849B TW091116241A TW91116241A TW558849B TW 558849 B TW558849 B TW 558849B TW 091116241 A TW091116241 A TW 091116241A TW 91116241 A TW91116241 A TW 91116241A TW 558849 B TW558849 B TW 558849B
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lithium
copper
particles
ion battery
transition metal
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TW091116241A
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Mark Nikolas Obrovac
Jeffrrey Raymond Dahn
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3M Innovative Properties Co
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    • 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
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    • 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
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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    • 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
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    • 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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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • H01M2004/028—Positive electrodes
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    • 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
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49002—Electrical device making
    • Y10T29/49108—Electric battery cell making

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Description

558849 A7
裝 訂
558849
銅、鋅、錯、鉬、鈮及其組合物。 在一個有用的實施例中，該粒子係被用來做為例如二氧 化經始基底陰極之鋰_過渡金屬氧化物基底陰極之添加物 。該粒子可以在電池内提供高電容鋰源，例如具有石墨陽 極的電池，否則會遭受高度不可逆的電容損失。
裝 本發明也以一製備一鋰離子電池之方法為特色，其包含 (a)準備一包含含有⑴具有微粒尺寸不大於約5〇奈米之過渡 金屬微粒，以及（ii)選自氧化鋰、硫化鋰、齒化鋰及其組合 物之含鋰微粒之粒子之陰極；以及（b)將該陰極與一電解質 和一陽極結合以形成該電池。在一實施例中，該陰極係由 球磨法（ball milling)包含過渡金屬和選自氧化鋰、硫化鋰、 鹵化链及其組合物之含鐘化合物之混合物所製備。 訂
該鋰離子電池顯示出高啟始電容以及在重複地充電—放 電循ί衣之後之好的電容維持率。此外，它們是很容易被製 造的，因為所有需要用來支持該電池反應的鋰原子可以被 包含在該陰極中，不像大部分的陽極般，其在含鋰（即放電） 狀態下在空氣中是相對穩定的。 本發明之一個或多個實施例的細節在伴隨的圖示和如下 之說明中被描述。其他本發明之特色、目的和優點從說明 和圖示，以及從申請專利範圍中將會變得顯而易見。 圖示簡單說明 圖1係一用來測試各種陰極組成之電化學電池之分解透視 圖。 圖2(a)和2(b)係在實施例1中所述之氧化二鋰/鐵複合物之 -5-
558849 A7
顯示萊維德修飾（Rietveld refinement)之X光繞射圖。 圖3係一併入實施例1中所述之氧化二經/鐵複合物之電化 學電池之電壓曲線圖。 圖4(a)和4(b)係在實施例2中所述之氧化二鋰/鈷複合物之 顯示萊維德修飾之X光繞射圖。 圖5(a)和5(b)係併入實施例2中所述之氧化二鋰/鈷複合物 之電化學電池之電壓曲線圖。 圖6(a)和6(b)係在實施例3中所述之硫化二鋰/鐵複合物之 顯示萊維德修飾之X光繞射圖。 圖7(a)和7(b)係併入實施例3中所述之硫化二鋰/鐵複合物 之電化學電池之電壓曲線圖。 在各個圖示中相同的參考標號表示相同的元件。 發明詳細說明 鐘離子電池包含一陽極、一陰極以及一電解質。在製造 時，其係在一基本上所有需要支持該電池反應的鋰原子都 在該陰極内的放電狀態。該陰極，包含較佳者具有直徑範 圍在約0.01至約30微米的粒子，其中過渡金屬微粒係由氧 化、硫化、鹵化鋰或其組合物之微粒來分離。過渡金屬微 粒和含鐘微粒兩者較佳者係不大於約5〇奈米，更佳者不大 於約20奈米。這些微粒的存在可以利用例如χ光繞射法的技 術被彳貞測到。 對於過渡金屬微粒來說許多種過渡金屬是適用的。特定 的例子包括鐵、鈷、鉻、鎳、釩、錳、銅、鋅、鍅、鉬、 說及其組合物。鐵和姑是特別被喜愛的。 558849 A7 ---~一 —_____Β7 五、發明説明（4 )~ ----- 如前所註，該電池，在製造時，係在一放電狀態下。在 充電期間，鋰原子被從該陰極去除，導致奈米尺寸的過渡 屬氣化物硫化物或函化物的形成。在後來的放電中， 鋰原子回到該陰極，導致過渡金屬微粒和含鋰氧化物、硫 化物或齒化物的重新形成。 前面所述的粒子可以單獨在陰極中使用或與例如鋰過渡 金屬氧化物、硫化物、鹵化物和等等諸如此類之陰極材料 結合做為一添加劑。例如，該粒子可以與例如二氧化鋰鈷 之傳統的陰極材料結合。要被加入的粒子的量係被選擇以 使可從粒子得到的鋰莫耳數與由該陽極消耗掉的不可逆的 鐘莫耳數一致。消耗掉的不可逆的鋰莫耳數與個別陽極特 性有關。因此，例如當陽極是石墨時，加入鋰過渡金屬氧 化物陰極的粒子的量基於链莫耳數約丨〇%。 該陰極較佳者係在高剪力（high shear)和高衝擊持續一段 適當的時間（通常在12-20小時的水準）下球磨過渡金屬粒子 和氧化、硫化或函化經來製備。或者，該陰極可以使用例 如濺鍍沈積或快速固化含有過渡金屬粒子和氧化、硫化或 鹵化鋰之熔融的金屬等技術來製備。在任一方法中，製備 較佳者係在例如氦或氬環境之惰性環境中執行。 該陰極與一陽極和一電解質結合以形成該鋰電子電池。 適合的陽極的例子包括鋰金屬、石墨和鋰合金組成，例如 在透納（Turner)，美國專利第6,203,944號，標題為『鋰電池 的電極』和透納，WO 00/03444，標題為『電極材料和組成 』中所述的類型。該電解質可以是液態或固態。固態電解 本纸張尺度適用中國國家標準(CNS) A4規格(210X 297公釐) 558849 A7
質的例子包括聚合物電解質，例如聚乙埽氧化物、聚四敗 乙稀、含氟共聚物和其組合物。液態電解質的例子包括乙 稀厌S文鹽、二乙基碳酸鹽、丙稀碳酸鹽和其組合物。該電 解質係與一鋰電解質鹽一起被提供。適合的鹽類的例子包 括六氟鋰磷（UPF6)、四氟鋰硼（LiBF4)和四氧鋰氣（LiC104)。 本發明現在將藉由如下的實施例被進一步說明。 實施例
球磨法程序 主動陰極複合物係使用一 SPEX 8000D擾拌研磨機執行球 磨法來製備。使用具有内部容積約64立方公分的硬鋼研磨 裝 瓶。通常，兩個直徑〇·5英吋的硬鋼球與反應物一起被加入 該研磨瓶 電化學電池的製備 訂
3硫化一鐘的陰極在一填充氦氣的手套箱（gi〇vebox)中如 下被製備。200毫克的主動陰極材料（如上所述般被製備）， 260毫克10%的在N-曱基p比洛烧gjsj (pyrr〇iidinone)内的Kynar Flex 2801溶液（一種商業上可由阿托化學公司（At〇chem)得 到的二氟乙烯-六氟丙烯共聚物），25毫克的超級S碳黑（商 業上可由比利時之MMM Carbon得到），以及額外的600毫克 的N-曱基p比洛院_ (pyrr〇Hdinone)在一個小的玻璃瓶内用黃 銅桿攙合在一起五分鐘以形成一膏狀物。該膏狀物用刮刀 塗在一具有0.43毫米縫隙的玻璃片上，然後置放在一部分 抽真空的小室（10千帕的氦）中12小時以除去N-曱基吡咯烷酮 (pyrrolidinone)。得到的乾膜然後被刮離該玻璃，研磨，並 -8 - 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐) 558849
且在壓力L3G帕下壓入一直社3公分的小球以形成該陰極 。該陰極然後被拿到一電化學電池被製造處之填充氬 手套箱中。 、 ；、 含氧化二鋰陰極係採用相同的程序來製備，除了原料利 用該黃銅桿攪拌之後形成的是一膠體之外。該膠體被挖出 至一玻璃板上並置放在一部分抽真空的小室（1〇千帕的氦）中 12小時以除去N-曱基吡咯烷酮（pyrr〇iidinone)。得到的材料 然後被刮離該玻璃，研磨，並且如前面在含硫化二鋰陰極 的例子中所述般壓入一電極内。 圖1顯示為含硫化二經和氧化二鐘陰極兩者所使用之電化 學電池10的分解透視圖。一不銹鋼罩24和特別的抗氧化盒 2 6容納該電池並分別扮演負極和正極的角色。該陰極12係 一如前述方法製備之含硫化二鋰或氧化二鋰的陰極。該陽 極14係一厚度為125微米的鋰箔；該陽極也作用為一參考電 極。該電池以2325錢幣電池硬體（c〇in-cell hardware)為特色 ，配置有一間隔盤（spacer plate)18(304不銹鋼）以及一盤狀 彈簧（disc spring)16(軟鋼，mild steel)。該盤狀彈簧係被選 擇以在該電池被壓縮關閉時約15巴（bar)的壓力會被施加至 電池的每一個電極。隔離板20係一Celgard #2502微孔的聚 丙稀薄膜（Hoechst-Celanese)，其已被用六氣链構溶解在以 體積30 : 70混合之乙婦碳酸鹽和二乙基碳酸鹽之1M的溶液 浸濕（三菱化工）。一襯墊27被用來做為一密封墊並隔離兩個 電極。 電池使用有±1%穩定度之固定電流循環器在溫度調節裝 -9 - 本紙張尺度適用中國國家標準(CNS) A4規格(210X 297公釐)
裝 訂
558849 A7 B7 五、發明説明（7 ) 置狀態在30°C以及一 C/60速率下循環。 X光繞射
利用配備有銅把材X光管和繞射光束分光單色儀 (111〇11〇(：111>〇11^〇1：)之西卩]子〇5000繞射儀來取得每一個試樣 的X光粉末繞射圖。微粒尺寸係利用薛洛方程式（Scherrer equation)和測量到的繞射線的寬度來估計。試樣係在一氣 密的試樣支架在氦氣環境下被測量。資料係利用萊維德修 飾程式來分析，如在R.J. Hill和C.J. Howard的固定波長X光 的萊維德分析以及中子粉末繞射圖的程式之LHPM 1，AAEC 版（盧卡司高度研究實驗室，澳洲）中所描述者；應用晶體雜 誌 18, 173 (1985) 〇 裝 實施例1 訂
一含有兩個0.5英吋的鋼球之64毫升的硬鋼瓶在氦環境下 被填充3.3克的混合的氧化二鋰（97%，可由Aldrich化學得 到）和鐵（99.98%，可由Aldrich化學得到）。使用的氧化二鐘 對鐵的莫耳比為1:1。該瓶被密封然後持續研磨16小時以製 造氧化二鋰/鐵的複合物。 複合物的X光繞射圖之萊維德修飾係被顯示在圖2(a)和 2(b)中。該圖係與假設為氧化二鋰和^ -鐵的混合物之修飾 一致。從波峰的寬度來看，試樣内之氧化二链和以·鐵的平 均微粒尺寸根據薛洛方程式估計分別約為丨丨奈米和14·4奈 含有該複合物之電化學電池的電壓曲線圖顯示在圖3中。 在從〇微安培小時/克（mAh/g)開始之第一次充電期間，大約
558849 A7
可得到_微安培小時/克的電容量^介於3 G伏特和丨〇伏特 之間的好的可逆性也被觀察到。 實施例2 、一含有兩個0.5英吋的鋼球之64亳升的硬鋼瓶在氦環境下 被填充3.3克的混合的氧化二鋰（97%，可由Alddch化學得 到）和鈷（_100筛號（mesh) , 99.9+% ,可由Aldrich化學得到） 。使用的氧化二鋰對鈷的莫耳比為^。該瓶被密封然後持 續研磨16小時以製造氧化二鋰/鈷的複合物。 複合物的X光繞射圖之萊維德修飾係被顯示在圖4(a)和 4(b)中。該圖係與假設為氧化二鐘、cep-姑、HCP-敍和可 能從研磨媒介以及α -鐵產生的C〇xFei-x不純物相的混合物 之修飾一致。從波峰的寬度來看，試樣内之氧化二鋰的平 均微粒尺寸為13.1奈米，CCP-鈷為5.9奈米，HCP-鈷為2.3 奈米，而CoxFek不純物相為10.3奈米，估計係根據薛洛方 程式。 含有該複合物之電化學電池的電壓曲線圖顯示在圖5(a)和 5(b)中。循環開始於〇微安培小時/克。在圖5(a)中，該電池 在0伏特和4伏特之間循環。這帶來一第一充電電容量約47〇 微安培小時/克，對應約1.5配方單元的經自該氧化二經/姑 電極去除。圖5(b)顯示氧化二鋰/鈷電池之前三個循環，其 中該最高電壓限制在3.5伏特。在第一次充電時，大約可得 到250微安培小時/克的電容量。該電池也在3·3伏特和〇伏特 之間顯示好的可逆性。 實施例3 -11 - 本紙張尺度適用中國國家標準(CNS) Α4規格(210 X 297公釐) 558849 A7
、一含有兩個0·5英吋的鋼球之64毫升的硬鋼瓶在氦環境下 被填充3.3克的混合的硫化二鋰（98%，可由Alddch化學得 到）和鐵（99.98%，可由Alddch化學得到）。使用的氧化二鋰 對鐵的莫耳比為2:1 ^該瓶被密封然後持續研磨16小時以製 造硫化二鋰/鐵的複合物。 複合物的X光繞射圖之萊維德修飾係被顯示在圖6(a)和 6(b)中。該圖係與假設為硫化二鋰和α -鐵的混合物之修飾 致從波峰的寬度來看，試樣内之硫化二鐘和“_鐵的平 均微粒尺寸根據薛洛方程式估計分別約為13奈米和2〇奈米。 含有該複合物之電化學電池的電壓曲線圖顯示在圖7(a)和 7(b)中。循環開始於0微安培小時/克。在圖7(&)中，該電池 在〇伏特和3伏特之間循環配方單位的經在此電壓可以 從硫化二鋰被去除。在圖7(b)中，該電池在其第一循環時在 3伏特和1伏特之間充電，在其第二循環時在3伏特和〇伏特 之間’而在剩餘的循環内在3伏特和1伏特之間。該第一充 電與在圖7(a)中所示的電池相似。放電至1伏特後，充電至3 伏特’然後放電至1伏特，該電池顯示大量的額外電容量。 隨後的介於1伏特和3伏特之間的循環顯現沒有電容量退化 、少量的極化以及絕佳的可逆性。 本發明之一些實施例已被描述。但是，可以理解的是各 種修飾可以在未背離本發明的精神和範圍之下實施。因此 ，其他實施例係在如下之申請專利範圍的範圍内。 -12 - 本紙張尺度適用中國國家標準(CNS) A4規格(210X 297公釐)

Claims (1)

  1. 558849
    ι· 一種鋰離子電池，包含·· U) —含有粒子之陰極，該粒子包括： (Ο具有微粒尺寸不大於約5〇奈米之過渡金屬微粒；及 (η)選自氧化鐘、硫化鋰、齒化鋰及其組合物之含鋰 微粒； (b) —不是鋰金屬的陽極；以及 (c) 一電解質。 2.如申請專利範圍第1項之鋰離子電池，其中該含鋰微粒 具有微粒尺寸不大於約5〇奈米。 3·如申請專利範圍第1項之鋰離子電池，其中該過渡金屬 微粒係選自鐵、钻、鉻、錄、叙、猛、銅、辞、錯、翻 、銳、及其組合物。 4·如申請專利範圍第1項之鋰離子電池，其中該陰極進一 步包含一與該粒子混合之鋰過渡金屬氧化物。
    5·如申請專利範圍第1項之鋰離子電池，其中該粒子直徑 範圍約自0.01微米至約30微米。 6. 一種锂離子電池，包含： (a) —含有粒子之陰極，該粒子包括： ⑴具有齡尺寸;f大於約5G奈米之過渡金屬微粒；及 (ii)選自硫化鋰、齒化鋰及其組合物之含鋰微粒； (b) —陽極；以及 ’ (c) 一電解質。 7·如申請專利範圍第6項之鋰離子電池，甘 电也其中該含鋰微粒 具有微粒尺寸不大於約50奈米。 -13-
    558849 A8 B8 C8 D8 六、申請專利範圍 8. 如申請專利範圍第6項之鋰離子電池，其中該過渡金屬 微粒係選自鐵、鈷、鉻、鎳、飢、锰、銅、鋅、錯、鉬 、銳及其組合物。 9. 如申請專利範圍第6項之鋰離子電池，其中該陰極進一 步包含一與該粒子混合之鋰過渡金屬氧化物。 10. 如申請專利範圍第6項之鋰離子電池，其中該粒子直徑 範圍約自0.01微米至約30微米。 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐)
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EP1415355A2 (en) 2004-05-06
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ATE385049T1 (de) 2008-02-15
JP4373211B2 (ja) 2009-11-25
WO2003015196A2 (en) 2003-02-20
WO2003015196A3 (en) 2003-11-13
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AU2002320418A1 (en) 2003-02-24
KR100920964B1 (ko) 2009-10-09

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