201230471 六、發明說明： 【發明所屬之技術領域】 [0001] 本發明涉及一種正極複合材料及其製備方法，以及應用 該正極複合材料之鋰離子電池。 [先前技術] [0002] 鋰離子電池主要由鼋極、隔膜以及電解液構成。其中， 鋰離子電池之發展很大程度上取決於電極活性材料性能 之提高。目前，經離子電池之正極活性材料主要有鈷酸 裡（LiCo〇2)、錄酸鐘（LiNi〇2)、猛酸經（LiMn2〇4) 以及鐵酸链（LiFePO/)等，負極活性材料主要係碳材料、 4 鈦酸鋰（Lijijp)等。為提高鋰離子電池電極活性材料201230471 VI. Description of the Invention: [Technical Field] [0001] The present invention relates to a positive electrode composite material, a method for preparing the same, and a lithium ion battery using the same. [Prior Art] [0002] A lithium ion battery is mainly composed of a drain, a separator, and an electrolyte. Among them, the development of lithium ion batteries largely depends on the improvement of the performance of electrode active materials. At present, the positive electrode active materials of the ion battery mainly include cobalt acid (LiCo〇2), acid clock (LiNi〇2), acid acid (LiMn2〇4), and ferric acid chain (LiFePO/), and the negative active material. Mainly carbon materials, 4 lithium titanate (Lijijp) and so on. To improve the active material of lithium ion battery electrode
4 b \ L 之性能，對鋰離子電池電極活性材料之顆粒表面採用其 他材料形成包覆，係對電極活性材料進行改性之常用方 法。先前技術已表明，在鈷酸鋰或其他電極活性物質顆 粒表面包覆磷酸鋁可提高鋰離子電池電極之熱穩定性（ 請參閱文獻 “Correlation between A1P0,nano-particle coating thickness on LiCoO cathode Q ，， and thermal stablility” J.Cho, E1ectrochim-ica Acta 48 (2003) 2807-281 1 及專利號為 7,326,498之美國專利）。 [0003] 然，由於填酸铭自身導電性較差，故，上述電極活性材 料之導電性也會因磷酸鋁之包覆而有所降低。 【發明内容】 [0004] 有鑒於此，提供一種導電性有所改善之具有較高熱穩定 性之正極複合材料及其製備方法，以及應用該正極複合 100100428 表單編號A0101 第3頁/共18頁 1002000723-0 201230471 材料之鋰離子電池實為必要。 [0005] 一種鋰離子電池正極複合材料，其包括正極活性材料顆 粒，其中，進一步包括包覆於該正極活性材料顆粒表面 之摻雜磷酸鋁層，該摻雜磷酸鋁層之材料係半導體性掺 雜之磷酸鋁。 [0006] 一種鋰離子電池正極複合材料之製備方法，其包括：提 供三價鋁源及摻雜元素源，將該三價鋁源和該掺雜元素 源加入溶劑中以形成含三價鋁離子及摻雜離子之溶液； 將待包覆之正極活性材料顆粒加入該含三價鋁離子及摻 雜離子之溶液中，形成一混合物；將磷酸根源溶液加入 該混合物進行反應，使該正極活性材料顆粒之表面形成 一摻雜磷酸鋁層，該摻雜磷酸鋁層之材料係半導體性摻 雜之磷酸鋁；熱處理該表面具有摻雜磷酸鋁層之正極活 性材料顆粒。 [0007] —種鋰離子電池，包括正極以及負極，其中，該正極包 括上述經離子電池正極複合材料。 [0008] 相較於先前技術，本發明之摻雜磷酸鋁層之材料係半導 體性掺雜之磷酸鋁，使經過摻雜後之磷酸鋁成為具有電 子導電機制或空穴導電機制之半導體，大大提高了導電 性，故，與先前之具有磷酸鋁包覆層之複合電極材料相 比，所述具有摻雜磷酸鋁包覆層之複合電極材料具有更 好之導電性。 【實施方式】 [0009] 下面將結合附圖及具體實施例對本發明提供之電極複合 100100428 表單編號A0101 第4頁/共18頁 1002000723-0 201230471 材料及其製備方法、以及應㈣電極複合㈣之链離子 電池進行詳細說明。 [0010] 請參閱圖丨及圖2,本發明實施例提供—種轉子電池電 極複合材料Η) ’其包括電極叫材料顆粒12及包覆於該 電極居性㈣齡m面之細魏㈣u。該換雜璃 酸铭層14之材料係半導體性換雜之魏銘。該摻雜碟酸 紹層14具有半導體性。 [0011] ο 該摻_酸减14具有半導體性係指通過對魏铭進行 半導體性摻雜使摻__層14之自由電子濃度高於空 六濃度、或空穴濃度高於自由電子濃度，從而使掺雜磷 酸紹層14顯半導體性。 [0012] ο 100100428 該捧雜磷酸鋁層14之材料由化學式“ 為摻雜元素，該M摻雜元素之選擇需;二能4摻雜到礙 酸紹之晶格中，具體為’該Μ摻雜元素之原子半徑需與銘 原子之原子半徑相近，不能大於鋁原子之原子半徑太多 。該Μ摻雜元素之價態優選為+2價或+ 4價，並且〇〈吖1。 另外’ Μ之摻雜量優選為1%〜2〇%，即〇 〇1$ng〇 2。所 述Μ可為+ 2價之金屬元素，如B c 中之—he、Cu及Mg 種或者幾種’也可為+ 4價之金屬元素，如v Ta、T. v ' Nb ' 可㈣及Zr中之一種或者幾種等。所述+2價之摻雜元素 雜.私之空穴濃度大於自由電子之濃度，從而使挣 砑酸鋁成為空穴導電機制之P型半導體，所述+ 4價 之摻雜π素可使碟酸銘之電子濃度大於空 而使摻雜;* <紙度，從 ’、曼之《4酸鋁成為電子導電機制之半導體，故 表價或+4價元素之推雜均可使接雜後之鱗酸銘成 1 第5頁/共18頁 1002000723-0 -nMnP〇表示，其 201230471 為半導體，從而提高了該磷酸鋁之導電性。 [0013] 所述摻雜磷酸鋁層14具有均勻之厚度、且呈連續之層狀 形態。該摻雜填酸銘層14在該電極複合材料1 〇中之質量 百分比為0. 1%至3%。該摻雜磷酸鋁層14之厚度優選為5 奈米至20奈米。該摻雜磷酸鋁層14為原位生成在該電極 活性材料顆粒12之表面。進一步地，在該掺雜填酸铭層 14與該電極活性材料顆粒12間之界面處可能形成界面擴 散。 [0014] 所述電極活性材料顆粒12可為正極活性材料顆粒或負極 活性材料顆粒，當所述電極活性材料顆粒12為正極活性 材料顆粒時，所述電極複合材料10為正極複合材料，當 所述電極活性材料顆粒12為負極活性材料顆粒時，所述 電極複合材料10為負極複合材料。所述電極活性材料顆 粒12可為正極活性材料顆粒或負極活性材料顆粒，所述 正極活性材料顆粒可以為未摻雜或摻雜之尖晶石結構之 锰酸鐘、層狀锰酸鋰、鎳酸鐘、钴酸裡、鱗酸鐵鐘、經 錄锰氧化物及鋰鎳銘猛氧化物中之一種或複數種。具體 地，該尖晶石結構之猛酸裡可以由化學式L i Μ n L 0 x 2-y y 4 表示’該鎳酸鋰可以由化學式Li Ni, L 表示，該鈷 X 1-y y ι 酸鋰之化學式可以由Li Co L 0表示，該層狀錳酸鋰 x 1 -y y 2 之化學式可以由L 0 ，該磷酸鐵鋰之化學式可 y y 2 以由LixFehyLyP〇4表示，該鐘鎳锰氧化物之化學式可以 由表示，該链錄姑猛氧化 物之化學式可以由Li Ni Co Mn Lf0Q表示’其中0. 1 Sx4 b \ L performance, the surface of the particle of the lithium ion battery electrode active material is coated with other materials, which is a common method for modifying the electrode active material. The prior art has shown that coating aluminum phosphate on the surface of lithium cobaltate or other electrode active material particles can improve the thermal stability of the lithium ion battery electrode (see the literature "Correlation between A1P0, nano-particle coating thickness on LiCoO cathode Q , , And thermal stablility" J. Cho, E1 ectrochim-ica Acta 48 (2003) 2807-281 1 and U.S. Patent No. 7,326,498). [0003] However, since the acid filling itself is inferior in electrical conductivity, the conductivity of the above electrode active material is also lowered by the coating of aluminum phosphate. SUMMARY OF THE INVENTION [0004] In view of the above, a positive electrode composite material having improved electrical conductivity and improved thermal stability is provided, and a method for preparing the same, and a positive electrode composite 100100428 is used. Form No. A0101, Page 3 of 18, 1002000723 -0 201230471 Lithium ion batteries for materials are necessary. [0005] A positive electrode composite material for a lithium ion battery, comprising a positive electrode active material particle, further comprising a doped aluminum phosphate layer coated on a surface of the positive electrode active material particle, wherein the material of the doped aluminum phosphate layer is a semiconductor doped Miscellaneous aluminum phosphate. [0006] A method for preparing a positive electrode composite material for a lithium ion battery, comprising: providing a trivalent aluminum source and a source of a doping element, adding the trivalent aluminum source and the source of the doping element to a solvent to form a trivalent aluminum ion And a solution of doping ions; adding the positive active material particles to be coated to the solution containing trivalent aluminum ions and doping ions to form a mixture; adding a phosphate source solution to the mixture to carry out the reaction, and the positive active material is made The surface of the particle forms a doped aluminum phosphate layer, and the material of the doped aluminum phosphate layer is a semiconducting doped aluminum phosphate; the surface of the positive electrode active material having a surface doped with an aluminum phosphate layer is heat-treated. A lithium ion battery comprising a positive electrode and a negative electrode, wherein the positive electrode comprises the above-described ion battery positive electrode composite material. [0008] Compared with the prior art, the material of the doped aluminum phosphate layer of the present invention is a semiconducting doped aluminum phosphate, so that the doped aluminum phosphate becomes a semiconductor having an electron conducting mechanism or a hole conducting mechanism, The conductivity is improved, so that the composite electrode material having a doped aluminum phosphate coating layer has better conductivity than the conventional composite electrode material having an aluminum phosphate coating layer. Embodiments [0009] The electrode composite 100100428 provided by the present invention will be provided with reference to the accompanying drawings and specific embodiments. Form No. A0101 Page 4 / 18 pages 1002000723-0 201230471 Materials and preparation methods thereof, and (4) Electrode compound (4) The chain ion battery is described in detail. Referring to FIG. 2 and FIG. 2, an embodiment of the present invention provides a rotor cell electrode composite material ’) which includes an electrode material particle 12 and a fine Wei (IV) u coated on the electrode (fourth) m-face of the electrode. The material of the smelting acid layer 14 is Wei Ming of semiconductor compatibility. The doped dish acid layer 14 is semiconducting. [0011] The doping-acid minus 14 has semiconductivity means that the free electron concentration of the doped layer 14 is higher than the empty six concentration or the hole concentration is higher than the free electron concentration by semiconductor doping Wei. Thereby, the doped phosphoric acid layer 14 is made semiconducting. [0012] ο 100100428 The material of the aluminum doped aluminum phosphate layer 14 is made of a chemical formula "doping element, the selection of the M doping element is required; the second energy 4 is doped into the acid lattice of the acid, specifically the 'Μ The atomic radius of the doping element needs to be close to the atomic radius of the Ming atom, and cannot be larger than the atomic radius of the aluminum atom. The valence state of the cerium doping element is preferably +2 or +4, and 〇<吖1. The doping amount of Μ is preferably 1% to 2%, that is, 〇〇1$ ng 〇 2. The Μ can be a metal element of + 2 valence, such as -he, Cu, and Mg in B c or several The species ' can also be a metal element of +4 valence, such as v Ta, T. v ' Nb ' can be one or more of Z 4 and Zr, etc. The doping element of the +2 valence is heterogeneous. a P-type semiconductor that is larger than the concentration of free electrons, so that the aluminum sulphonate is a hole-conducting mechanism, and the +4 valence doping π can make the electron concentration of the dish acid larger than the space to make the doping; * < Paper degree, from 'Mann's "4 acid aluminum into a semiconductor electronic conduction mechanism, so the price of the table or the +4 valence element can make the squamous after the squash 1 page 5 / a total of 18 pages 10 02000723-0 -nMnP〇 indicates that 201230471 is a semiconductor, thereby improving the conductivity of the aluminum phosphate. [0013] The doped aluminum phosphate layer 14 has a uniform thickness and a continuous layered morphology. The mass percentage of the acid-filled layer 14 in the electrode composite material 1 is 0.1% to 3%. The thickness of the doped aluminum phosphate layer 14 is preferably 5 nm to 20 nm. 14 is formed in situ on the surface of the electrode active material particles 12. Further, interface diffusion may be formed at the interface between the doped acid-filled layer 14 and the electrode active material particles 12. [0014] The material particles 12 may be positive electrode active material particles or negative electrode active material particles, and when the electrode active material particles 12 are positive electrode active material particles, the electrode composite material 10 is a positive electrode composite material, when the electrode active material particles 12 are In the case of the negative electrode active material particles, the electrode composite material 10 is a negative electrode composite material. The electrode active material particles 12 may be positive electrode active material particles or negative electrode active material particles, and the positive electrode active material The granules may be undoped or doped spinel structure of manganate clock, layered lithium manganate, nickel acid clock, cobalt acid, iron sulphate, manganese oxide and lithium nickel Specifically, the sulphur acid of the spinel structure may be represented by the chemical formula L i Μ n L 0 x 2-yy 4 'The lithium nickelate may be represented by the chemical formula Li Ni, L, the cobalt The chemical formula of X 1-yy lithium acid can be represented by Li Co L 0 , and the chemical formula of the layered lithium manganate x 1 -yy 2 can be represented by L 0 , and the chemical formula of the lithium iron phosphate can be represented by LixFehyLyP〇4 , the chemical formula of the nickel-manganese oxide can be expressed by the chemical formula of the chain can be represented by Li Ni Co Mn Lf0Q '0. 1 Sx
λ c d e f Zλ c d e f Z
Sl.l，0Sy<l ’ 〇Sz<1.5，〇sa-z<〇.5， 100100428 表單編號A0101 第6頁/共18頁 1002000723-0 201230471 b + z<l. 5，0<c<l，0<d<l，0<e<l，OSf SO. 2， c + d + e + f = l。L和R選自驗金屬元素、驗土金屬元素、第 13族元素、第14族元素、過渡族元素及稀土元素中之一 種或複數種，優選地，L和R選自Mn、Ni、Cr、Co、V、Sl.l,0Sy<l ' 〇Sz<1.5,〇sa-z<〇.5, 100100428 Form No. A0101 Page 6 of 18 1002000723-0 201230471 b + z<l. 5,0<c<l , 0 < d < l, 0 < e < l, OSf SO. 2, c + d + e + f = l. L and R are selected from one or more of a metal element, a soil metal element, a group 13 element, a group 14 element, a transition group element, and a rare earth element. Preferably, L and R are selected from the group consisting of Mn, Ni, and Cr. , Co, V,
Ti、A1、Fe、Ga、Nd及Mg中之至少一種。所述負極材料 可以為鈦酸鋰、石墨、有機裂解碳及中間相碳微球 (MCMB)中之一種或複數種。該鈦酸鋰為非摻雜之鈦酸鋰 * 或摻雜之鈦酸鋰，該非摻雜之鈦酸鋰或摻雜之鈦酸鋰具 有尖晶石結構。具體地，該非摻雜之鈦酸鋰之化學式為 O Li ,TiE01Q ;該摻雜之鈦酸鋰之化學式Li“ Λ Ti,〇19 4 512 (4-g) g 5 12 或u、01；5表示，其中0<gS0. 33，且0<hS0· 5At least one of Ti, A1, Fe, Ga, Nd, and Mg. The negative electrode material may be one or a plurality of lithium titanate, graphite, organic pyrolysis carbon, and mesocarbon microbeads (MCMB). The lithium titanate is undoped lithium titanate* or doped lithium titanate, and the undoped lithium titanate or doped lithium titanate has a spinel structure. Specifically, the undoped lithium titanate has the chemical formula O Li , TiE01Q ; the doped lithium titanate has the chemical formula Li “ Λ Ti, 〇 19 4 512 (4-g) g 5 12 or u, 01; Indicates that 0 <gS0. 33, and 0 < hS0· 5
4 n C b-h; 1 L ，A選自驗金屬元素、驗土金屬元素、第13族元素、第14 族元素、過渡族元素及稀土元素中之一種或複數種，優 選為Mn、Ni ' Cr ' Co ' V、Al、Fe、Ga、Nd、Nb及Mg 中 之至少一種。 [0015] 上述摻雜磷酸鋁層14可以在隔絕鋰離子電池電解液與電 極活性材料顆粒12之間之電子遷移之同時使鋰離子通過 ，從而一方面避免了鋰離子電池電極與電解液之間之副 反應，提高了電池之熱穩定性，另一方面，由於所述摻 雜填酸銘層14相較於構酸銘具有較好之導電性，從而進 一步提高了先前之磷酸鋁包覆之電極活性材料顆粒12之 導電性。 [0016] 本發明實施例提供一種上述電極複合材料10之製備方法 ，其包括以下步驟： [0017] 步驟一，提供三價鋁源及摻雜元素源，將該三價鋁源和 100100428 表單編號A0101 第7頁/共18頁 1002000723-0 201230471 該摻雜元素源加入溶劑中以形成含三價鋁離子及摻雜離 子之溶液； [0018] 步驟二，將待包覆之電極活性材料顆粒加入該含三價鋁 離子及摻雜離子之溶液中，形成一混合物； [0019] 步驟三，將磷酸根源溶液加入該混合物進行反應，使該 電極活性材料顆粒之表面形成一摻雜磷酸鋁層，該摻雜 磷酸鋁層之材料係半導體性摻雜之磷酸鋁；以及 [0020] 步驟四，熱處理該表面具有摻雜磷酸鋁層之電極活性材 料顆粒。 [0021] 在上述步驟一中，該溶劑選擇為可使三價鋁源解離形成 Al3+，並可使摻雜元素源解離形成摻雜元素之離子即可 。該溶劑可為水或者易揮發性有機溶劑，優選地，該溶 劑為揮發性有機溶劑，如乙醇、丙酮、二氣乙烧和氣仿 中一種或者幾種之混合。相對於採用水作為溶劑，以有 機溶劑如乙醇作為溶劑，可以避免在步驟二中電極活性 材料顆粒與水反應使電極活性材料之性能降低。所述三 價鋁源及摻雜元素源可溶於上述溶劑中，並且與步驟三 中之磷酸根源反應生成摻雜磷酸鋁，該除摻雜磷酸鋁外 之副產物可通過加熱方式去除。該三價鋁源可為硝酸鋁 、或亞硝酸鋁等。該摻雜元素源中之摻雜元素可為二價 或四價，所述二價摻雜元素源為硝酸鎳（Νι(Ν〇3)2)、硝 酸鎮（Mg(N〇3)2) '硝酸銅（Cu(N〇3)2)或硝酸亞鐵 (Fe(N〇3)2)，所述四價摻雜元素源為確酸鈒（V(N〇3)4) 、硝酸鈮（Nb(NO。），）、或硝酸锆（ZjKNOJJ。 3 4 3 4 100100428 表單編號A0101 第8頁/共18頁 1002000723-0 201230471 [0022]在上述步驟二中，該雷梅、、壬 ㈣子及摻雜離子之溶液:材溶於上述含三 :在該電極活性材料顆粒之表面均勻附著=;目： 雜元素之離子。由於Al3 +和摻雜元素θΑ1和摻 在溶液巾存在，相3^之 子㈣子形式 表面，對；、極活性材料顆粒之 ^電極活性材料她形成原子級之包覆。進一 乂 可控制該電極活性材料H Λ 性材料顆粒與上述溶液之極活 蓋該電極活性材料顆粒 “液旎夠覆 〇 糊狀。形成糊狀混合物之=:係:得到之混合物呈 入量剛魏A Μ, ^要係為了控制溶液之加 包覆層。具體地，2材料顆粒細形成—摻雜嶙酸鋁4 n C bh; 1 L , A is selected from one or more of the metal element, the earth metal element, the group 13 element, the group 14 element, the transition element and the rare earth element, preferably Mn, Ni ' Cr At least one of 'Co' V, Al, Fe, Ga, Nd, Nb, and Mg. [0015] The doped aluminum phosphate layer 14 can pass lithium ions while isolating electron transfer between the lithium ion battery electrolyte and the electrode active material particles 12, thereby avoiding the lithium ion battery electrode and the electrolyte on the one hand. The side reaction improves the thermal stability of the battery. On the other hand, since the doped acid-filled layer 14 has better conductivity than the acid-forming layer, the previous aluminum phosphate coating is further improved. The conductivity of the electrode active material particles 12. [0016] An embodiment of the present invention provides a method for preparing the above electrode composite material 10, which includes the following steps: [0017] Step one, providing a trivalent aluminum source and a doping element source, and the trivalent aluminum source and the 100100428 form number A0101 Page 7 of 18 1002000723-0 201230471 The doping element source is added to the solvent to form a solution containing trivalent aluminum ions and doping ions; [0018] Step 2, adding the electrode active material particles to be coated Forming a mixture in the solution containing trivalent aluminum ions and doping ions; [0019] Step 3, adding a phosphate source solution to the mixture to carry out a reaction, so that the surface of the electrode active material particles forms a doped aluminum phosphate layer, The material of the doped aluminum phosphate layer is a semiconducting doped aluminum phosphate; and [0020] step four, heat treating the surface of the electrode active material particles doped with an aluminum phosphate layer. [0021] In the above step 1, the solvent is selected such that the trivalent aluminum source can be dissociated to form Al3+, and the doping element source can be dissociated to form ions of the doping element. The solvent may be water or a volatile organic solvent. Preferably, the solvent is a volatile organic solvent such as one or a mixture of ethanol, acetone, diethylene bromide and gas. The use of water as a solvent and an organic solvent such as ethanol as a solvent can prevent the electrode active material particles from reacting with water in the second step to lower the performance of the electrode active material. The trivalent aluminum source and the dopant element source are soluble in the above solvent, and react with the phosphate source in the third step to form a doped aluminum phosphate, and the by-product other than the doped aluminum phosphate can be removed by heating. The trivalent aluminum source may be aluminum nitrate or aluminum nitrite. The doping element in the source of the doping element may be divalent or tetravalent, and the source of the divalent doping element is nickel nitrate (Νι(Ν〇3)2), nitric acid (Mg(N〇3)2) 'Chromium nitrate (Cu(N〇3)2) or ferrous nitrate (Fe(N〇3)2), the source of the tetravalent doping element is bismuth (V(N〇3)4), bismuth nitrate (Nb(NO.),), or zirconium nitrate (ZjKNOJJ. 3 4 3 4 100100428 Form No. A0101 Page 8 / Total 18 pages 1002000723-0 201230471 [0022] In the above step two, the Remy, 壬 (4) a solution of a sub-ion and a doping ion: the material is dissolved in the above-mentioned three-containing: uniformly adhered on the surface of the electrode active material particle; the objective: an ion of a hetero element. Since the Al3+ and the doping element θΑ1 are present in the solution towel, the phase 3^ (4) sub-form surface, pair; polar active material particles of the electrode active material she forms an atomic coating. Further control of the electrode active material H Λ material particles and the above solution of the electrode cover the electrode The active material particles "liquid 旎 〇 〇 。 。 。 。 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成 形成. In particular the coating, the fine particles of the second material to form - Mountain of doped, aluminum
之體積比:;Α，δχ溶液之體積輿該電極活性材料顆粒 之體積比約从丨_:4()，優物地丨2Q 極活性材料顆粒之粒 '-電 入旦m 馒選為小於Μ微米。該溶液之加 里β通過需要形成之摻雜 料之質量百分比加以^ 覆層佔電極複合材 …h ’優選地，該摻雜她包覆 [0023] 〇 層㈣電極複合材料中之質量百分比為o.u蝴。 =當將所述電極活性材料顆粒加入上述溶液中 後’為形成的之糊狀私物，㈣3+ 均勾地附著在所«極活性材料雜之表面 述混合物，該具體 τ«所 賴拌。另外，當所：二限，可為磁力攪拌或機 時，為避免«_之2之溶劑為揮發性有機溶劑 &、、 輝么，可在所述攪拌過程_不斷 加入所述有機溶劑以 混合物呈糊狀。充揮發之有機溶劍，並保持所述 100100428 表單編號Α0101 苐9頁/共】8頁 1002000723-0 201230471 [0024] 在上述步驟三中，該磷酸根源溶液可選擇為含有磷酸根 離子之溶液並可與上述步驟一中之三價鋁源及摻雜元素 源反應形成摻雜磷酸鋁，且使形成之副產物可在步驟四 中去除，該磷酸根離子可以為正磷酸根離子（Ρ0,3_)、磷 4 酸二氫根離子（HJ0/)及磷酸一氫根離子（HPO/D中之 2 4 4 一種或幾種之混合。該填酸根源溶液包括水作為溶劑， 以及溶解於該溶劑之可溶性磷酸根源，如磷酸（HJ0,) 3 4 或磷酸氨鹽。該磷酸氨鹽包括磷酸二氫銨（NHP0,)、 4 2 4 磷酸氫二銨（（NWHP0,)及磷酸三銨（（NHJJO,)中之 4 2 4 4 3 4 一種或幾種之混合。此外，為避免水對所述電極活性材 料顆粒性能之影響，可使水儘量少，僅需使水能夠完全 溶解所述磷酸根源溶液即可。 [0025] 該磷酸根源溶液加入至所述糊狀混合物時，該磷酸根離 子與附著於電極活性材料顆粒表面之Al3 +和摻雜元素離 子反應，從而在電極活性材料顆粒表面原位形成一層均 勻之摻雜磷酸鋁層。優選地，該磷酸根源溶液可以逐滴 加入該糊狀混合物，並加以攪拌，從而使該磷酸根離子 與該A 13 +和摻雜元素離子能夠在該電極活性材料顆粒表 面均勻之反應。該磷酸根源溶液之加入量可通過需要形 成之摻雜元素離子之磷酸鋁包覆層佔電極複合材料顆粒 之質量百分比加以確定。 [0026] 在上述步驟四中，該熱處理之目的係使該摻雜磷酸鋁層 與電極活性材料顆粒在界面處更好之結合，形成電極複 合材料，並去除殘留之溶劑及在步驟三中生成摻雜磷酸 鋁時之反應副產物，如硝酸銨。通過該熱處理，在摻雜 100100428 表單編號A0101 第10頁/共18頁 1002000723-0 201230471 鱗=層與電極活性材料顆粒界面處可能形成界面 〜、'處理溫度可以為4〇 、 優選為〇.5至2小時。 賴處理之時間 [0027] Ο 由於本方法先將電㈣驗 及摻雜離子之、容液Φ 到k鋁離子 于之办液中，再在該溶液中加入可以與 寿摻雜7L素離子反應生成摻㈣酸銘之鱗酸根源溶 從而在電極活性材料顆粒表面原位生成_層連續之2 碟酸2層。由於液相之溶液與附目之電極活性材料顆粒 進仃此合，可以先使鋁離子和摻雜元素離子均勻之勺 在該電極时㈣齡之表面，故，純反應後由= :和摻雜元素離子生成之摻雜元素離子竊軸沈機也 能夠更均勻包覆在該電極活性材料顆粒之表面。與先合 成鱗酸銘顆粒’再通過吸附作用使鱗酸铭顆粒吸附到電 極活性材料顆粒表面之方式相比較，本方法避免了由於 固固混合產生之吸附不均勻，導致磷酸鋁包覆不均之現 象，適合大規模工業化應用◊另外，本方法可在電極活 性材料顆粒表面生成一層厚度均勾且連續之摻雜元素離 子之磷酸鋁層，而非將磷酸鋁顆粒堆積在電極活性材料 顆粒表面。該摻雜元素離子之磷酸鋁層可以在隔絕電解 液與電極活性材料之間之電子遷移之同時使離子通過， 從而在完成鋰離子之嵌入和脫出之同時避免電解液在較 鬲或較低電壓下分解，故使該電極活性材料顆粒可以在 較高或較低電壓下具有更好之電池電化學性能及容量保 持性能。另外，由於，本發明之摻雜磷酸鋁層中之磷酸 鋁進行了半導體性摻雜，使經過摻雜後之磷酸鋁成為具 100100428 表單編號A0101 第11頁/共18頁 1002000723-0 201230471 有電子導電機制或空穴導電機制之半導體，大大提高了 導電性，故，所述具有摻雜磷酸鋁包覆層之複合電極材 料具有更好之導電性。 [0028] 本發明實施例進一步提供一種鋰離子電池，該鋰離子電 池包括正極、負極、以及位於該正極及負極之間之非水 電解質。該正極包括正極集流體及設置在該正極集流體 表面之正極材料層，該負極包括負極集流體及設置在該 負極集流體表面之負極材料層。 [0029] 上述鋰離子電池之結構中除正極材料層不同於先前技術 中之正極材料層外，其他元件之材料均可從先前技術中 選擇。 [0030] 該正極材料層由上述正極複合材料、導電劑以及黏結劑 均勻混合形成。 [0031] 實施例 [0032] 本實施例中，所述鋰離子電池電極複合材料10為正極複 合材料，所述正極複合材料為姑酸链複合材料。其中， 所述電極活性材料顆粒12為未經摻雜之鈷酸鋰顆粒，所 述摻雜磷酸鋁層14之成分為Aln QRNin uPOj。該摻雜磷 0.95 0.05 4 酸銘層14之厚度為10奈米，且在該電極複合材料10中之 質量百分比為1%。 [0033] 上述鈷酸鋰複合材料顆粒之製備過程中，先將硝酸鋁和 硝酸鎳在乙醇中溶解形成含三價鋁離子及鎳離子之溶液 ，其中墙酸銘和頌酸鎳按照A1 : N i為0. 9 5 : 0. 0 5之摩爾量 進行稱取。上述含三價鋁離子及鎳離子之溶液之體積為 100100428 表單編號A0101 第12頁/共18頁 1002000723-0 201230471 30毫升，摩爾濃度為0· 16摩爾/升。該鈷酸鋰顆粒之加入 量為100g。該鱗酸根源溶液為（NH4)2HP〇4水溶液。該熱 處理溫度為400°c。 [0034] 综上所述，本發明確已符合發明專利之要件，遂依法提 ❹ [0035] 出專利申請。惟，以上所述者僅為本發明之較佳實施方 式，自不能以此限制本案之申請專利範圍。舉凡熟悉本 案技藝之人士援依本發明之精神所作之等效修飾或變化 ，皆應涵蓋於以下申請專利範圍内。 【圖式簡單說明】 圖1為本發明實施例提供之鋰離子電池電極複合材料之結 構示意圖。 [0036] 圖2為本發明實施例提供之鋰離子電池電極複合材料之製 備流程圖。 [0037] 【主要元件符號說明】 電極複合材料： [0038] ◎ [0039] 電極活性材料顆粒：12 摻雜磷酸鋁層：14 100100428 表單編號A0101 « 弟id頁/共1只百 Λ Ά 1002000723-0Volume ratio: Α, volume of δχ solution 体积 The volume ratio of the electrode active material particles is about 丨::4(), and the 物2Q of the active material 颗粒2Q 活性 电 m - Μ microns. The addition of β of the solution by the mass percentage of the dopant to be formed is applied to the electrode composite ... h '. Preferably, the doping of the coating is [0023] The mass percentage of the (4) electrode composite is ou butterfly. = When the electrode active material particles are added to the above solution, the resulting paste-like private object, (4) 3+ is attached to the surface of the mixture of the extremely active materials, and the specific τ« is mixed. In addition, when the second limit can be magnetic stirring or machine, in order to avoid the solvent of «_2 is a volatile organic solvent &,, hui, the organic solvent can be continuously added during the stirring process. The mixture is in the form of a paste. Filling the volatilized organic solution sword and keeping the 100100428 Form No. Α0101 苐9 pages/total] 8 pages 1002000723-0 201230471 [0024] In the above step three, the phosphate source solution may be selected as a solution containing phosphate ions and The doped aluminum phosphate may be reacted with the trivalent aluminum source and the doping element source in the above step 1, and the by-product formed may be removed in step 4. The phosphate ion may be orthophosphate ion (Ρ0, 3_ a phosphorus tetrahydrogen dihydrogen ion (HJ0/) and a monohydrogen phosphate ion (a mixture of two or four of the HPO/D). The acid source solution includes water as a solvent, and is dissolved in the solvent. a soluble phosphate source such as phosphoric acid (HJ0,) 3 4 or an ammonium phosphate salt. The ammonium phosphate salt includes ammonium dihydrogen phosphate (NHP0,), 4 2 4 diammonium hydrogen phosphate ((NWHP0), and triammonium phosphate (( 4J 4 4 3 4 in NHJJO,) Mixing one or more. In addition, in order to avoid the influence of water on the performance of the electrode active material particles, water can be made as little as possible, and only water is required to completely dissolve the phosphoric acid. The root solution can be used. [0025] The phosphate source solution is added To the paste mixture, the phosphate ions react with Al3 + and doping element ions attached to the surface of the electrode active material particles to form a uniform doped aluminum phosphate layer in situ on the surface of the electrode active material particles. The phosphate solution may be added dropwise to the paste mixture and stirred to allow the phosphate ion to react uniformly with the A 13 + and doping element ions on the surface of the electrode active material particle. The amount of the solution added can be determined by the mass percentage of the aluminum phosphate coating layer of the doping element ions to be formed in the electrode composite material particles. [0026] In the above step four, the purpose of the heat treatment is to make the doped aluminum phosphate. The layer and the electrode active material particles are better combined at the interface to form an electrode composite material, and remove the residual solvent and reaction by-products such as ammonium nitrate when the aluminum phosphate is doped in the third step. Miscellaneous 100100428 Form No. A0101 Page 10 / Total 18 Page 1002000723-0 201230471 Scale = Layer and Electrode Active Material Particle Interface It is possible to form an interface ~, 'the processing temperature can be 4 〇, preferably 〇. 5 to 2 hours. The time of the treatment [0027] Ο Since the method firstly tests the electric (four) and the doping ions, the liquid Φ to the k-aluminum Ion in the solution, and then added to the solution can be reacted with the 7L elemental ions to form a sulphate source which is doped with the acid (4) acid to form a continuous layer of 2 disc acid 2 on the surface of the electrode active material particles. Since the liquid phase solution and the attached electrode active material particles are combined, the aluminum ions and the doping element ions can be uniformly placed on the surface of the electrode at the age of (four), so, after the pure reaction, =: The doping element ion-trapping machine formed by doping element ions can also be more uniformly coated on the surface of the electrode active material particles. Compared with the method of first synthesizing squamous acid granules and then adsorbing squamous acid particles onto the surface of the electrode active material particles by adsorption, the method avoids uneven adsorption due to solid-solid mixing, resulting in uneven coating of aluminum phosphate The phenomenon is suitable for large-scale industrial application. In addition, the method can form a layer of aluminum phosphate having a thickness of a continuous and doped element ion on the surface of the electrode active material particle instead of depositing the aluminum phosphate particle on the surface of the electrode active material particle. . The doped element ion aluminum phosphate layer can pass ions while injecting electrons between the electrolyte and the electrode active material, thereby preventing the electrolyte from being relatively low or low while completing the insertion and extraction of lithium ions. Decomposition under voltage, so that the electrode active material particles can have better battery electrochemical performance and capacity retention performance at higher or lower voltages. In addition, since the aluminum phosphate in the doped aluminum phosphate layer of the present invention is semiconducting, the doped aluminum phosphate becomes 100100428. Form No. A0101 Page 11 / 18 pages 1002000723-0 201230471 Electronic The semiconductor of the conductive mechanism or the hole conducting mechanism greatly improves the conductivity, and therefore, the composite electrode material having the doped aluminum phosphate coating layer has better conductivity. [0028] Embodiments of the present invention further provide a lithium ion battery including a positive electrode, a negative electrode, and a nonaqueous electrolyte between the positive electrode and the negative electrode. The positive electrode includes a positive electrode current collector and a positive electrode material layer disposed on the surface of the positive electrode current collector, the negative electrode including a negative electrode current collector and a negative electrode material layer disposed on the surface of the negative electrode current collector. [0029] The structure of the above lithium ion battery may be selected from the prior art except that the positive electrode material layer is different from the positive electrode material layer of the prior art. [0030] The positive electrode material layer is formed by uniformly mixing the above-described positive electrode composite material, a conductive agent, and a binder. [0031] In the embodiment, the lithium ion battery electrode composite material 10 is a positive electrode composite material, and the positive electrode composite material is a succinic acid chain composite material. The electrode active material particles 12 are undoped lithium cobalt oxide particles, and the composition of the doped aluminum phosphate layer 14 is Aln QRNin uPOj. The doped phosphorus 0.95 0.05 4 acid layer 14 has a thickness of 10 nm, and the mass percentage in the electrode composite 10 is 1%. [0033] In the preparation process of the above lithium cobaltate composite particles, aluminum nitrate and nickel nitrate are first dissolved in ethanol to form a solution containing trivalent aluminum ions and nickel ions, wherein the wall acid and nickel niobate are in accordance with A1 : N i is 0. 9 5 : 0. 0 5 molar amount is weighed. The volume of the above solution containing trivalent aluminum ions and nickel ions is 100100428. Form No. A0101 Page 12 of 18 1002000723-0 201230471 30 ml, molar concentration of 0·16 mol/L. The lithium cobaltate particles were added in an amount of 100 g. The sulphate source solution is an aqueous solution of (NH4)2HP〇4. The heat treatment temperature was 400 °C. [0034] In summary, the present invention has indeed met the requirements of the invention patent, and the patent application is [0035] according to the law. However, the above description is only a preferred embodiment of the present invention, and it is not possible to limit the scope of the patent application of the present invention. Equivalent modifications or variations made by persons skilled in the art in light of the spirit of the invention are intended to be included within the scope of the following claims. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view showing the structure of a lithium ion battery electrode composite material according to an embodiment of the present invention. 2 is a flow chart of preparation of a lithium ion battery electrode composite material according to an embodiment of the present invention. [Explanation of main component symbols] Electrode composite material: [0038] Electrode active material particles: 12 doped aluminum phosphate layer: 14 100100428 Form number A0101 « Brother id page / total 1 hundred Λ 2000 1002000723- 0