201201441 六、發明說明： 【發明所屬之技術領域】 [0001] 本發明涉及一種鋰離子電池電極漿料及應用該電極漿料 製備的電極片。 【先前彳支術】 [0002] 在鋰離子電池的工業生產中通常是將鋰離子電池的電極 漿料塗覆在鋁箔等極片載體上，經過機器刮塗、滾壓、 烘乾等步驟，再經過裁剪、捲繞製成可使用的電極片。 ^ [0003] 先前技術中鋰離子電池電極漿料的組成成分一般包括活201201441 VI. Description of the Invention: [Technical Field] [0001] The present invention relates to a lithium ion battery electrode slurry and an electrode sheet prepared using the electrode slurry. [Previous sputum support] [0002] In the industrial production of lithium-ion batteries, the electrode slurry of a lithium-ion battery is usually coated on a pole piece carrier such as aluminum foil, and subjected to steps such as blade coating, rolling, and drying. Then, it can be cut and wound to form a usable electrode sheet. ^ [0003] The composition of the lithium ion battery electrode slurry in the prior art generally includes alive
G 性組分、導電組分、高分子交聯劑及溶劑。其中活性組 分為正極活性物質如鈷酸鋰、錳酸鋰或磷酸鐵鋰，或負 極活性物質如石墨。導電組分可是乙炔黑、奈米碳管或 石墨。1¾分子父聯劑起到黏結活性組分和導電組分的作 用，常用丁苯橡膠（SBR)或聚偏氟乙烯（PVDF)。溶劑起 到溶解高分子交聯劑的作用，通常為水或非水性有機溶 劑，如N-甲基°比洛烧酮（NMP )等，溶劑在製作電極片的 Q 烘乾步驟中去除。電極漿料的性能好壞對電極片的製作 過程、電極片性能及鋰離子電池的性能都有很大的影響 〇 [0004] 然，即使採用相同組分形成的電極漿料製備的鋰離子電 池，其性能也可能不同。如，當電極漿料的各種組分加 入的先後順序不同時，最終得到的鋰離子電池的倍率性 能可能差別很大。這可能是由於導電組分在電極漿料中 的分散不均勻所導致。先前技術中常採用在電極漿料中 加入分散劑的方式改善導電組分在電極漿料中的分散性 099119776 表單編號A0101 第3頁/共18頁 0992034979-0 201201441 能。公告日為2008年8月6日的中國專利ZL 200480008658. 1公開了一種用於改進電極漿料的分散性 能的分散劑，這種分散劑具有能夠表面吸附的聚合物骨 架和具有非離子表面活性劑性質的側鏈。然，在實際應 用時，這種高分子聚合物分散劑在與水性溶劑進行配合 時能具有一定的分散效果，但在應用於非水性有機溶劑 時，由於大分子量的高分子聚合物分散劑自身的分散及 黏度問題，對電極漿料的分散性能改善則不明顯。 【發明内容】 [0005] 有鑒於此，提供一種適用於有機溶劑且能夠提高鋰離子 電池性能的電極漿料，及應用該方法製備的電極片實為 必要。 [0006] 一種鋰離子電池電極漿料，其包括活性姐分、導電組分 、高分子交聯劑、有機溶劑及曲拉通。 [0007] —種鋰離子電池電極片，其包括一集流體及形成於該集 流體表面的電極材料’該電極材料包括活性組分、導電 組分、高分子交聯劑及曲拉通。 [0008] 相較於先前技術，本發明在採用有機溶劑的電極漿料中 添加曲拉通，在不影響漿料黏度的情況下可使活性組分 和導電組分在電極漿料中均勻分散，得到具有較高分散 性能的電極漿料，使鋰離子電池的倍率性能得到改善。 【實施方式】 [0009] 下面將結合附圖及具體實施例對本發明提供的電極漿料 及其製備方法，及應用該方法製備的電極片作進一步的 099119776 表單編號A0101 第4頁/共18頁 0992034979-0 201201441 詳細說明。 [0010] 本發明提供一種電極漿料，其包括活性組分、導電組分 、高分子交聯劑、有機溶劑及辛基苯基聚氧乙烯醚 (Octyl phenol poly(ethyleneglycol ether)，G component, conductive component, polymer crosslinking agent and solvent. The active component is classified into a positive electrode active material such as lithium cobaltate, lithium manganate or lithium iron phosphate, or a negative electrode active material such as graphite. The conductive component may be acetylene black, carbon nanotube or graphite. The 13⁄4 molecular parent binder acts to bind the active component and the conductive component, usually styrene butadiene rubber (SBR) or polyvinylidene fluoride (PVDF). The solvent functions to dissolve the polymer crosslinking agent, usually water or a non-aqueous organic solvent such as N-methylpyrrolidone (NMP), and the solvent is removed in the Q drying step of the electrode sheet. The performance of the electrode paste has a great influence on the fabrication process of the electrode sheet, the performance of the electrode sheet and the performance of the lithium ion battery. [0004] However, even the lithium ion battery prepared by using the electrode paste formed by the same composition is used. , its performance may also be different. For example, when the order of addition of the various components of the electrode paste is different, the rate performance of the finally obtained lithium ion battery may vary greatly. This may be caused by uneven dispersion of the conductive component in the electrode slurry. In the prior art, the dispersing agent in the electrode slurry is often used to improve the dispersibility of the conductive component in the electrode paste. 099119776 Form No. A0101 Page 3 of 18 0992034979-0 201201441 Yes. Chinese Patent ZL 200480008658. 1 published on August 6, 2008 discloses a dispersant for improving the dispersibility of an electrode paste having a polymer skeleton capable of surface adsorption and having a nonionic surface activity Side chain of the nature of the agent. However, in practical applications, the polymer dispersant can have a certain dispersion effect when combined with an aqueous solvent, but when applied to a non-aqueous organic solvent, the high molecular weight polymer dispersant itself The dispersion and viscosity problems are not obvious for the dispersion performance of the electrode slurry. SUMMARY OF THE INVENTION [0005] In view of the above, it is necessary to provide an electrode paste which is suitable for an organic solvent and which can improve the performance of a lithium ion battery, and an electrode sheet prepared by the method. [0006] A lithium ion battery electrode slurry comprising an active ingredient, a conductive component, a polymer crosslinking agent, an organic solvent, and a Triton. A lithium ion battery electrode sheet comprising a current collector and an electrode material formed on a surface of the current collector. The electrode material comprises an active component, a conductive component, a polymer crosslinking agent, and a Triton. Compared with the prior art, the present invention adds a Triton in an electrode slurry using an organic solvent, and uniformly disperses the active component and the conductive component in the electrode slurry without affecting the viscosity of the slurry. The electrode slurry having higher dispersion performance is obtained, and the rate performance of the lithium ion battery is improved. [Embodiment] The electrode paste provided by the present invention and the preparation method thereof, and the electrode sheet prepared by the method are further provided as a further 099119776 Form No. A0101 Page 4 / Total 18 pages in conjunction with the accompanying drawings and specific embodiments. 0992034979-0 201201441 Detailed description. [0010] The present invention provides an electrode slurry comprising an active component, a conductive component, a polymer crosslinking agent, an organic solvent, and an Octyl phenol poly (ethyleneglycol ether).
X x = 9〜10，俗稱曲拉通）。 [0011] 該活性組分為正極活性物質或負極活性物質中的一種。 該正極活性物質可為磷酸鐵鋰、錳酸鋰、鈷酸鋰及鎳酸 鋰中的一種或複數種，該負極活性物質可為石墨、有機 > 裂解碳及中間相碳微球（MCMB)中的一種或複數種，該導 電組分可為石墨、乙炔黑及奈米碳管中的一種或複數種 ，該有機溶劑可為NMP、二甲基甲醯胺（DMF)、二乙基 甲醯胺（DEF)、二曱基亞砜（DMS0)、四氫呋喃及醇類中 的一種或複數種，該高分子交聯劑可為PVDF、聚四氟乙 烯（PTFE)及SBR中的一種或複數種。可以理解，該正極 活性物質、負極活性物質、導電組分、有機溶劑及高分 子交聯劑也可採用其他常用的材料。 ) [0012] 在該電極漿料中，該活性組分、導電組分及高分子交聯 劑的總質量與該有機溶劑的質量之比可為3:1〜4:1，優選 為3:1，從而可使該電極漿料具有較好的流變性，並利於 分散。 [0013] 在該活性組分、導電組分及高分子交聯劑中，該活性組 分的質量佔總質量的75%~90%，優選為80%，該導電組分 的質量佔總質量的5%〜1 5%，優選為10%，該高分子交聯 劑的質量佔總質量的5%〜15%，優選為10%。 099119776 表單編號 A0101 第 5 頁/共 18 頁 0992034979-0 201201441 [0014] 本實施例中所用曲拉通的平均分子量約為647。該曲拉通 佔電極漿料總質量的0. 25%~1. 25%，優選為0. 5%。 [0015] 該鋰離子電池電極漿料可藉由以下步驟製備： [0016] 首先，提供活性組分、導電組分、高分子交聯劑、有機 溶劑及曲拉通；及 [0017] 其次，將該活性組分、導電組分、高分子交聯劑、有機 溶劑及曲拉通均勻混合。具體地，可先將該曲拉通溶解 在該有機溶劑中，再將所述活性組分、導電組分及高分 子交聯劑與溶有該曲拉通的有機溶劑混合。經過試驗證 明，所述活性組分、導電組分及高分子交聯劑的加入順 序對電極漿料的性能並無顯著影響，即，當該分散劑採 用曲拉通時，無論將活性組分、導電組分及高分子交聯 劑一同加入有機溶劑後進行混合，還是逐一加入有機溶 劑進行混合，均可使導電組分均勻的分散在活性組分之 間。 [0018] 先前技術中作為分散劑的有機高分子聚合物的分子量在 1 0, 000至30, 000之間，具有較強的增稠作用，且本身分 散十分困難，故對採用非水性溶劑的電極漿料性能的改 進不明顯。而本申請中，由於曲拉通的分子量較小，本 身可容易地在有機溶劑中分散，且曲拉通的加入對漿料 的黏度幾乎不產生影響，提高了電極漿料的性能。並且 ，所述混合的方式可是球磨、超聲震盪或研磨，甚至是 普通的機械攪拌也可達到有效分散導電組分及活性組分 的目的，大大簡化了電極漿料的製備工藝。 099119776 表單編號A0101 第6頁/共18頁 0992034979-0 201201441 [0019] 〇 本發明實齡m-步提供—脑離子電池電極片，其包 括-集流體及形成於集流體表㈣電極材料。該集流體 可是銅践料’該㈣為將所料轉料供乾後 剩下的物質，包括活性組分、導電組分、高分子交聯劑 曲拉通該曲拉通的質里佔電極材料總質量的1 優選為2%。該電極片厚度㈣，且聽厚度約為5〇微米 ~300微米。該電極片的製備方法包括以下步驟：提供一 集流體；將該電„料塗覆在該集流體表面；及將該電 極水料在小於120 C的溫度下洪乾。該電極衆料中的有機 溶劑藉由該烘乾步驟去除，用岭分散活性組分和導電組 刀的曲拉通在小於12〇oc不揮發或分解，故以雜質的形式 留在電極材料中。然，實驗證明少量的曲拉通不會對鐘 離子電池的性能造«彡響，錢夠有效祕進活性組分 及導電組分的分散，提高鐘離子電池的倍率性能。 國纟實施例以曲拉通作為分⑽製備正極電極聚料，並將 該電極漿料塗覆於正極集流體表面製成正極電極片，並 與未加入曲拉通的正極電極片進行對比。 [0021] f先製備待測正極電極片。將曲拉通溶解在置中，配製 成曲拉通質量百分含量為1%的曲拉通/NMP溶液，將PVDF 溶解在NMP中，配製成PVDF質量百分含量為1〇WpyDF/ NMP溶液，將1. 6g磷酸鐵鋰、〇· 2g乙炔黑、2g所述 PVDF/NMP溶液加入至4 2g所述曲拉通/NMp溶液中，用 玻璃棒充分授拌均勻’製備成電極漿料’並將該電極漿 料到塗在鋁箔表面，並在1〇(rc下烘乾，得到正極電極片 099119776 表單編號A0I01 第7頁/共18頁 0992034979-0 201201441 [0022] 其次製備對比電極片。將1. 6g磷酸鐵鋰、0. 2g乙炔黑、 2g所述PVDF/NMP溶液加入至4.2gNMP中，製成不含曲拉 通的電極漿料，並同樣地將電極漿料刮塗在鋁箔表面， 烘乾得到對比電極片。 [0023] 請參閱圖卜4，可發現，加入曲拉通的正極電極片中，在 磷酸鐵鋰大顆粒週圍分散有大量乙炔黑小顆粒。而未加 入曲拉通的正極電極片中，複數磷酸鐵鋰大顆粒聚集在 一起，並未與乙炔黑均勾分散。 [0024] 將上述待測正極電極片與對比電極片在相同的條件下分 別與相同的負極金屬鋰片、電解液及隔膜組裝成半電池 ，並採用1〔（0.6111八/<：1112)，3〇(1.8111八/〇1112)及 5C( 3. 0mA/cm2)電流對上述兩種電池進行充放電循環測 試。電池的隔膜採用聚乙烯/丙烯多孔膜（Cel gard 2400 )。電解液為 lmol/L 的 LiPF /EC + MC + DEC ( 6 1 :1 :1，v/v/v)溶液，其中電解液的溶劑為碳酸乙烯酯 ，碳酸二乙酯及碳酸二甲酯以體積比1:1:1混合，電解質 鹽為六氟磷酸鋰。 [0025] 請參閱圖5〜7，藉由測試發現，雖然在小電流下充放電時 ，加入曲拉通與未加曲拉通的電極片性能差別並不明顯 ，但隨著充放電倍率增大，加入曲拉通的電極片顯示出 較高的比容量及容量保持率，故曲拉通的加入有效的提 高了鋰離子電池的倍率性能。 [0026] 本技術方案在含有機溶劑的電極漿料中添加曲拉通，無 需調節漿料黏度即可使活性組分和導電組分在電極漿料 099119776 表單編號A0101 第8頁/共18頁 0992034979-0 201201441 中均勻分散，得到具有較高分散性能的電極漿料，使鐘 離子電池的倍率性能得到改善。 [0027] 知上所述，本發明確已符合發明專利之要件，遂依法提 出專利申請。惟，以上所述者僅為本發明之較佳實施例 ，自不能以此限制本案之申請專利範圍。舉凡習知本案 技藝之人士挺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】 [0028] 圖1為本發明實施例採用含曲拉通的電極漿料製備的電極 片的低放大倍率掃描電鏡照片。 [0029] 圖2為採用不含曲拉通的電極漿料製備的電極片的低放大 倍率掃描電鏡照片。 [0030] 圖3為本發明實施例採用含曲拉通的電極.漿料製備的電極 片的高放大倍率掃描電鏡照片。 [0031] 圖4為採用不含曲拉通的電極漿料製備的電極片的高放大 倍率掃描電鏡照片。 [0032] 圖5為採用含有曲拉通及不含曲拉通的碟酸鐵鍾正極電極 片在1C倍率下的循環性能測試曲線。 [0033] 圖6為採用含有曲拉通及不含曲拉通的磷酸鐵链正極電極 片在3C倍率下的循環性能測試曲線。 [0034] 圖7為採用含有曲拉通及不含曲拉通的填酸鐵鐘正極電極 片在5C倍率下的循環性能測試曲線。 【主要元件符號說明】 099119776 表單編號A0101 第9頁/共18頁 0992034979-0 201201441[0035]無 099119776 表單編號A0101 第10頁/共18頁 0992034979-0X x = 9~10, commonly known as Triton). [0011] The active component is one of a positive electrode active material or a negative electrode active material. The positive electrode active material may be one or a plurality of lithium iron phosphate, lithium manganate, lithium cobaltate, and lithium nickelate, and the negative electrode active material may be graphite, organic > pyrolysis carbon and mesocarbon microbeads (MCMB) One or more of the conductive components may be one or more of graphite, acetylene black and carbon nanotubes, and the organic solvent may be NMP, dimethylformamide (DMF), diethyl One or more of decylamine (DEF), dimercaptosulfoxide (DMS0), tetrahydrofuran, and an alcohol, and the polymer crosslinking agent may be one or plural of PVDF, polytetrafluoroethylene (PTFE), and SBR. Kind. It is to be understood that the positive electrode active material, the negative electrode active material, the conductive component, the organic solvent and the high molecular crosslinking agent may be other commonly used materials. [0012] In the electrode slurry, the ratio of the total mass of the active component, the conductive component, and the polymer crosslinking agent to the mass of the organic solvent may be 3:1 to 4:1, preferably 3: 1, so that the electrode slurry can have better rheology and facilitate dispersion. [0013] In the active component, the conductive component and the polymer crosslinking agent, the mass of the active component accounts for 75% to 90%, preferably 80% of the total mass, and the mass of the conductive component accounts for the total mass. 5% to 15%, preferably 10%, and the mass of the polymer crosslinking agent is 5% to 15%, preferably 10%, based on the total mass. 099119776 Form No. A0101 Page 5 of 18 0992034979-0 201201441 [0014] The average molecular weight of the Triton used in this example is about 647. 5%。 The 5% of the total mass of the electrode is 0. 25%~1. 25%, preferably 0. 5%. [0015] The lithium ion battery electrode slurry can be prepared by the following steps: [0016] First, an active component, a conductive component, a polymer crosslinking agent, an organic solvent, and a Triton; and [0017] The active component, the conductive component, the polymer crosslinking agent, the organic solvent, and the Triton are uniformly mixed. Specifically, the Triton can be first dissolved in the organic solvent, and the active component, the conductive component and the high molecular crosslinking agent are mixed with the organic solvent in which the Triton is dissolved. It has been proved by experiments that the order of addition of the active component, the conductive component and the polymer crosslinking agent has no significant effect on the performance of the electrode slurry, that is, when the dispersant adopts Triton, regardless of the active component The conductive component and the polymer cross-linking agent are added together with an organic solvent for mixing, or the organic solvent is added one by one for mixing, and the conductive component can be uniformly dispersed between the active components. [0018] The organic high molecular polymer as a dispersing agent in the prior art has a molecular weight of between 1 000 and 30,000, has a strong thickening effect, and is very difficult to disperse itself, so that a non-aqueous solvent is used. The improvement in electrode paste performance is not obvious. In the present application, since the molecular weight of Triton is small, it can be easily dispersed in an organic solvent, and the addition of Triton has little effect on the viscosity of the slurry, and the performance of the electrode slurry is improved. Moreover, the mixing method may be ball milling, ultrasonic vibration or grinding, or even ordinary mechanical stirring, the purpose of effectively dispersing the conductive component and the active component is achieved, and the preparation process of the electrode slurry is greatly simplified. 099119776 Form No. A0101 Page 6 of 18 0992034979-0 201201441 [0019] The present invention provides a brain-ion battery electrode sheet comprising a current collector and an electrode material formed on the current collector meter (4). The current collector may be a copper material. (4) is a material remaining after the material to be dried, including an active component, a conductive component, a polymer cross-linking agent, and a ruthenium-based electrode. The total mass of the material 1 is preferably 2%. The electrode sheet has a thickness (four) and a thickness of about 5 Å to 300 μm. The method for preparing the electrode sheet comprises the steps of: providing a current collector; coating the electric material on the surface of the current collector; and drying the electrode water at a temperature of less than 120 C. The organic solvent is removed by the drying step, and the templating flux of the active component and the conductive group knife is not volatilized or decomposed at less than 12 〇 oc, so it remains as an impurity in the electrode material. However, the experiment proves a small amount. The Triton will not make a noise on the performance of the ion battery. The money is effective enough to secrete the dispersion of the active component and the conductive component, and improve the rate performance of the ion battery. The National Example is based on Triton. (10) preparing a positive electrode aggregate, and coating the electrode slurry on the surface of the positive electrode current collector to form a positive electrode sheet, and comparing with the positive electrode sheet to which no Triton is added. [0021] Preparing a positive electrode to be tested first Dissolve the Triton in a set, prepare a Triton/NMP solution with a mass percentage of 1% Triton, dissolve the PVDF in NMP, and prepare a PVDF mass percentage of 1〇.克克铁铁铁, 2 g of acetylene black, 2 g of the PVDF/NMP solution was added to 42 g of the Triton/NMp solution, and the mixture was thoroughly mixed with a glass rod to prepare an electrode slurry and the electrode slurry was applied to an aluminum foil. The surface of the electrode, and the first electrode sheet is 0. 2 g of acetylene black and 2 g of the PVDF/NMP solution were added to 4.2 g of NMP to prepare an electrode paste containing no triton, and the electrode paste was similarly scraped on the surface of the aluminum foil, and dried to obtain a comparative electrode sheet. 0023] Please refer to Figure 4, it can be found that a large amount of acetylene black particles are dispersed around the large particles of lithium iron phosphate in the positive electrode sheet of Triton, and the complex phosphoric acid is not added to the positive electrode sheet of Triton. The large particles of iron and lithium are aggregated and are not dispersed with acetylene black. [0024] The positive electrode sheet to be tested and the comparative electrode sheet are respectively assembled under the same conditions with the same negative metal lithium sheet, electrolyte and separator. Half-battery and use 1[(0.6111 eight) /<:1112), 3〇 (1.8111 八/〇1112) and 5C (3.0 mA/cm2) currents were tested for charge and discharge cycles of the above two batteries. The separator of the battery was made of polyethylene/propylene porous film (Cel gard) 2400). The electrolyte is a 1 mol/L LiPF /EC + MC + DEC (6 1 :1 :1, v/v/v) solution, wherein the solvent of the electrolyte is ethylene carbonate, diethyl carbonate and carbonic acid The methyl ester was mixed at a volume ratio of 1:1:1, and the electrolyte salt was lithium hexafluorophosphate. [0025] Referring to FIG. 5 to FIG. 7 , it is found by the test that although the performance of the electrode sheets with the addition of the Triton and the non-Traton is not obvious when charging and discharging at a small current, the charging and discharging ratio increases. Large, the electrode sheet added to the Triton shows a higher specific capacity and capacity retention rate, so the addition of Triton is effective to improve the rate performance of the lithium ion battery. [0026] In the technical solution, a trimadine is added to an electrode slurry containing an organic solvent, and the active component and the conductive component can be made in the electrode paste without adjusting the viscosity of the slurry. 099119776 Form No. A0101 Page 8 of 18 0992034979-0 201201441 evenly dispersed, the electrode slurry with higher dispersion performance is obtained, and the rate performance of the ion battery is improved. [0027] As described above, the present invention has indeed met the requirements of the invention patent, and has filed a patent application according to 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 those 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 [0028] FIG. 1 is a low-magnification scanning electron micrograph of an electrode sheet prepared by using an electrode paste containing a Triton according to an embodiment of the present invention. 2 is a low magnification scanning electron micrograph of an electrode sheet prepared using an electrode paste containing no templating. [0029] FIG. 3 is a high-magnification scanning electron micrograph of an electrode sheet prepared by using an electrode containing a trimaline according to an embodiment of the present invention. [0030] FIG. [0031] FIG. 4 is a high magnification scanning electron micrograph of an electrode sheet prepared using an electrode paste without a Triton. [0032] FIG. 5 is a cycle performance test curve of a positive electrode sheet of a disc iron iron containing a Triton and without a Triton at a 1 C rate. 6 is a cycle performance test curve of a positive electrode plate of an iron phosphate chain containing a Triton and a Triton-free, at a 3 C rate. 7 is a cycle performance test curve of a positive electrode electrode sheet containing an acid-filled iron bell containing a Triton and a Triton-free at 5 C rate. [Main component symbol description] 099119776 Form No. A0101 Page 9 of 18 0992034979-0 201201441[0035]None 099119776 Form No. A0101 Page 10 of 18 0992034979-0