TW201320450A - Manufacturing method of using modified artificial graphite as cathode material of lithium battery - Google Patents

Manufacturing method of using modified artificial graphite as cathode material of lithium battery Download PDF

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TW201320450A
TW201320450A TW100140643A TW100140643A TW201320450A TW 201320450 A TW201320450 A TW 201320450A TW 100140643 A TW100140643 A TW 100140643A TW 100140643 A TW100140643 A TW 100140643A TW 201320450 A TW201320450 A TW 201320450A
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artificial graphite
temperature
carbon
predetermined time
preparation
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TWI434453B (en
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Yu-Shiang Wu
Shian-Tsung Chou
Po-Kun Chen
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Long Time Technology Corp
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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

Abstract

The present invention provides a manufacturing method of using modified artificial graphite as cathode material of lithium battery, which employs a polyacrylamide polymer to encapsulate an artificial ball-type graphite/carbon/nano-silicon composite material, which yields the first columbic efficiency of 89.1% with both charge and discharge at 0.1 C and the first irreversible capacity decreased from 95.1 to 55.0 mAhg-1; and, after 50 charge and discharge cycles, the charge capacity is 410.1 mAhg-1, and the capacity retention ration is 91.5%. Thus, by employing the polyacrylamide to encapsulate the artificial ball-type graphite/carbon/nano-silicon composite material to fabricate the cathode material of lithium battery and during the assembly of cathode material of lithium battery, the present invention may prevent the graphite and carbon material from directly contacting the electrolyte and the damage caused by the volume expansion of nano-silicon.

Description

改質人造石墨作為鋰電池負極材料之製備方法Modified artificial graphite as a preparation method of lithium battery anode material

本發明係關於一種改質人造石墨作為鋰電池負極材料之製備方法，尤指一種將一人造石墨、一煤焦瀝青和一奈米矽混合，經過一高溫碳化程序後，再與一聚丙烯胺高分子聚合物溶液均勻混合，並經加熱乾燥以獲得一鋰離子電池負極材料。The invention relates to a modified artificial graphite as a preparation method of a lithium battery anode material, in particular to an artificial graphite, a coal tar pitch and a nano 矽 mixed, after a high temperature carbonization procedure, and then a polyacrylamide The polymer solution is uniformly mixed and dried by heating to obtain a lithium ion battery anode material.

鋰離子電池的負極材料在最近這幾年被廣泛的研究，因為傳統上以鋰金屬做為鋰電池負極材料存在著許多缺點，其中包括鋰金屬表面產生樹枝狀結晶物析出，除了有安全上的問題外，循環壽命也受影響。這些因素都會使電池失效。The anode materials for lithium-ion batteries have been extensively studied in recent years because of the many disadvantages of using lithium metal as a negative electrode material for lithium batteries, including the precipitation of dendritic crystals on the surface of lithium metal, in addition to safety. In addition to the problem, the cycle life is also affected. These factors will cause the battery to fail.

而現今鋰離子電池最被廣泛應用的莫過於碳系統，目前商業化鋰離子電池所使用之負極材料為石墨，其中石墨又可分為人造石墨與天然石墨。而人造石墨中的介穩相球狀碳(MCMB)，繁雜的製程且需採用石墨化爐處理，造成生產成本過高的問題。在天然石墨方面，則由於在電池進行充放電過程中，其第一次不可逆性較大，目前改善此缺點可用表面改質方式，在石墨表面披覆上一層含碳層，經碳化熱處理後形成非晶質碳材，透過這層非晶質碳膜，可以抑制鋰錯化合物嵌入石墨層間，降低其不可逆電容量。在石墨表面包覆瀝青(Pitch)，雖然有較小的比表面積，有較低的第一次不可逆性，且可以改善石墨負極材與電解液的相容性，生產成本較為低廉，但是隨著充放電次數的增加，其電容量會持續衰退，造成循環壽命變差。Nowadays, the most widely used lithium-ion battery is the carbon system. At present, the negative electrode material used in commercial lithium-ion batteries is graphite, and graphite can be divided into artificial graphite and natural graphite. The metastable phase spheroidal carbon (MCMB) in artificial graphite has a complicated process and needs to be treated by a graphitization furnace, which causes a problem of excessive production cost. In the aspect of natural graphite, since the first irreversibility is large during the charging and discharging process of the battery, the current surface modification method can be improved by surface modification, and a carbon layer is coated on the surface of the graphite to form a carbonized heat treatment. The amorphous carbon material, through this layer of amorphous carbon film, can inhibit the intercalation of lithium-substituted compounds between the graphite layers and reduce the irreversible capacitance. Pitch coated on the graphite surface, although having a small specific surface area, has a low first irreversibility, and can improve the compatibility of the graphite negative electrode material with the electrolyte, and the production cost is relatively low, but with As the number of charge and discharge increases, the capacity of the battery continues to decline, resulting in poor cycle life.

基於先前日本專利特開第2002-117851號是採用聚烯丙基胺水溶液與石墨粉混合，加熱到120℃一邊攪拌一邊加熱到水攪乾後，將粉末真空乾燥烘乾，得其粉末可做為鋰離子電池負極材料，然而此固態攪拌乾燥法應用於大量生產時，由於水分乾燥裡外不均，容易造成石墨粉顆粒互相黏貼聚集，不利於粒徑包覆與分散，於電極塗佈過程產生不均的現像。Based on the prior Japanese Patent Laid-Open No. 2002-117851, a polyallylamine aqueous solution is mixed with graphite powder, heated to 120 ° C while stirring, heated to water and stirred, and the powder is vacuum dried and dried to obtain a powder thereof. It is a negative electrode material for lithium ion batteries. However, when this solid state stirring and drying method is applied to mass production, it is easy to cause graphite powder particles to adhere to each other due to uneven moisture inside and outside, which is not conducive to particle size coating and dispersion. Produce an uneven image.

而中國專利(第CN101800304A號)採用天然鱗片石墨微粉與黏結劑(如聚乙烯醇(PVA)、羧甲基纖維素(CMC)、聚乙烯醇縮丁醛(PVB))混合，經噴霧乾燥後，再經600~1000℃碳化熱處理，其研究發現碳化後可得到20~50 μm的球形石墨粉體，電容量測試後有較高的比容量與好的充放電循環性能，但上述方法發現首次庫倫效率為80~88%，其首次庫倫效率偏低，加上其為低含碳量之黏結劑經碳化處理，其碳化生產過程中低分子量散失造成空氣污染需加以處理，導致生產成本較高等缺點。中國專利(第CN101916846A號)將石墨與有機聚合物或高分子導電物質相混合，經噴霧乾燥烘乾處理得到負極複合材料，首次庫倫效率為93~95%，放電電容量約360 mAhg-1且有好的循環壽命，但其電容量已無法達到目前的需求。The Chinese patent (No. CN101800304A) uses natural flake graphite powder and a binder (such as polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC), polyvinyl butyral (PVB)), after spray drying. After carbonization heat treatment at 600~1000 °C, it was found that spherical graphite powder of 20~50 μm can be obtained after carbonization. After capacity test, it has higher specific capacity and good charge-discharge cycle performance, but the above method is the first time. The coulombic efficiency is 80~88%. Its first coulombic efficiency is low, and its binder with low carbon content is carbonized. The low molecular weight loss in the carbonization production process causes air pollution to be treated, resulting in higher production cost. Disadvantages. The Chinese patent (No. CN101916846A) mixes graphite with an organic polymer or a polymer conductive material, and is spray-dried and dried to obtain a negative electrode composite material, the first coulombic efficiency is 93 to 95%, and the discharge capacity is about 360 mAhg -1 and It has a good cycle life, but its capacity has not been able to meet current demand.

因此，如何提升負極材料放電電容量、降低奈米矽材之不可逆電容量、改善奈米矽體積膨脹並降低生產成本，為亟待業界解決之課題。Therefore, how to improve the discharge capacity of the anode material, reduce the irreversible capacity of the nano-coffin, improve the volume expansion of the nano-tantalum and reduce the production cost is an urgent problem to be solved by the industry.

本發明之目的即在提供一種改質人造石墨作為鋰電池負極材料之製備方法，本發明之次一目的係在提供一種改質人造石墨作為鋰電池負極材料之製備方法，將一聚丙烯胺高分子聚合物與一去離子水混合一第一預定時間，以獲得一聚丙烯胺高分子聚合物溶液，接續將一人造石墨、一煤焦瀝青和一奈米矽混合後經由一高溫炭化程序形成一人造石墨/碳/矽複合材料之粉體，再將該人造石墨/碳/矽複合材料粉體和該聚丙烯胺高分子聚合物溶液均勻混合一第二預定時間，以獲得均勻混合之漿料，並對該漿料加熱到一第一預定溫度使溶劑揮發後，獲得一粉料，且將該粉料經真空烘箱以一第二預定溫度加熱乾燥，持溫時間為一第三預定時間，最後獲得一人造石墨複合材，因該人造石墨複合材被該聚丙烯胺高分子聚合物所包覆，在製成該鋰離子電池負極材料後，能夠藉以改善該鋰電池充放電的循環穩定度及減少固態電解液界面薄膜(SEI)所造成的電阻之目的。The object of the present invention is to provide a modified artificial graphite as a preparation method of a lithium battery anode material, and the second object of the present invention is to provide a modified artificial graphite as a preparation method of a lithium battery anode material, which has a high polyacrylamide. The molecular polymer is mixed with a deionized water for a first predetermined time to obtain a polyacrylamide high molecular polymer solution, and then an artificial graphite, a coal tar pitch and a nano 矽 are mixed and formed by a high temperature carbonization process. a powder of artificial graphite/carbon/ruthenium composite material, and uniformly mixing the artificial graphite/carbon/ruthenium composite powder and the polyacrylamide high polymer solution for a second predetermined time to obtain a uniformly mixed pulp After the slurry is heated to a first predetermined temperature to volatilize the solvent, a powder is obtained, and the powder is heated and dried by a vacuum oven at a second predetermined temperature for a third predetermined time. Finally, an artificial graphite composite material is obtained, and the artificial graphite composite material is coated with the polyacrylamide high molecular polymer, and after the anode material of the lithium ion battery is fabricated, In order to improve the cycle stability of the lithium battery charge and discharge and reduce the resistance caused by the solid electrolyte interface film (SEI).

為達成上述本發明目的之技術手段在於：一聚丙烯胺高分子聚合物溶解於一去離子水，並攪拌混合一第一預定時間，以獲得一聚丙烯胺高分子聚合物溶液；將一人造石墨、一煤焦瀝青和一奈米矽混合後經由一高溫炭化程序形成一人造石墨/碳/矽複合材料之粉體；將該人造石墨/碳/矽複合材料粉體和該聚丙烯胺高分子聚合物溶液均勻混合一第二預定時間；將前一步驟之漿料均勻混合後加熱到一第一預定溫度使溶劑揮發，以獲得一粉料；將該粉料經真空烘箱以一第二預定溫度加熱乾燥，持溫時間為一第三預定時間，以獲得一人造石墨複合材，並將人造石墨複合材製成一鋰離子電池負極材料。The technical means for achieving the above object of the present invention is that a polyacrylamide high molecular polymer is dissolved in a deionized water and stirred and mixed for a first predetermined time to obtain a polyacrylamide high molecular polymer solution; After mixing graphite, a coal tar pitch and a nano bismuth, a powder of artificial graphite/carbon/ruthenium composite material is formed through a high temperature carbonization process; the artificial graphite/carbon/ruthenium composite powder and the polyacrylamide are high The molecular polymer solution is uniformly mixed for a second predetermined time; the slurry of the previous step is uniformly mixed and heated to a first predetermined temperature to volatilize the solvent to obtain a powder; the powder is passed through a vacuum oven to a second The predetermined temperature is heated and dried, and the holding time is a third predetermined time to obtain an artificial graphite composite material, and the artificial graphite composite material is made into a lithium ion battery negative electrode material.

為便於　貴審查委員能對本發明之技術手段及運作過程有更進一步之認識與瞭解，茲舉實施例配合圖式，詳細說明如下。In order to facilitate the review committee to have a further understanding and understanding of the technical means and operation process of the present invention, the embodiments are combined with the drawings, and the details are as follows.

本發明所提供之「改質人造石墨作為鋰電池負極材料之製備方法」，係將一聚丙烯胺高分子聚合物溶解於一去離子水，以混合獲得一聚丙烯胺高分子聚合物溶液，再將一人造石墨/碳/矽複合材料粉末和該聚丙烯胺高分子聚合物溶液均勻混合1~3小時，在均勻混合後經加熱至70~90℃使溶劑揮發，以獲得一粉料，並將該粉料放置到真空烘箱加熱到90~150℃，且加熱烘乾時間為8~12小時，使該粉末完全乾燥，即獲得一表面改質之負極材料(即一人造石墨/碳/矽複合材料)，藉以解決習用之多型態碳材料(例如：天然石墨、煤碳、碳纖維和介穩相球狀碳MCMB)，具充放電速度慢、電容量低及價格昂貴等缺點。The method for preparing a modified artificial graphite as a negative electrode material for a lithium battery provided by the present invention comprises dissolving a polyacrylamide high molecular polymer in a deionized water to obtain a polyacrylamide high molecular polymer solution. Then, an artificial graphite/carbon/ruthenium composite material powder and the polyacrylamide high molecular polymer solution are uniformly mixed for 1 to 3 hours, and after uniformly mixing, the solvent is volatilized by heating to 70 to 90 ° C to obtain a powder. And the powder is placed in a vacuum oven to be heated to 90-150 ° C, and the heating drying time is 8 to 12 hours, so that the powder is completely dried, that is, a surface-modified anode material (ie, an artificial graphite / carbon /矽Composite materials), to solve the multi-type carbon materials (such as: natural graphite, coal, carbon fiber and metastable phase spheroidal carbon MCMB), with shortcomings such as slow charge and discharge, low capacitance and high price.

請參閱第1圖所示，本發明所提供之改質人造石墨作為鋰電池負極材料之製備方法，依據下列步驟進行之：步驟S10，將一聚丙烯胺高分子聚合物溶解於一去離子水，並攪拌混合一第一預定時間，以獲得一聚丙烯胺高分子聚合物溶液。Referring to FIG. 1 , the modified artificial graphite provided by the present invention is prepared as a negative electrode material for a lithium battery according to the following steps: Step S10, dissolving a polyacrylamide high molecular polymer in a deionized water. And stirring and mixing for a first predetermined time to obtain a polyacrylamide high molecular polymer solution.

步驟S20，將一人造石墨、一煤焦瀝青和一奈米矽混合後經由一高溫碳化程序形成一人造石墨/碳/矽複合材料之粉體。In step S20, an artificial graphite, a coal tar pitch and a nano bismuth are mixed to form a powder of an artificial graphite/carbon/ruthenium composite material through a high temperature carbonization process.

步驟S30，將該人造石墨/碳/矽複合材料粉體和該聚丙烯胺高分子聚合物溶液均勻混合一第二預定時間。In step S30, the artificial graphite/carbon/ruthenium composite material powder and the polyacrylamide high molecular polymer solution are uniformly mixed for a second predetermined time.

步驟S40，將步驟S30之漿料均勻混合後加熱到一第一預定溫度使溶劑揮發，以獲得一粉料。In step S40, the slurry of step S30 is uniformly mixed and heated to a first predetermined temperature to volatilize the solvent to obtain a powder.

步驟S50，將該粉料經真空烘箱以一第二預定溫度加熱乾燥，持溫時間為一第三預定時間，即得到本發明之人造石墨複合材，並將其作為一鋰離子電池負極材料。In step S50, the powder is heated and dried in a vacuum oven at a second predetermined temperature for a third predetermined time, that is, the artificial graphite composite of the present invention is obtained and used as a negative electrode material of a lithium ion battery.

在本實施例中，該聚丙烯胺高分子聚合物係指一聚苯胺(Polyaniline)、一聚苯硫醚(Polyphenylene Sulfide)、一聚吡咯(Polypyrrole)、一聚噻吩磺酸鹽類(PEDOT)、一聚乙炔系、一聚噻唑系、一聚烯N基胺類等。In the present embodiment, the polyacrylamide polymer refers to polyaniline, polyphenylene sulfide, polypyrrole, polythiophene sulfonate (PEDOT). , a polyacetylene system, a polythiazole system, a polyene N-amine, and the like.

在本實施例中，該聚丙烯胺高分子聚合物與該去離子水進行攪拌混合之第一預定時間為需持續10~50分鐘，使該聚丙烯胺高分子聚合物能夠完全溶解在該去離子水中。In this embodiment, the first predetermined time for the polyacrylamide high molecular polymer to be stirred and mixed with the deionized water is required to last for 10 to 50 minutes, so that the polyacrylamide high molecular polymer can be completely dissolved therein. Ionic water.

在本實施例中，該人造石墨、該煤焦瀝青和該奈米矽混合後經由該高溫碳化程序形成該人造石墨/碳/矽複合材料之步驟中，該高溫碳化程序為一碳化熱處理，在該碳化熱處理期間通入一氮氣(N2)作為保護，並將該碳化熱處理之升溫速度以1~10℃/min，升至所需熱處理的溫度800~1200℃，且持續進行該碳化熱處理的持溫處理時間為1~15小時，待該碳化熱處理完畢後，讓該人造石墨/碳/矽複合材料冷卻再取出，再對該人造石墨/碳/矽複合材料添加固含量0.1~20wt%的聚丙烯胺高分子聚合物溶液，將兩者均勻攪拌一第四預定時間，待均勻攪拌完全後，再經一加熱乾燥程序，而該加熱乾燥程序則控制在一第三預定溫度及一第五預定時間內，便可得到由該聚丙烯胺高分子聚合物包覆之人造石墨/碳/矽複合材料粉體。In this embodiment, in the step of forming the artificial graphite/carbon/ruthenium composite material by mixing the artificial graphite, the coal tar pitch and the nano bismuth, the high temperature carbonization process is a carbonization heat treatment. During the carbonization heat treatment, a nitrogen gas (N 2 ) is introduced as a protection, and the temperature increase rate of the carbonization heat treatment is raised to a temperature of 800 to 1200 ° C at a temperature of 1 to 10 ° C/min, and the carbonization heat treatment is continued. The temperature treatment time is 1 to 15 hours. After the carbonization heat treatment is completed, the artificial graphite/carbon/ruthenium composite material is cooled and then taken out, and the artificial graphite/carbon/ruthenium composite material is added with a solid content of 0.1 to 20 wt%. The polyacrylamide high molecular polymer solution is uniformly stirred for a fourth predetermined time, after being uniformly stirred completely, and then subjected to a heating drying process, and the heating and drying process is controlled at a third predetermined temperature and a fifth The artificial graphite/carbon/ruthenium composite powder coated with the polyacrylamide polymer can be obtained within a predetermined period of time.

再者，將該人造石墨/碳/矽複合材料與該聚丙烯胺高分子聚合物溶液進行攪拌的第四預定時間為10~120分鐘，而該加熱乾燥程序的第三預定溫度為100~200℃，及該第五預定時間為30~120分鐘。Furthermore, the fourth predetermined time for stirring the artificial graphite/carbon/ruthenium composite material and the polyacrylamide high molecular polymer solution is 10 to 120 minutes, and the third predetermined temperature of the heating and drying program is 100 to 200. °C, and the fifth predetermined time is 30 to 120 minutes.

又，該人造石墨、該煤焦瀝青和該奈米矽混合後，經過該高溫碳化程序，會使該煤焦瀝青在高溫中裂解成一低結晶碳，該低結晶碳會在該人造石墨和該奈米矽上形成一低結晶碳披覆，使得該奈米矽包覆在該人造石墨上形成一複合材料，再將該聚丙烯胺高分子聚合物包覆在該複合材料上，形成穩定石墨的層狀結構，並同時對該奈米矽之體積膨脹有緩衝效應，讓該奈米矽在高溫中不會膨脹過度。Moreover, after the artificial graphite, the coal tar pitch and the nano bismuth are mixed, the high temperature carbonization process causes the coal tar pitch to be cracked into a low crystalline carbon at a high temperature, and the low crystalline carbon will be in the artificial graphite and the Forming a low-crystalline carbon coating on the nano-ply, so that the nano-ruthenium is coated on the artificial graphite to form a composite material, and the polyacrylamide high-molecular polymer is coated on the composite material to form stable graphite. The layered structure, and at the same time, has a buffering effect on the volume expansion of the nano 矽, so that the nano 矽 does not expand excessively at high temperatures.

在本實施例中，該人造石墨/碳/矽複合材料粉體與該聚丙烯胺高分子聚合物溶液進行均勻混合的第二預定時間為1~3小時。In this embodiment, the artificial graphite/carbon/ruthenium composite material powder is uniformly mixed with the polyacrylamide high molecular polymer solution for a second predetermined time of 1 to 3 hours.

而該人造石墨/碳/矽複合材料粉體與該聚丙烯胺高分子聚合物溶液均勻混合後，進行加熱到該第一預定溫度，其所需的溫度為70~90℃。After the artificial graphite/carbon/ruthenium composite material powder is uniformly mixed with the polyacrylamide high molecular polymer solution, it is heated to the first predetermined temperature, and the temperature required is 70 to 90 °C.

在本實施例中，將所獲得的粉料在真空烘箱以該第二預定溫度進行加熱乾燥，並持續加熱在該第三預定時間，其中該第二預定溫度所需的溫度為100~200℃，該第三預定時間為8~12小時。In this embodiment, the obtained powder is heated and dried in the vacuum oven at the second predetermined temperature, and is continuously heated at the third predetermined time, wherein the temperature required for the second predetermined temperature is 100 to 200 ° C. The third predetermined time is 8 to 12 hours.

參看表1所示，樣本A1與A2、A3為經由不同的複合材配製而成，其中樣本A1為一人造石墨和一煤焦瀝青(重量比20:4)均勻混合後經熱處理1000℃/1小時，配置成一人造石墨碳複合材料。樣本A2為一人造石墨、一煤焦瀝青和一奈米矽(重量比20:4:3)均勻混合後經熱處理1000℃/1小時，配置成一人造石墨/碳/矽複合材料。樣本A3為該人造石墨/碳/矽複合材料粉末(重量比20:4:3)和該聚丙烯胺高分子聚合物溶液(固含量3 wt%)均勻混加熱80℃後，在放入100℃真空烘箱內進行乾燥所得之粉體。Referring to Table 1, samples A1 and A2 and A3 were prepared through different composite materials, wherein sample A1 was uniformly mixed with an artificial graphite and a coal tar pitch (weight ratio of 20:4) and then heat treated at 1000 ° C / 1 Hours, configured as an artificial graphite carbon composite. Sample A2 was uniformly mixed with an artificial graphite, a coal tar pitch and a nano 矽 (weight ratio of 20:4:3) and then heat treated at 1000 ° C / 1 hour to form an artificial graphite / carbon / ruthenium composite material. Sample A3 is a mixture of the artificial graphite/carbon/bismuth composite powder (weight ratio 20:4:3) and the polyacrylamide high molecular polymer solution (solid content 3 wt%) uniformly heated at 80 ° C, and then placed in 100 The powder obtained by drying in a vacuum oven at °C.

請參閱第2(a)圖至第2(d)圖所示，為該人造石墨/碳/奈米矽複合材料，及該聚丙烯胺高分子聚合物包覆球型人造石墨/碳/奈米矽複合材料之掃描式電子顯微鏡(SEM)分析，其中第2(a)圖為球型人造石墨表面型態，第2(b)圖可以看出當瀝青包覆球型人造石墨經碳化，其表面較無包覆時光滑，第2(c)圖為煤焦瀝青包覆球型人造石墨及15 wt%奈米矽經碳化，可以看出奈米矽分佈在球型人造石墨上，第2(d)圖為聚丙烯胺包覆球型人造石墨/碳/奈米矽，可以發現石墨與石墨之間較無凝聚在一起，且表面比無聚丙烯胺包覆時還光滑，所以樣本A3有較佳的表面特性。Please refer to Figures 2(a) to 2(d) for the artificial graphite/carbon/nano-ruthenium composite, and the polyacrylamide high molecular polymer coated spherical artificial graphite/carbon/nai Scanning electron microscopy (SEM) analysis of rice bran composites, in which the second (a) figure shows the surface type of spherical artificial graphite, and the second (b) shows that when the pitch-coated spherical artificial graphite is carbonized, The surface is smoother than when it is not coated. The second (c) picture shows that the coal tar pitch coated spherical artificial graphite and 15 wt% nano 矽 are carbonized, and it can be seen that the nano 矽 is distributed on the spherical artificial graphite. 2(d) is a polyacrylamide-coated spherical artificial graphite/carbon/nanophthalene. It can be found that there is no aggregation between graphite and graphite, and the surface is smoother than that without polyamine coating, so the sample is A3 has better surface characteristics.

在本實施中，該人造石墨/碳/奈米矽複合材料在製作過程中，為使用固含量在5~20wt%的奈米矽與該人造石墨、該煤焦瀝青混合後，經該高溫碳化程序製作成該人造石墨/碳/矽複合材料，該人造石墨和製作完成之人造石墨/碳/矽複合材料為一球型狀，而在第2(c)圖中的人造石墨/碳/矽複合材料為使用固含量15wt%的奈米矽與該人造石墨、該煤焦瀝青混合，再經該高溫碳化程序製作而成。In the present embodiment, the artificial graphite/carbon/nano-ruthenium composite material is carbonized by the high-temperature carbonization after mixing with the artificial graphite and the coal tar pitch using a nano-plutonium having a solid content of 5 to 20 wt%. The process is made into the artificial graphite/carbon/bismuth composite material, which is a spherical shape of the finished artificial graphite/carbon/bismuth composite material, and the artificial graphite/carbon/矽 in the second (c) diagram. The composite material is prepared by mixing nano-ruthenium having a solid content of 15% by weight with the artificial graphite and the coal tar pitch, and then performing the high-temperature carbonization process.

以下是將該石墨複合材樣本A1、A2、A3之粉體，作為鋰離子動力電池負極材料塗佈與電池組裝之實施例：電池負極材料塗佈：The following is an example of coating the powder of the graphite composite samples A1, A2, and A3 as a negative electrode material for lithium ion battery and battery assembly: battery negative material coating:

1.先將0.1wt%微量草酸與10wt%之聚偏氟乙烯(Polyvinylidene fluoride(PVDF))黏結劑(Binder)，混入一N-甲基呲咯烷酮(N-methyl prrolidone(NMP))溶劑中，均勻攪拌20分鐘，使得該聚偏氟乙烯(PVDF)能均勻分散於該NMP溶劑之混合液中。1. First mix 0.1wt% trace oxalic acid with 10wt% polyvinylidene fluoride (PVDF) binder (Binder), mixed with N-methyl porolidone (NMP) solvent The mixture was uniformly stirred for 20 minutes to uniformly disperse the polyvinylidene fluoride (PVDF) in the mixed solution of the NMP solvent.

2.將該石墨複合材A1、A2、A3粉末置入攪拌均勻之該混合液，持續攪拌20分鐘。2. The powder of the graphite composites A1, A2, and A3 was placed in the mixture which was uniformly stirred, and stirring was continued for 20 minutes.

3.該混合液形成泥漿狀物，以130μm刮刀均勻塗佈在一銅箔上，以100℃烘乾去除殘留溶劑，以25%之碾壓率進行碾壓，再以150℃烘乾。3. The mixture was formed into a slurry, uniformly coated on a copper foil with a 130 μm doctor blade, dried at 100 ° C to remove residual solvent, crushed at a rolling ratio of 25%, and dried at 150 ° C.

電池組裝：Battery assembly:

1.將塗佈完整之負極極片裁成直徑13 mm的圓板，正極極片則採用一鋰金屬箔片。1. The coated negative electrode piece is cut into a circular plate with a diameter of 13 mm, and the positive electrode piece is made of a lithium metal foil.

2.將一硬幣型電池所需之組件，於乾燥氣氛控制室中依序組裝，並添加一電解質液(1M LiPF6(溶質)，EC+EMC+DMC(溶劑)，而該EC+EMC+DMC(溶劑)的溶液比例為1:1:1)，即完成該硬幣型電池。2. Assemble the components required for a coin-type battery in a dry atmosphere control room, and add an electrolyte solution (1M LiPF 6 (solute), EC+EMC+DMC (solvent), and the EC+EMC+ The solution ratio of DMC (solvent) was 1:1:1), that is, the coin type battery was completed.

3.將組裝完成之硬幣型電池進行連續充放電性能測試，其充放電速率為0.2 C，定電流密度進行連續充放電50次，充電截止電壓為2 V(vs. Li/Li+)，放電截止電壓為0.005V(vs. Li/Li+)。3. The assembled coin-type battery was tested for continuous charge and discharge performance. The charge and discharge rate was 0.2 C, the continuous current density was continuously charged and discharged 50 times, and the charge cut-off voltage was 2 V (vs. Li/Li + ). The cutoff voltage is 0.005 V (vs. Li/Li + ).

4.將組裝完成之硬幣型電池進行交流阻抗分析，頻率範圍為10-2-106 Hz，施以一微小的擾動電壓20mV AC振幅(Amplitude)，將測試樣品塗佈並組裝成該硬幣型電池，在OCV之下以及該硬幣型電池經充放電後，測試其交流阻抗頻譜的變化。4. The assembled coin-type battery is subjected to AC impedance analysis at a frequency range of 10 -2 -10 6 Hz, and a small disturbance voltage of 20 mV AC amplitude (Amplitude) is applied to coat and assemble the test sample into the coin type. The battery, under the OCV and after the coin-type battery is charged and discharged, tests the change in the AC impedance spectrum.

請參閱第3圖所示，從圖中可以看到樣本A1(AG/C)、樣本A2(AG/C/Si)、樣本A3(AG/C/Si/PAA)的第一次放電電容量，分別為332、475.6和448.3 mAhg-1。在第一次充放電之不可逆電容量中樣本A2(AG/C/Si)有較大的不可逆電容量為95.0mAhg-1。原因為當在製備材料時因著研磨過篩造成部分奈米矽外露至表面，使該奈米矽直接與該電解液接觸造成不穩定的固態電解液界面薄膜(SEI)的產生，所以造成有較大的第一次不可逆電容量。另外，由樣本A3可發現利用該聚丙烯胺高分子聚合物包覆該人造石墨/碳/奈米矽複合材料時，因為可以防止外露的奈米矽直接與該電解液接觸，而形成穩定的固態電解液界面薄膜，所以使得第一次不可逆電容量由95.0下降至55.0 mAhg-1。如下表2所示：明顯看出樣本A3有較佳的電化學特性。Please refer to Figure 3 for the first discharge capacity of sample A1 (AG/C), sample A2 (AG/C/Si), and sample A3 (AG/C/Si/PAA). , 332, 475.6 and 448.3 mAhg -1 respectively . In the irreversible capacity of the first charge and discharge, the sample A2 (AG/C/Si) had a large irreversible capacity of 95.0 mAhg -1 . The reason is that when the material is prepared, a part of the nano enamel is exposed to the surface due to the grinding, so that the nano 矽 directly contacts the electrolyte to cause an unstable solid electrolyte interface film (SEI), so Larger first irreversible capacity. In addition, it can be found from the sample A3 that when the artificial graphite/carbon/nano-ruthenium composite material is coated with the polyacrylamide high-molecular polymer, since the exposed nano bismuth can be prevented from directly contacting the electrolyte, a stable formation is formed. The solid electrolyte interface film, so the first irreversible capacity decreased from 95.0 to 55.0 mAhg -1 . As shown in Table 2 below: It is apparent that sample A3 has better electrochemical properties.

請參閱第4圖所示，可以看到石墨複合材A1、A2、A3的循環次數與放電容量關係圖，由圖可發現樣本A2(AG/C/Si)起初有較高的放電電容量，但隨著循環次數的增加而放電電容量大幅的下降。而樣本A3(AG/C/Si/PAA)則有較好的循環穩定度。在50次充放電循環後的電容量保持率樣本A3高於樣本A2，所以利用該聚丙烯胺高分子聚合物包覆，不僅將材料表面改質增加韌性，還能防止材料直接接觸到該電解液時造成材料上的變質，而且還可以防止進行充放電時該奈米矽的膨脹所造成極片的龜裂，由上可知，該石墨奈米矽複合材料添加了該聚丙烯胺高分子聚合物後，除了可填補原本石墨表面包覆經碳化熱處理所造成非晶質碳的微孔洞外，該聚丙烯胺高分子聚合物也可以改善該奈米矽經充放電時所產生的膨脹特性，提升材料的穩定度，因此A3複合材會有較高的電容量與較佳的循環穩定性。Referring to Figure 4, you can see the relationship between the number of cycles of the graphite composites A1, A2, and A3 and the discharge capacity. It can be seen from the figure that the sample A2 (AG/C/Si) initially has a higher discharge capacity. However, as the number of cycles increases, the discharge capacity drops significantly. Sample A3 (AG/C/Si/PAA) has better cycle stability. The capacity retention rate sample A3 after 50 charge and discharge cycles is higher than the sample A2, so the use of the polyacrylamide high molecular polymer coating not only improves the surface of the material to increase the toughness, but also prevents the material from directly contacting the electrolysis. When the liquid causes deterioration of the material, it can also prevent cracking of the pole piece caused by the expansion of the nano bismuth during charging and discharging. It is known from the above that the graphite nano 矽 composite material is added with the polyacrylamide polymer polymerization. After the material, in addition to filling the micropores of the amorphous carbon surface caused by the carbonization heat treatment on the surface of the graphite, the polyacrylamide high molecular polymer can also improve the expansion characteristics of the nano enamel during charge and discharge. To improve the stability of the material, the A3 composite has higher capacitance and better cycle stability.

請參閱第5圖所示，為該聚丙烯胺高分子聚合物包覆球型人造石墨/碳/奈米矽複合材料之交流阻抗分析圖譜。從圖中可以發現一半圓屬較高頻率範圍以及小半圓的附近為較低頻率範圍。在較高頻率範圍的半圓可以觀察出由固態電解液界面薄膜(SEI)所產生的阻抗，在較低頻率範圍可以觀察出由電子轉移時所產生的阻抗。由圖中可以看到樣本A2(AG/C/Si)有較高的界面電阻，原因為固態電解液界面薄膜(SEI)所造成的，所以使得有較高的第一次不可逆電容量。當利用PAA高分子聚合物包覆AG/C/Si時(如樣本A3)，發現降低了固態電解液界面薄膜(SEI)及電荷轉移所產生的電阻。所以可以知道PAA高分子聚合物包覆AG/C/Si，可以降低比表面積(BET)，減少與該電解液直接的接觸，可降低固態電解液界面薄膜(SEI)所產生的阻抗。另外，PAA高分子聚合物也提供了極片良好的導電網，可增加電子的傳導，降低電荷轉移所產生的電阻。由上可知，該聚丙烯胺高分子聚合物成功包覆在該球型狀之人造石墨/碳/奈米矽複合材料，能防止因充放電之後奈米矽的膨脹使得極片的龜裂造成電容量大幅的下降。所以利用該聚丙烯胺高分子聚合物包覆該球型狀之人造石墨/碳/奈米矽複合材料，不僅能改善充放電循環穩定度，也能減少固態電解液界面薄膜(SEI)所造成的電阻。Please refer to Figure 5 for the AC impedance analysis of the polyacrylamide polymer coated spherical artificial graphite/carbon/nano-ruthenium composite. It can be seen from the figure that the half circle belongs to the higher frequency range and the vicinity of the small semicircle is the lower frequency range. The impedance produced by the solid electrolyte interface film (SEI) can be observed in a semicircle of a higher frequency range, and the impedance generated by electron transfer can be observed in a lower frequency range. It can be seen from the figure that the sample A2 (AG/C/Si) has a higher interface resistance due to the solid electrolyte interface film (SEI), so that it has a higher first irreversible capacitance. When the PAA polymer was coated with AG/C/Si (such as sample A3), it was found that the resistance generated by the solid electrolyte interface film (SEI) and charge transfer was lowered. Therefore, it can be known that the PAA polymer coated with AG/C/Si can reduce the specific surface area (BET), reduce the direct contact with the electrolyte, and reduce the impedance generated by the solid electrolyte interface film (SEI). In addition, PAA polymer also provides a good conductive mesh for the pole piece, which can increase the conduction of electrons and reduce the resistance generated by charge transfer. It can be seen from the above that the polyacrylamide high molecular polymer is successfully coated on the spherical artificial graphite/carbon/nano-ruthenium composite material, which can prevent the crack of the pole piece caused by the expansion of the nano-pick after the charge and discharge. The capacity has dropped dramatically. Therefore, coating the spherical artificial graphite/carbon/nano-ruthenium composite material with the polyacrylamide high-molecular polymer can not only improve the stability of the charge-discharge cycle, but also reduce the solid electrolyte interface film (SEI). The resistance.

藉此可知，本發明改質人造石墨作為鋰電池負極材料之及其製備方法，由該聚丙烯胺高分子聚合物與該去離子水混合該第一預定時間，以獲得該聚丙烯胺高分子聚合物溶液，接續將該人造石墨、該煤焦瀝青和該奈米矽混合後經由該高溫炭化程序形成該人造石墨/碳/矽複合材料之粉體，再將該人造石墨/碳/矽複合材料粉體和該聚丙烯胺高分子聚合物溶液均勻混合該第二預定時間，以獲得均勻混合之漿料，並對該漿料加熱到該第一預定溫度使溶劑揮發後，獲得該粉料，且將該粉料經真空烘箱以該第二預定溫度加熱乾燥，持溫時間為該第三預定時間，最後獲得該人造石墨複合材，因該人造石墨複合材被該聚丙烯胺高分子聚合物所包覆，在製成該鋰離子電池負極材料後，能夠藉以改善該鋰電池充放電的循環穩定度及減少固態電解液界面薄膜(SEI)所造成的電阻之目的。It can be seen that the modified artificial graphite of the present invention is used as a negative electrode material for a lithium battery and a preparation method thereof, and the polyacrylamide high molecular polymer is mixed with the deionized water for the first predetermined time to obtain the polyacrylamide polymer. a polymer solution, which is followed by mixing the artificial graphite, the coal tar pitch and the nano bismuth to form a powder of the artificial graphite/carbon/germanium composite material through the high-temperature carbonization process, and then the artificial graphite/carbon/germanium composite The material powder and the polyacrylamide high molecular polymer solution are uniformly mixed for the second predetermined time to obtain a uniformly mixed slurry, and the slurry is heated to the first predetermined temperature to volatilize the solvent to obtain the powder. And heating the powder to the second predetermined temperature in a vacuum oven for a third predetermined time, and finally obtaining the artificial graphite composite material, wherein the artificial graphite composite material is polymerized by the polyacrylamide polymer The material is coated, and after the anode material of the lithium ion battery is fabricated, the cycle stability of the lithium battery charge and discharge can be improved and the resistance caused by the solid electrolyte interface film (SEI) can be reduced. Purpose.

上列詳細說明係針對本發明之一可行實施例之具體說明，惟該實施例並非用以限制本發明之專利範圍，凡未脫離本發明技藝精神所為之等效實施或變更，均應包含於本案之專利範圍中。The detailed description of the preferred embodiments of the present invention is intended to be limited to the scope of the invention, and is not intended to limit the scope of the invention. The patent scope of this case.

S10~S50．．．步驟S10~S50. . . step

第1圖為本發明人造石墨/碳/奈米矽複合材料之製備流程圖；Figure 1 is a flow chart showing the preparation of the artificial graphite/carbon/nano-ruthenium composite material of the present invention;

第2圖為本發明人造石墨複合材料經掃描式電子顯微鏡(SEM)掃描後之電子顯示圖；2 is an electronic display diagram of the artificial graphite composite material of the present invention after scanning electron microscope (SEM) scanning;

第3圖為人造石墨複合材料樣本A1、A2、A3之充放電電容量圖；Figure 3 is a charge and discharge capacity diagram of artificial graphite composite samples A1, A2, and A3;

第4圖為人造石墨複合材料樣本A1、A2、A3之50次循環次數之放電電容量圖；以及Figure 4 is a discharge capacity diagram of the number of cycles of the artificial graphite composite samples A1, A2, and A3;

第5圖為人造石墨複合材料樣本A1、A2、A3之交流阻抗分析圖譜。Figure 5 is an AC impedance analysis of artificial graphite composite samples A1, A2, and A3.

S10~S50．．．步驟S10~S50. . . step

Claims (10)

一種改質人造石墨作為鋰電池負極材料之製備方法，包括下列步驟：一聚丙烯胺高分子聚合物溶解於一去離子水，並攪拌混合一第一預定時間，以獲得一聚丙烯胺高分子聚合物溶液；將一人造石墨、一煤焦瀝青和一奈米矽混合後經由一高溫炭化程序形成一人造石墨/碳/矽複合材料之粉體；將該人造石墨/碳/矽複合材料粉體和該聚丙烯胺高分子聚合物溶液均勻混合一第二預定時間；將前一步驟之漿料均勻混合後加熱到一第一預定溫度使溶劑揮發，以獲得一粉料；以及將該粉料經真空烘箱以一第二預定溫度加熱乾燥，持溫時間為一第三預定時間，以獲得一人造石墨複合材，並將人造石墨複合材製成一鋰離子電池負極材料。A modified artificial graphite as a preparation method of a lithium battery anode material comprises the following steps: a polyacrylamide high molecular polymer is dissolved in a deionized water, and stirred and mixed for a first predetermined time to obtain a polyacrylamide polymer a polymer solution; mixing an artificial graphite, a coal tar pitch and a nano bismuth to form a powder of an artificial graphite/carbon/ruthenium composite material through a high temperature carbonization process; the artificial graphite/carbon/ruthenium composite material powder And uniformly mixing the polyacrylamide polymer solution for a second predetermined time; uniformly mixing the slurry of the previous step and heating to a first predetermined temperature to volatilize the solvent to obtain a powder; and the powder The material is heated and dried by a vacuum oven at a second predetermined temperature for a third predetermined time to obtain an artificial graphite composite material, and the artificial graphite composite material is made into a lithium ion battery anode material. 如申請專利範圍第1項所述之製備方法，其中該第一預定時間，係為以10至15分鐘持續攪拌混合。The preparation method of claim 1, wherein the first predetermined time is continuous stirring for 10 to 15 minutes. 如申請專利範圍第1項所述之製備方法，其中該第二預定時間，係為以1至3小時進行均勻混合。The preparation method of claim 1, wherein the second predetermined time is uniform mixing for 1 to 3 hours. 如申請專利範圍第1項所述之製備方法，其中該第一預定溫度，係為以70至90℃的溫度進行加熱。The preparation method of claim 1, wherein the first predetermined temperature is heating at a temperature of 70 to 90 °C. 如申請專利範圍第1項所述之製備方法，其中該第二預定溫度，係為以100至200℃的溫度持續加熱。The preparation method according to claim 1, wherein the second predetermined temperature is continuous heating at a temperature of 100 to 200 °C. 如申請專利範圍第1項所述之製備方法，其中該第三預定時間，係為以8至12小時的時間進行加熱乾燥。The preparation method according to claim 1, wherein the third predetermined time is heat drying in a period of 8 to 12 hours. 如申請專利範圍第1項所述之製備方法，其中該高溫碳化程序，係為一碳化熱處理，在該碳化熱處理期間通入一氮氣(N2)作為保護，並將該碳化熱處理之升溫速度以1~10℃/min，升至所需熱處理的溫度800~1200℃，且持續進行該碳化熱處理的持溫處理時間為1~15小時，待該碳化熱處理完畢後，讓該人造石墨/碳/矽複合材料冷卻再取出，再對該人造石墨/碳/矽複合材料添加固含量0.1~20wt%的聚丙烯胺高分子聚合物溶液，將兩者均勻攪拌一第四預定時間，待均勻攪拌完全後，再經一加熱乾燥程序，而該加熱乾燥程序則控制在一第三預定溫度及一第五預定時間內，便可得到由該聚丙烯胺高分子聚合物包覆之人造石墨/碳/矽複合材料粉體。The preparation method according to claim 1, wherein the high-temperature carbonization process is a carbonization heat treatment, during which a nitrogen gas (N 2 ) is introduced as a protection, and the temperature increase rate of the carbonization heat treatment is 1~10 °C / min, the temperature to the desired heat treatment is 800~1200 °C, and the temperature holding treatment time of the carbonization heat treatment is 1~15 hours. After the carbonization heat treatment is completed, the artificial graphite/carbon/ The composite material is cooled and then taken out, and a polyamine polymer solution having a solid content of 0.1 to 20% by weight is added to the artificial graphite/carbon/ruthenium composite material, and the two are uniformly stirred for a fourth predetermined time, and the mixture is completely stirred. Then, after a heating and drying process, and the heating and drying process is controlled at a third predetermined temperature and a fifth predetermined time, the artificial graphite/carbon coated by the polyacrylamide polymer can be obtained.矽 Composite powder. 如申請專利範圍第7項所述之製備方法，其中該第四預定時間，係為以10至120分鐘進行均勻攪拌。The preparation method according to claim 7, wherein the fourth predetermined time is uniform stirring for 10 to 120 minutes. 如申請專利範圍第7項所述之製備方法，其中該第三預定溫度，係為以100至200℃的溫度進行加熱乾燥程序。The preparation method according to claim 7, wherein the third predetermined temperature is a heating and drying process at a temperature of 100 to 200 °C. 如申請專利範圍第7項所述之製備方法，其中該第五預定時間，係為以30至120分鐘進行加熱乾燥程序。The preparation method according to Item 7, wherein the fifth predetermined time is a heating and drying process of 30 to 120 minutes.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114156485A (en) * 2020-09-07 2022-03-08 黄炳照 Composite modification layer and application thereof in anode-free lithium battery
WO2023039074A1 (en) * 2021-09-08 2023-03-16 Koppers Delaware, Inc. Dispersion of coal tar pitch for coating graphitic materials and use in li-ion battery electrode production

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TWI660539B (en) * 2018-02-14 2019-05-21 國家中山科學研究院 Silicon-carbon anode material coated with nano-silicon with asphalt and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114156485A (en) * 2020-09-07 2022-03-08 黄炳照 Composite modification layer and application thereof in anode-free lithium battery
WO2023039074A1 (en) * 2021-09-08 2023-03-16 Koppers Delaware, Inc. Dispersion of coal tar pitch for coating graphitic materials and use in li-ion battery electrode production

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