TWI302761B - Coated carbonaceous particles particularly useful as electrode materials in electrical storage cells, and methods of making the same - Google Patents

Description

1302761 玖、發明說明： 【發明所屬之技術領域】 本申請案係2002年1月31日提出申請之仍在申請中之申 請案第10/066,080號的部分延續。 明 本發明係關於有用作為電池之電極的石墨材料。更特定 言之，本發明係、關於特別有用作為電極材料之塗覆的碳質 顆粒，以及該塗覆之碳質顆粒之製備方法。 【先前技術】 碳質材料由於其之效率及合理成本而被廣泛使用於亦 稱為「電池」之蓄電池中。有各種形式的碳質材料被使用 。-此種碳質材料為石墨，已知其有用於亦稱為「可再充 電電池」之可再充電的蓄電池。在一顯著的例子中，已知 石墨材料有用作為可再充電之㈣子「u_離子」蓄電池中 之陽極材料。U-離子電池主要被使用作為可搞式ϋ裝 中之電源。 相對於其他種類的可再充電電池，即例如，鏡-鶴及鎳 金屬氫化物蓄電池，L1·離子電池由料之相當高的儲 量=其ΐ易再充電特性而愈來愈受歡迎。基於此種每單 位質量或單位體積之較高的儲存容量，由於其較類似等級 的鎳-鎘及鎳-金屬氫化物蓄電池小，因而可製造滿足特定 儲存及電流傳送需求的Li_離予電池。因此，^_離子電池 廣被使用於愈來愈多的裝置，即 电/ 、咖^ 目機、數位錄影機 “.，八中由效用或消費者的觀點來看特別希访 小尺寸的裝置。然而，可再充電之-離予蓄電池並非沒；1302761 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The present invention relates to a graphite material useful as an electrode for a battery. More specifically, the present invention relates to a coated carbonaceous particle particularly useful as an electrode material, and a process for producing the coated carbonaceous particle. [Prior Art] Carbonaceous materials are widely used in batteries called "batteries" because of their efficiency and reasonable cost. Various forms of carbonaceous materials are used. - This carbonaceous material is graphite, which is known for use in rechargeable batteries, also known as "rechargeable batteries." In a significant example, graphite materials are known to be useful as anode materials in rechargeable (IV) sub-"u_ion" batteries. U-ion batteries are mainly used as power sources in the armored package. Compared to other types of rechargeable batteries, i.e., mirror-heel and nickel metal hydride batteries, L1·ion batteries are increasingly popular due to their relatively high reserves = their easy recharging characteristics. Based on such higher storage capacity per unit mass or unit volume, because of its smaller rating of nickel-cadmium and nickel-metal hydride batteries, it is possible to manufacture Li_off batteries that meet specific storage and current delivery requirements. . Therefore, ^_ ion batteries are widely used in more and more devices, namely electric /, coffee machine, digital video recorder "., eight from the point of view of utility or consumer's point of view, especially visit small-sized devices However, the rechargeable-discharged battery is not without;

S6864.DOC 1302761 缺點，其中部分係視其之構造材料而定。 普遍類型的Ll-離子蓄電池包括由中間相碳微雜 或微米尺寸化中間相錢維（MMCF)形成之電柄。炊而， 1 於此等材料所需之相當複雜的製程，因而—Μ:及 觀CF皆相當昂貴。其他類型的Li_離子蓄電池包括由衍生 =屯化天㈣墨或合成石墨之粉碎或研磨石墨 電雖然此等材料展現令人滿έ的儲存容量，但不幸地 、、於其ϋ環中展現低的起始充電效率。血刑上， 此寺材料之充電效率範圍寬廣，通常係自低至約飢 至約9〇%。已知此等粉碎或研磨石墨材料之效率係強列地 ; 見粉：或研磨石墨顆粒之形態而定。此等粉狀之粉碎或研 材料，其〈不規則的特性，因而其經常會有低殖 度’此會限制由其㈣之任何電㈣ 艮 :=充電之蓄電池的操作特性。此外，由於其之Li :::广要將此等粉狀之粉碎或研磨石墨材料加工成 在此種由粉狀之粉碎或研磨石墨材料形成 粉狀材斜、本不艮的^作特性邵分係可歸因於在此等 &lt;表面上形成鈍性薄膜所致。 薄膜描述為固態電解質界面(「阳」)。此8 = =耗可計量之量，經常係顯著量之當電池組= ，予在於陰極中㈣離予（典型上係15至5〇%)。 因此’技藝中確實持續需要“於蓄電 之可再充電之蓄電池之製造的心： π 要有用於此種蓄電池之製造之改良材料的改艮製S6864.DOC 1302761 Disadvantages, some of which are dependent on the material of construction. A common type of L1-ion battery includes an electric handle formed of mesophase carbon micro- or micro-sized mesophases (MMCF). , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , Other types of Li_ion batteries include pulverized or ground graphite by derivatization = bismuth (four) ink or synthetic graphite. Although these materials exhibit a pleasing storage capacity, unfortunately, they exhibit low levels in the ankle ring. The initial charging efficiency. In terms of bloody punishment, this temple material has a wide range of charging efficiencies, usually from as low as about hunger to about 9%. It is known that the efficiency of such pulverized or ground graphite materials is strong; see powder: or the morphology of the ground graphite particles. Such powdered pulverized or ground materials have <irregular characteristics, so they often have low colonization' which limits the operating characteristics of any battery (4) 艮 := charged by its (4). In addition, due to its Li ::: extensively, these powdered pulverized or ground graphite materials are processed into such a powdery material that is pulverized or ground by a powdery pulverized or ground graphite material. The lineage can be attributed to the formation of a passive film on these &lt;surfaces. The film is described as a solid electrolyte interface ("yang"). This 8 = = measurable amount, often a significant amount when the battery pack =, in the cathode (four) away (typically 15 to 5 〇%). Therefore, there is a real need in the art for the manufacture of rechargeable batteries for storage of electricity: π There must be a modification of improved materials for the manufacture of such batteries.

86864.DOC ^02761 万去，以及包含該改良材料 【發明内容】 良材枓〈改艮的蓄電池。 本發明之一態樣提供包各涂费、山 ^ ^ μ ^ ^ Im ^όϋ ^ μ # ^ 塗層亦可經石墨化。此等塗:：:成，且此 蓄:：，特別係可再充電之蓄電池;:::其〜 生自各種來源。另外，心==率的碳材料，其可衍 並他舲丛 為有用包極或未明確說明於此之 ’、太所需之任何操作或製造步驟中尤其有利。 毛月义再一怨樣為具有由經氧化之碳殘留物形忒# 料形成之實質以㈣m ^物开乂成材 此塗層亦可經石墨化。 叙’覆的碳質顆粒， 法本裔明《再—態樣提供此種塗覆之碳質顆粒的製備方 ，本發明之又再—態樣係關於該塗覆之碳質顆粒於蓄兩 池’尤其係於可再充電之電池中之用途。 ： 備得之塗覆粉末不僅可描*古+ 式乃所氣 製造的優異加工性冋无笔效率，並且亦可提供電極 本發明之又再—態樣提供包括該塗覆之碳質顆粒之誓 電池’尤其係可再充電電池的製備方法。 &quot; 本發明义此等及其他態樣及特徵將可由以下之發明說 明及其之較佳具體實施例而更加明白。 Λ ^ 【實施方式】86864.DOC ^02761 million to go, and including the improved material [Summary of the invention] Good material 枓 <modified battery. One aspect of the present invention provides a coating of each coating, and the coating of ^ ^ μ ^ ^ Im ^ όϋ ^ μ # ^ can also be graphitized. These coatings:::, and this storage::, especially rechargeable batteries;::: Its ~ from various sources. In addition, a carbon material having a heart == ratio, which may be derived from any of the operations or manufacturing steps that are too useful or not necessary, is particularly advantageous. Mao Yueyi again complained that it had the essence formed by the oxidized carbon residue, and that the coating could also be graphitized by (4) m ^ material opening. The carbonaceous particles of the coating, the method of preparing the coated carbonaceous particles, the re-synthesis of the present invention relates to the coated carbonaceous particles The pool 'is especially useful for rechargeable batteries. : The prepared coating powder can not only describe the excellent processability and the penless efficiency of the gas production, but also provide the electrode. The re-supplement of the present invention provides the coated carbonaceous particles. The swearing battery is especially a method of preparing a rechargeable battery. This and other aspects and features of the invention will be apparent from the description and appended claims. Λ ^ [Embodiment]

86864.DOC 1302761 本4明&lt; 1樣提供塗覆之碳質顆粒之 此材料使用作為蓄電池，尤其 充：：二^ 極時’其展現改良的操作特性。此方電池中，電 提供碳質材料之顆粒； ：又U下列步~ · 塗：該顆粒之表面上提供可溶解之碳殘留物形成材料之 、、、ϋ由使用氧化劑俊兮觀* 而使塗覆之顆 蜊使Θ顆粒進行氧化反應 粒穩定化； 接著將塗覆之顆粒碳化；及 其後視需要（但其為較佳）將塗覆之顆粒石墨化。 此方法提供具有實質±平滑塗層之顆粒較佳。 本發明之實施需要碳質材料之顆粒。其可得自各種來源 ’其之例子包括㈣、石油及煤洛煤焦、合成及天炊石= 、衍生自有機及天^聚合物之軟相及其他在先前技藝= 極〈製造中已知之碳質材料的來源，雖然在此未說明此； 來源。碳質材料之較佳來源包括烺製或未煅製石油煤焦， 以及天減合成石墨。碳f材料之特佳來源包㈣製^ 娘製之高度結晶的「針狀观。因此，較佳的碳質材料 係石墨或當加熱至220(rc以上之石墨化溫度時形成石墨。 此種材料之微細顆粒係經由研磨、壓碎、磨粉或經由任何 其他可用於提供具有適用於形成電極之顆粒尺寸之粉狀= 質材料之方式而方便地提供。雖然咸信本發明之原理可廯 用至不同大小及顆粒大小分佈之碳質顆粒，但較佳的碳= 顆粒具有至多約1 50微米之平均顆粒大小，自約5微米至約86864.DOC 1302761 This document provides a coated carbonaceous particle which is used as a battery, particularly when it is charged with a second electrode, which exhibits improved handling characteristics. In the battery of the square, the particles of the carbonaceous material are supplied by electricity; : U is the following steps: · Coating: the surface of the particle is provided with a soluble carbon residue forming material, and the ϋ is made by using an oxidizing agent* The coated ruthenium granulates the ruthenium particles by oxidation reaction; the coated granules are then carbonized; and the coated granules are graphitized as desired (but preferred). This method preferably provides particles having a substantial ± smooth coating. The implementation of the present invention requires particles of a carbonaceous material. It can be obtained from a variety of sources - examples of which include (iv), petroleum and coal charcoal, synthesis and sapphire = soft phase derived from organic and natural polymers and others known in the prior art = extreme manufacturing The source of carbonaceous materials, although this is not stated here; source. Preferred sources of carbonaceous materials include tantalum or uncalcined petroleum coal char, as well as sky-reduced synthetic graphite. The special source of carbon f material (4) is a highly crystalline "needle-like view" made by Niang. Therefore, the preferred carbonaceous material is graphite or graphite when heated to 220 (the graphitization temperature above rc). The fine particles of the material are conveniently provided by grinding, crushing, milling or by any other means which can be used to provide a powdered material having a particle size suitable for forming an electrode. Carbonaceous particles of varying size and particle size distribution are used, but preferred carbon = particles have an average particle size of up to about 50 microns, from about 5 microns to about

86864.DOC 1302761 70械米更佳，及在約5微米至約々 大+ A估杜τ 心乾Ν内又平均顆粒 為特佳。此外，在此等範圍内，顆粒大小&gt; 不夕於1〇重量％之顆粒小於5微米，不多於 : =微米較佳;此外，除了此-顆粒大小分 二果、粒大小係約1 0微米至約30微米又更佳。 根據本發明古&amp; &gt; i ^ „ 月万法又一步驟，碳質顆粒具有—可 殘留物形成材料作為塗覆材料。可使用作為塗覆㈣之= 佳材料為可與氧化劑反應之碳殘留物形成材料乂 :物包，溶點及於熱分解後具高碳產率 用广塗覆材料的例子包括來自石油、化學製程 = 族殘留物；爽白祕將 重万 木自紙漿工業之木質素；酚系樹脂 ==諸如:及聚丙稀腈。可使用作為塗覆材料之特佳 、及煤“青’及可容易取得且經觀察有效作為 可挺解之碳殘留物㈣㈣之木f素。 乍為 應:瞭碳殘留物形成材料可為當經氧化，接著再在惰性 ϋ熱分解至850。。之碳化溫度或再更高之溫度時形成 員貝上為碳」之殘留物的任何材料。應明瞭「眚皙上為 碳屬示殘留物係至少9〇重量％之碳，以至少95重量％ 人1乂佳％殘留物形成材料當碳化時形成以碳殘留物形 材料之原始質量計至少10%，及以至少40%較佳，及至 少60%更佳之碳殘留物亦較佳。 _可知任何可氧化’接著再熱分解產生碳殘留物之有機化 5物使用作為塗覆材料。然而，在將有機化合物溶解於溶 劑中〈塗覆方法中’包括各種分子量之芳族化合物由於化86864.DOC 1302761 70 mechanical meters are better, and in the range of about 5 microns to about 々 large + A estimated Du τ heart dry 又 inside the average particle is particularly good. Further, in such a range, the particle size &gt; is not less than 5 Å by weight of the particles less than 5 μm, not more than: = μm is preferable; moreover, in addition to this - the particle size is divided into two fruits, and the particle size is about 1 More preferably, from 0 micrometers to about 30 micrometers. According to another step of the present invention, the carbonaceous particles have a residue-forming material as a coating material. It can be used as a coating (4) = a preferred material is a carbon which can react with an oxidizing agent. Residue forming material 乂: package, melting point and high carbon yield after thermal decomposition. Examples of wide coating materials include petroleum, chemical process = group residue; cool white secret will be heavy wood from the pulp industry Lignin; phenolic resin == such as: and polyacrylonitrile. It can be used as a coating material, and coal "cyan" and wood which can be easily obtained and observed to be effective as a carbon residue (4) (4) Prime. The carbon residue forming material may be oxidized and then thermally decomposed to 850 in an inert state. . Any material that forms a residue of carbon on the shell when the carbonization temperature or higher is at a higher temperature. It should be understood that "the carbon is at least 9% by weight of carbon in the sputum, and at least 95% by weight of the 乂%% of the residue forming material is formed at least in the original mass of the carbon residue-form material when carbonized. 10%, and preferably at least 40%, and at least 60% more preferably carbon residue. _ It is known that any organic compound 5 which can be oxidized and then thermally decomposed to produce carbon residue is used as a coating material. In the process of dissolving an organic compound in a solvent (in a coating method), aromatic compounds of various molecular weights are included.

86864.DOC -10- 1302761 口物μ4&lt;相互溶解而為較佳。較佳的 溶點及於熱分解之後且* 已括具冋 塔歷青）。 一㈣u合物（例如’石油及煤 可使用任何用於塗覆碳質顆粒之有 的例子來說，有用的技術包括非限制性 利用適當溶劑形成溶液之方输殘留物:==或 =ΓΓ如將經液化之碳殘留物形成材料嘴塗於 材料中二著質顆粒浸泡於經液化之碳殘留物形成 碳殘留物形成材㈣==弄其他有用的技術包括使 情況中可能^料擇性地沈搬於碳質顆粒上，此在-些 再一可使用的技術包括將碳 提供於碳質顆粒上，諸如麵由將此成材科疋乾塗層 mun, π由和此寺材料混合或滾動，直 Ή,田物材料之塗層提供於碳質顆粒之表 之後接著使乾塗層融合，而於碳質 、 層。雖然可實施任何此等+ , 上鍉供一金 她任仃此寺宝覆技術，但較佳 碳質顆粒上提供竣殘留物形成材料之相當 二::: =群集或凝聚減至最少的方法。沈= :…反殘留物形成材料之量亦可有寬廣的變化，$ =了:分係視包括塗層之均勻度及碳質顆粒之特定 二t:二素而定。雖然塗層之量可自少至 得：:二：：(以經由在塗覆前後將乾顆粒稱重而别 := 對於塗覆顆粒總質量之百分比表示)，但塗 曰之里“、，，令2·5重量％至約25重量％較佳，自约5重量％襄86864.DOC -10- 1302761 The mouth substance μ4&lt; is mutually soluble and is preferred. The preferred melting point and after thermal decomposition and * have been included in the tower. A (four) compound (for example, 'oil and coal can be used in any of the examples for coating carbonaceous particles, useful techniques include non-limiting use of a suitable solvent to form a solution to the residue: == or =ΓΓ If the liquefied carbon residue forming material is applied to the material, the second granule is immersed in the liquefied carbon residue to form a carbon residue forming material. (4) == Other useful techniques include making the situation possible. The ground is moved onto the carbonaceous particles, and some of the other techniques that can be used include providing carbon on the carbonaceous particles, such as by coating the cadmium with a dry coating, π by mixing with the temple material or Rolling, straight, the coating of the field material is provided on the surface of the carbonaceous particles and then the dry coating is fused, but in the carbonaceous, layer. Although any such + can be implemented, the captain is allowed to pay for a gold. Temple treasure coating technology, but the preferred carbonaceous particles provide equivalent materials for the formation of ruthenium residues::: = clustering or condensation reduction method. Shen = : ... anti-residue material formation can also have a wide range of changes , $ = : the system includes the uniformity of the coating and carbon The specific two ts of the granules are determined by the two factors. Although the amount of the coating can be as small as possible: : 2:: (to weigh the dry granules before and after coating: : = percentage of the total mass of the coated granules Represented), but in the case of ",,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,

86864.DOC -11 - 1302761 约20重量％更佳。 根據以下六、本丨 上而形成卿:4=、：種經由使材料沈殿於顆粒之表面 。首先a:、'成材料之均勻塗層之特別有用的方法 / &quot;蚊殘留物形成材料於適當溶劑中之濃 石反殘留物形姑姑拉、、、 &lt; /辰/合/ 夜 劑或溶劑之…1溶龜由將竣殘留物形成材料與溶 (即塗覆)材料二”而製備得。溶劑應可與碳殘留物形成 解。二Γ=，且其應將全部或大部分的塗覆材料溶 選摆#、 有機化合物或不同溶劑之混合物。溶,之 形成材料之適當溶定。用於溶解碳殘留物 啦、四M:、rJ包括’例如，苯、甲苯、二〒苯”奎 冊商標Tetrl·:、丙酮、％己烷、四氫茬(由加_以註 使用石、、甴或1^、售^ W、水、甲基峨P各咬酮等等。當 ，諸如甲=殘留物形成材料時，舉例來說 劑為較佳一由 、四風呋喃、四氫萘、萘之溶 溫度二對碳殘留物形成材料之比及溶液 A又係，4制成使碳殘留物形成材料可完全 丄 2至及=中典型上’溶劑對碳殘留物形成材料=低 劑•點之溫度物形成材料係在爾 —、=溶劑對溶液比低於約2:1之濃溶液稱為助㈣溶 及:、终夕瀝青型材料形成濃助熔劑溶液，其中 二 《溶劑對遞青比與溶劑混合時，、瀝青 田·土· 相同溶劑或較不可溶解破殘留物形成材料二：釋= 容劑混合物將導致碳殘留物形成塗覆材料的部分沈殿'。86864.DOC -11 - 1302761 is preferably about 20% by weight. According to the following six, this is the formation of the Qing: 4 =,: the species through the material on the surface of the particles. First a:, 'a particularly useful method for forming a uniform coating of materials / &quot;mosquito residue forming materials in a suitable solvent in the form of a thick stone anti-residue aunt pull,,, &lt; /chen / combined / night agent or The solvent 1 is prepared by forming a crucible residue forming material and a dissolving (ie, coating) material. The solvent should be capable of forming a solution with the carbon residue. Dioxane = and it should be all or most Coating material Dissolve pendulum #, organic compound or a mixture of different solvents. Dissolve, the appropriate dissolution of the formed material. Used to dissolve carbon residue, four M:, rJ including 'for example, benzene, toluene, diphenylbenzene "Kitui trademark Tetrl::, acetone, % hexane, tetrahydroanthracene (by adding _ to use stone, 甴 or 1 ^, selling ^ W, water, methyl 峨 P each biting ketone, etc.. For example, when the material is formed as a residue, for example, the ratio of the solvent to the temperature of the two-carbon residue-forming material and the solution A of the tetrahydrofuran, tetrahydronaphthalene, naphthalene, and the solution A are made. The carbon residue forming material can be completely 丄2 to and = typically in the 'solvent to carbon residue forming material=lower agent•point temperature The material is in the form of a concentrated solution of the solvent-to-solution ratio of less than about 2:1, and the solution of the solvent is formed into a thick flux solution, wherein the solvent-to-cyanine ratio and solvent are When mixing, asphalt field, soil, same solvent or less soluble residue, forming material 2: release = the mixture of the capacitor will cause the carbon residue to form part of the coating material.

86864.DOC -12- l3〇276l ==,粒之懸浮液之存在下發生此稀釋及 乍為此澱之成核邵位。結果為碳殘留物 果、 上之特別均勻的塗層。 、a顆粒 碳質顆粒之塗覆可經由將顆 成村料之溶液中或與其混合而達成。當將；；^留物形 殘留物形成材料之溶液時，— :乂直接加至碳 混合物，以達成碳殘留物形成二:部1=加=:得之 :】可與用於製備碳殘留物形成材料之溶液的溶劑相： 、或者’可經由將顆粒於用於形成碳殘 、 ::T同溶劑、溶劑之組合或不同溶劑〜:: :::以低於溶劑之'1 點較佳，而製備得碳質材料之：； 之溶液結合，而使一此部2懸子硬與碳殘留物形成材料 勻地沈積於碳質顆粒殘留物形成材料實質上均 係❻表面上之竣殘留物形成材料之總量及形能 序係視竣殘留物形成材料於心成材科的份量而定，其依 解度的差異而定。始溶液及於最終溶液中之溶 存在範園寬廣的分二=物：成材料為_，典型上 嶋使材料分級，衝。㈣將 ： 子1*及咼熔點，及並丛ΑΑ π、、Α 田q刀 當低分子量及低H 相較於原始歷青將係相 破殘留物形成材料於一定溶劑或溶劑混合物中之溶解86864.DOC -12- l3〇276l ==, this dilution occurs in the presence of the suspension of the granules and the nucleation of the nucleation. The result is a particularly uniform coating of carbon residue. The coating of a particulate carbonaceous particles can be achieved by mixing or mixing the solutions of the constituents. When the residue of the residue is formed into a solution of the material, 乂: is directly added to the carbon mixture to achieve the formation of carbon residue. 2: part 1 = addition =: which: can be used to prepare carbon residue The solvent phase of the solution of the material forming material: or 'can be used to form a carbon residue, ::T with a solvent, a combination of solvents or a different solvent ~::::: Preferably, the prepared carbonaceous material is combined with the solution, so that a portion of the 2 suspension and the carbon residue forming material are uniformly deposited on the carbonaceous particle residue forming material substantially on the surface of the crucible. The total amount and shape order of the material forming material depend on the amount of the residue forming material in the heart material, and the degree of dependence depends on the degree of solution. The initial solution and the solution in the final solution are broadly divided into two parts: the material is _, and the enamel is usually graded and rushed. (4) Will: Sub- 1* and 咼 melting point, and ΑΑ ΑΑ π, Α q q 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当 当

86864.DOC -13- 1302761 度係視土括’例如，濃度、溫度、及壓力之各種因素而定 。如^所說明’濃助熔劑溶液之稀釋會使溶解度減小。 由万、及歹免田物形成材料於有機溶劑中之溶解度隨溫度而择 ::产=經由在高溫下開始製程及在塗覆過程中逐漸降； =二步增進塗層之沈殿。碳殘留物形成材料可在環 兄或減£下及在約·5t至約彻。〇之溫度下沈積。 = 炭殘留物形成材料之總比及溶液溫度，可控制二 备之沈㈣殘留㈣成材料 於碳殘留物形成材料之最終稀釋溶液中之塗覆 粒之懸浮液-般具有大於約2之溶輪殘留物:二 =及以大於約4較佳。舉例來說，當選擇石油或煤〜 :作為碳：留物形成材料及選擇甲苯作為溶劑時，對：:： 〜夜《甲苯對㈣之比應為低於 。 殘留物形切料、及結合溶劑之混合物、碳 5較佳。熟悉技藝人士當明瞭在塗覆程序μ以大於 對碳殘留物形成歷青比係視對程 户^ = /谷剜 儘可能少的溶劑，而在另一方 ⑥希-使用 碳質顆粒可分散於溶劑中。 而要足夠的溶劑’以使 當沈澱步驟完成時，使用習知之 心分離、或過滤，將塗覆顆粒自溶劑、^顆=万說，離 留物形成材料之混合物分離。接著視、二及故殘 粒以將殘留的瀝青(或其他形成碳之殘而留物:：劑洗務顆 移除，及使用習知之方法乾燥。 田y材料）溶液86864.DOC -13- 1302761 Degrees are determined by factors such as concentration, temperature, and pressure. As explained, the dilution of the concentrated flux solution reduces the solubility. The solubility of the material formed by the 10,000 and the 歹 田 in the organic solvent is determined by the temperature: production = by starting the process at a high temperature and gradually decreasing during the coating process; = two steps to enhance the coating of the slab. The carbon residue forming material can be at or below the ring and at about 5t to about. Deposition at the temperature of 〇. = total ratio of carbon residue forming material and solution temperature, which can control the preparation of the second (4) residual (iv) suspension of the coating material in the final dilution solution of the carbon residue forming material - generally having a solubility of greater than about 2 Round residue: two = and preferably greater than about 4. For example, when selecting petroleum or coal ~: as a carbon: residue forming material and selecting toluene as a solvent, the ratio of::: to night "toluene to (four) should be lower than. The residue-shaped cut, the mixture of the combined solvents, and carbon 5 are preferred. It is well known to those skilled in the art that in the coating procedure μ, the solvent is formed to be as large as possible for the carbon residue, and the solvent is as small as possible, while on the other side, the carbonaceous particles are dispersed. In the solvent. Sufficient solvent is required so that when the precipitation step is completed, the coated particles are separated from the solvent, the mixture of the retentate forming materials by conventional separation or filtration. Then, depending on the second, the residual particles to remove the residual bitumen (or other carbon-forming residue: the agent wash particles, and use the conventional method to dry. Field y material) solution

86864.DOC -14- 1302761 於將塗覆顆粒分_夕犍 碳殘留物邢成鉍4丄 ' 田的液體包括溶劑及殘留的 请h〜 扪用自知炙万法諸如，比方說，在 減土下煞餾或在高溫下蒗 a 自# &amp;、^ …^ 而知洛劑自溶液回收。溶劑 自殘留义碳形成材料之分、 —# 系在鬲溫下進行，以致碳殘留 物保持為液體形熊 ^ ,+ ^ ^ ^ 口使用不同的溶劑於製備塗覆材 料洛液及沈澱溶液，則 ^ t| 、此而要夕段瘵餾系統於回收多種 洛劑。可將回收的溶劑直接误门s &lt; „ . ^ 罝接迗回土系統及再利用於製程中 ，同時將碳殘留物形成材料自製程排出。 根據本發明方法之再一 八十、人 冉 乂釭，使碳質顆粒之塗層成為部 刀或元全不可溶解，以 , . 虱化知疋化較佳。碳質顆粒之86864.DOC -14- 1302761 In the coating of particles, the residue of Xingcheng 铋4丄', the liquid including the solvent and the residue, please h~ 扪 use the self-knowledge method such as, for example, under the soil reduction Distillation or at high temperature 蒗a from # &amp;, ^ ... ^ and the agent is recovered from the solution. The solvent is separated from the residual carbon-forming material, and the ## is carried out at a temperature of 鬲, so that the carbon residue remains as a liquid-shaped bear, and the ^^^^ port is prepared by using different solvents to prepare the coating material and the precipitation solution. Then ^ t|, and thus the retort system is used to recover a variety of agents. The recovered solvent can be directly mistakenly s &lt; „ . ^ 罝 迗 迗 迗 及 及 及 及 及 及 及 及 及 及 及 , 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳 碳, so that the coating of the carbonaceous particles becomes a part of the knife or the element is insoluble, so that the phlegm is better. The carbonaceous particles are

土席你t由使用氧化劑太搞A .. ]在通③的反應條件下使該顆粒進行 虱化反應而穩定化。一护品+ ^ 又 〇 ’僅需要溫和至中度的反鹿 二:型上’氧化反應係經由使塗覆之碳質顆粒與氧： 和^:l接觸’或經由使塗覆之碳^顆粒與氧化劑在溫 &gt; t ^ 彳在同，皿下活化而令人滿意地進 二(與之接射在_叫大崎）或在適度的 ::^大約彻。c)下進行。氧化劑之活化典型上將係在 度的高溫下進行。將氧化反應之溫度維持在 , 丁〈坪間v點’以確保在氧化反應過程 超過塗覆材料之熔點較佳。 當明瞭本發明方法之此+ # H &amp; n V ^的貫施万式係视在反應條 , ^戍巩也疋所利用之氧化劑的形態而定 。同樣地，可實施各種氧化 、 、、 虱化反應万法及反應條件，且其被 認為係在本發明之範園内。The soil mat is used to stabilize the granules by using an oxidizing agent. The granules are subjected to a deuteration reaction under the reaction conditions of the passage 3. A protective product + ^ 〇 'only needs mild to moderate anti-deer two: type 'oxidation reaction by contacting the coated carbonaceous particles with oxygen: and ^: l' or by coating the carbon ^ The granules are oxidized with the oxidizing agent at the same temperature, t ^ 彳 in the same dish, and satisfactorily enters into the second (with it in the _ called Osaki) or in the moderate:: ^ about. c) proceed. The activation of the oxidant is typically carried out at elevated temperatures. The temperature of the oxidation reaction is maintained at a point V to ensure that the melting point of the coating material is better during the oxidation reaction. It is to be understood that the method of the method of the present invention, which is based on the morphology of the reaction strip, is determined by the morphology of the oxidant used in the reaction strip. Similarly, various oxidation, and deuteration reactions and reaction conditions can be carried out, and it is considered to be within the scope of the present invention.

86864.DOC -15- 1302761 當氧化劑為固體時，僅需要將固態氧化劑放置成與塗覆 &lt;碳質顆粒充分地密切接觸，以致在適當的反應條件下， 可得到令人滿意的氧化程度。此係經由形成氧化劑之液態 溶液，將此溶液塗布至塗覆顆粒及乾燥而最有效地完成： 當貫際可行時，於單一步驟中同時塗布碳殘留物形成材料 及氧化劑塗層較佳。當需要時’可使氧化劑達到適當的反 應條件，以確保氧化反應之開始及成功。此種條件可在環 境壓力及溫度條件（大約20t，丨大氣壓）下進行，然而，視 氧化劑之特性、碳殘留物形成（塗覆）材料之特性、以及部 刀視可使用於氧化反應之任何反應容器之特性及形式而定 ，可能希望自環境修改溫度及/或壓力或兩者。典型上，將 溫度提高至40(TC可促進起始及後續的氧化反應，但事實上 ，可成功地使用在塗覆材料之瞬間熔融溫度下之任何溫度 1於任何反應容器之特性，可使用任何習慣上使用= 應容器或裝置。關於固態氧化劑之實fS，舉非限制性的例 子來說包括· *機及有機氧化劑諸如金屬氧化物及鹽 諸如鹼硝酸鹽及鹼硫酸鹽諸如&amp;MN〇3及“404所表示，其 指示鹼金屬，以及Μ,〇χ，其中代表過渡金屬。固態 I化例子更包括無機鹽諸如硝酸納（NaN〇3)及有機鹽 ，以及說明於以下實施例中之化合物。 當氧化劑為液體時，氧化船堇需以可與塗覆之碳質顆粒 相容之液體形態提供。清楚知曉氧化劑之本身不需構成液 體的100%，反之，氧化劑可以其中包含—或多種氧化劑之 溶液、懸浮液、或其他流體提供。預期當氧化劑係以溶液86864.DOC -15- 1302761 When the oxidizing agent is a solid, it is only necessary to place the solid oxidizing agent in intimate contact with the coated &lt;carbonaceous particles so that a satisfactory degree of oxidation can be obtained under appropriate reaction conditions. This is most efficiently accomplished by applying a solution of the oxidizing agent to the coated particles and drying the solution by applying a liquid solution of the oxidizing agent: When it is practicable, it is preferred to simultaneously apply the carbon residue forming material and the oxidizing agent coating in a single step. When necessary, the oxidant can be brought to the appropriate reaction conditions to ensure the onset and success of the oxidation reaction. Such conditions can be carried out under ambient pressure and temperature conditions (approximately 20 t, 丨 atmospheric pressure), however, depending on the characteristics of the oxidant, the characteristics of the carbon residue forming (coating) material, and any of the knives that can be used for the oxidation reaction Depending on the nature and form of the reaction vessel, it may be desirable to modify the temperature and/or pressure or both from the environment. Typically, the temperature is increased to 40 (TC promotes the initial and subsequent oxidation reactions, but in fact, any temperature at the instant melting temperature of the coating material can be successfully used in any reaction vessel, and can be used Any customary use = container or device. For solid oxidants fS, by way of non-limiting example, include organic solvents and organic oxidants such as metal oxides and salts such as alkali nitrates and alkali sulfates such as &amp; MN 〇3 and "404 indicate that it indicates an alkali metal, and ruthenium, osmium, which represents a transition metal. Solid-state examples include inorganic salts such as sodium nitrate (NaN〇3) and organic salts, and are illustrated in the following examples. When the oxidant is a liquid, the oxidized ship is required to be provided in a liquid form compatible with the coated carbonaceous particles. It is clear that the oxidant itself does not need to constitute 100% of the liquid, and conversely, the oxidant may contain - Provided as a solution, suspension, or other fluid of a plurality of oxidants. It is expected that when the oxidant is a solution

86864.DOC -16- 1302761 或懸洋液提供時，可能希望包括乾燥步驟，以將塗覆顆粒 乾燥。預期當氧化劑係以液體形態存在時，其亦可與塗覆 之碳質顆粒相容，即液體之任何部分並不會不期望地使可 溶解之碳殘留物形成材料或碳質顆粒之本身降解或溶解。 舉非限制性的例子來說，以液體形態提供之氧化劑的例子 包括各種氧化酸諸如硝酸、過氯酸、轉酸、硫酸以及含氧 化，諸如過氧化物及KMn〇4之水性及非水性溶液。其他的 «氧化劑包括過氧化物及芳基醌，以及說明於一或多個 實施例中之化合物。 氧化反應之條件的特性對於其％之氧化劑係為液體形 態之本發明的實施並不重要。反之，反應條件僅需適合於 確保提供至碳質顆粒之至少一部分之塗層的氧化，以致至 於其上形成穩定的塗層。可使用任何習知的反應器及適當 的反應條件。如先前所說明，關於固態氧化劑，反應條件 可在環境溫度及壓力條件下進行，或可能視塗層、竣質顆 粒之特性、反應容器、及當然視所利用之氧化劑之特性而 需要不同的條件。關於反應容器’可方便地使用視需要經 加壓的攪拌反應容器。 當氧化劑為氣態時，再次僅需使此氣態氧化劑與塗覆之 碳質顆粒在適當的反應條件下充分地密切接觸，以確 殘留物形成材料之氧化反應。根據本發明之此態樣，氣. 氧化劑由於在適當的反應條件下可容易地達到與塗覆之I 質顆粒的良好混合及接觸，因而其在許多情況中可最方便 地使用。舉非限制性的例子來說，氣態氧化劑之例子包括 86864.DOC -Π- 1302761 ^ ^ ^ 氣怨氧化物及齒素。較佳的氧化劑包括氧、 氧化氮氣體、以及在特定條件下之環境空氣（其當然包括顯 著比例的氧氣）。 關於其中之氧化劑為氣態所需之反應條件，同樣地，此 種反應條件僅需適合於確保存在於碳質顆粒上之碳殘留物 Z成材料的氧化即可。在—些條件下，環境壓力及溫度可 牝足夠’㉟同樣如參照先前說明之其他形態之氧化劑所說 明，最好可確保建立稍高的溫度及/或壓力，即在m⑻。c d乾圍内之溫度及/或稍高的壓力，即大氣壓，以 =發或維持氧化反應。同樣地，應明瞭適當的反應條件係 Γ7度地視用S塗覆峡質顆粒之碳殘留物形成材料之特性、 特定的氣態氧㈣、以及反應容器之本身而定。有用的反 應容器係必然可容納’或使氣態氧化劑與塗覆之竣質顆粒 轉之容器，且雖然可使用許多習知之容器，但使用流體 =床反應器為較佳。利用其中之氣流包含氣態氧化劑之流86864.DOC -16- 1302761 or when provided with a suspension, it may be desirable to include a drying step to dry the coated particles. It is contemplated that when the oxidant is present in liquid form, it may also be compatible with the coated carbonaceous particles, i.e., any portion of the liquid does not undesirably degrade the soluble carbon residue forming material or the carbonaceous particles themselves. Or dissolve. By way of non-limiting example, examples of oxidizing agents provided in liquid form include various oxidizing acids such as nitric acid, perchloric acid, transacids, sulfuric acid, and aqueous and non-aqueous solutions containing oxidizing agents such as peroxides and KMn〇4. . Other &quot;oxidants include peroxides and aryl oximes, as well as the compounds illustrated in one or more embodiments. The characteristics of the conditions of the oxidation reaction are not critical to the practice of the invention in which the % oxidant is in a liquid state. Conversely, the reaction conditions need only be adapted to ensure oxidation of the coating provided to at least a portion of the carbonaceous particles such that a stable coating is formed thereon. Any conventional reactor and suitable reaction conditions can be used. As previously stated, with respect to the solid oxidant, the reaction conditions can be carried out under ambient temperature and pressure conditions, or depending on the characteristics of the coating, the enamel particles, the reaction vessel, and of course the characteristics of the oxidizing agent utilized. . Regarding the reaction vessel', it is convenient to use a stirred reaction vessel which is pressurized as needed. When the oxidant is in a gaseous state, it is again necessary to bring the gaseous oxidant into intimate contact with the coated carbonaceous particles under appropriate reaction conditions to confirm the oxidation reaction of the residue forming material. According to this aspect of the invention, the gas oxidizing agent is most conveniently used in many cases because it can easily achieve good mixing and contact with the coated I particles under appropriate reaction conditions. By way of non-limiting example, examples of gaseous oxidants include 86864.DOC-Π- 1302761 ^ ^ ^ gas oxide and dentate. Preferred oxidizing agents include oxygen, nitroxides, and ambient air under certain conditions (which of course includes a significant proportion of oxygen). As for the reaction conditions required for the oxidizing agent to be in a gaseous state, similarly, such reaction conditions need only be suitable for ensuring oxidation of the carbon residue Z-forming material present on the carbonaceous particles. Under these conditions, ambient pressure and temperature may be sufficient. '35. As noted with reference to other forms of oxidant as previously described, it may be desirable to ensure that a slightly higher temperature and/or pressure is established, i.e., at m(8). c d The temperature inside the dry circumference and / or a slightly higher pressure, that is, atmospheric pressure, to / or maintain oxidation reaction. Similarly, it should be understood that the appropriate reaction conditions are based on the characteristics of the carbon residue forming material of the S-coated gorge particles, the specific gaseous oxygen (IV), and the reaction vessel itself. Useful reaction vessels are inevitably capable of holding or transferring the gaseous oxidant to the coated enamel particles, and although many conventional vessels can be used, it is preferred to use a fluid=bed reactor. Utilizing a gas stream containing a gaseous oxidant

::化床反應器由於能可靠地確保在氣態氧化劑與塗覆之J::Chemical bed reactor can reliably ensure the presence of gaseous oxidant and coating J

質顆粒之間之有效的密切接觸而為較佳。 4厂K 根據本發明方法之再一步驟’接著視所使用 _定化之塗覆之碳質顆㈣化及/或石墨化。當用於以 取化之塗覆顆粒之碳質材料係高竣材料諸如馈製^ 、天然石墨或合成石墨時’可沒有介於其間之碳化+ :'、、、 直接將顆粒石墨化。另外’當碳質材料為石、罢日:知而 將經穩定化之塗覆顆粒竣化即可形成有用=由 材料係較軟的碳諸如綠煤焦（green cQk ::當碳質 何生自天然或Effective intimate contact between the particles is preferred. 4 Plant K According to a further step of the process of the invention, the carbonaceous particles (4) and/or graphitization of the coated coatings are then used. When the carbonaceous material used for the coated particles is a sorghum material such as a feed, natural graphite or synthetic graphite, there may be no carbonization +: ', and the particles are directly graphitized. In addition, when the carbonaceous material is stone, it is known that the stabilized coated particles are deuterated to form useful = softer carbon such as green coal char (green cQk: when carbon is born Natural or

86864.DOC -18- 1302761 合成聚合物之軟碳時，將經穩定化之塗覆顆粒碳化至約400°C 至約2000°C之溫度，接著再將顆粒在約2200°C以上之溫度 下石墨化較佳。 根據此進一步的步騾，塗覆及經穩定化之碳質顆粒的加 熱係在適當的反應條件下進行，以確保其之高度或完全的 碳化。關於確保碳化所需之溫度，希望其係經由以受控制 之方式將溫度自起始溫度（通常係環境溫度）提高至落於約 400至約200(TC之以上指示之範圍内，及以在約550°C至約 1500°C之範圍内較佳之最終碳化溫度而達成。 關於升溫，其可基於經反應之塗覆碳質顆粒之特性、以 及所使用之反應條件及裝置而改變。關於裝置，典型上可 相當令人滿意地使用習知之烘箱，雖然使用在碳化過程中 可維持特定大氣之密閉烘箱較佳。可維持減壓之密閉烘箱 ，尤其係真空烘箱特別有利。 關於碳化程序之大氣條件，大氣可為至高約850°C之環 境空氣，但在高於約400°C之溫度下的惰性大氣為較佳。當 氧大部分在加熱或於真空中加熱之過程中移除時，環境空 氣係可接受的大氣。適當的惰性大氣包括氮、氬、氦等等 ，其不與經加熱之塗覆碳質顆粒反應。 關於溫度條件，其可寬廣地變化，但經反應之塗覆碳質 顆粒為達成其之碳化所接受的升溫速率一般係在0.5°C -20°C / 分鐘左右。此一控制升溫可確保達到良好的碳化結果。然 而，將塗覆之碳質顆粒逐漸加熱至最終碳化溫度，且在程 序中所使用之最終碳化溫度之前有至少一中間熱處理步驟 86864.DOC -19- 1302761 :其中將塗覆之碳質顆粒加熱至一中間溫 溫度下維持一段♦ 又及在及宁恥 度之期間可改變：：二奋此中間溫度或維持此種中間溫 瞭包括-或^瞭其係視不同的程序而定。應明 期間右刹1夕、此等其間將顆粒維持於此種中間溫度下之 列：事會Γ足合或存在於竣質顆粒上之塗層的其他排 : 於咸信提供多於一個將塗覆顆粒維持於恒 :’:趣理步驟可賦予塗覆之碳質顆粒較諸僅經歷—個 … 處理步w顆粒的改良特性，因而實施數個 此種中間熱處理步驟較實施單—的熱處理步驟更佳。更應 ^瞭在，覆《故質顆粒的加熱過程中，必需特別注意確保 加為私序中所達到之溫度及在加熱程序之任何部分中 ㈣=速率皆不會超過碳質顆粒上之塗層的瞬間溶點。更 間=言之’塗層之熱降解係受控制升溫的影響，其中將程 :溫度維持在塗層之瞬間溶點或以下（其中該少容點一般係 隨程序中之時間而增高)。鑑於此需求，較佳的加熱程序係 展現較緩慢之升溫速率者。將參照一或多個實施例說明此 種熱處理步騾之特佳例子。 於達到碳化程序之最大溫度利用後，可使經碳化之塗覆 之石反貝顆粒冷卻至環境溫度，雖然此並非必要條件。同栌 地’可如期地控制冷卻速率，即在約3。〇_1〇〇艺/分鐘内， 雖然經觀察到此冷卻速率典型上較碳化程序中之升溫速率 不具限制性。 本發明之最佳態樣導致於個別的碳質顆粒上提供平滑 塗層。於塗層之穩定化之後跟著經穩定化之塗覆顆粒之栌86864.DOC -18- 1302761 When the soft carbon of the polymer is synthesized, the stabilized coated particles are carbonized to a temperature of from about 400 ° C to about 2000 ° C, and then the particles are at a temperature of about 2200 ° C or higher. Graphitization is preferred. According to this further step, the heating of the coated and stabilized carbonaceous particles is carried out under appropriate reaction conditions to ensure their high or complete carbonization. With regard to the temperature required to ensure carbonization, it is desirable to increase the temperature from the initial temperature (usually ambient temperature) to a range of from about 400 to about 200 (indicated above TC) in a controlled manner, and Achieving a preferred final carbonization temperature in the range of from about 550 ° C to about 1500 ° C. With regard to elevated temperature, it can vary based on the characteristics of the reacted coated carbonaceous particles, as well as the reaction conditions and equipment used. Conventional ovens are typically used quite satisfactorily, although it is preferred to use a closed oven that maintains a particular atmosphere during carbonization. A closed oven that maintains reduced pressure, particularly a vacuum oven, is particularly advantageous. Conditions, the atmosphere may be ambient air at a temperature of up to about 850 ° C, but an inert atmosphere at temperatures above about 400 ° C is preferred. When oxygen is mostly removed during heating or heating in a vacuum, Ambient air is an acceptable atmosphere. Suitable inert atmospheres include nitrogen, argon, helium, etc., which do not react with heated coated carbonaceous particles. The change, but the rate of temperature increase of the reacted coated carbonaceous particles to achieve carbonization is generally between 0.5 ° C and -20 ° C / min. This controlled temperature rise ensures good carbonization results. The coated carbonaceous particles are gradually heated to a final carbonization temperature and there is at least one intermediate heat treatment step 86864.DOC-19-1302761 before the final carbonization temperature used in the procedure: wherein the coated carbonaceous particles are heated to a middle Maintaining a section at temperature and temperature ♦ can be changed during and during the period of sorrow: the second intermediate temperature or the maintenance of such intermediate temperature includes - or ^ it depends on different procedures. In the meantime, during which the particles are maintained at such intermediate temperatures: other rows of coatings that will suffocate or exist on the enamel particles: more than one of the coatings provided by Xianxin Constant: ': The interesting step can impart improved properties to the coated carbonaceous particles as compared to only the processing of the particles. Therefore, it is better to carry out several such intermediate heat treatment steps than to perform the single-heat treatment step. Should be ^ In the heating process of the granules, special care must be taken to ensure that the temperature reached in the private sequence and in any part of the heating process (four) = the rate does not exceed the instant dissolution of the coating on the carbonaceous particles. Point. In other words, the thermal degradation of the coating is affected by the controlled temperature rise, wherein the temperature is maintained at the instant melting point or below of the coating (where the small capacitance generally increases with the time in the program). In view of this demand, a preferred heating procedure exhibits a slower rate of temperature rise. A particularly preferred example of such a heat treatment step will be described with reference to one or more embodiments. The carbonized coated stone anti-shell particles are cooled to ambient temperature, although this is not a requirement. The cooling rate can be controlled as scheduled, ie within about 3. 〇_1〇〇 / min, although It is observed that this cooling rate is typically not limiting as compared to the rate of temperature increase in the carbonization procedure. The preferred aspect of the invention results in a smooth coating on individual carbonaceous particles. After stabilization of the coating followed by stabilization of the coated particles

86864.DOC -20- 13〇2761 以達成k覆顆粒之碳化，而有極少或沒有個別顆 。塊或自黏較佳。期望的結果係當將個別顆粒融人且 必需將其壓碎或破開，以提供自由流動粉末時特性形成之 颁型〈具有極少或沒有破裂表面的塗覆顆粒。咸 使用作為可再充電之蓄電池，尤其係可再充:二 、-池中《％極材料時，此種破裂表面會促成低電化學 效率，因而希望使其減至最少或將其避免。 切根據此處教授之本發明方法的—特佳具體實施例，碳殘 :物形成材料係以流體形態提供。本發明人觀察到當碳殘 二物形成材料自液體沈殿時，會在個別碳質顆粒與周圍液 K界面形成平滑塗層。當接著碳化時可維持平滑塗層。 隹乂車乂不利，但當碳殘留物形成塗層係以固體提供時， :望將其融合於碳質顆粒之表面上，以於其上形成平滑塗 ^毛明之穩足化步驟係經進行於使塗層之表面對後續 步驟不溶解。由於氧化穩定化可使塗層之表面對後 ^的奴化步驟不熔解，因而氧化穩定化可使於塗覆程序中 、生之平滑表面保留於本發明之最終的塗覆顆粒中。 、希望經穩定化之塗覆顆粒之熱處理係以受控制的方式 j仃以使顆粒之融合減至最小。熟悉技藝人士當知曉經 同度％疋化之不熔解的塗覆顆粒可於碳化過程中相當積極 及陕速地加熱。相對地，經相當溫和穩定化之塗覆顆粒需 要車乂、、爰k的加熱，以避免塗層之過度熔解及顆粒之融合。 L疋化及熱處理過程中使用流體化床尤其有利於防止塗86864.DOC -20- 13〇2761 to achieve the carbonization of the k-coated particles with little or no individual particles. Block or self-adhesive is preferred. The desired result is when the individual particles are melted and must be crushed or broken to provide a characteristic of the formation of the free flowing powder (coated particles with little or no fracture surface). Salt is used as a rechargeable battery, especially rechargeable: In the case of the % pole material in the tank, such a ruptured surface contributes to low electrochemical efficiency and it is therefore desirable to minimize it or avoid it. According to a particularly preferred embodiment of the method of the invention taught herein, the carbon residue: material forming material is provided in a fluid form. The inventors have observed that when the carbon residue forming material is from the liquid chamber, a smooth coating is formed at the interface between the individual carbonaceous particles and the surrounding liquid K. A smooth coating can be maintained when carbonized. Brake is not good, but when the carbon residue forming coating is provided as a solid, it is expected to be fused to the surface of the carbonaceous particles to form a smoothing process on which the smoothing process is carried out. The surface of the coating is rendered insoluble for subsequent steps. Since the oxidative stabilization does not melt the surface of the coating against the post-encapsulation step, the oxidative stabilization allows the smooth surface which is produced during the coating process to remain in the final coated particles of the present invention. It is desirable that the heat treatment of the stabilized coated particles be controlled in a controlled manner to minimize particle fusion. Those skilled in the art will be aware that the coated particles which are not melted by the same degree of deuteration can be heated quite aggressively in the carbonization process. In contrast, coated particles that are relatively mildly stabilized require heating of the rut, 爰k to avoid excessive melting of the coating and fusion of the particles. The use of a fluidized bed during L deuteration and heat treatment is particularly advantageous for preventing coating

86864.DOC -21 - 1302761 覆顆粒之結塊及融合。 本發明之特佳具體會 產生塗覆顆粒之自由汸&quot;於碳化及/或石墨化步驟之後 極少或沒有融合，但二^粉末’此顆粒於顆粒之間展現 利用攪拌棒，或經由在拇由間早的機械擾動，諸如 由流動的粉末。當在顆粒：=之間摩擦而破碎成為自 致生成新破裂表面之機 x 些融合，及使用會導 日月之較佳具體實施例“二匕等顆粒時，在本發 面積的多於10%， 石、及表面不包含顆粒之總表 滑的塗層。 、夕义2%較佳。其被視為係實質上平 ==使用之前將經碳化之塗覆碳 但由於可將利用本 土化季乂佳 粒直接使用於各種應用中之塗覆信 (尤其係可再充電之電池)中之;：形：電極，特別係電池 如炎昭以下…）中❹極’因而石墨化並非必要。 離子電池中之陽極特別有利。 愤用作為鐘 ==由將經竣化之塗物顆粒加 =:?到之溫度之又更高的高溫而將其石墨_ 於心、！二重優點’其中最顯著的為石墨化程序經常可 = 質顆粒中產生更規則的晶體晶格。特定的改良 2晶格提供更規則及均勾的結構，且咸信其亦可改良包 覆之碳質顆粒之電池的充電容量。特別值 4本發明之經石墨化之塗覆顆粒在Ο.Ο至0 5伏特 之低位能下II現高容量。此對於由此等 再86864.DOC -21 - 1302761 Agglomerate agglomeration and fusion. A particularly preferred embodiment of the invention will result in a free coating of the particles &quot; little or no fusion after the carbonization and/or graphitization step, but the powder 'this particle appears between the particles using a stir bar, or via a thumb By early mechanical disturbances, such as by flowing powder. When the particles are rubbed between the particles:=, the machine is broken into self-generated new rupture surfaces, and the fusion is used, and the preferred embodiment of the ray is used, %, stone, and surface do not contain the total slippery coating of the particles. 2% is better. It is considered to be substantially flat == carbonized coated carbon before use but due to local use The quaternary glutinous granules are directly used in coating letters (especially rechargeable batteries) in various applications;: shape: electrodes, especially batteries such as Yanzhao below...) bungee poles - thus graphitization is not necessary. The anode in the ion battery is particularly advantageous. Inverted as a bell == by the addition of the deuterated coating particles to the higher temperature of the temperature to the higher the temperature of the graphite - the heart, the double advantage of which Most notably, the graphitization procedure often produces a more regular crystal lattice in the granules. The specific modified 2 lattice provides a more regular and uniform structure, and it can also improve the coated carbonaceous granules. Charging capacity of the battery. Special value 4 Graphitized coating of the present invention Particles to 05 volts at low Ο.Ο II can now high capacity. This suppresses the like and then

86864.DOC -22- 1302761 疋電池高度有利。 石墨化亦可將不純物移除。當將不純的碳諸如天缺石里 =用作為本發明之碳質顆粒的來源時，此純化步mm 關於通當的石墨化條件，再次應明瞭 塗覆碳質顆粒之特定的特性，以及產生石 化《 條件而改變。一般而…、 &quot;、化所需之反應 .,„ δ，亦可万便地使用利用於碳化步驟 ，：同裝置’此種裝置僅需可將溫度進一步提高至可觀定 至4生石墨化之效果的溫度或溫度範圍即可。血 ^ 墨化係在約220(TC _320(rc之、、w &quot; 土 ，石 弓你 度靶圍内•生，雖然在此步 較低或較高的溫度。其僅需於此步驟中可得 ▽滿思的石墨化程度，以致可獲致 關於方法侔件，希访r奋里。 大氣中進行。石里化^、人、王、化係在諸如先前所說明之惰性 使經碳化之塗覆化之後立即進行，在此情況， 復反貝顆粒保留於反應裝置，即烬 :溫度提高至適當的石墨化溫度。關於此升溫速率，希访 /、係維持在與碳化步驟所使用者相同的速率下，雖心 视經碳化之塗覆破暂班^、、U 雖然亦可 速率。 特性而利用較大或較小的升溫 本發明之一較佳態 成材料塗覆方法。不管覆万法’或碳殘留物形 質顆粒上提供均勾的石户覆方法皆於碳 、_、又殘田物形成塗層。塗覆可以許多方 、，但使塗覆材料在碳質顆粒之懸浮液的存在下沈r ,别有利。此塗覆方法產生經控制組合物之均勾塗層及產86864.DOC -22- 1302761 The battery is highly advantageous. Graphitization can also remove impurities. When impure carbon such as celestial stone is used as the source of the carbonaceous particles of the present invention, this purification step mm again clarifies the specific characteristics of the coated carbonaceous particles and the generation of the normalized graphitization conditions. Petrochemical "conditions change. In general, ..., &quot;, the reaction required for the process., „ δ, can also be used in a carbonization step, the same device: this device only needs to be able to further increase the temperature to visible to 4 biographitization The effect of the temperature or temperature range can be. Blood ^ inkification system is about 220 (TC _320 (rc, w &quot; soil, stone bow within your target range • raw, although lower or higher at this step Temperature, which only needs to be full of graphitization in this step, so that the method can be obtained, and the visit is in the atmosphere. In the atmosphere, the stone, the person, the king, the chemical system, etc. The inertness previously described is carried out immediately after the carbonization coating, in which case the anti-rebel pellets remain in the reaction apparatus, i.e., the temperature is raised to an appropriate graphitization temperature. Regarding the rate of temperature rise, Maintaining at the same rate as the user of the carbonization step, although the carbonized coating is temporarily applied, the U can also be used at a rate. State material coating method. Regardless of the method or carbon residue The stone household coating method on the shaped particles is formed by carbon, _, and residual materials. The coating can be applied in many ways, but the coating material is allowed to sink in the presence of the suspension of carbonaceous particles. This method of coating produces a uniform coating and production of the controlled composition.

86864.DOC -23- 1302761 生鬆散的複合物顆粒粉末，以致經塗覆瀝青之顆粒不會凝 聚，且於後續的方法步驟中不需進一步的研磨程序。 '本發明之另-較佳態樣係為在塗層之碳化前於塗覆顆 粒上進行之氧化反應。咸信氧化反應可提供特定的技術效 益。首先，咸信經反應之塗覆顆粒於氧化之後相當不溶解 ’其由後續方法步驟’及顆粒之後續處理的觀點來看特別 有利。其次，咸信經反應之塗覆顆粒具有當使用作為電極 ’尤其係當將經反應之塗覆顆粒使用於可再充電之蓄電池 :特別係可再充電之Li-離子電池中之陽極材料時可產生高 政率之表面。 口 本發明之另一較佳態樣# A ZA止庄r 4 4石墨化步驟。將在此亦稱為 複合物顆粒粉末或塗覆顆粒耠支 釭扣末夂垩覆乏碳質顆粒在高於 22〇〇°C之溫度下碳化/石墨化較 琢佔、、入嗜 此於虱化後又高溫熱處 理使垩覆顆粒粉末產生非當古 度王非吊阿的谷量及充電效率。 石墨化材料之幾近所有的高臾曰你+ λ 寺、，、工 沪下〜 ^ % Μ係纽G至0.5伏特之低位 月匕下發生尤其有利。 本發明之再一態樣考声將 号您爿^蚊化及/或石墨化之塗覆碳 貝顆杈使用於電極，尤其兩 % + “田甩池，特別係可再充電之電 池中的1%極。根據本發明之 備古、土 W褕，考慮一種蓄電池之製 去，其包括下列步驟：將 物形成材㈣成之塗層f”//、有由經減之碳殘留 料加 曰足宝覆微細碳質顆粒的塗覆石墨材 竹加入至畜電池之陽極中。 根據本發明之此態樣， 粒係使用習知之技術而形之塗覆之碳質顆 乂為％極，尤其係陽極。雖然在86864.DOC -23- 1302761 The loose composite granule powder is produced such that the coated asphalt particles do not coagulate and no further grinding procedures are required in subsequent process steps. Another preferred aspect of the invention is the oxidation reaction carried out on the coated particles prior to carbonization of the coating. Salty oxidation reactions provide specific technical benefits. First, the coated particles of the salty reaction are relatively insoluble after oxidation, which is particularly advantageous from the standpoint of the subsequent process steps and subsequent processing of the particles. Secondly, the salt coated reaction coated particles have when used as an electrode, especially when the reacted coated particles are used in a rechargeable battery: particularly an anode material in a rechargeable Li-ion battery. Produce a surface of high political rates. Another preferred aspect of the invention # A ZA 止庄 r 4 4 graphitization step. Carbonized/graphitized, which is also referred to herein as composite granule powder or coated granules, at a temperature higher than 22 ° C, is more suitable for carbonization/graphitization. After deuteration and high-temperature heat treatment, the glutinous granule powder can produce the amount of non-depreciation and the charging efficiency. Nearly all of the graphitized materials, you + λ Temple,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, A further aspect of the present invention is to use the coated carbon shells of your mosquitoes and/or graphitized electrodes for electrodes, especially two% + "Tianchichi, especially in rechargeable batteries. 1% pole. According to the preparation of the ancient and soil, the preparation of a battery includes the following steps: coating the material forming material (4) into a coating f"//, having a carbon residue added The coated graphite material of the lame-coated fine carbonaceous particles is added to the anode of the livestock battery. According to this aspect of the invention, the granules are coated with carbonaceous ruthenium in the form of a conventional technique, in particular an anode. Although at

86864.DOC -24- 1302761 藏白特別說明，但可考慮使用用於組裝此等览極之已知技 β的製造技術’以及有助於形成此種電極之已知技藝的裝 置ι由使用此處教授之塗覆之碳質顆粒而得之一特殊優 在於由於其之塗層’因而其幾乎不會融合在一起，因： 而產生可流動的粉末。此種可流動粉末不僅可促進法覆之 碳質材料之輸送，並且由於其提供良好的填充度及:勾度 =有助：最終的電極。由於每單位電極體積之增加的電荷 性可使電池之總尺寸減小’同時可維持其之良好的 2性，因而此—良好的填充度當然對任何電池，尤直 有=極形成其之-部分之可再充電之電池之 有非常高的第一循環效率。此高效率係由= 學循产時Ϊ生。當碳電極對鋰金屬在0及1伏特之間電化 上係&gt;90。/ h 人貝顆弟-循環效率典型 、, °。相比之下，在塗覆前之碳質顆粒中之第一計 效率低塊，及其在利用先前於技藝中所 術製得之塗覆顆粒中典型上係90%以；：所知曉…技 T發明之另'態樣係由於實施塗覆 或比容量的增加。在本發明之經k重I 容量典型上增加2至5%。 ▲《堡覆顆粒中，比 ::定較佳具體實施例之本發明之 艾本發明的實施例中。 力万、以下 實施柯86864.DOC -24- 1302761 Illustrated in particular, but it is conceivable to use the manufacturing technique of the known technique for assembling such a pole, and the device ι which is known to contribute to the formation of such an electrode. One of the professor's coated carbonaceous particles is particularly advantageous because of its coating' so that it hardly fuses together, resulting in a flowable powder. This flowable powder not only promotes the transport of the coated carbonaceous material, but also provides good fillability and: hook-up = help: the final electrode. Since the increased charge per unit electrode volume can reduce the overall size of the battery 'while maintaining its good two properties, so this good filling degree is of course for any battery, especially = Some rechargeable batteries have very high first cycle efficiencies. This high efficiency is produced by the student. When the carbon electrode is charged to lithium metal between 0 and 1 volt, it is &gt;90. / h People with a younger brother - typical cycle efficiency, °. In contrast, the first low efficiency block in the carbonaceous particles prior to coating, and typically 90% in the coated particles produced by the prior art;: known... Another aspect of the invention is due to the implementation of coating or an increase in specific capacity. The k-weight I capacity of the present invention is typically increased by 2 to 5%. ▲ In the Fort granules, the preferred embodiment of the present invention is in the embodiment of the present invention. Liwan, the following implementation of Ke

86864.DOC -25- 1302761 利用以下技術評估粉末顆粒之充電容量以及不可逆的 充電容量損耗。 先知釦末顆粒（5克）之樣品與3.82克之包含〇·382克聚偏 一氟乙烯（PVDF，例如，Aldrich Chemical c〇.，111〇 )及3.44 克1-甲基峨略呢酮（NMp，例如，乂时化ch㈣id c〇·，^·) ^♦液被底混合，亦於其中加入〇 〇82克之乙炔黑（具有肋 平方米克之有放表面積，例如，Aifa Aesar)，以形成均勻 料水…接著利用刮板以手將此料漿流延，而於電沈積銅箔 (1〇械米’例如 ’ Fuduka Meul &amp; p〇wder c〇·，Ltd·)之 粗糙面上形成具約10毫克/平方公分之載入量㈣膜。接著 將流延薄膜於電熱板上在大約】⑼。c下乾燥，並利用輕壓機 加壓土期I始、度（大約！·4克/平方公分）。於使m蓴膜冷卻 《後’然後自薄膜衝出面積15平方公分之碟狀物，並將其 稱重以測定石墨粉末之量。接著將此碟在真空中在8(rci 溫度下進一步乾燥大約15分鐘，然後再將碟轉移至密封盒 中:而不使碟暴露至環境空氣。將密封盒填充具低於丨卯㈤ 之氧及濕氣值之超純氬氣。 接著在使用作為試驗電池之標準幣型電池（c〇in ceii) (2025尺寸）的製造中，將此碟使用作為陽極。試驗電池之 另一電極為純鋰之箱（100微米，例如，Alfa人以訂）。在試 驗電池中使用雙層隔離物—作為在碳電極侧上之第一層 的玻璃氈（GF/B玻璃微纖維過濾器，Whatmaninternati〇n二86864.DOC -25- 1302761 The following techniques were used to evaluate the charge capacity of the powder particles and the irreversible charge capacity loss. A sample of the Prosthetic granules (5 g) and 3.82 g of 〇·382 g of polyvinylidene fluoride (PVDF, for example, Aldrich Chemical c〇., 111 〇) and 3.44 g of 1-methyl fluorenone (NMp) For example, 乂时化ch(四) id c〇·, ^·) ^♦ The liquid is mixed with the bottom, and 82 grams of acetylene black (with a ribbed square gram of surface area, for example, Aifa Aesar) is added thereto to form a uniform Feed water... Then, the slurry is cast by hand using a squeegee, and formed on the rough surface of the electrodeposited copper foil (1 〇 米 ' ' ' ' Fuduka Meul &amp; p〇wder c〇·, Ltd.) A loading of about 10 mg/cm 2 (four) membrane. The cast film is then placed on a hot plate at approximately [9]. Dry under c, and use a light press to pressurize the soil period I, the degree (about! 4g / cm ^ 2). The m 莼 film was cooled "post" and then a disk of 15 cm 2 was punched out from the film and weighed to determine the amount of graphite powder. The dish is then further dried in vacuum at 8 (rci temperature for about 15 minutes, and then transferred to a sealed box: without exposing the dish to ambient air. The sealed box is filled with oxygen below 丨卯(五) Ultra-pure argon with a moisture value. Next, in the manufacture of a standard coin-type battery (20 尺寸 size) used as a test battery, the dish was used as an anode. The other electrode of the test battery was pure. Lithium box (100 micron, for example, Alfa). Double layer spacer used in the test cell - glass mat as the first layer on the carbon electrode side (GF/B glass microfiber filter, Whatmaninternati〇) n two

Ltd·)及作為在鋰箔上之第二層的多孔性聚丙烯薄膜（以 Celgard⑧2300賭得，例如’ Celgard Inc_)。試驗電池之電Ltd.) and a porous polypropylene film as a second layer on a lithium foil (available from Celgard 82300, for example, 'Celgard Inc.). Test battery power

86864.DOC -26- 1302761 解質為於碳酸乙二酯（EC)/碳酸二乙酯（DEC)/碳酸二曱酽 (娜）溶劑、混合物（4_30)中之】M咖6^ Industrial)。根據習知技術利用前述組件製造試驗電池，但 改變粉末顆粒之樣品，以確保製得加入根據任一示範貪施 例或根據其中一比較實施例之粉末顆粒樣品的至少—二: 幣型電池。在室溫（大約饥）下測試此等粉末作為在^ = 離物/鋰金屬之幣型電池形態中的陽極材料。對各樣品製造 二或三個電池’所記述之充電容量及充電效率係此等^ 的平均值。 ％ / 特疋粉末顆粒樣品之容量及充電效率係根據以下方案 測疋。利用標準的電化學試驗站（BT_2〇43型， Instrument C〇rp·)，先使組裝好的試驗電池在丨毫安培（大約 67毫安^克）下放電至0伏特’及在〇伏特下維持2小口時，或 私/爪降低土低於5〇微安培為止，無論何者先發生。其 後使組裝好之試驗電池在1毫安培下充電至2伏特，其間使 =在无兒過程中通過之電荷於計算石墨粉末之比容量，同 1=用在无電過程中通過之總電荷對在放電過程中通過之 ~電荷之比於測定第一循環效率。 實施例1 隹=製備碳質粉末。先利用錘式磨將「綠」顆粒針狀煤 ’接著再利用射流磨研磨成微細粉末。接著將所得 ?質材料之研磨顆粒分級，以移除小w微米之顆粒。所 仔&lt; 碳質粉末具有女f 丄 ^ 大小在〇.5械米及約50微米之間之範圍 内的顆粒，及约15,微米之平均顆粒大小。86864.DOC -26- 1302761 is solvated in ethylene carbonate (EC) / diethyl carbonate (DEC) / dioxonium carbonate (Na) solvent, mixture (4_30)] M coffee 6 ^ Industrial). The test cell was fabricated using the foregoing assembly according to the prior art, but the sample of the powder particles was changed to ensure that at least a two-coin type battery incorporating the powder particle sample according to any of the exemplary embodiments or according to one of the comparative examples was prepared. These powders were tested at room temperature (approximately hungry) as anode materials in the form of a coin/lithium metal coin cell. The charging capacity and charging efficiency described in the manufacture of two or three batteries for each sample are the average values of these. The capacity and charging efficiency of the % / special powder particle sample were measured according to the following scheme. Using a standard electrochemical test station (BT_2〇43, Instrument C〇rp·), the assembled test cell is first discharged to 0 volts at 丨 milliamperes (approximately 67 mAh) and under volts Maintain 2 small mouths, or private / claw lower soil below 5 〇 micro amps, whichever occurs first. Thereafter, the assembled test cell was charged to 2 volts at 1 mA, during which the charge of the graphite powder was calculated during the absence of the process, and the specific charge of the graphite powder was used. The ratio of the charge passed during the discharge is determined by measuring the first cycle efficiency. Example 1 隹 = Preparation of a carbonaceous powder. First, the "green" granule acicular coal was firstly pulverized by a hammer mill and then ground to a fine powder by a jet mill. The abrasive particles of the resulting material are then classified to remove small w micron particles. The carbonaceous powder has particles of a size in the range of 〇5 mechanical meters and about 50 micrometers, and an average particle size of about 15, micrometers.

86864.DOC -27- 1302761 將在14(TC下之於4克TetraHn⑧（CigHi2)中之4克低熔點石 油瀝青（21〇°C梅特勒（Mettler)軟化點，75%亞爾可（Alc〇r) 碳殘留物，&lt; 1 00 ppm灰分各向同性石油瀝青）置於實驗室燒 杯中。將20克之如前所述而製得之碳質粉末與7〇〇毫升之在 12〇°C下之二甲苯（αΗ〆。2^)2)結合於第二個實驗室燒杯 中。將第一個燒杯之内容物逐漸加至第二個燒杯之内容物 中，及於添加之後，使所得之混合物在連續攪拌下於128〇c 下加熱及維持15分鐘。接著將熱源移除，及邊維持連續攪 拌邊使混合物冷卻至環境溫度（大約22t：)。經由先將混合 物於真空漏斗上過濾，其後再於真空中在120。(：下乾燥至少 3小時，而將生成之固體自經冷卻之混合物移除。由於瀝青 在Tetrahn®中之溶解度相對於瀝青在不同溫度下在大量二 甲苯中之落解度的差異，因而在碳質粉末顆粒上發生較高 熔點瀝青的選擇性沈澱。經乾燥之塗覆碳質粉末顆粒之最 終重量為約21 · 1克。碳質粉末上之沈澱瀝青之量係由以下 方程式測定： (最終重量-起始重量）/最終重量=沈澱瀝青之量 因此，證實碳質粉末上之沈澱瀝青之量佔塗覆之碳質粉 末顆粒之總質量的5重量％。 進行一個別貫驗，以測定由此實施例所製得之塗層的熔 點及碳殘留物產率。將各向同性瀝青於Tetralin⑧中之相同 落液加至相同量的二甲苯中，僅除了未將碳質顆粒分散於 一甲苯中。生成之瀝青沈澱物具有3 1〇它之熔點及之亞 爾可碳殘留物。86864.DOC -27- 1302761 4 grams of low melting point petroleum bitumen at 14 TC in 4 g TetraHn8 (CigHi2) (21 ° ° C Mettler softening point, 75% Alcoa (Alc 〇r) Carbon residue, &lt; 1 00 ppm ash isotropic petroleum pitch) placed in a laboratory beaker. 20 g of the carbonaceous powder prepared as described above and 7 〇〇 ml at 12 ° ° The xylene (αΗ〆.2^) 2) under C was combined in a second laboratory beaker. The contents of the first beaker were gradually added to the contents of the second beaker, and after the addition, the resulting mixture was heated and maintained at 128 ° C for 15 minutes with continuous stirring. The heat source is then removed and the mixture is allowed to cool to ambient temperature (approximately 22 t:) while maintaining continuous agitation. The mixture was filtered through a vacuum funnel and then at 120 in vacuo. (: drying for at least 3 hours, and removing the formed solids from the cooled mixture. Because of the difference in the solubility of bitumen in Tetrahn® relative to the degree of resolution of bitumen in a large amount of xylene at different temperatures, Selective precipitation of higher melting point asphalt occurs on the carbonaceous powder particles. The final weight of the dried coated carbonaceous powder particles is about 21 · 1 gram. The amount of precipitated asphalt on the carbonaceous powder is determined by the following equation: Final weight - starting weight) / final weight = amount of precipitated asphalt Therefore, it was confirmed that the amount of precipitated pitch on the carbonaceous powder accounted for 5% by weight of the total mass of the coated carbonaceous powder particles. The melting point and carbon residue yield of the coating prepared in this example were measured. The same drop of the isotropic pitch in Tetralin 8 was added to the same amount of xylene except that the carbonaceous particles were not dispersed in one. In toluene, the resulting asphalt precipitate has a melting point of 31 Å and a residue of Alcohol.

86864.DOC -28- 1302761 接著經由將粉末與9克之硝酸鈉（NaN〇3)(Acs.試劑，例 LT’Baker’ 11^_)&lt;1.5重量％水溶液徹底混合，而使法 覆之碳質粉末氧化。接著將混合物在真空中在啊下_ 、’其後再將乾燥混合物移至骑升之銘氧㈣並***至直 至爐:。'然後將料在真空條件下在rc/分鐘之速率下自、 大約環境溫度緩慢加熱至325。〇，此時將掛瑪在直办中在 =，下Λ持2小時。此緩慢加熱步驟提供適當的二反應 二广：ί任何進一步的加工步驟或處理之前將沈積 '、θ乳化及較化，且可使瀝青塗層形成較有規則的分子 «構7、此氧化步驟之後’可接著使經穩 質:末顆粒在又更高之溫度下破化，而使其之 有交化，及使塗層有極少或沒有熔解的可能性。 所:! Γ 了 Γ經進—步之加工而使用經穩定化之塗覆之碳 貝’’刀顆粒’但根據本發明之較佳具體實施例，實施進— 步的方法步驟，以最終將顆粒石墨化。 、 Τ在325 C下2小時之熱調理步驟之後，將含有經穩定化 《塗覆 &lt;碳質粉末顆粒之掛螞於氬氣中在rc/分鐘之速率 下進一步加熱至35(rc之溫度，此時將㈣在％代下 ^時^後將含有經穩定化之塗覆之碳質粉末顆粒之㈣ L二t速率下進一步加熱至赋之溫度，此時將掛 〇 乂呵/皿度下維持2小時。接著將含有經穩定化之塗覆 =粉末顆粒之㈣在rc/分鐘之速率下進一步加熱至 =加:時將㈣在_下維持2小時，其後中斷 相’、、、&amp;使烘箱之内容物冷卻至環境溫度（大約22。〇86864.DOC -28- 1302761 followed by thoroughly mixing the powder with 9 grams of sodium nitrate (NaN〇3) (Acs. reagent, LT 'Baker' 11^_) &lt; 1.5% by weight aqueous solution to make the carbon coated The powder is oxidized. The mixture is then placed in a vacuum under _, then the dry mixture is moved to the argon (4) and inserted until the furnace:. 'The material was then slowly heated to about 325 at about rc/min under vacuum conditions. Hey, at this time, Hang Ma will be held in the direct office for 2 hours. This slow heating step provides the appropriate two-reaction: ί emulsification and grading of any further processing steps or treatments, and allowing the asphalt coating to form a more regular molecule «Structure 7, this oxidation step It can then be stabilized: the final particles break at a higher temperature, making them cross-linked, and leaving the coating with little or no melting potential. The use of stabilized coated carbon shells ''knife particles' is used in the processing of the steps but, in accordance with a preferred embodiment of the invention, the method steps are further carried out to ultimately Graphitization of the particles. Τ After 2 hours of heat conditioning at 325 C, the stabilized “coated & carbonaceous powder particles are further heated to argon at a rate of rc/min. At this time, (4) will be further heated to the temperature at the L 2 rate of the stabilized coated carbonaceous powder particles after the % generation, and then the temperature will be hanged. It is maintained for 2 hours. Then, (4) containing the stabilized coating = powder particles is further heated to = plus at the rate of rc / minute: (4) is maintained at _ for 2 hours, after which the phase ', ,, &amp; The contents of the oven are allowed to cool to ambient temperature (approximately 22. 〇

86864.DOC -29- 1302761 。此外’應明瞭可於_或多個熱處理步驟之後使用經穩定 化^覆义碳質粉末顆粒而不經進一步加工，但根據本發 明足較佳具體實施例，最終將顆粒石墨化。 於塗覆之碳質粉末顆粒冷卻之後，經由將其轉移至石黑 掛瑪，接著再將㈣引入至具有氬大氣之感應爐，及先在 13C/分鐘之速率下將料加熱至28_之溫度，其後再在 5C/分鐘之速率下將掛禍加熱至編，此時將感應爐之 =度在30_下維持45分鐘之期間而將其石墨化，之後咸 h石墨化基本上完成。接著將經石墨化之塗覆之粉 顆粒自坩堝移出。 + 义生成之粉末顆粒展現良好的粉末流動性，且其看來並未 务生顆粒之融合。卜卜每&gt; ^ I、 只例《石墨粉末之電化學試驗的結 果頒示於比較實施例2後之表丨中。 實施例2 ，據參照實施们說明於上之方法步驟製造塗覆之碳質 ^末^的再—樣品。然而，根據此實施例，-開始狀5 :貝她例1中說明的低熔點石油瀝青置於第一實驗室燒 其加至8·5克之在 :―A至燒杯之内容物保持與實施例1相同，但所得之回 。的乾燥塗覆碳質粉末顆粒展現約22 3克之最終乾燥重量 、、人^此成息’測得以塗覆之碳質粉末顆粒之總質量計， -覆之碳質粉末顆粒上之塗層為約1〇重量％ :燥顆粒與9克之硝酸⑽卿.c咖 ，1加.）《3.8重1%水溶液徹底混合。接著將混合物於86864.DOC -29- 1302761. Furthermore, it should be understood that the stabilized carbonaceous powder particles may be used after _ or a plurality of heat treatment steps without further processing, but in accordance with a preferred embodiment of the present invention, the particles are finally graphitized. After the coated carbonaceous powder particles are cooled, they are transferred to the black stone, then (4) is introduced into the induction furnace with an argon atmosphere, and the material is heated to 28_ at a rate of 13 C/min. The temperature is then heated to a temperature at a rate of 5 C/min. At this time, the degree of the induction furnace is graphitized while maintaining the temperature for 30 minutes, and then the salty graphitization is substantially completed. . The graphitized coated powder particles are then removed from the crucible. + The powder particles produced by the formula exhibit good powder fluidity and it does not appear to be a fusion of the particles. The results of the electrochemical test of graphite powder are presented in the table after Comparative Example 2, respectively. Example 2, a re-sample of a coated carbonaceous material was prepared according to the method steps described above with reference to the examples. However, according to this embodiment, - the starting form 5: the low-melting petroleum pitch described in Example 1 is placed in the first laboratory to be added to 8·5 g in the: -A to beaker contents retention and examples 1 is the same, but the return is. The dry coated carbonaceous powder particles exhibit a final dry weight of about 22 3 grams, and the total mass of the coated carbonaceous powder particles is measured, and the coating on the coated carbonaceous powder particles is About 1% by weight: dry granules and 9 grams of nitric acid (10) qing. c coffee, 1 plus.) "3.8 heavy 1% aqueous solution thoroughly mixed. Then the mixture is

86864.DOC -30- 1302761 施例 下乾燦。接著使乾燥混合物氧化，及根據實 … 步驟熱處理，直至製得經石墨化之塗覆之碳 的=顆粒為止。實施例2之經石墨化之粉末顆粒展現良好 之石刀黑Γ力性且其看來並未發生顆粒之融合。此實施例 表i中刀末《私化學试驗的結果顯示於比較實施例2後之 實施例3 根據參照實施例！說明於 . 粉末顆粒的再一#品二:万法！:驟製造塗覆之碳質 〜 ^…、而，根據此貫施例，提供10克之 燒:中石油瀝青，將其加至在第一實驗室 之内容物保持與實施⑷相同，但所得之回收的乾 此=，質：末顆粒展現約22·7克之最終乾燥重量。基於 lj仔以土覆《蚊質粉末顆粒之總質量計，塗覆之 :=末顆粒上之塗層為約12重量％。接著將此等乾燥顆 在80t下參水溶液徹底混合。接著將混合物於真空中 中說明、r。接著使乾燥混合物氧化，及根據實施例1 末顆驟熱處理，直至製得經石墨化之塗覆之碳質粉 其看:並:發:::::融末：粒::見'良：：的粉末流動性，且 學試驗的結果顯示於比”墨粉末之電化 實施例4 根據參照實施例1說明於上之方法步驟製造塗覆之碳質86864.DOC -30- 1302761 Example Dry down. The dried mixture is then oxidized and heat treated according to the procedure until the graphitized coated carbon = particles are produced. The graphitized powder particles of Example 2 exhibited good stone knife blackness and it appeared that no particle fusion occurred. This example shows the results of the private chemical test in Table i. The results of the private chemical test are shown in Comparative Example 2, Example 3 according to the reference example! Description in . Powder granules again #品二: 万法! : Produce coated carbonaceous material ~ ^..., and according to this embodiment, provide 10 grams of burning: petroleum pitch, which is added to the contents of the first laboratory to maintain the same as the implementation (4), but the recovered Dry = this quality: the final granules exhibit a final dry weight of about 22.7 grams. Based on the total mass of the mosquito-coated powder particles, the coated: = coating on the final particles was about 12% by weight. The dried granules were then thoroughly mixed at 80 Torr. The mixture is then illustrated in a vacuum, r. The dried mixture is then oxidized and subjected to the final heat treatment according to Example 1 until the graphitized coated carbonaceous powder is prepared: and::::::: melt: grain:: see 'good: : powder flowability, and the results of the experimental test are shown in the "Electrochemical Example 4 of the Ink Powder". The coated carbonaceous material is produced according to the method step described above with reference to Example 1.

86864.DOC -31 - 1302761 粉末顆粒的再一樣品。然而，根據此實施 一 施例1之低熔點石；t t 守5克 &lt; 貫 〜15克之在14(rc下之了__ _ 卜實驗室燒杯中。第：實驗室燒杯 所得之回收的乾燥塗覆碳質粉末顆 、2、⑽克^終乾燥重量。基於此訊息，測得以塗覆 又石反i粉末顆粒之總質量計，H ' 厣為的17舌旦〇/ 土覆乏蛟貝粉末顆粒上之塗 (;_ 接著將此等乾燥顆粒與10克之硝酸制 (NaN03)(A-c-s·^^^ =:ΓΓ接著將混合物於真空中在8〇。。下乾燥。接 者使乾燥混合物氧化，及招摅與 牧 及根據m列1中說明之步驟 ’直至製得經石墨化之塗覆之«粉末顆粒為止。所= 粉末:粒展現良好的粉末流動性，且其看來並未發生顆和 :::。此實施例之石墨粉末之電化學試驗的結果顯示： 比較實施例2後之表丨中。 實施例5 才艮據參照實施m說明於上之方法步驟製造塗 料顆粒的再—樣品。“，根據此實施例，㈣克之會 施例1之低熔點石油瀝音 八 (Γ ^ 月及20克《在14〇〇C下之Tetrall_ ⑺12)置於第一實驗室燒杯中。第二實驗室燒杯之内容物 =持與實施例1相同，但所得之时的乾燥塗覆碳質粉末顆 :展,::25广最終乾燥重量。基於此訊息’測得以塗 极《故貝粉末顆粒之總f量計，塗覆之碳質粉末顆粒上之 二層為約21重量％。接著將此等乾燥顆粒㈣克 ⑽卿.C.S.試劑，例如，咖一86864.DOC -31 - 1302761 A further sample of powder particles. However, according to this embodiment, the low melting point stone of Example 1; tt is 5 grams &lt; 15 grams to 15 grams in 14 (rc under the __ _ _ laboratory beaker. Section: dryness of the recovered from the laboratory beaker) Coated carbonaceous powder, 2, (10) g ^ final dry weight. Based on this information, the total mass of the coated and anti-i powder particles was measured, and H ' 厣 was 17 tongue 〇 / soil-covered mussel Coating on powder granules (; _ then these dry granules are made with 10 g of nitric acid (NaN03) (Acs·^^^ =: ΓΓ then the mixture is dried under vacuum at 8 Torr. The mixture is dried. Oxidation, and toads and pastures and according to the procedure described in column 1 of 'before the preparation of the graphitized coated «powder particles. = powder: the particles show good powder flow, and it does not appear to The occurrence of granules and::: The results of the electrochemical tests of the graphite powder of this example are shown: Comparing the characterizations after Example 2. Example 5 The method of the above method is used to produce the coating granules according to the description of the reference m. Re-sample.", according to this embodiment, (4) gram will be the low melting point of the oil of Example 1 Eight (Γ ^ month and 20 g "Tetrall_ (7) 12 at 14 ° C) were placed in the first laboratory beaker. The contents of the second laboratory beaker = the same as in Example 1, but the drying at the time of the harvest Coated carbonaceous powder: exhibition, :: 25 wide final dry weight. Based on this message, the total amount of the coated carbon powder particles is about 21, and the coating on the carbonaceous powder particles is about 21 % by weight. Then dry these particles (four) grams (10) Qing. CS reagent, for example, coffee one

86864.DOC • 32 - 1302761 液徹底混合。接著將混合物於真空中在8〇它下乾燥。接著 使乾煤奶5物氧化，及根據實施例1中說明之步，驟熱處理， 直至製得經石墨化之塗覆之碳質粉末顆粒為止。所得之粉 末顆粒展現良好的粉末流動性，且其看來並未發生顆粒之 融合。此實施例之石墨粉末之電化學試驗的結果顯示於比 較實施例2後之表丨中。 比較實施例1 作為一比較實施例，將實施例1之相同的經研磨綠針狀 煤焦碳質粉末石墨化，及独離子電池中測試作為陽極竣 此比較貫施例展示使用未塗覆之經石墨化之碳質粉末顆 :此等未'塗覆之碳末顆粒之石、墨化係經由將其轉移 至石墨坩堝，將坩堝***至具有氬大氣之感應爐中，及I 在13°C/分鐘之速率下將坩堝加熱至28〇〇它之溫度，其後再 在5°C/分鐘之速率下將_加熱錢㈣，此時將感應捧 之溫度在3_。〇；下維持45分鐘之期間而達成。於此等力^ 後’咸信石墨化基本上完成。然後使含有未塗覆之 碳質粉末㈣之„冷卻至環境溫度，其後再將粉末顆粒 自㈣移出。生成之未塗覆之粉末顆粒展現良好的粉末、Γ 動性。此比較實施例之^粉末之電化學試驗的結果^ 於比較實施例2後之表1中。 /、 關於再-比較實施例’利用20克之「如研磨的」… 綠」碳質顆粒’將其與9克之硝_(N創獻cs_ =86864.DOC • 32 - 1302761 The solution is thoroughly mixed. The mixture was then dried under vacuum at 8 Torr. The dry coal milk 5 was then oxidized and subjected to a heat treatment according to the procedure described in Example 1 until the graphitized coated carbonaceous powder particles were obtained. The resulting powder particles exhibited good powder fluidity and it appeared that no particle fusion occurred. The results of electrochemical tests of the graphite powder of this example are shown in the surface after Comparative Example 2. Comparative Example 1 As a comparative example, the same ground green needle-like coal char carbon powder of Example 1 was graphitized, and the test was conducted as an anode in a single ion battery. This comparative example shows the use of uncoated. Graphitized carbonaceous powder particles: These uncoated carbon particles, inkized by inserting them into graphite crucible, inserting rhodium into an induction furnace with argon atmosphere, and I at 13° The crucible is heated to a temperature of 28 Torr at a rate of C/min, and then _heated at a rate of 5 ° C/min (four), at which time the temperature of the induction is at 3 _. 〇; reached under the 45-minute period. After this force ^ after the salty graphitization is basically completed. The uncoated carbonaceous powder (4) is then allowed to cool to ambient temperature, after which the powder particles are removed from (4). The resulting uncoated powder particles exhibit good powder and turbidity. This comparative example ^Results of Electrochemical Test of Powders ^ In Table 1 after Comparative Example 2. /, About Re-Comparative Example 'Using 20 grams of "as ground"... Green" carbonaceous particles' and 9 grams of nitrate _(N creation cs_ =

86864.DOC -33- 1302761 ’例如 ’ J.T.Baker，Inc.)之 ι·5重 0 A〉谷〉夜混合於實降當 燒杯中。接著將混合物於真空中在80t下乾燥，其後接著 將乾燥混合物提供至銘氧掛禍，並***至真空爐中。接著 使此等樣品進行如概逑於實施例！中之相同的熱處理步驟 ，即在真空條件下在〗它/分於少、去、玄，丁 A a 刀叙《速率下自大約環境溫度加 '為至_，其後再在真空中在3饥下維持2小時 立另=在氬氣中在lt/分鐘之速率下進―步加熱 =Γ:維持2小時，及謝 土 41GC^度，其後再在真空中維持2 有此等未塗覆夕石卢所九士 接者知吕 率下進牛：知末之爾氬氣中在5U分鐘之速 Γ: 至8，C之溫度，然後在85。。。下維持2小時 ，乏後中斷加熱，及使烨0、 争 20。〇。 紅相《内客物冷卻至環境溫度（大約 實施:二;:=1=顆粒之石墨化係利用參照比較 塗覆之粉末顆粒展 石里古、 牙末’瓜動性。此比較f施似少 學試驗的料顯示於下表1。 表1记述如使用說明於 之根據各實施购及比二例，之電試驗程序測得 七個樣品的結果。 ”孢例卜2製備得之粉末顆粒之86864.DOC -33- 1302761 ' For example, 'J.T. Baker, Inc.) ι·5 weight 0 A> Valley> night mixed in the real beaker. The mixture was then dried in vacuo at 80 t, after which the dry mixture was then supplied to a vacuum and inserted into a vacuum oven. These samples are then carried out as outlined in the examples! In the same heat treatment step, that is, under vacuum conditions, it is divided into less, de, and sin, and A A knife is said to increase the rate from about ambient temperature to _, and then in vacuum in 3 Keep hunger for 2 hours, stand another = argon gas at a rate of lt / minute, step heating = Γ: maintain 2 hours, and Xie Tu 41GC ^ degrees, then maintain in vacuum 2 have such uncoated At the end of the night, Shijiu Shilu’s picker knows the rate of entering the cow: the end of the argon gas at 5U minutes: to 8, the temperature of C, then at 85. . . After maintaining for 2 hours, the heating is interrupted after the exhaustion, and the 烨0, contends 20. Hey. Red phase "The internal guest is cooled to ambient temperature (approx. implementation: two;: = 1 = the graphitization of the granules is compared with the coated powder granules in the limestone, the end of the teeth, the melon kinetics. This comparison f The materials of the lesser test are shown in the following Table 1. Table 1 shows the results of seven samples measured according to the electrical test procedure of each of the two versions, as described in the instructions for use. It

86864.DOC '34、 130276186864.DOC '34, 1302761

可以看見當塗覆之'—— 環效率自5G%大大地^ =1。增加至1G重量％時，第-循 96%時，效率不會—96%。結果亦顯示當其達到约 之材料產生較未經處理°此外’根據本發明處理 起里义材枓高的容量。 實施例6 利用市售之具有低於44微米顆粒大小 石入墨粉末（購自’例如，L。咖之KS,製造根據本發^ 塗覆之碳質粉末顆粒的再—例子。將在14代下之於邮 tralmO(C1()Hi2)中之8 5克低熔點石油瀝青（21〇它梅特勒 軟化點’ 75%亞爾可碳殘留物，&lt;1〇〇 ppm灰分各向同性石 油瀝青）置於第一個實驗室燒杯中。將2〇克之經研磨天然石 墨粉末顆粒之樣品置於包含在12〇t；下之7〇〇毫升二甲苯 (C6H4(C2H3)2)之第二個實驗室燒杯中。將第一個燒杯之内 86864.DOC -35- 1302761 容物逐漸加至第二個燒杯之内容物中，及於添加之 所得之混合物在連續攪拌下於128。。下加熱及維持1〜 。其後將熱源移除’及邊維持連續擾拌邊使混合物冷； 環境溫度（大約2〇。〇。經由先將混合物於真空二 ，其後再於真空中在12(rc 過濾 广孕乙尿土少3小時，而將生成 固體自經冷卻之混合物移除。如實施例之論述，由 青在Tetralm®中之溶解度相對於瀝青在不同溫度下在二甲此 苯中μ解度的差異，因而選擇性沈殿導致較聽點歷青 之沈殿及沈積於碳暂絡古斑止、 貝知末顆权上。測得經乾燥之塗覆碳質 粉末顆粒之最終重量為約22 3克，同時測得碳質粉末上： 沈深又遞^青之為塗霜士石卢所». 乃土復又奴貝粉末顆粒之總質量的10重量％。 接著將經乾燥之塗覆之竣質粉末顆粒與9克之硝酸納 (NaN〇3)(AX.S·試劑，例如].ΤΒ㈣ine.)之38重量％水 溶液徹底混合。接荖將、、日人此&gt; + — 按耆和化合物在真空中在80°C下乾燥。接 著使乾燥混合物進行如概述於實施例丨中之相同的熱處理 乂 ” &gt; p在真工‘件下在1。。/分鐘之速率下自大約環境溫 度加熱至325°C ’其後再在真空中在3抓下維持2小時。接 下來’將顆粒在氬氣中在lt/分鐘之速率下進—步加熱至 350 C纟後在350 C下維持2小時，及接著在Γ(：/分鐘之速 率下加熱至41(TC之溫度，其後再維持2小時。接著將含有 塗覆《碳質粉末之掛瑪在5t/分鐘之速率下進一步加熱至 8 5 0 〇 溫度，缺^德尤^。广 ，、便在850 C下維持2小時，之後中斷加熱， 及使=箱之内容物冷卻至環境溫度（大約饥）。 此寺塗覆之碳質粉末顆粒之石墨化係經由將其轉移至It can be seen that when the coating is applied, the ring efficiency is greatly from =1 to =1. When it is increased to 1 G weight%, the efficiency is not -96% when the first cycle is 96%. The results also show that when it reaches about the material, the material is produced more untreated. In addition, the capacity of the material is treated according to the present invention. Example 6 Using a commercially available stone-incorporated powder having a particle size of less than 44 microns (available from ', for example, KS of L., a re-example of the production of carbonaceous powder particles coated according to the present invention. Will be in the 14th generation. Under the mail of trlmO (C1 () Hi2) 8 5 grams of low melting petroleum pitch (21 〇 its METTLER softening point '75% Alecco carbon residue, &lt; 1 〇〇 ppm ash isotropic oil The asphalt was placed in the first laboratory beaker. A sample of 2 g of the ground natural graphite powder particles was placed in a second volume of 7 ml of xylene (C6H4 (C2H3) 2) contained at 12 Torr. In a laboratory beaker, the contents of 86864.DOC -35- 1302761 in the first beaker are gradually added to the contents of the second beaker, and the resulting mixture is added under continuous stirring at 128°. Heat and maintain 1~. After that, remove the heat source' and maintain the continuous disturbing edge to make the mixture cold; ambient temperature (about 2 〇. 〇. by first mixing the mixture in vacuum two, then vacuum in 12 ( Rc filters the gestation of the urinary soil for 3 hours, and removes the solids from the cooled mixture. For example, the solubility of Qing in Tetralm® is different from that of asphalt at different temperatures in the benzene. Therefore, the selective sedation leads to the sacred temple and the deposition of carbon in the ancient The final weight of the dried coated carbonaceous powder particles was determined to be about 22 3 grams, and the carbonaceous powder was measured at the same time: Shen Shen and Chen Qingzhi were coated with frost stone. Lushen». 10% by weight of the total mass of the saponin powder. The dried coated enamel powder particles are then neutralized with 9 grams of sodium nitrate (NaN〇3) (AX.S. reagent, for example ]. (4) in.) 38% by weight of the aqueous solution was thoroughly mixed. Then, the Japanese, &gt; + - the hydrazine and the compound were dried in vacuum at 80 ° C. Then the dry mixture was carried out as outlined in the examples 丨The same heat treatment 乂" &gt; p is heated to approximately 325 ° C from approximately ambient temperature at a rate of 1 / minute, and then maintained in vacuum for 3 hours under vacuum. Down', the pellets are heated in argon at a rate of lt/min and heated to 350 C纟 at 350 Maintain for 2 hours at C, and then heat to 41 (the temperature of TC at 速率(:/min), followed by another 2 hours. Then the rate of coating the carbonaceous powder at 5t/min Further heating to a temperature of 850 ° ,, lacking ^ 尤 ^ ^ wide, and then maintained at 850 C for 2 hours, then interrupted heating, and the contents of the = box cooled to ambient temperature (about hunger). The graphitization of the coated carbonaceous powder particles is transferred to

86864.DOC -36- 1302761 •禍’將„插人至具有氬大氣之感應爐中，及先在 jc/分鐘之速率下將坩堝加熱至28〇〇t：之溫度，其後再在 二/分鐘之速率下將掛瑪加熱至3〇，c，此時將感應爐之 ~度在30峨下維持45分鐘之期間而達成。於此等加教步 ，後，咸信石墨化基本上完成。然後使含有塗覆之碳質 ^末顆粒之㈣冷卻至環境溫度（大約22。〇,其後再將粉 =粒自掛卿出。生成之粉末顆粒展現良好的流動性。 ”她例《石墨粉末之電化學試驗的結果顯示於比較會 例5後之表2中。 實施例7 、利用何生自具有在w米及約5()微米之間之範圍内之顆 粒大小及約20微米之平均顆粒大小之烺製石油針狀煤焦 (懷製溫度mot)的顆粒製造根據本發明之塗覆之碳” 末顆粒的再一樣品。與實施例6所說明之方法類似，將^ 140°C下之於8.5克Tetrali_(Ci〇Hi2)中之8·5克低溶點石油 歷青（21G°C梅特勒軟化點’ 75%亞爾可碳殘留物，侧 ppm灰分各向同性石油瀝青)置於第一個實驗室燒杯中。將 20克之經研磨烺製石油煤焦粉末顆粒之樣品置於包 ⑽下之700毫升二甲苯（C6H4(C2H3)2)之第二個實驗❹ 杯中。將第-個燒杯之内容物逐漸加至第二個燒杯之内容 物中，及於添加之後，使所得之混合物在連續攪拌下於 128°C下加熱及維持15分鐘。其後將熱源移除，及邊維 連續揽拌邊使混合物冷卻至環境溫度（大約22。〇。細由先 將混合物於真空漏斗上過滤’其後再於真空中86864.DOC -36- 1302761 •Cause 'to insert into the induction furnace with argon atmosphere, and first heat the crucible to a temperature of 28〇〇t: at a rate of jc/min, then again at two/ At the rate of minutes, the hangma is heated to 3 〇, c, and the induction furnace is maintained at a temperature of 30 维持 for 45 minutes. After this step, the salty graphitization is basically completed. Then, (4) containing the coated carbonaceous particles is cooled to ambient temperature (about 22. 〇, and then the powder = granules are self-sustained. The resulting powder particles exhibit good fluidity.) The results of the electrochemical tests of the graphite powders are shown in Table 2 after Comparative Example 5. Example 7 using a particle size having a range between w meters and about 5 () microns and about 20 microns A further sample of the coated carbon needles according to the present invention is produced from the particles of the average oil particle size of the oily needle coal char (the temperature of the mot). Similar to the method described in the embodiment 6, the At 85 °C in the 8.5 g Tetrali_(Ci〇Hi2), the low melting point of the petroleum calendar (21G °C Mettler soft Point '75% Alecco carbon residue, side ppm ash isotropic petroleum pitch) placed in the first laboratory beaker. Place 20 grams of the sample of ground tantalum petroleum coal coke powder particles under the package (10) In the second experimental bowl of 700 ml of xylene (C6H4(C2H3)2), the contents of the first beaker were gradually added to the contents of the second beaker, and after the addition, the resulting mixture was allowed to Heating and maintaining at 128 ° C for 15 minutes with continuous stirring. Thereafter, the heat source was removed, and the mixture was continuously cooled to ambient temperature (about 22. 〇. Fine by first filtering the mixture on a vacuum funnel 'Then after the vacuum

86864.DOC -37- 1302761 少罙至少3小時，而網i座士、a — 、成足固骨豆自經冷卻之混合物移 貫她例1中之論述，由主 除。如 、瀝同在Tetralln⑧中之溶解度相斟、人 瀝青在不同溫度下在- 、 又相對万； 、 甲本中义落解度的差異，因而、明姐 性沈殿導致較㈣點瀝青之沈殿及H = 。測得經乾燥之塗覆碳質粉末顆粒之最終重量為=: ’同時測得碳質粉末上之沈搬瀝青之量為 ;^ 顆粒之總質量的10重量％。 人貝右末 接者H乾燥疋塗覆之碳f粉末顆粒與 卿雜,試劑，例一a—之 施例5後之表2中 t液徹辰混合。接著將混合物在真空中在m：下乾燥。接 歧乾燥混合物進行如概述於實施例6中之相同的穩定化 =及石、f、化步驟。生成之粉末顆粒展現良好的流動性 、訑例之石墨粉末之電化學試驗的結果顯示於比較膏 實施例8 利用具有在1微米及約5〇微米之間之範圍内之顆粒大小 、、、勺〇彳放米之平均顆粒大小之經研磨的「綠」石油針狀煤 焦製造塗覆之碳質粉末顆粒。與實施例6所說明之方法類似 ，將在14〇°C下之於10克Tetralin®(C1GH12)中之1〇克低熔點 石油瀝青（2 l〇t梅特勒軟化點，75%亞爾可碳殘留物，&lt;1〇〇 ppm灰刀各向同性石油瀝青）置於第一個實驗室燒杯中。將 20克之經研磨天然石墨粉末顆粒之樣品置於包含在12〇。匕 下之700笔升一甲苯（C6H4(C2H3)2)之第二個實驗室燒杯中 。將第一個燒杯之内容物逐漸加至第二個燒杯之内容物中86864.DOC -37- 1302761 The ensign is at least 3 hours, and the mixture of the net i, the a-, and the solid bone-peas from the cooled mixture moves through the discussion in her example 1, divided by the main. For example, the solubility of Letong in Tetralln8 is opposite, that of human asphalt is at - and relatively 10,000 at different temperatures; and the difference in the degree of solution between the two, so that the sister of the Ming Dynasty leads to the (four) point of the asphalt and H = . The final weight of the dried coated carbonaceous powder particles was measured as =: '. The amount of the settled bitumen on the carbonaceous powder was also measured as 10% by weight of the total mass of the particles. The right end of the person is the H dry 疋 coated carbon f powder particles and the mixture, the reagent, the first one a-the second embodiment of the second example, the t liquid is mixed. The mixture was then dried under vacuum at m:. The dry mixture was subjected to the same stabilization as in Example 6 and the steps of stone, f, and crystallization. The resulting powder particles exhibit good fluidity, and the results of electrochemical tests of graphite powders of the examples are shown in Comparative Paste Example 8 using a particle size having a range between 1 micrometer and about 5 micrometers, The coated "green" petroleum needle coal char is produced from the average particle size of the rice to produce coated carbonaceous powder particles. Similar to the method described in Example 6, 1 gram of low melting point petroleum pitch (2 l〇t METTLER softening point, 75% Yar) in 10 g of Tetralin® (C1GH12) at 14 °C Carbon residue, &lt;1 〇〇 ppm gray knife isotropic petroleum pitch) was placed in the first laboratory beaker. A sample of 20 grams of ground natural graphite powder particles was placed at 12 Torr. In the second laboratory beaker of 700 liters of toluene (C6H4 (C2H3) 2). Gradually add the contents of the first beaker to the contents of the second beaker

86864.DOC -38- 1302761 ，及於添加之後，使所得之混合物在連續攪拌下於128t 加熱及維持15分鐘。其後將熱源移除，及邊維持連鲭攪拌 邊令卻至環境溫度(大約2rc)。經由先將混合物 万；八玉漏+上過濾，其後再於真空中在120。〇下乾燥至 :時:而將生成之固體自經冷卻之混合物移除。如；：例1 ' mtrahn_《溶解度相對於歷青在 不同狐度下在二甲苯中之溶解度的差異，因而選擇 導致較高溶點歷青之沈殿及沈積於碳質粉末顆粒上。μ 碳質粉末顆粒之最終重量為卿，二 一 尤澱瀝青之量為塗覆之碳質粉末顆粒之她 質量的13重量％。 不木、拉义總 接著知經乾燥 &lt; 塗覆之碳質粉末顆 溶液徹底混合。接著將混合物在真空中在8代下乾;t 著使乾燥混合物進料概述Μ施例6中 ^^ = 化方法。生成之粉末顆二= -也例芡石墨粉末之電化學試 於比較實施例5後之表2中。 的m果頌不 比較實施例3 程，㈣物於前文之標題「電化學試驗 石愛於末、；評估如說明於實施例6中之市售經研磨合成 =末讀品的電性能特性。購得之經研磨合成石 ί ”係以取得的狀態使用，其未根據本發明之方心 覆。電性能評估之結果說明於下表万法主86864.DOC -38-1302761, and after the addition, the resulting mixture was heated and maintained at 128 t with continuous stirring for 15 minutes. The heat source is then removed and the ambient temperature (about 2 rc) is maintained while stirring. The mixture was first filtered through a mixture of 10,000 and eight liters, followed by a vacuum at 120. Dry under the armpit until: The resulting solid is removed from the cooled mixture. For example: Example 1 'mtrahn_' solubility is different from the solubility of Eclipta in xylene at different foxes, thus selecting the higher melting point of the sapphire and depositing on the carbonaceous powder particles. The final weight of the μ carbonaceous powder particles is qing, and the amount of the yue yam pitch is 13% by weight of the mass of the coated carbonaceous powder granules. Do not wood, pull the total and then know the dried &lt; coated carbon powder solution thoroughly mixed. The mixture is then dried under vacuum for 8 generations; t is used to feed the dry mixture as outlined in Example 6. The resulting powder particles 2 = - also an electrochemical example of graphite powder was tested in Table 2 after Comparative Example 5. The results of Example 3 were not compared with (4) in the previous section entitled "Electrochemical Tests for Stones, and the evaluation of the electrical properties of commercially available milled synthetic = final readings as described in Example 6. The purchased ground synthetic stone 使用 is used in the obtained state, which is not covered according to the present invention. The results of the electrical performance assessment are described in the table below.

86864.DOC •39- 1302761 、 比較實施例4 為作為比較用，亦利用說、 程序」下之程序評估如說日月於實m =題「電化學試驗 針狀煤焦之樣品的電性能特性。購得之磨烺製石油 樣品係以取得的狀態使用，1未根：：：研磨烺製煤焦之 但使其料如概述於實施例6中之:^方法塗覆， 能評估之結果說明於下表2中。 ，、處理步驟。電性 、 比較實施例5 為作為比較用，亦利用命二、 程庠下、 況明於則又之標題「電化學試矜 」下〈私序評估如說明於實施 狀煤焦之樣品的電性能特性 广「汗“」針 接口# ，苒侍&lt;經研磨「綠」煤舞爻 樣=以取得的狀態使用，其未根據本發明之方法塗覆^ 、進行如概述於實施例6中之相同的熱處理步驟。電性 能評估之結果說明於下表2中。 笔性86864.DOC •39- 1302761, Comparative Example 4 is used for comparison, and the program under the program is used to evaluate the electrical performance characteristics of the sample of the electrochemical test needle coal char. The purchased honed petroleum sample is used in the obtained state, 1 unrooted::: pulverized coal char is made but the material is as outlined in Example 6: ^ method coating, the result of evaluation The description is given in Table 2 below, and the processing steps. Electrical properties, Comparative Example 5 is used for comparison, and also uses the title of "Secondary Electrochemistry" under the heading "Electrochemical Test". Evaluation of the electrical performance characteristics of the sample described in the embodiment of the coal char "Khan" needle interface #, 苒 & 经 磨 磨 磨 " " " " " " " " " " " " " " " " " " " " " " " " " " " The same heat treatment step as outlined in Example 6 was carried out by coating. The results of the electrical performance assessment are illustrated in Table 2 below. Pen

86864.DOC 1302761 如由1己述於表2中之結果所明顯可見，根據本發明之組 石物（貝施例6、7及8)展現高效率（&gt;94%)。由未根據本發明 塗覆之相同材料所組成之比較實施例展現甚低於根據本發 明宝覆4相同材料的效率，以及展現較高的不可逆容量損 耗0 、根據另-種將塗層提供至顆粒之技術製造根據本發明 之塗覆之碳質粉末顆粒的再一樣品。 將20克之低溶點石油遞青⑵代梅特勒軟化點，μ%亞 爾可碳殘留4勿，&lt;100ppm灰分各向同性石油歷青）謂克之86864. DOC 1302761 As is apparent from the results of 1 described in Table 2, the compositions according to the present invention (Bei Shi, Examples 6, 7, and 8) exhibited high efficiency (&gt; 94%). A comparative example consisting of the same material not coated according to the invention exhibits a very lower efficiency than the same material according to the invention, as well as exhibiting a higher irreversible capacity loss 0, providing a coating according to another The granule technique produces a further sample of the coated carbonaceous powder particles in accordance with the present invention. 20 grams of low melting point oil is given to the blue (2) generation of METTLER softening point, μ% Alcohol residue 4, &lt;100ppm ash isotropic oil calendar)

甲基峨咯相_P，例如，杨㈣C— c〇.，W 置於實驗室燒杯中，而形ώ T、丄、r ±、 ’ /成石油瀝青&lt; 20重量％溶液。將 溶液錢拌下加熱至大㈣。C，此時引人20克之實施例8 &lt;經研磨「綠」針狀煤焦顆粒，及將燒杯之内 拌15分鐘，以確保均白_ 技_ ^ 勻度。接耆經由先利用真空漏斗 混合物，其後料真空中在_下㈣至少5小時，μ 生成之固體自混合物移降、Η 、 ， 則仵經乾燥之塗覆碳質粉末顆 =終重蝴23.5克，及測得碳質粉末上之沈 q為u之碳質粉末顆粒之總f量的15重量％。 接下來將經乾燥之塗覆之竣質粉 納⑽n〇3)(a.c.s.試劑 /、克 &lt;硝版 maker，Inc·)之3重晋0/ =溶液徹底混合。接著將混合物在真空中在帆下乾燥，。 將乾燥混ί物置於50毫升之鋁氧輯並***至 内。其後使塗覆之碳f粉末顆粒進行如說明於實施Methyl fluorene phase _P, for example, yang (tetra) C-c 〇., W is placed in a laboratory beaker, and T, 丄, r ±, ‘ / into petroleum pitch &lt; 20% by weight solution. Mix the solution and heat it to a large (four). C, at this time, 20 g of Example 8 was introduced; the "green" needle coal char particles were ground, and the beaker was mixed for 15 minutes to ensure uniformity. After the first use of the vacuum funnel mixture, and then in the vacuum in the _ under (four) for at least 5 hours, the μ-formed solids are transferred from the mixture, Η, then the dried coated carbonaceous powder particles = final weight 23.5克, and 15% by weight of the total amount of f of the carbonaceous powder particles having a sinking q of u on the carbonaceous powder. Next, the dried coated enamel powder (10) n 〇 3) (a.c.s. reagent /, gram &lt; nitrate model, Inc.) was re-mixed. The mixture was then dried under a sail in a vacuum. The dry mixture was placed in 50 ml of aluminum oxide and inserted. Thereafter, the coated carbon f powder particles are subjected to implementation as described

86864.DOC -41 &gt; 1302761 例1中之相同的熱處理步騾，及最終製得經石墨化之塗覆之 後質粉末顆粒。 根據說明於前文之標題「電化學試驗程序」下之程序評 估粉末顆粒之充電容量以及不可逆的充電容量損耗。電性 能評估之結果說明於下表3。 表3 塗覆之瀝青 容量 不可逆的容量 效率 —~--- —(%)— (mAh/g) 損耗（mAh/g) (%) 例9 1------ 15 339 29 92 、根據另種將塗層提供至顆粒之技術製造根據本發明 之’至覆之碳質粉末顆粒的再一樣品。 、知20克义低熔點石油瀝青（21〇它梅特勒軟化點，乃％亞 爾1¼殘留物’&lt;100ppm灰分各向同性石油瀝青)及肋克之 b甲基吨咯淀酮（NMP，例如，Aldrichchemicaic f於實驗室燒杯中，而形成石油《之 /合液在攪拌下加熱至大約60。〇此時引A 中阱估u此時引入20克足如實施例7 〇 1石油針狀煤焦（烺製溫度丨丨〇〇 杯之内容物再多攪拌15八於 ^ 及如挺86864.DOC -41 &gt; 1302761 The same heat treatment step in Example 1, and finally the graphitized coated post-powder powder particles. The charge capacity of the powder particles and the irreversible charge capacity loss were evaluated according to the procedure under the heading "Electrochemical Test Procedure" in the previous section. The results of the electrical performance assessment are illustrated in Table 3 below. Table 3 irreversible capacity efficiency of coated asphalt capacity—~---(%)—(mAh/g) loss (mAh/g) (%) Example 9 1–15 339 29 92 Another technique for providing a coating to a granule produces a further sample of the 'coated carbonaceous powder particles according to the present invention. Know 20 grams of low-melting petroleum pitch (21 〇 its METTLER softening point, which is % yel 11⁄4 residue '&lt;100ppm ash isotropic petroleum pitch) and ribb b methyl tonaloxone (NMP, For example, Aldrichchemicaic f is in a laboratory beaker, and the oil formed is heated to about 60 with stirring. At this point, the well in the A is estimated to be introduced at this time. 20 gram of the foot is introduced as in Example 7 Coal char (the temperature of the cup is more than 15% in the contents of the cup) and

⑴ 讀5刀‘，以確保均勻度。接著細U 利用真空漏斗過滹混人物，Α %; *耆、、'工由先(1) Read 5 knives to ensure uniformity. Then use the vacuum funnel to mix the characters, Α%; *耆,, 'Work by first

石丨 二此口物其後再於真空中在100t：Ti”Q 土”小時，而將生成 ♦杈 塗覆碏皙扒古啦 W 口物私除。測得經乾燥之 旻人/、♦刀末顆粒之最終重晋 里為約21克，同時測得碳質粉The stone 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨 丨It is measured that the dried 旻人/, ♦ knife end granules are about 21 grams in the final re-introduction, and the carbon powder is measured at the same time.

86864.DOC -42- 1302761 末上 &lt; 沈澱瀝青之量為塗覆之碳質粉末顆粒之總質量的5 重量％ 〇 接下來將經乾燥之塗覆之碳質粉末顆粒與u克之硝酸鈉 (NaN03)(A.C.S·試劑，例如，JTBaker，Inc)之 3重量 ％水溶 液徹底混合。接著將混合物在真空中在8(rc下乾燥，其後 接著將乾燥混合物置於鋁氧坩堝中並***至真空爐内。其 後使塗覆之碳質粉末顆粒進行如說明於實施例丨中之相同 的熱處理步驟，及最終製得經石墨化之塗覆之碳質粉末顆 粒。 根據說明於前文之標題「電化學試驗程序」下之程序評 估粉末顆粒之充電容量以及不可逆的充電容量損耗。電性 能評估之結果說明於下表4。 表4 塗覆之瀝青 容量 不可逆的容量 ~~-—— 效率（0/0) -_(%) (mAh/g) 損耗（mAh/g) 例10 __ 5 343 —---—--°j 22 ~·—, 94 如此貫施例所說明，低至5重量％之於煤焦微細粉末上之 歷青塗層值或低至4重量％之塗覆之碳殘留物仍可根據本 發明顯著地抑制不可逆的容量損耗。 實施例11 製造示範使用木質素作為碳質粉末顆粒之可溶解之硬 殘留物形成材料塗層之根據本發明之塗覆之碳質粉末顆^86864.DOC -42- 1302761 Last &lt; The amount of precipitated bitumen is 5% by weight of the total mass of the coated carbonaceous powder particles. 〇 Next, the dried coated carbonaceous powder particles and u grams of sodium nitrate ( A 3 wt% aqueous solution of NaN03) (ACS·reagent, for example, JT Baker, Inc.) was thoroughly mixed. The mixture was then dried under vacuum at 8 (rc), after which the dry mixture was placed in an aluminoxane and inserted into a vacuum oven. The coated carbonaceous powder particles were then subjected to the same as described in the Examples. The same heat treatment step, and finally the production of the graphitized coated carbonaceous powder particles. The charging capacity of the powder particles and the irreversible charge capacity loss were evaluated according to the procedure under the heading "Electrochemical Test Procedure". The results of the electrical performance evaluation are shown in Table 4. Table 4 The irreversible capacity of the coated asphalt capacity ~~-—— Efficiency (0/0) -_(%) (mAh/g) Loss (mAh/g) Example 10 __ 5 343 —------°j 22 ~·—, 94 As described in this example, as low as 5% by weight on the coal char fine powder, the value of the calendar coating is as low as 4% by weight. The coated carbon residue can still significantly inhibit irreversible capacity loss according to the present invention. Example 11 Manufacture of a coating according to the invention using lignin as a soluble hard residue forming material coating of carbonaceous powder particles Carbonaceous powder ^

86864.DOC -43- 1302761 的一樣品。另外，此實施例示範單一步驟的塗覆及氧化方 法。 於實驗室燒杯中，將2.0克之木質素（Alkali Kraft，例如 ，Aldrich Chemicals Co.，Inc.)及 0.3 克之硝酸鈉（NaN03)混 合於9克之1 Μ KOH水溶液中。此木質素具有約47%之碳殘 留物及300°C之熔點。接著將20克如實施例1所使用之經研 磨「綠」顆粒針狀煤焦 業的貫驗室摻混機（Waring 5 1BL31型）使實驗室燒杯之内 容物徹底混合。將混合物自實驗室摻混機移出，並於真空 中在80°C下乾燥12小時。測得經乾燥之塗覆碳質粉末顆粒 之最終重量為約22.4克，同時測得碳質粉末上之沈澱木^ 素之量為塗覆之碳質粉末顆粒之總質量的丨〇重量％。 接著使經乾燥之塗覆之碳質粉末顆粒進行如說明於會 施例1中之相同的熱處理步驟，及最終製得經石墨化之泠: 之碳質粉末顆粒。 土復 根據說明於前文之標題「電化學試驗程序」下之。、、… 估粉末顆粒之充電容量以及不可逆的 序汗 能邮仏、 」尤私备I扣耗。電性 月匕汗估又結果說明於下表5 0A sample of 86864.DOC -43- 1302761. Additionally, this example demonstrates a single step coating and oxidation process. In a laboratory beaker, 2.0 g of lignin (Alkali Kraft, for example, Aldrich Chemicals Co., Inc.) and 0.3 g of sodium nitrate (NaN03) were mixed in 9 g of a 1 KOH aqueous solution. This lignin has about 47% carbon residue and a melting point of 300 °C. Next, 20 g of a laboratory blender (Waring 5 1BL31 type) of the ground "green" granule needle coal used in Example 1 was used to thoroughly mix the contents of the laboratory beaker. The mixture was removed from the laboratory blender and dried in vacuum at 80 ° C for 12 hours. The final weight of the dried coated carbonaceous powder particles was measured to be about 22.4 g, and the amount of precipitated wood on the carbonaceous powder was measured as the % by weight of the total mass of the coated carbonaceous powder particles. The dried coated carbonaceous powder particles were then subjected to the same heat treatment step as described in Example 1, and finally, the graphitized crucible: carbonaceous powder particles were obtained. According to the description under the heading "Electrochemical Test Procedures". ,,... Estimate the charging capacity of the powder particles and the irreversible order of sweat. The results of the monthly lunar sweat estimate are shown in the table below.

不可逆的容量 21 根據實施例&quot;之組合物之效率顯示較諸如關於表二 i|jMmAh/g) _ ^—Irreversible capacity 21 The efficiency of the composition according to the example &quot; is more like, for example, Table 2 i|jMmAh/g) _ ^-

86864.DOC -44- 1302761 較實施例5所記述之結果之顯著及驚人的改良，其顯示由實 施本發明所達成的驚人改良。 實施例12 製造示範使用糖作為碳質粉末顆粒之可熔解之礙殘留 物形成材料塗層之根據本發明之塗覆之碳質粉末顆粒的一 樣品。此糖具有約25%之碳殘留物。 於實驗室中，將3克之白糖（House Recipe⑧，Sys⑶86864.DOC -44- 1302761 A significant and surprising improvement over the results described in Example 5, which shows a dramatic improvement achieved by the practice of the present invention. Example 12 A sample of the coated carbonaceous powder particles according to the present invention was exemplified using a sugar as a meltable carbonaceous powder particle. This sugar has about 25% carbon residue. In the laboratory, 3 grams of white sugar (House Recipe8, Sys (3)

Corporation配銷）及〇·3克之硝酸鋼（NaN〇3)溶解於9克之去 離子水中。接著將2〇克如實施例i所使用之經研磨「綠」顆 粒針狀煤焦顆粒置於實驗室燒杯中，及利用商業的實驗室 =混機（waring 5胤31型）使實驗室燒杯之内容物徹底混 合。其後將混合物自實驗室燒杯移出，並於真空中在8(rc 、、】時測得煤焦顆粒上之塗覆糖之量為約丨3重量〇/0。 接著使經乾燥之塗覆之碳質粉末顆粒進行如說明於眘 施例1中之相同的穩定化、碳化及石墨化步驟，及最終製得 經石墨化之塗覆之碳質粉末顆粒。 根據說明於前文之標題「 3 估粉末顆粒之充電容量以/ 序」下之程序評 Λ, ^ , 及不可圯的充電容量損耗。電性 月匕汗估&lt;結果說明於下表6。The Corporation distributes and 3 g of nitric acid (NaN〇3) is dissolved in 9 g of deionized water. Next, 2 g of the ground "green" particle needle coal char particles used in Example i were placed in a laboratory beaker, and the laboratory beaker was made using a commercial laboratory = mixing machine (waring 5胤31 type). The contents are thoroughly mixed. Thereafter, the mixture was removed from the laboratory beaker and the amount of coated sugar on the coal char particles was measured at 8 (rc, , ) in a vacuum of about 〇3 wt〇/0. The dried coating was then applied. The carbonaceous powder particles were subjected to the same stabilization, carbonization and graphitization steps as described in the caution application example 1, and finally the graphitized coated carbonaceous powder particles were obtained. According to the description in the foregoing title "3" It is estimated that the charging capacity of the powder particles is evaluated by the procedure under /, ", and the non-defective charging capacity loss. The electrical monthly sweating estimate" is shown in Table 6 below.

86864.DOC -45. 1302761 表6 塗覆之糖 容量 ~&quot; -___ 不可逆的容量 效率 ___ (%) (mAh/g) JU^(mAh/g) (〇Δ\ 例12 13 303 ——-A3 V /〇) 93 製造示範使用環境空氣作為碳質粉末顆粒之可熔解之 碳殘留物形成材料塗層之氧化劑之根據本發明之塗覆之碳 質粉末顆粒的一樣品。 將在140°C下之於8.5克Tetralin⑧（Ci〇Hi2)中之8·5克低熔 點石油歷青（2HTC梅特勒軟化點，75%亞爾可碳殘留物， &lt;100 ppm灰分各向同性石油瀝青，說明於實施例υ置於實 驗室燒杯中。將20克之如參照實施例!而說明及製造之碳質 粉末與700毫升之在】机下之二甲苯（ 於 第二個實驗室燒杯中。將第一個燒杯之内容二^ L内容物中，及於添加之後，使所得之混合物在 下於約128t；下加熱及維持15分鐘。接著將熱源移 =及4持連續檀拌邊使混合物冷卻至環境溫度（大約 C)。經由先將混合物於真空漏斗上過攄，… 中在120°C下乾燥黾，丨以τ访 广 、/、工 混合物移除〜3小時’而將生成之固體自經冷卻之 旦經㈣之粉末重22.3克。測得碳質粉末上之沈殿歷青之 里佔堡覆《碳質粉末顆粒之總f量的Μ重量％。86864.DOC -45. 1302761 Table 6 Coated Sugar Capacity~&quot; -___ Irreversible Capacity Efficiency ___ (%) (mAh/g) JU^(mAh/g) (〇Δ\ Example 12 13 303 —— -A3 V /〇) 93 A sample of the coated carbonaceous powder particles according to the present invention is exemplified using ambient air as the oxidant of the meltable carbon residue forming material coating of the carbonaceous powder particles. 8.5 g of low melting point petroleum azurol (2HTC Mettler softening point, 75% Alecco carbon residue, &lt;100 ppm ash each) in 8.5 g of Tetralin 8 (Ci〇Hi2) at 140 °C The isotropic petroleum pitch, which is illustrated in the example, is placed in a laboratory beaker. 20 grams of carbonaceous powder as described and described in the Reference Example! and 700 ml of xylene under the machine (in the second experiment) In the chamber beaker, the contents of the first beaker are separated from the contents of the first beaker, and after the addition, the resulting mixture is heated and maintained for 15 minutes under about 128 t; then the heat source is shifted = and 4 is held continuously. While the mixture is allowed to cool to ambient temperature (approximately C), the mixture is dried on a vacuum funnel by drying the crucible at 120 ° C, and the mixture is removed by τ, and the mixture is removed for ~3 hours. The resulting solid was weighed 22.3 g from the cooled powder (4). The weight % of the total amount of carbon of the carbonaceous powder particles was measured on the carbonaceous powder.

86864.DOC -46- 1302761 其後將塗覆之硬質粉末顆粒置於實驗室規模的流體化 2反應器中，並在】❿分鐘之加熱速率下自環境溫度加熱 土 275 C A在275 C下停㈣分鐘，同時使用空氣作為流 體化氣體使塗覆之碳皙扒古μ，、 ”如末顆粒流體化。接著將經反應之 粉末顆粒移入至管$泸（ 山 、 g式壚（Llnberg/Blue Μ)中，及於純氬氣中 =化’並在5 C/分鐘之加熱速率下自環境加熱至μ旳，及 :旦達到此溫度，則使塗覆之碳質粉末顆粒在此溫度下維 、2广時、。接耆將塗覆之碳質粉末顆粒取出並使其冷卻。 覆《（貝心末顆粒 &lt; 石墨化係經由接著將其轉移至 土坩尚甘禍***至具有氬大氣之感應爐中86864.DOC -46- 1302761 The coated hard powder particles are then placed in a laboratory-scale fluidized 2 reactor and heated at ambient heating temperature 275 CA at 275 C at a heating rate of ❿ minute. (4) Minutes, using air as the fluidizing gas to make the coated carbon ,μ, "if the particles are fluidized. Then move the reacted powder particles into the tube 泸 (山, g式垆 (Llnberg/Blue Μ), and in pure argon = heating 'and heating from the environment to μ 在 at a heating rate of 5 C / min, and: when this temperature is reached, the coated carbonaceous powder particles are at this temperature Dimensions, 2 hours, and then the coated carbonaceous powder particles are taken out and allowed to cool. Overlay (Beixin granules &lt; Graphitization is transferred to the soil by the subsequent transfer to the argon Atmospheric induction furnace

Ut/分鐘之速率下將㈣加熱至测。〇之溫度，其後再2(4) is heated to the measurement at a rate of Ut/min. The temperature of the sputum, followed by 2

Lc度=速率:將_加熱至3_，此時將感她 ct ▲持45分鐘（期間而達成。於此等加❹ 暴^後，咸信石墨化基本上完成。然後使含有 =顆粒之爾卻至環境溫度’之後將粉末顆粒自= 生成乏粉末顆粒展現良好的粉末流動性，且並 並未發生顆粒之融合。 /、有來 根據說明於前文之標題「電化學試驗程序」下之程序, 估粉末顆粒之充電容量以及不可逆的充電容量損耗。气:: 果說明表 7 〇Lc degree = rate: heat _ to 3_, at this time will feel her ct ▲ hold for 45 minutes (during the period. After this crowning violent ^, the salty graphitization is basically completed. Then make the = granules However, after the ambient temperature, the powder particles showed good powder fluidity from the generation of the spent powder particles, and the fusion of the particles did not occur. /, according to the procedure under the above-mentioned title "Electrochemical Test Procedure" , estimate the charging capacity of the powder particles and the irreversible loss of charge capacity. Gas:: Description Table 7 〇

塗覆之瀝青 容量 不可逆的容量 ---- _(%) _ 」mAh/g) 損耗（mAh/g) 例13 ——— —10 330 1 --- 〇 J 14Coated asphalt capacity Irreversible capacity ---- _(%) _ "mAh/g) Loss (mAh/g) Example 13 ——— —10 330 1 --- 〇 J 14

86864.DOC -47- 1302761 貫施例14 衣k tf範使用環境空氣作為碳質粉末顆粒之可熔解之 石反殘留物形成材料塗層之氧化劑之根據本發明之塗覆之碳 質粉末顆粒的再一樣 舲20克之低熔點石油瀝青（2丨〇艺梅特勒軟化點，乃％亞 爾可杈殘邊物，&lt;1〇〇 ??1]1灰分各向同性石油瀝青）及克之 甲基吡咯啶酮（NMP，例如，Aldnch Chemical c〇.，Inc.) 置於實驗室燒杯中，而形成石油瀝青之20重量％溶液。將 /合液在心拌下加熱至大約6〇。〇，此時引入Μ克之如說明於 實施例7之懷製針狀煤焦石油煤焦（娘製溫度1 loot：)，及將 k杯《内谷物再多攪拌15分鐘，以確保均勾度。接著經由 =用真更漏斗過滤混合物，其後再於真空中在⑽。C下乾 =少5小時’而將生成之固體自混合物移除。測得經乾燥 貝粉末顆粒之最終重量為約2ι·5克，同時測得緩 貝&quot;青之量為塗覆之碳質粉末顆粒之總質量 的7重1 % 〇 其後將塗覆之碳質始^丈 、 、云m卜 實施例13所說明之 度加孰至275。「 C/“K加熱速率下自環境溫 度力，、.、土 275 C，及在275。〇下停 作為流體化氣體使塗覆之^二刀知’同時使用空氣 、、 土覆夂妓質粉末顆粒流體化。接荽4夕麵 反應之粉末顆粒移入至如實施例13所說 = 於純氨氣中碳化，並在5t/分鐘之加 ^切中，及 至8…-旦達到此溫度，則使塗覆二自鳩熱 此溫度下維持2小時。接著牵、。又貝粉末顆粒在 接讀…碳質粉末顆粒取出並使86864.DOC -47- 1302761 Example 14 using ambient air as a refractory stone of carbonaceous powder particles as a oxidizing agent for coating a coating of a material, according to the coated carbonaceous powder particles of the present invention Another 20 grams of low melting point petroleum asphalt (2 丨〇 梅 梅 软化 软化 软化 乃 乃 乃 乃 乃 乃 乃 乃 乃 乃 乃 乃 乃 乃 乃 乃 乃 乃 乃 乃 乃 梅 梅 梅 梅 梅 梅 梅 梅 梅 梅 梅 梅 软化 软化 梅 软化 梅 梅 梅 梅The pyrrolidone (NMP, for example, Aldnch Chemical c., Inc.) is placed in a laboratory beaker to form a 20% by weight solution of petroleum pitch. Heat / mix the mixture to about 6 在 under heart mixing. 〇, at this time, introduce the gram of the needle in the acicular coal charcoal coke of Example 7 (mother temperature 1 loot:), and k cup "inner grain for another 15 minutes to ensure uniformity . The mixture was then filtered through a = funnel, followed by (10) in vacuo. The C was dried = less 5 hours' and the resulting solid was removed from the mixture. The final weight of the dried scallop powder particles was determined to be about 2 ι·5 g, and the amount of squash was measured as 7 wt% of the total mass of the coated carbonaceous powder granules, which will be coated thereafter. The degree of carbon quality is increased to 275 as described in Example 13. "C/"K heating rate from ambient temperature, , , soil 275 C, and at 275. The underside of the crucible is used as a fluidizing gas to cause the coating to be simultaneously fluidized by using air and soil-coated enamel powder particles. The powder particles of the 4th-side reaction are transferred to the carbonization in pure ammonia gas as described in Example 13, and in the addition of 5t/min, and to the temperature of 8... Maintain at this temperature for 2 hours. Then take the lead. The shell powder particles are taken in... the carbonaceous powder particles are taken out and

86864.DOC -48- 1302761 其冷卻。 此等冷导 、 々、主復足碳質粉末顆粒之石墨化係經由接著將其轉 私土石墨坩堝，將坩堝***至具有氬大氣之感應爐中，及 先在UC/分鐘之速率下將坩堝加熱至28〇〇它之溫度，其後 C /刀备之速率下將掛瑪加熱至3000°C，此時將感應 爐之恤度在3〇〇〇它下維持45分鐘之期間而達成。於此等加 熱步驟之後’咸信石墨化基本上完成。然後使含有未塗覆 &lt;蛟貝粉末顆粒之坩堝冷卻至環境溫度，之後將粉末顆粒 自坩堝移出。 根據說明於前文之標題「電化學試驗程序」下之程序評 估知末顆粒之充電容量以及不可逆的充電容量損耗。電性 能1平估之結果說明於下表8。 ~表8 塗覆之渥青 容量 不可逆的容量 效率 (%) (mAh/g) 損耗（mAh/g) (%) 例14 7 — 334 29 92 比較實施例6 為作比較用’利用以下方案製備未進行氧化反應步驟之 愛覆之碳質粉末顆粒之樣品。 將在140°C下之於8.5克丁etralin®(C10H12)中之8.5克低熔 點石油瀝青（210°C梅特勒軟化點，75%亞爾可碳殘留物， &lt;100 ppm灰分各向同性石油瀝青，如說明於實施例丨）置於86864.DOC -48- 1302761 its cooling. The graphitization of the cold-conducting, crucible, and primary complex carbonaceous powder particles is then inserted into the induction furnace with an argon atmosphere, and then at a rate of UC/min. The crucible is heated to a temperature of 28 〇〇, and then the temperature of the C/knife is heated to 3000 ° C. At this time, the induction furnace is reached at a temperature of 3 〇〇〇 for 45 minutes. . After these heating steps, the salty graphitization was substantially completed. The crucible containing the uncoated &lt;mussel powder particles is then cooled to ambient temperature before the powder particles are removed from the crucible. The charge capacity of the granules and the irreversible charge capacity loss were evaluated according to the procedure under the heading "Electrochemical Test Procedure" in the previous section. The results of the electrical performance evaluation are shown in Table 8 below. ~ Table 8 Non-reversible capacity efficiency (%) (mAh/g) loss (mAh/g) (%) Example 14 7 - 334 29 92 Comparative Example 6 For comparison, use the following scheme A sample of the carbonaceous powder particles of the love coating which was not subjected to the oxidation reaction step. 8.5 g of low melting point petroleum bitumen at 210 ° C in 8.5 g of etralin® (C10H12) (Mettler softening point at 210 ° C, 7 % Alecco carbon residue, &lt; 100 ppm ash Isotropic petroleum asphalt, as illustrated in the examples)

86864.DOC -49- 1302761 貝驗室燒杯中。將2〇克之如參昭會、a 皙扒古&amp; 1 …、焉她例1而說明及製造之碳 ，、叔末與700毫升之在12〇。〇下 於m -伽舍人、 —甲本（c6h4(c2h3)2)結合 M 一 固燒杯之内容物逐漸加至 罘一個埏杯之内容物中，及於添力口 . ^ 在連續攪拌下於約128。。下加教 使所付之⑽口 铲私,, …夂維持15分鐘。接著將熱源 和除’及邊維持連鲭攪拌邊使 _ 、 使匕a物冷卻至環境溫度（大約 )。經由先將混合物於真空漏 , ,.1Λη〇 柯寸上過濾，其後再於真空 中在120 C下乾燥至少3 、Η入仏 &gt; 向知生成又固體自經冷卻之 '/m合物移除。 測知竣質粉末上之沈濟拜音 &amp;、&amp; 兄叔瀝同 &lt;量佔塗覆之碳質粉末顆 粒之、、、心質量的10重量％。 其後根據以下方案辦：淦蘿+ # # Α班、、、 覆乏灭貝粉末顆粒於純氬氣中 自％故溫度加熱：5。〇 /分鐘之第_ 、、 、 里心弟加滅速率至200°C及於該 溫度下停留3〇分鐘，接著2°c /分於、〜 里妖嘗2匕/刀叙又第二加熱速率至35(rc 及於該溫度下停留2小時，並次 八 在5 C /为鐘之弟三加熱速率 下加熱至8 5 0 °C及於該溫度下停切 攻曰々 /又r片田2小時，及最後使塗覆之 碳質粉，難在rc/分鐘之速率下冷卻至環境溫度（大約 22 C )觀祭到回收得的碳質粉末顆粒凝聚成單一餅塊，將 f自#禍取出’並先壓碎成較小塊，然後再球磨成粉末形 態。 此等塗覆之碳質粉末顆粒之石墨化係經由接著將並轉 移至石墨料’將㈣插人至具有氬大氣之感應爐中，及 先在13 C/分鐘之速率下將坩堝加熱至28〇〇。〇之溫度，其後 再在5C/分鐘（速率下將掛碼加熱至3麵。c，此時將感應86864.DOC -49- 1302761 in the beaker of the laboratory. 2 gram of such as the sacred meeting, a 皙扒古 &amp; 1 ..., 焉 her example 1 to illustrate and manufacture the carbon, the uncle and 700 ml at 12 〇. Under the continuous stirring, the content of M-Gashe, - A (c6h4 (c2h3) 2) combined with M-solid beaker is gradually added to the contents of a cup, and added to the mouth. ^ Under continuous stirring About about 128. . The next step is to make the (10) mouth shovel private, ... 夂 for 15 minutes. Then, the heat source and the side are kept while stirring, and the 匕a is cooled to ambient temperature (about). By first filtering the mixture under vacuum, filtering, and then drying at 120 C in vacuum at least 3, enthalpy 仏 > to form a solid and self-cooled '/m compound Remove. It is known that the Shenyin &amp;&amp; brothers and stalks on the enamel powder account for 10% by weight of the coated carbonaceous powder particles. After that, according to the following scheme: dill + # # Α班,,, 满无贝 shell powder particles in pure argon gas from the temperature of the heating: 5. 〇 / minutes of the first _,,, 里 heart brother to increase the rate to 200 ° C and stay at this temperature for 3 〇 minutes, then 2 ° c / min in, ~ 妖 妖 尝 2 匕 / knife and second heating The rate is up to 35 (rc and stays at this temperature for 2 hours, and the second is heated to 850 °C at 5 C / for the third heating rate of the clock and at this temperature, the cutting attack/r-field is 2 hours. And finally, the coated carbonaceous powder is difficult to cool to ambient temperature (about 22 C) at a rate of rc/min. The recovered carbonaceous powder particles are condensed into a single cake, and the f is taken out from #祸'First crushed into smaller pieces and then ball milled into a powder form. The graphitization of these coated carbonaceous powder particles is then inserted into the graphite furnace to transfer (4) to the induction furnace with argon atmosphere. Medium, and first heat the crucible to 28 在 at a rate of 13 C/min. The temperature of the crucible is then heated to 3 sides at 5 C/min (at a rate, c, at this time

86864.DOC -50- 1302761 出 爐之溫度在300〇t：下維持45分鐘之期間而達成。於此等加 熱步驟之後，咸信石墨化基本上完成1後使含有碳= 末顆粒之坩堝冷卻至環境溫度’之後將粉末顆粒自坩堝^ 根據說明於前文之標題「電化學試驗程序」下之程序坪 =粉末顆粒之充電容量以及不可逆的充電容量損耗， 能評估之結果說明於下表9。 兒 --—— ---&quot; ——---- —… ___表9 塗覆之瀝青 容量 ----- 不可逆的容量 (%) (mAh/g) 損療毛 Γ ΤΠ A Vi / rr、 比較例6 10 \ ΑΑΑΖ V AX/ ^ J 300 &quot;&quot;&quot;*&quot; 一*--— _352 效率 46 ,…了、 儿六,小对取/及己逑之結果w =未經氧化，但於惰性大氣中碳化之、經塗覆歴青之碳$ 、’末果、粒產生不良的充電容量及不良的充電效率。 比較實施例7 為作進-步比較，利用與用於製造比較實施㈣之組^ 匆:似 &lt; 方案製備未進行氧化反應步騾之塗覆之碳質粉3 、之认W。根據本比較實施例之比較樣品的差異在於γ ^明於實施例10中之相同方式製備塗覆之碳質粉末顆粒 1 了其未經氧化。於碳化之後，觀察到碳質粉末顆粒溪 單—餅塊。接著將碳粉末團塊自_取出，並先壓农 、1塊，然後再在石墨化之前球磨成粉末形態。 如同先珂比較實施例之評估，根據說明於前文之標是86864.DOC -50- 1302761 The temperature at which the furnace was released was maintained at 300 〇t: for 45 minutes. After the heating step, the graphitization of the salt is substantially completed, and then the crucible containing carbon = the final particles is cooled to ambient temperature, and then the powder particles are self-treated according to the description under the heading "Electrochemical Test Procedure". Procedure ping = charge capacity of powder particles and irreversible charge capacity loss, the results of which can be evaluated are shown in Table 9 below.儿--—— ---&quot; ——-----... ___ Table 9 Asphalt capacity coated ----- Irreversible capacity (%) (mAh/g) Damage treatment Γ A Vi / rr, Comparative Example 6 10 \ ΑΑΑΖ V AX/ ^ J 300 &quot;&quot;&quot;*&quot; A *--- _352 efficiency 46,..., children 6, small pairs of take and / 逑 results w = The carbon, which is carbonized in an inert atmosphere, which is carbonized in an inert atmosphere, produces a poor charging capacity and poor charging efficiency. Comparative Example 7 For the comparison of the steps, a carbonaceous powder 3 which was not coated with an oxidation reaction step was prepared by using the same method as that used for the production of (4). The difference of the comparative samples according to the present comparative example was that the coated carbonaceous powder particles 1 were prepared in the same manner as in Example 10, and were not oxidized. After carbonization, a carbonaceous powder granule was observed. The carbon powder agglomerates are then taken out from the _, and then pressed, 1 piece, and then ball milled into a powder form before graphitization. As before, the evaluation of the comparative example is based on the above description.

86864.DOC -51- 1302761 %化學武驗程序」下之程序評估根據本比較實施例之粉 末顆粒之充電容量以及不可逆的充電容量損耗。電性能評 估之結果說明於下表1 〇。 ——.___ I --— -~-—--- 表10 塗覆之渥青 L__I%) —----- 容量 (mAh/g) 不可逆的容量 損耗（mAh/g) 效率 (〇Δ\ 列 7 5 317 _______、 〇 / 106 V /0) 75 由此等結果，尤其係當將實施例10、13及14(其中塗覆顆 ^根據本發明在後化之前氧化）與比較實施例6及7(其中塗 復果、粒未經氧化）比較時，可明瞭由氧化所造 化學效率。 、1迨示範知液怨氧化劑使用於碳質粉末顆粒之可熔 之竣殘留物形成材料塗層之根據本發明之塗覆之碳質粉 顆粒的再—樣品。 知在140 C下之於8.5克Tetrali_(Ci❶H12)中之8.5克低 點石油歷青（2抓梅特勒軟化點，咖亞爾可碳殘留物 侧PPm灰分各向同性石油歷青，如說日祕實施例〇置 二驗室燒杯中。將2〇克之如參照實施例丨而說明及製造心 貝人ί末杨毫升之在赋下之：甲苯（c6h4(C2H3)2)i ::實驗室燒杯中。將第-個燒杯之内容物逐漸加. 二:Γ内容物中，及於添加之後，使所得之… 在連，W下於约⑽下加熱及維持15分鐘。接著將熱3The procedure under 86864.DOC -51- 1302761% Chemical Test Procedure" evaluates the charge capacity of the powder particles according to the comparative example and the irreversible charge capacity loss. The results of the electrical performance assessment are described in Table 1 below. ——.___ I --- -~----- Table 10 coated indigo L__I%) --------- Capacity (mAh / g) Irreversible capacity loss (mAh / g) Efficiency (〇 Δ Column 7 5 317 _______, 〇 / 106 V /0) 75 and so on, especially when Examples 10, 13 and 14 (where the coated particles are oxidized prior to post-treatment according to the invention) and comparative examples When 6 and 7 (in which the coated fruit and the granules are not oxidized), the chemical efficiency by oxidation is known. A re-sample of the coated carbonaceous powder particles according to the present invention for use in a coating of a fusible residue-forming material of carbonaceous powder particles. Knowing that at 8.5 g in 8.5 g of Tetrali_(Ci❶H12), 8.5 g of low-point petroleum calendar (2 grabs the METTLER softening point, and the Gayar carbon residue side PPm ash isotropic oil, such as The Japanese secret embodiment is placed in a two-chamber beaker. Two grams of the sample are described and described in the following example: the toxin is added: toluene (c6h4(C2H3)2)i::experiment In the chamber beaker, gradually add the contents of the first beaker. Second: in the contents of the crucible, and after the addition, make the obtained... Heat and maintain at about (10) for 15 minutes. Then heat 3

86864.DOC -52- 1302761 移除，及邊維持連續攪掉達使混合物冷卻至環境溫度（大约 22C)。經由先將混合物於真空漏斗上過滤，其後再於直办 中在⑽下乾燥至少3小時，而將生成之固體自經冷卻： ==回Γ得之生成之經乾燥之塗覆碳質粉末顆粒 主: &lt;取終乾燥重量。測得碳質粉末上之沈殿歷 &quot;里孟覆 &lt;杈質粉末顆粒之總質量的10重量％。 接下來將經㈣之㈣制青之料倒人 下之确酸（職3)之35重量％水溶液之第三個燒杯中^ 混合物邊撥拌邊維持於此溫度下。其後經由先將混 2勿於真^斗上H以去離子水徹底洗I L其後再於真空中在阶下乾燥至叫、時，而 2著將时的塗覆之”粉末㈣引人^氧 ^於氯大氣中在5〇c/分鐘之第—速率下自環境溫度加散 : 850 c(溫度，此時使_在該溫度下維持2小時，之後 使掛瑪在rc/分鐘之速率下冷卻至環境溫度（大約2 ΪΙΪΓ之碳質粉末顆粒自掛瑪移出。生成之粉末顆粒 粉末流動性，且其看來並未發生顆粒之融合。 :後順塗覆之碳質粉末顆粒提供至石墨掛 褐***至具有氬大氣之感應爐中，及先在速86864.DOC -52- 1302761 Remove, and maintain continuous agitation to allow the mixture to cool to ambient temperature (approximately 22 C). The mixture is filtered on a vacuum funnel, and then dried at (10) for at least 3 hours in a straight line, and the resulting solid is cooled from the following: == The dried coated carbonaceous powder is formed by reversal Granule Master: &lt; Take the final dry weight. The weight of the sacred calendar on the carbonaceous powder was measured and 10% by weight of the total mass of the tannin powder particles. Next, the (4) cyan material is poured into the third beaker of the 35 wt% aqueous solution of the acid (3) and the mixture is maintained at this temperature. Then, by first mixing 2, do not use it on the real bucket, wash the IL thoroughly with deionized water, then dry it in the vacuum to the temperature, and then apply the "coated powder" (four). ^Oxygen in the chlorine atmosphere at a rate of 5 °c / min - rate from the ambient temperature: 850 c (temperature, at this time _ at this temperature for 2 hours, after which hangs in rc / min Cooling to ambient temperature at a rate (approximately 2 碳 of carbonaceous powder particles are removed from the stagnation. The resulting powder granules have fluidity and it does not appear to have granule fusion. : Post-coated carbonaceous powder granules are provided Insert graphite brown into the induction furnace with argon atmosphere, and first at speed

加熱至2_之溫度，其後再在5。。二 轉=加熱至则代，此時將感應壚之溫度在鳩0 =叫鐘之期間而將其石墨化。於此等加熱步驟之後， 咸信石墨化基本上完成。然後使含有塗覆之碳質粉末LHeat to a temperature of 2 mm and then at 5. . Two revolutions = heating to the next generation, at which time the temperature of the induction enthalpy is graphitized during the period of 鸠0 = chime. After these heating steps, the saltitization of the salt is substantially completed. Then coated with coated carbonaceous powder L

86864.DOC •53- 1302761 冷卻至環境溫度，之後將粉末顆粒自坩堝移出。生 顆：松束顆粒展現良好的粉末流動性，且其看來並未發生 禾、杈 &lt; 融合。 估^說明於前文之標題「電化學試驗程序」下之程序評 二顇粒之充電容量以及不可逆的充電容量損耗。電性 % ^估之結果說明於下表丨丄。86864.DOC •53- 1302761 Cool to ambient temperature and then remove the powder particles from the crucible. Raw: Loose granules exhibit good powder flow and it does not appear to have fused, fused & fused. Estimate the charge capacity and irreversible charge capacity loss of the procedure under the heading "Electrochemical Test Procedure" in the previous section. The results of the electrical % estimate are shown in the table below.

貫施例16 製造亦利用如實施例15所使用之液態氧化劑之根據本 毛明〈塗覆之碳質粉末顆粒的再—樣品。如實施例14中之 說明製備經乾燥之經塗覆„之粉末，及在竣化及石墨化 之前如實施例15中之說明於硝酸溶液中氧化。 如同先前實施例之評估，根攄命、 很取祝明於煎又义標題「電化 學試驗程序」下之程序評估妨缺、 、 7」卩 斤^古根據本實施例之粉末顆粒之充 電容量以及不可逆的充電宏香士口^ ^ J 兒备里知耗。電性能評估之結果說 明於下表1 2。 0 86864.DOC -54- 1302761 ---—-_ —---- 表12 ----— -—--- 塗覆之瀝青 (%)— 容量 (mAh/g) r—&quot;- 不可逆的容量 損耗（mAh/s:) τ~-- 效率 93 例16 u—___ 7 338 一 26 ^ u 一队\t貝物不稍粒及其所 得之優異的電性質顯示液態氧化劑之效用。 實施例1 7 將未烺燒之針狀煤焦於錘式磨中壓碎，然後再於射流卢 中研磨及分級以移除灰塵。所得之粉末具有自约g 5至二 微米之顆粒及15微米之平均顆粒大小。經由將祝如實施 例Π所使用之相同的低溶點石油渥青（193。〇梅特勒軟化點 ’ 75%亞爾可碳殘留物’低灰分各向同性石油歷幻溶解於 5〇晕升玻璃燒瓶中之在⑽下之24克之二τ苯(acs試劑 ，例如’ Flsher Scientlflc)中’而製備得第一溶液。同時將 3〇克之綠針狀煤焦粉末及毫升之：甲苯於麵毫升玻 璃燒瓶中邊連續揽拌邊加熱至13〇t。將歷青.二甲苯溶液 逐漸倒入至煤焦粉末懸浮液中，及於添加之後，將所得之 w 口物在13GC在連續揽拌下加熱及維持15分鐘。接著將熱 源移除：及邊維持連續攪拌邊使混合物冷卻至環境溫度 (大約22 C )。經由先將混合物於真空過遽漏斗上過濾，其 後再以200¾升《二甲苯洗務粉末及於真空中在⑽。c下乾 燥約3小時，而將生成之固體自經冷卻之混合物分離。生成 粉末之總重量為30克。計算得煤焦粉末上之沈殿瀝青之Example 16 A re-sample of the coated carbonaceous powder particles according to the present invention was also produced using a liquid oxidant as used in Example 15. The dried coated powder was prepared as described in Example 14, and oxidized in a nitric acid solution as described in Example 15 prior to deuteration and graphitization. As in the evaluation of the previous examples, roots, I would like to take a look at the procedure under the heading "Electrochemical Test Procedures" in the title of "Electrochemical Test Procedures", and the charge capacity of the powder particles according to this example and the irreversible charge of Hongxiangshikou ^ ^ J Knowing the consumption. The results of the electrical performance evaluation are shown in Table 1 2 below. 0 86864.DOC -54- 1302761 ------_---- Table 12 ----- ----- coated asphalt (%) - capacity (mAh / g) r-&quot;- Irreversible capacity loss (mAh/s:) τ~-- Efficiency 93 cases 16 u-___ 7 338 A 26 ^ u A team of \t shells not a little grain and the excellent electrical properties obtained show the effect of liquid oxidant. Example 1 7 Unburned needle coal char was crushed in a hammer mill and then ground and classified in a jet to remove dust. The resulting powder had particles from about g 5 to 2 microns and an average particle size of 15 microns. By the same low-solution point petroleum indigo (193. 〇 Mettler softening point '75% Alecco carbon residue' low ash isotropic petroleum illusion will be dissolved in 5 〇 halo The first solution was prepared by adding 24 g of di-taubenzene (acs reagent, for example, 'Flsher Scientlflc) in (10) in a liter glass flask. At the same time, 3 g of green needle coal char powder and ML: toluene were prepared. The ML glass flask was heated to 13 〇t while continuously mixing. The celite-xylene solution was gradually poured into the coal tar powder suspension, and after the addition, the obtained w-mouth was continuously stirred at 13GC. Heat and maintain for 15 minutes. The heat source is then removed: and the mixture is allowed to cool to ambient temperature (approximately 22 C) while maintaining continuous agitation. The mixture is first filtered through a vacuum funnel, followed by a 2003⁄4 liter. The xylene washing powder was dried in vacuum at (10) c for about 3 hours, and the resulting solid was separated from the cooled mixture. The total weight of the resulting powder was 30 g. The calculated pitch of the asphalt on the coal char powder was calculated.

86864.DOC -55- 1302761 量為總質量之約1 8 _ 7重量％。 將其餘的瀝青-二甲苯溶液倒入至蒸發燒瓶中，以於真空 中在120 C下回收二甲苯及收集瀝青殘留物。使用梅特勒軟 化點技術測得瀝青殘留物之軟化點為約6(rc。 經由將粉末與1〇克之硝酸鈉（NaN〇3)(ACS.試劑，j.T Baker)之1 〇.3重畺％水溶液徹底混合而使乾燥粉末氧化。將 混合物在真空中在8(rc下乾燥，然後再置於鋁氧坩堝中並 轉移至真空爐内。將爐在5。口分鐘之速率下自環境溫度加 煞土 200 C，然後再在rc/分鐘之速率下至325它，此時將 坩堝在真空中在325t下維持2小時。 經由將粉末於氮大氣中在Kc/分鐘之速率下加熱至3俯 :此時將㈣在35(rc下維持2小時，而將經穩定化之樣品 &amp;化其後將含有經穩定化之塗覆之碳質顆粒之掛螞在 == 率Λ進—步加熱至戰，此時將掛碼在此較高溫 =在5^ 著將含有經狀化之塗覆之”顆粒之 ° 刀4里之速率下進一步加熱至850°c，此時/ 在850°c下唯祛9 ί # 此時知掛瑪 溫(約；她小時，之後㈣^ 大氣中之感靡被士、 τ问，；、、、谩將坩堝引入至 之速率下^ 而將其石墨^先將料在啡/分 羊下加滅至2_。〇，其後再在代/分鐘之速率下力 至3000t，此眭赋代&amp; ^、 里又逑辜下加: 此時將感應爐 度在侧t 期間’，信石墨化基本上完成。 f45“里- 使Kb學試驗程相試經石墨化之， 〜果示於;^86864.DOC -55- 1302761 The amount is about 18 -7 wt% of the total mass. The remaining bitumen-xylene solution was poured into an evaporation flask to recover xylene at 120 C in vacuo and to collect bitumen residue. The softening point of the asphalt residue was determined to be about 6 (rc by using METTLER's softening point technique. 1 〇.3 by passing the powder with 1 gram of sodium nitrate (NaN〇3) (ACS. Reagent, jT Baker) The % aqueous solution is thoroughly mixed to oxidize the dry powder. The mixture is dried in vacuum at 8 (rc) and then placed in an aluminox furnace and transferred to a vacuum furnace. The furnace is at ambient rate at a rate of 5 minutes. Add the alumina 200 C and then at a rate of rc/min to 325, at which point the crucible is maintained at 325 t for 2 hours in a vacuum. The powder is heated to 3 at a rate of Kc/min in a nitrogen atmosphere. Pitch: At this time, (4) is maintained at 35 (rc for 2 hours), and the stabilized sample &amp; afterwards will contain the stabilized coated carbonaceous particles at the rate of == Heating up to the war, at this time the hanging code is heated at this higher temperature = at a rate of 5 ° containing the "coated" "particles" of the knife 4, at this time / at 850 ° c下唯祛9 ί # At this time, I know that hanging Ma Wen (about; her hour, after (four) ^ feelings in the atmosphere are asked by the priest, τ,;,, 谩 坩Introduced to the rate ^ and the graphite is first added to the brown / min sheep to 2_. 〇, then at the rate of generation / minute force to 3000t, this endurance generation &amp; ^, 逑 逑辜下加: At this time, the induction furnace degree is in the side t period, and the letter graphitization is basically completed. f45 “Li--the Kb test test phase is graphitized, ~ fruit is shown in; ^

86864.DOC -56- 1302761 使用娘製針狀煤焦粉末於製備碳質心顆粒。先利用鐘 式磨將”石油針狀煤焦（在蘭壓碎成小塊、·， 利用射流磨研磨成微細粉末，然後再分級。所得之粉末且 有大小在〇.5至約5G微米之範圍内的顆粒，及約 : 均顆粒大小。 千 根據說明於實施例17之程序將馈製煤焦粉末塗覆石油 瀝青:生成粉末之總重量為36·7克。煤焦粉末上之沈殿避 青之量為總質量之約1 8.2%。 如實施例17中之說明將乾燥粉末穩定化、碳化及石墨化 ，僅除了使用Η)克之硝酸納之1〇重量％溶液（穩定化步⑹ 。使用電化學試驗程序測試經石墨化之粉末，結果示於表 13。 ' 實施例1 9 將實施例17之未烺製石油針狀煤焦粉末塗覆具有155。〔 之梅特勒軟化溫度之經浸熱之傾析油餾出液石油瀝青。石 油歷青具有寬廣的分子大小分体，且包含顯著量的低分子 量分子及約10%之高分子二甲苯不溶解化合物。 經由將5 0克之經浸熱之石油歷青溶解於⑽毫升玻璃燒 瓶中之在丨2(^下之50克之二甲苯（ACS試劑， Scientific，Pittsburgh，PA)中，而製備得第一溶液。同時將 30克之綠針狀煤焦粉末及700毫升之二甲苯於7〇〇毫升玻璃 燒瓶中邊連續禮掉邊加熱至not。邊將混合物連續攪拌， 86864.DOC -57- 1302761 一〒冬落液逐漸倒入至煤焦粉末懸浮液中。接著 知:口物加热至135它，及連續攪拌15分鐘。將熱源移除， 及以、隹持連纟買攪拌邊使混合物冷卻至環境溫度（約22°C )。 和生成之固自經冷卻之混合物分離，並以200毫升之二甲 苯洗I及如貫施例17中之說明乾燥。生成粉末之總重量 為3 6·5克。煤焦粉末上之沈澱瀝青之量為約17.8重量％。 如實施例17中之說明將乾燥粉末穩定化、碳化及石墨化 僅除了在％定化步驟中使用1〇克之硝酸鈉（ν&amp;ν〇3)之9 7 重里/〇/谷液。使用電化學試驗程序測試經石墨化之粉末， 結果示於表13。 實施例20 將實施例18之烺製針狀煤焦粉末塗覆說明於實施例19 之中間瀝:青產物。 經由將25克之經浸熱之石油瀝青溶解於5〇毫升玻璃燒 瓶中之在120°C下之25克之二甲苯（ACS試劑，例如， Scientific)中，而製備得第一溶液。同時將15克之烺製煤焦 粉末及150毫升之二甲苯於1〇〇〇毫升不銹鋼容器中邊連婧 攪拌邊加熱至160°C。邊將混合物連續攪拌，邊於氮氣壓力 下將瀝青-二甲苯溶液逐漸注入至煤焦粉末懸浮液中。接著 將混合物加熱至2 10°C，及連續攪拌1 5分鐘。將熱源移除， 及邊維持連續攪拌邊使混合物冷卻至環境溫度（約22t )。 將生成之固體自經冷卻之混合物分離，並如實施例1 7中之 說明洗滌。生成粉末之總重量為16.8克。煤焦粉末上之、、尤 澱瀝青之量為約10·7重量％。 86864.DOC -58- 1302761 將乾燥粉末與6克之硝酸鈉（NaN03)(A_C.S·試劑，例如， J.T.Baker)之4.5重量％水溶液徹底混合。將混合物於真空中 在80 C下乾燥，然後如實施例17中之說明穩定化、碳化及 石墨化。使用電化學試驗程序測試經石墨化之粉末，結果 不於表1 3。 實施例21 將說明於實施例18之烺製針狀煤焦粉末塗覆如實施例 19所說明之經浸熱之石油瀝青。 經由將25克之經浸熱之石油瀝青溶解於5〇毫补玻璃燒 瓶中之在120°C下之25克之二甲苯中，而製備得第/溶液。 同時將15克之烺製針狀煤焦粉末及丨5()毫升之二甲苯於 1000毫升不銹鋼容器中邊連續攪拌邊加熱至9(rc。邊將混 合物連續攪拌，邊將瀝青-二甲苯溶液逐漸倒入至煤焦粉末 懸浮液中。接著將混合物於環境壓力下加熱至190。〇，及在 190 c下連續攪拌15分鐘。將熱源移除，及邊維持連讀檀掉 邊使混合物冷卻至環境溫度（約饥）。將生成之固體自混 合物移除，如實施例17中之說明洗滌及乾燥。乾燥 末之總重量為n_9克。煤焦粉末上之沈澱 16.2重量％。 里為、、，勺 將乾燥粉末與6克之硝酸鈉（A.c.s•試劑，例86864.DOC -56- 1302761 Preparation of carbonaceous core particles using mother-made needle coal char powder. First use the bell mill to "oil needle coal char (crushed into small pieces, crushed into fine powder by jet mill, and then graded. The obtained powder has a size of 〇.5 to about 5G micron. The particles in the range, and about: the average particle size. According to the procedure of Example 17, the coal char powder is coated with petroleum pitch: the total weight of the produced powder is 36·7 g. The amount of cyan is about 8.2% of the total mass. The dry powder is stabilized, carbonized, and graphitized as described in Example 17, except that a 1% by weight solution of ruthenium nitrate is used (stabilization step (6). The graphitized powder was tested using an electrochemical test procedure and the results are shown in Table 13. 'Example 1 9 The untanned petroleum acicular coal char powder of Example 17 was coated with 155. [Mettler softening temperature The distilled oil distillate petroleum pitch is immersed in heat. The petroleum calendar has a broad molecular size fraction and contains a significant amount of low molecular weight molecules and about 10% of the polymer xylene insoluble compound. The dip-heated petroleum calendar is dissolved in (10) In a milliliter glass flask, 50 g of xylene (ACS reagent, Scientific, Pittsburgh, PA) was prepared in a 1/2 glass flask to prepare a first solution, and 30 g of green needle coal char powder and 700 ml were simultaneously prepared. The xylene was heated to not in a 7-ml glass flask and continuously stirred. The mixture was continuously stirred, 86864.DOC -57- 1302761, and the winter falling liquid was gradually poured into the coal char powder suspension. : The mouth is heated to 135, and continuously stirred for 15 minutes. The heat source is removed, and the mixture is cooled and brought to ambient temperature (about 22 ° C) with the stirring of the crucible. The mixture was separated and washed with 200 ml of xylene and dried as described in Example 17. The total weight of the resulting powder was 36.5 g. The amount of precipitated bitumen on the coal coke powder was about 17.8% by weight. Stabilizing, carbonizing, and graphitizing the dry powder as described in Example 17 except that 1 gram of sodium nitrate (ν &amp; ν〇3) of 9 gram/min/valley was used in the % characterization step. Test the test procedure to test the graphitized powder, the results are shown in 13. Example 20 Coating of the acicular coal char powder of Example 18 is illustrated in the middle leaching: cyan product of Example 19. By dissolving 25 grams of the dilute petroleum pitch in a 5 liter glass flask. The first solution was prepared in 25 g of xylene (ACS reagent, for example, Scientific) at 120 ° C. At the same time, 15 g of the coke powder and 150 ml of xylene were placed in a 1 ml stainless steel container. The middle side was heated while stirring to 160 ° C. While continuously stirring the mixture, the pitch-xylene solution was gradually injected into the coal char powder suspension under nitrogen pressure. The mixture was then heated to 2 10 ° C and stirred continuously for 15 minutes. The heat source was removed and the mixture was allowed to cool to ambient temperature (about 22 t) while maintaining continuous stirring. The resulting solid was separated from the cooled mixture and washed as described in Example 17. The total weight of the resulting powder was 16.8 grams. The amount of the asphalt on the coal char powder was about 10.7% by weight. 86864.DOC -58- 1302761 The dry powder was thoroughly mixed with a 4.5 wt% aqueous solution of 6 g of sodium nitrate (NaN03) (A_C.S. reagent, for example, J.T. Baker). The mixture was dried under vacuum at 80 C and then stabilized, carbonized and graphitized as described in Example 17. The graphitized powder was tested using an electrochemical test procedure and the results are not shown in Table 13. Example 21 The acicular coal char powder described in Example 18 was coated with a dip-coated petroleum pitch as described in Example 19. The /solution was prepared by dissolving 25 grams of the dilute petroleum pitch in 25 grams of xylene at 120 ° C in a 5 inch glass froth. At the same time, 15 g of acicular coal-like coke powder and 丨5 () ml of xylene were heated to 9 (rc) while continuously stirring in a 1000 ml stainless steel container. While continuously stirring the mixture, the asphalt-xylene solution was gradually added. Pour into the coal char powder suspension. The mixture is then heated to 190 at ambient pressure. 〇, and continuously stirred for 15 minutes at 190 c. The heat source is removed and the mixture is cooled while maintaining the continuous reading of the sandalwood. Ambient temperature (about hunger). The resulting solid was removed from the mixture and washed and dried as described in Example 17. The total weight of the dry ends was n-9 g. The precipitate on the coal char powder was 16.2% by weight. , spoon with dry powder and 6 grams of sodium nitrate (Acs• reagent, for example

Baker)之7重量。/〇水溶液徹底混合。將混合 」口 LT· 、、 ^貫施例1 7 Φ 之說明乾燥，穩定化，碳化及石墨化。使啦 、 &amp;用電化學每备 序測試經石墨化之粉末，結果示於表丨3。 。1 實施例22Baker) 7 weight. /〇 The aqueous solution is thoroughly mixed. Dry, stabilize, carbonize, and graphitize the mixture of LT· and . The graphitized powder was tested by electrochemical, and the results are shown in Table 3. . 1 Example 22

86864.DOC -59- 1302761 將實施例18之馈製針狀煤焦粉末塗覆由45份使用於實 施例19中之經浸熱.青及55份使用於實施例17中之低溶 點石油瀝青(193t梅特勒軟化點，75%亞爾可碳殘留物， 低灰分各向同性石油瀝青）所組成之瀝青混合物。 經由將40克之瀝青混合物溶解於5〇毫升玻璃燒瓶中之 在9(TC下之43克之二甲苯中，而製備得第一溶液。同時將 14_6克 &lt;烺製煤焦粉末及2〇〇毫升之二甲苯於⑺⑻毫升不 銹鋼容器中邊連續攪拌邊加&amp;16(rc。邊將混合物連續攪 拌，邊將瀝青-二甲苯溶液逐漸倒入至煤焦粉末懸浮液中。 接著將混合物加熱至21(rc，並連續攪拌15分鐘。接著將熱 源移除，及邊維持連續攪拌邊使混合物冷卻至環境溫度 (大約22t)。將生成之固體分離，如實施例17中之說明洗 滌及乾燥。乾燥塗覆粉末之總重量為17.2克。煤焦粉末上 之沈殿瀝青之量為約17_8重量％。 將乾燥粉末與6克之硝酸鈉（NaN〇3)(A_C.S.試劑，例如， J.T.Baker)之6.5重量％水溶液徹底混合。將混合物如實施例 17中之說明乾燥，穩定化，碳化及石墨化。使用電化學試 驗程序測試經石墨化之粉末，結果示於表13。 實施例23 使用如貫施例丨7所使用之相同的低熔點石油瀝青（1 Μ艺 私特勒軟化點’ 75%亞爾可碳殘留物，低灰分各向同性石 油瀝青）塗覆烺製石油針狀煤焦。石油煤焦係以與實施例i 8 所說明4類似方式製備得，但顆粒大小係在〇·1至5〇微米之 間，及平均顆粒大小為約16微米。86864.DOC -59- 1302761 The feed acicular coal coke powder of Example 18 was coated with 45 parts of the dip-heated cyan used in Example 19 and 55 parts of the low-solution point oil used in Example 17. Asphalt mixture of bitumen (193t METTLER softening point, 75% Alecco carbon residue, low ash isotropic petroleum bitumen). The first solution was prepared by dissolving 40 g of the asphalt mixture in a 5 cc glass flask at 43 g of 43 g of TC. At the same time, 14-6 g of &lt; 烺Coke powder and 2 〇〇 ml were prepared. The xylene was continuously stirred in a (7) (8) ml stainless steel vessel while stirring &lt;16 (rc.) while continuously stirring the mixture, the asphalt-xylene solution was gradually poured into the coal char powder suspension. The mixture was then heated to 21 (rc, and stirring for 15 minutes. The heat source was then removed and the mixture was allowed to cool to ambient temperature (about 22 t) while maintaining continuous stirring. The resulting solid was separated and washed and dried as described in Example 17. Drying The total weight of the coated powder was 17.2 g. The amount of the pitch asphalt on the coal char powder was about 17-8 wt%. The dry powder was mixed with 6 g of sodium nitrate (NaN〇3) (A_C.S. reagent, for example, JTBaker) The 6.5% by weight aqueous solution was thoroughly mixed. The mixture was dried, stabilized, carbonized and graphitized as described in Example 17. The graphitized powder was tested using an electrochemical test procedure and the results are shown in Table 13. Example 23 Co., Ltd. is coated with the same low-melting petroleum pitch (1 私 私 勒 勒 勒 勒 勒 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 Coal char. The petroleum coal coke was prepared in a similar manner to that described in Example i 8 except that the particle size was between 〇·1 and 5 μm and the average particle size was about 16 μm.

86864.DOC -60- 1302761 經由將320克之石油瀝青溶解於5〇〇毫升玻璃燒瓶中之 在100 C下之320克之二甲苯（A C S,試劑，例如，Fis^r Scnentmc)中，而製備得第一溶液。同時將468克之煤焦粉 末及1280克之二曱苯於6公升不銹鋼壓力容器中邊連續攪 拌邊加熱至120 C。邊將混合物連續攪拌，邊將瀝青-二甲 苯溶液逐漸倒人至煤焦粉末懸浮財。接著將混合物加熱 至160 C，並連續攪拌15分鐘。接著將熱源移除，及邊維持 連續攪拌邊使混合物冷卻至環境溫度（大約22它）。將生成 之固體分離，如實施例17中之說明洗滌及乾燥，僅除了在 洗滌步驟中使用750毫升之二甲苯。生成粉末之總重量= 564克。煤焦粉末上之沈澱瀝青之量為約17重量％。 將乾燥粉末與225克之硝酸鈉（NaN〇3)(A.Cs•試劑，例如 ’ J.T.Baker)之6.4重量％水溶液徹底混合。將混合物於真空 中在80°C下乾燥。於乾燥後，將44克經塗覆氧化劑之粉末 置於一旁以使用於實施例24,及如實施例17中之說明將“Ο 克之粉末穩定化，碳化及石墨化。使用電化學試驗程序測 試經石墨化之粉末，結果示於表丨3。 此實施例說明在石墨化之前不需要個別的碳化步驟。將 44克於實施例23中製備得之經塗覆氧化劑之粉末於氯環境 中加熱至45〇°C 2小時，然後冷卻至環境溫度（大約22r )。 然後將經穩定化之粉末轉移至石m及經由如實施例 17中之說明於感應爐中在氬氣中加熱至3〇〇〇七而石墨化。 如電化學試驗程序中之說明㈣生成之料，結果示於表86864.DOC -60- 1302761 Prepared by dissolving 320 grams of petroleum pitch in 320 grams of xylene (ACS, reagent, eg, Fis^r Scnentmc) at 100 C in a 5 liter glass flask A solution. At the same time, 468 g of coal coke powder and 1280 g of diphenylbenzene were heated to 120 C while continuously stirring in a 6-liter stainless steel pressure vessel. While continuously stirring the mixture, the asphalt-xylene solution was gradually poured to the coal char powder suspension. The mixture was then heated to 160 C and stirred continuously for 15 minutes. The heat source is then removed and the mixture is allowed to cool to ambient temperature (about 22 Torr) while maintaining continuous agitation. The resulting solid was separated and washed and dried as described in Example 17, except that 750 ml of xylene was used in the washing step. The total weight of the resulting powder = 564 grams. The amount of precipitated pitch on the coal coke powder was about 17% by weight. The dry powder was thoroughly mixed with a 6.4% by weight aqueous solution of 225 g of sodium nitrate (NaN〇3) (A.Cs•reagent, for example, 'J.T. Baker). The mixture was dried at 80 ° C in vacuo. After drying, 44 grams of the coated oxidant powder was placed aside for use in Example 24, and the powder of the gram was stabilized, carbonized, and graphitized as described in Example 17. Testing using an electrochemical test procedure The graphitized powder, the results are shown in Table 3. This example illustrates that no individual carbonization step is required prior to graphitization. 44 grams of the powder of the coated oxidant prepared in Example 23 is heated in a chlorine atmosphere. 2 hr to 45 ° C, then cooled to ambient temperature (about 22 rpm). The stabilized powder was then transferred to stone m and heated to 3 Torr in an induction furnace in an induction furnace as described in Example 17. Graphite. As shown in the description of the electrochemical test procedure (4), the results are shown in the table.

86864.DOC -61 - 1302761 13。 實施例25 將球形石墨顆粒塗覆實施例Π中使用之石油瀝青。石墨 顆粒為商業的巾間相碳微珠（MCMB)粉末（購自日本大阪氣 骨豆股份有限公司⑴saka Gas c〇 LTD)iMCMB_6 28)。 經由將7·5克之說明於實施例17之低熔點石油瀝青（i93C&gt;c 梅特勒I人化點’ 75°/〇亞爾可碳殘留物，低灰分各向同性石 油瀝青）溶解於50毫升玻璃燒瓶中之在9〇r下之7.5克之二 甲笨（A.C.S.忒劑，例如，Fisher Scientific)中，而製備得第 溶液同時將20克MCMB粉末及150毫升二甲苯於5〇〇毫 2玻璃燒瓶中邊連續攪拌邊加熱至138t;。邊將混合物連續 攪拌，邊將瀝青··二甲苯溶液逐漸倒入粉末懸浮液 :二接著將混合物加熱至138。(：，並連續攪拌15分鐘。接著 將熱源移除，及邊維持連續攪拌邊使混合物冷卻至環境溫 度（大約22 C )。將生成之固體分離，如實施例17中之說明 洗滌及乾燥。生成粉末之總重量為219克。mcmb粉末上 之沈澱瀝青之量為約8 · 7重量％。 將乾燥粉末與6克之硝酸鈉（NaN〇3)(Ac s•試劑，例如， er)之4.8重！ ％水溶液徹底混合。將混合物如實施例 17中之說明乾、燥，穩定化，碳化及石墨化。使用電化學試 驗程序測試經石墨化之粉末，結果示於表13。 實施例26 使用甲冬替代二甲苯作為溶劑，而進行說明於實施例I?86864.DOC -61 - 1302761 13. Example 25 Spherical graphite particles were coated with the petroleum pitch used in the example. The graphite particles were commercial inter-phase carbon microbeads (MCMB) powder (purchased from Osaka Sugabe Co., Ltd. (1) saka Gas c〇 LTD) iMCMB_6 28). By dissolving 7.5 grams of the low melting point petroleum pitch (i93C&gt;c METTLER I humanized point '75°/〇 arcocarbon residue, low ash isotropic petroleum pitch) described in Example 17 in 50 In a milliliter glass flask, 7.5 g of dimethyl benzoate (ACS sputum, for example, Fisher Scientific) at 9 Torr, and the first solution was prepared while 20 g of MCMB powder and 150 ml of xylene at 5 〇〇 2 The glass flask was heated to 138 t with continuous stirring. While the mixture was continuously stirred, the bitumen·xylene solution was gradually poured into the powder suspension: Second, the mixture was heated to 138. (:, and stirring was continued for 15 minutes. The heat source was then removed and the mixture was allowed to cool to ambient temperature (about 22 C) while maintaining continuous stirring. The resulting solid was separated and washed and dried as described in Example 17. The total weight of the resulting powder was 219 g. The amount of precipitated pitch on the mcmb powder was about 8.7 wt%. The dry powder was 4.8 with 6 g of sodium nitrate (NaN〇3) (Ac s•reagent, for example, er) The % aqueous solution was thoroughly mixed. The mixture was dried, dried, stabilized, carbonized and graphitized as described in Example 17. The graphitized powder was tested using an electrochemical test procedure and the results are shown in Table 13. Example 26 Axyl as a solvent instead of xylene is described in Example I?

86864.DOC -62- 1302761 經由將Μ使用於實施例17中之·青溶解於π毫升玻璃 燒瓶中之在赃下之11克之甲苯中，而製備得第n 同時將20克使用於實施例18中之懷製針狀煤焦粉末及15〇 毫升二曱料画毫升破璃燒瓶中邊連續攪拌邊加熱至 Μ。邊將混合物連續攪拌，邊將渥青·甲苯溶液逐漸倒入 至煤焦粉末懸浮液中。接著將混合物加熱至跡c，並連缋 檀拌15分鐘。接著將熱源移除’及邊維持連績攪拌邊使混 合物冷卻至環境溫度（大約22。〇。將生成之固體分離，如 實施例η中之說明洗蘇及乾燥，僅除了在洗蘇步驟中使用 200毫升之曱苯及將樣品在100。。下乾燥。生成粉末之總重 量為22.6克。如實施例17中之說明一计算得煤焦粉末上之沈 搬瀝青之量為約11 · 5重量％。 將生成之經塗覆瀝青之粉末轉移至5〇毫升之鋁氧坩堝 中，然後再置於管式爐内，及在i。〇 /分鐘下加熱至3⑻。◦ °， 接著再在200耄米汞柱（26.7 kPa)之絕對壓力下在3〇〇。〇下 停留10小時。在200毫米汞柱（26·7 kpa)下存在足夠的氧， 而可使經堡覆氧化劑之顆粒在加熱及停留循環中穩定化。 接著以與實施例17中說明之相同方式將塗覆顆粒碳化及石 墨化。（A.C.S.試劑，例如，J TBaker)。使用電化學試驗程 序測試經石墨化之粉末，結果示於表丨3。 比較實施例8 經由將60克使用於實施例19中之經浸熱之石油瀝青溶 解於100毫升玻璃燒杯中之4〇克之二甲苯（ACS試劑，例如 ’ Flsher Scientiflc)中，及於水浴中加熱至8(TC，而製備得86864.DOC -62- 1302761 was prepared by dissolving hydrazine in Example 17 in a π ml glass flask in 11 gram of toluene under a crucible to prepare nth while 20 g was used in Example 18. In the middle of the needle-shaped coal char powder and 15 ml of the two-dimensional paint, the flask was heated to the crucible with continuous stirring. While continuously stirring the mixture, the indigo/toluene solution was gradually poured into the coal char powder suspension. The mixture was then heated to trace c and simmered for 15 minutes. The heat source is then removed and the mixture is allowed to cool to ambient temperature (approximately 22. 〇. The resulting solid is separated, as described in Example η, washed and dried, except in the wash step The total weight of the resulting powder was 22.6 g using 200 ml of toluene and the sample was dried at 100. The amount of the settled bitumen on the coal char powder was calculated to be about 11 · 5 as described in Example 17. % by weight. Transfer the resulting coated bitumen powder to 5 ml of aluminoxane, then place it in a tube furnace and heat to 3 (8) at i.〇/min. ◦ °, then again Under the absolute pressure of 200 汞Hg (26.7 kPa) at 3 〇〇. Stay for 10 hours under 〇. There is enough oxygen at 200 mmHg (26·7 kpa), which can make the particles of the oxidant Stabilization in the heating and residence cycles. The coated particles were then carbonized and graphitized in the same manner as described in Example 17. (ACS reagent, eg, J TBaker). Graphitized powder was tested using an electrochemical test procedure The results are shown in Table 3. Example 8 was prepared by dissolving 60 grams of the dilute petroleum pitch used in Example 19 in 4 grams of xylene (ACS reagent, eg 'Flsher Scientiflc) in a 100 ml glass beaker and heating in a water bath to 8 (TC, prepared

86864.DOC -63- 1302761 第一溶液。溶劑對瀝青比為約2比i。同時將2〇克說明於實 施例18中之煅製煤焦粉末及80克之二甲苯於200毫升玻璃 少先杯中邊連績攪拌邊加熱至8 0 °C。邊將混合物連續攪拌， 邊將歷青-二甲苯溶液逐漸倒入至煤焦粉末懸浮液中。接著 將熱源移除，及邊維持連續攪拌邊使混合物冷卻至環境溫 度（大約22°C )。將生成之固體分離，如實施例18中之說明 洗務及乾燥’僅除了在洗滌步騾中使用30克之二甲苯。生 成粉末之總重量為20.5克。煤焦粉末上之沈澱瀝青之量為 約2重量％。 將乾燥粉末轉移至5〇毫升之鋁氧坩堝中，置於管式爐内 ’及在約100托爾（torr)(133 kPa)空氣壓力下在rc/分鐘下 綾悛加熱至300°C，並在300°C下停留10小時。然後利用純 氮氣冲洗s式爐，及如實施例丨7中之說明將粉末碳化。接 著如實施例17中之說明將經碳化之顆粒石墨化。使用電化 子4骀私序測試經石墨化之粉末，結果示於表13。結果顯 π未經充分塗覆瀝青材料之煤焦顆粒產生不良的充電效率。 比較實施例9 万、50毛升之玻璃燒杯中，將2 5克之中間相瀝青粉末（梅 特勒軟化點大，conoco，Inc.製造）及5〇克之二甲苯 (A^S試劑’例如’❿化Seiemifie)在紙下加熱。歷青 僅微溶於二甲苯中。同時將15克如實施例Η所使用之相同 的綠针狀煤焦粉末及15()毫升之二甲苯於则毫升不鎮鋼壓 力容器中邊連續攪拌邊加熱至16〇t。邊將混合物連婧攪拌 ，邊將中間相-二甲笑、々、产、、、 甲冬/合履〉王入至煤焦粉末懸浮液中。然後86864.DOC -63- 1302761 First solution. The solvent to pitch ratio is about 2 to i. At the same time, 2 g of the calcined coal char powder described in Example 18 and 80 g of xylene were heated to 80 ° C while stirring in a 200 ml glass cup. While continuously stirring the mixture, the cyan-xylene solution was gradually poured into the coal char powder suspension. The heat source is then removed and the mixture is allowed to cool to ambient temperature (about 22 ° C) while maintaining continuous agitation. The resulting solid was separated as described in Example 18 for washing and drying&apos; except that 30 grams of xylene was used in the wash step. The total weight of the resulting powder was 20.5 grams. The amount of precipitated pitch on the coal char powder was about 2% by weight. The dry powder was transferred to 5 liters of aluminum oxime, placed in a tube furnace' and heated to 300 ° C at rc/min under an air pressure of about 100 torr (133 kPa). And stay at 300 ° C for 10 hours. The s furnace was then flushed with pure nitrogen and the powder was carbonized as described in Example 丨7. The carbonized particles were then graphitized as described in Example 17. The graphitized powder was tested using an electrochemical 4 骀 private sequence, and the results are shown in Table 13. As a result, it was revealed that the coal char particles which were not sufficiently coated with the asphalt material produced poor charging efficiency. In a glass fired beaker of Comparative Example 90, 50 liters, 25 g of mesophase pitch powder (Mettler softening point, manufactured by Cooco, Inc.) and 5 g of xylene (A^S reagent 'for example' Suiemifie) heated under paper. Eclipta is only slightly soluble in xylene. At the same time, 15 g of the same green needle-like coal char powder as used in Example 及 and 15 () ml of xylene were heated to 16 Torr in continuous stirring with a milliliter of non-steel pressure vessel. While stirring the mixture, the mesophase - dimethyl xiao, 々, 产, ,,,,,,,,,,,,,,,,,,,,,,,,,,, then

86864.DOC -64- 1302761 將混合物進-步加熱至·。c，並連續攪拌15分鐘。接著將 熱源移除，及邊維持連續攪拌邊使混合物冷卻至環境溫度 (大、、、勺20 C ) I生成之固體分離，如實施例丄7中之說明洗 務及乾燥，僅除了在洗滌步驟中使用3Q克之二甲苯。生成 粉末之總重量為16·8克。煤焦粉末上之沈澱渥青之量為約 10·7重里％。&amp;而’觀察到中間相瀝青並未塗覆煤焦顆粒 ，而係呈個別微細顆粒之形態。 將乾燥粉末與6克之硝酸納（ACS.試劑’例如’ jt.86864.DOC -64- 1302761 Heat the mixture to -. c, and stirring continuously for 15 minutes. The heat source is then removed, and the mixture is cooled to ambient temperature (large, ,, spoon 20 C). The solid formed by the separation is maintained as described in Example 丄7, except for washing. 3Q grams of xylene was used in the step. The total weight of the resulting powder was 16.8 grams. The amount of precipitated indigo on the coal char powder was about 10.7% by weight. &amp; and it was observed that the mesophase pitch was not coated with coal char particles, but in the form of individual fine particles. Dry the powder with 6 grams of sodium nitrate (ACS. Reagents such as 'jt.

Baker)之4.5重量％水溶液徹底混合。將混合物如實施例η 中之說月乾h化’碳化及石墨化。使用電化學試驗 程序測試經石墨化之粉末，結果示於表13。 μ 比較實施例10 根據說明於實施例17中之程序將於實施例18中製備得 4未堂覆〈懷製煤焦粉末碳化及石墨化。使用電化學試驗 程序測試生成之粉末，結果示於表13。 比較實施例11 使用電化學試驗程序測試取得之商業中間相碳微珠 (MCMB)(MCMB-6-28，曰本大阪氣體股份有限公司）之球形 石、I顆粒，結果不於表13。可將未塗覆之MCMB之充電效 率數據與實施例25比較，且其說明實施例25之塗覆材料相 對於未塗覆材料的改良性質。The 4.5% by weight aqueous solution of Baker) was thoroughly mixed. The mixture was carbonized and graphitized as described in Example η. The graphitized powder was tested using an electrochemical test procedure and the results are shown in Table 13. μ Comparative Example 10 According to the procedure described in Example 17, the preparation of Example 4 was carried out in accordance with the carbonization and graphitization of the coal char powder. The resulting powder was tested using an electrochemical test procedure and the results are shown in Table 13. Comparative Example 11 The spherical phase I and I particles of the commercial mesocarbon microbeads (MCMB) (MCMB-6-28, Sakamoto Osaka Gas Co., Ltd.) obtained were tested using an electrochemical test procedure, and the results are not shown in Table 13. The charge efficiency data for the uncoated MCMB can be compared to Example 25, and which illustrates the improved properties of the coated material of Example 25 relative to the uncoated material.

86864.DOC -65- 1302761 表13 實施例 瀝青塗覆值 容量 容量損耗 效率 (%) (mAh/g) (mAh/g) (%) 17 18.7 326 14 95.8 18 18.2 329 16 95.4 19 17.8 330 16 95.4 20 10.7 324 16 95.3 21 16.2 330 16 95.5 22 17.8 325 15 95.7 23 17.0 330 16 95.4 24 17.0 326 15 95.6 25 8.7 300 16 95.0 26 11.5 335 17 95.2 比較8 2 299 365 45.0 比較9 10.7 294 441 40.0 比較10 0 290 453 39 比較11 0 298 21 93.3 實施例27 此實施例展示在天然石墨粉末上使用石油瀝青於改良 效率及材料加工能力。 利用射流磨研磨天然石墨薄片（Aldrich Chemical Company，Milwaukee，WI)並將其分級。所得之粉末具有在 86864.DOC -66- 1302761 〇_1及約40微米之間之大小範圍内的顆粒，且具有u微米之 平均顆粒大小。使20克所得之石墨粉末懸浮於15〇立方公分 之二甲苯中。將U克說明於實施韻之低熔點石油歷青 (1饥梅特勒軟化點，75%亞爾可碳_勿，低灰分各向 同性歷青）溶解利克二甲苯之溶液力口至石墨顆粒之縣浮 液中。以與實施例Π所說明之相同方式塗覆石墨顆粒，而 屋生22.7克之具有約12%之、瀝青塗覆值的乾塗覆顆粒。將 塗覆〈粉末與1.38克30% NaN03、8.3克水及〇·8克丙酮(促 進潤濕）混合，乾燥然後再如實施例17中之說明穩定化，碳 化及石墨化。使用電化學試驗程序測試經石墨化之粉末， 結果示於表14。 實施例2 8 此貫施例使用與實施例27所使用者相同的天然石墨，但 其具有在0·1及約50微米之間之大小範圍内的顆粒及約15 微米之平均顆粒大小。使2 〇克之粉末懸浮於丨5 〇立方公分之 二甲苯中。將11克說明於實施例17之低熔點石油瀝青（193它 梅特勒軟化點，75%亞爾可碳殘留物，低灰分各向同性瀝 青）溶解於11克二甲苯之溶液加至石墨顆粒之懸浮液中。如 貫施例1 7中之說明塗覆石墨顆粒。生成之乾燥塗覆粉末重 23克，且具有約13重量％之瀝青塗覆值。將粉末與1.45克 30%硝酸鈉（NaN〇3)、8·〇克水及〇·7克丙酮（促進潤濕）混合 ，乾燥然後再如實施例丨7中之說明穩定化，碳化及石墨化 。使用電化學試驗程序測試經石墨化之粉末，結果示於表 14 〇86864.DOC -65- 1302761 Table 13 Example Bitumen Coating Value Capacity Capacity Loss Efficiency (%) (mAh/g) (mAh/g) (%) 17 18.7 326 14 95.8 18 18.2 329 16 95.4 19 17.8 330 16 95.4 20 10.7 324 16 95.3 21 16.2 330 16 95.5 22 17.8 325 15 95.7 23 17.0 330 16 95.4 24 17.0 326 15 95.6 25 8.7 300 16 95.0 26 11.5 335 17 95.2 Comparison 8 2 299 365 45.0 Comparison 9 10.7 294 441 40.0 Comparison 10 0 290 453 39 Comparison 11 0 298 21 93.3 Example 27 This example demonstrates the use of petroleum pitch on natural graphite powder for improved efficiency and material processing capabilities. Natural graphite flakes (Aldrich Chemical Company, Milwaukee, WI) were ground using a jet mill and classified. The resulting powder had particles in the size range of 86864.DOC -66 - 1302761 〇_1 and about 40 microns and had an average particle size of u microns. 20 g of the obtained graphite powder was suspended in 15 〇 cubic centimeters of xylene. U g is described in the implementation of rhyme low melting point petroleum calendar (1 hung METTLER softening point, 75% Yarco carbon _ do not, low ash isotropic blue calendar) solution of liquefied xylene solution to the graphite particles The county floats. The graphite particles were coated in the same manner as described in the Examples, and 22.7 g of dry coated particles having an asphalt coating value of about 12% were produced. The coated <powder was mixed with 1.38 g of 30% NaN03, 8.3 g of water and 8 g of acetone (promoted wetting), dried and then stabilized, carbonized and graphitized as described in Example 17. The graphitized powder was tested using an electrochemical test procedure and the results are shown in Table 14. EXAMPLE 2 8 This example uses the same natural graphite as the user of Example 27, but which has particles in the size range between 0.1 and about 50 microns and an average particle size of about 15 microns. 2 g of the powder was suspended in 丨 5 〇 cubic centimeters of xylene. 11 g of the low melting point petroleum pitch (193 Mettler softening point, 75% Alecco carbon residue, low ash isotropic pitch) described in Example 17 was dissolved in 11 g of xylene solution and added to the graphite particles. In the suspension. The graphite particles were coated as described in Example 17. The resulting dry coated powder weighed 23 grams and had an asphalt coating value of about 13% by weight. The powder was mixed with 1.45 g of 30% sodium nitrate (NaN〇3), 8·g of water and 7 g of acetone (promoting wetting), dried and then stabilized, carbonized and graphite as described in Example 丨7. Chemical. The graphitized powder was tested using an electrochemical test procedure and the results are shown in Table 14

86864.DOC -67· 1302761 實施例29 如實施例28中之說明利用射流磨研磨天然石黑、薄片 (Asbury Graphite Co.，Asbury，NJ)，並利用風選機將其分級 。所得之粉末具有在0.1及約40微米之間之大小範圍内的署貝 粒，且具有約13微米之平均顆粒大小。使20克之粉末雖、、字 於150立方公分之二甲苯中。將π克說明於實施例17之低緣 點石油瀝青（193°C梅特勒軟化點，75%亞爾可碳殘留物， 低灰分石油瀝青）溶解於11克二甲苯之溶液加至石墨顆粒 之懸浮液中。如實施例17中之說明塗覆石墨顆粒。生成之 粉末重23克且具有約13重量％之瀝青塗覆值。將粉末與 1.5 1克30%硝酸鈉（NaN〇3)、8.0克水及0.7克丙酮（促進潤濕) 混合，乾燥然後再如實施例17中之說明穩定化，碳化及石 墨化。使用電化學試驗程序測試經石墨化之粉末，、纟士果厂、 於表14。 實施例30 此實施例使用與實施例29所使用者類似的天然石黑粉 末’但其具有在0.1及50微米之間之顆粒大小範園及15微米 之平均顆粒大小。使20克之粉末懸浮於150立方公分之一甲 苯中。將Π克說明於實施例17之低熔點石油青（丨们^梅 特勒軟化點，75%亞爾可碳殘留物，低灰分各向同性石、、由 瀝青）溶解於Π克二甲苯之溶液加至石墨顆粒之顯、、字、夜中 。如實施例17中之說明塗覆石墨顆粒。生成之塗覆粉末重 23.1克，且具有約13重量％之瀝青塗覆值。接著將^末與 1.57克30%硝酸鋼（NaN03)、8.0克水及〇·7克丙酮（促進^潤濕')86864.DOC -67· 1302761 Example 29 Natural stone black, flakes (Asbury Graphite Co., Asbury, NJ) were ground using a jet mill as described in Example 28 and classified using a wind trainer. The resulting powder has a size of the shell in the range of between 0.1 and about 40 microns and has an average particle size of about 13 microns. 20 g of the powder, in the word of 150 cubic centimeters of xylene. Πg of the low-edge petroleum pitch (193°C METTLER softening point, 75% Alecco carbon residue, low ash petroleum pitch) dissolved in 11 g of xylene solution added to the graphite particles of Example 17 In the suspension. The graphite particles were coated as described in Example 17. The resulting powder weighed 23 grams and had an asphalt coating value of about 13% by weight. The powder was mixed with 1.5 1 g of 30% sodium nitrate (NaN〇3), 8.0 g of water and 0.7 g of acetone (promoting wetting), dried and then stabilized, carbonized and graphiteized as described in Example 17. The graphitized powder was tested using an electrochemical test procedure, the Gentleman's Fruit Factory, in Table 14. EXAMPLE 30 This example used a natural stone black powder similar to that of Example 29 but having a particle size range between 0.1 and 50 microns and an average particle size of 15 microns. 20 g of the powder was suspended in 150 cubic centimeters of toluene. The low-melting petroleum cyanine of Example 17 (we have a Mettler softening point, 75% Alecco carbon residue, low ash isotropic stone, and asphalt) dissolved in gram of xylene The solution is added to the display, the word, and the night of the graphite particles. The graphite particles were coated as described in Example 17. The resulting coated powder weighed 23.1 grams and had an asphalt coating value of about 13% by weight. Then we will end with 1.57 grams of 30% nitric acid (NaN03), 8.0 grams of water and 7 grams of acetone (promoting ^ wetting ')

86864.DOC 1302761 混合，乾燥然後再如〃…。q 4 〜Ίϋ，碳化及石 墨化。使用電化學試驗程序測試經石墨化之粉末，結果示 於表14。 ' θ 實施例3 1 此實施例使用與實施例2 9所使用者類似的天然石墨粉 末’但其具有在0.1及約50微米之間之顆粒大小範圍及㈣ 微米之平均顆粒大小。使20克之粉末懸浮於15〇立方公分之 —甲苯中。將15克說明於實施例17之低熔點石油瀝青（193它 梅特勒軟化點，75%亞爾可碳殘留物，減分各向同性石 ’由瀝青）洛解於15克二甲苯之溶液加至石墨顆粒之懸浮液 中。如實施例17中之說明、塗覆石墨顆粒。生成之塗覆粉末 重24.3克，且具有約17·6重量％之瀝音塗覆值。將粉㈣ 2.26克30%硝酸銅（NaN〇3)、7.〇克水及〇·7克丙嗣（促進潤濕） =合，乾燥然後再如實施例17中之說明穩定化，碳化及石 '1、化。使用電化學試驗程序測試經石墨化之粉末，钟、 於表14。 、、、口 不 實施例32 以與貝她例27中說明之相同方式將實施例3〇所使用之 :然石墨粉末塗覆與實施例27相同的瀝青溶液。經乾燥的 土復歷青重23.2克，其顯示約13·8重量％之歷青塗覆值。將 粉末與U克30%靖酸納（NaN〇3)、7〇克水及〇·7克丙綱（促 進潤濕)混合’乾燥然後再如實施例17中之說明穩定化，碳 化及石墨化。使用電化學試驗程序測試經石墨化之粉末Γ 結果示於表14。86864.DOC 1302761 Mix, dry and then simmer.... q 4 ~ Ίϋ, carbonization and graphite. The graphitized powder was tested using an electrochemical test procedure and the results are shown in Table 14. 'θ Example 3 1 This example uses a natural graphite powder similar to that of the user of Example 29. However, it has a particle size range between 0.1 and about 50 microns and an average particle size of (4) microns. 20 g of the powder was suspended in 15 〇 cubic centimeter of toluene. 15 grams of the low melting point petroleum pitch described in Example 17 (193 Mettler softening point, 75% Alecco carbon residue, reduced isotropic stone 'by bitumen) is dissolved in 15 g of xylene solution Add to the suspension of graphite particles. Graphite particles were coated as described in Example 17. The resulting coated powder weighed 24.3 grams and had a grading coating value of about 17.6% by weight. Powder (4) 2.26 g of 30% copper nitrate (NaN〇3), 7. gram of water and 〇7 g of propylene (promoting wetting) = dry, then stabilized as described in Example 17, carbonization and Stone '1, Hua. The graphitized powder, clock, is shown in Table 14 using an electrochemical test procedure. No, Example 32 The same procedure as described in Example 27 was used. The graphite powder was coated with the same asphalt solution as in Example 27. The dried soil had a green weight of 23.2 grams, which showed a green coating value of about 13.8% by weight. The powder was mixed with U grams of 30% Nasphate (NaN〇3), 7 g of water and 7 g of propyl (promoted wetting) to dry and then stabilized, carbonized and graphite as described in Example 17. Chemical. The graphitized powder was tested using an electrochemical test procedure. The results are shown in Table 14.

86864.DOC 1302761 實施例3 3 利用射流磨研磨天然石墨薄片（Nashu，中國），並將其於 工氣中分級。所得之粉末具有在〇1及約4〇微米之間之大小 範圍内的顆粒，及約12微米之平均顆粒大小。使20克之生 成粉末懸浮於150立方公分之二甲苯中。將丨丨克說明於實施 例17之低^點石油瀝青（193它梅特勒軟化點，乃％亞爾可 碳殘留物，低灰分各向同性瀝青）溶解於丨丨克二甲苯之溶液 加土石墨顆粒之懸浮液中。以如實施例1 7中說明之相同方 覆石墨顆粒。生成之粉末重23.〇克且具有13%之瀝青 塗覆值。將粉末與1·71克30%硝酸鈉（NaN〇3)、8 〇克水及〇·7 克丙酮（促進潤濕）混合，乾燥然後再如實施例17中之說明 穩定化，碳化及石墨化。使用電化學試驗程序測試經石墨 化之粉末，結果示於表14。 使用如實施例33中說明之相同顆粒製備塗覆之天然石 墨粉末。使20克之粉末懸浮於15〇立方公分之二甲苯中。將 14克說明於實施例17之低熔點石油瀝青⑽。c梅特勒軟化 點，75〇/〇亞爾可碳殘留物，低灰分各向同性石油渥青）溶解 於Μ克二甲苯之溶液加至石墨顆粒之懸浮液中。經乾燥的 塗覆石墨顆粒重23.9克，其顯示約163重量％之塗覆值。將 塗覆粉末與1.91克30%硝酸鈉（NaN〇3)、8 〇克水及〇 酮(促進潤濕)混合，乾燥然後再如實施例17中::°:克： 化，碳化及石墨化。使用電化學試驗程序測詞經石墨 粉末’結果示於表14。86864.DOC 1302761 Example 3 3 Natural graphite flakes (Nashu, China) were ground using a jet mill and classified in the process gas. The resulting powder has particles in the size range between 〇1 and about 4 〇 microns, and an average particle size of about 12 microns. 20 g of the resulting powder was suspended in 150 cubic centimeters of xylene. The solution of the low-point petroleum pitch of Example 17 (193 Mettler softening point, which is a residual Yarco carbon residue, low ash isotropic pitch) dissolved in gram of xylene is described. In the suspension of soil graphite particles. The graphite particles were coated in the same manner as described in Example 17. The resulting powder weighed 23. grams and had a 13% asphalt coating value. The powder was mixed with 1.71 g of 30% sodium nitrate (NaN〇3), 8 g of water and 7 g of acetone (promoting wetting), dried and then stabilized, carbonized and graphite as described in Example 17. Chemical. The graphitized powder was tested using an electrochemical test procedure and the results are shown in Table 14. The coated natural graphite powder was prepared using the same granules as described in Example 33. 20 grams of the powder was suspended in 15 cubic centimeters of xylene. 14 g of the low melting point petroleum pitch (10) of Example 17 is illustrated. c. METTLER softening point, 75 〇/〇 arcocarbon residue, low ash isotropic petroleum phthalocyanine) The solution dissolved in gram of xylene is added to the suspension of graphite particles. The dried coated graphite particles weighed 23.9 grams, which showed a coating value of about 163% by weight. The coated powder was mixed with 1.91 g of 30% sodium nitrate (NaN〇3), 8 g of water and anthrone (promoting wetting), dried and then as in Example 17:: °: g: carbonized, graphite Chemical. The results of the measurement of the graphite powder by the electrochemical test procedure are shown in Table 14.

86864.DOC -70- Ϊ302761 比較實施例12 -1 4 如實施例1 7中之說明將實施例29、3 1、及33中所使用之 經研磨的石墨粉末碳化及石墨化。使用電化學試驗程序对 試經石墨化之粉末，結果示於表14。 令人驚奇地，研磨仔之天然石墨粉末具有較經石墨化之 針狀煤焦粉末高甚多的充電效率及較高容量，但研^得: 天然石墨粉末對銅基材具有非常差的黏著。然而，於 塗覆及熱處理之後’利用天然石墨製得之塗覆可= 地分散於PVDF/膽塗覆溶液中，及良好地黏著至铜^易86864.DOC -70- Ϊ302761 Comparative Example 12 -1 4 The ground graphite powders used in Examples 29, 31, and 33 were carbonized and graphitized as described in Example 17. The graphitized powder was tested using an electrochemical test procedure, and the results are shown in Table 14. Surprisingly, the natural graphite powder of the grind has a higher charging efficiency and higher capacity than the graphitized acicular coal coke powder, but the natural graphite powder has a very poor adhesion to the copper substrate. . However, after coating and heat treatment, the coating made of natural graphite can be dispersed in the PVDF/biliary coating solution and adhered well to the copper.

86864.DOC -71- 1302761 實施例35 此爲施例展示在穩定化步騾中使用流體化床反應器及 使用二氣作為氧化/穩定化試劑。 經由將320克之實施例17所使用之低熔點瀝青（i93t梅 特勒軟化點，75%亞爾可碳殘留物，低灰分各向同性石油 瀝青）落解於500毫升玻璃燒瓶中之在100°C下之320克之二 甲苯中，而製備得第一溶液。同時將54〇克之實施例丨8中所 吏用之t研磨的娘製針狀煤焦粉末及1 2 § 〇毫升之二甲苯於 6公升之不銹鋼容器中邊連續攪拌邊加熱至12(rc。邊將混 合物連續攪拌，邊將瀝青/二甲苯溶液逐漸倒入至煤焦粉末 懸浮液中。接著將混合物於環境壓力下加熱至1 601：，並連 績攪拌1 5分鐘。接著將熱源移除，及邊維持連續攪拌邊使 混合物冷卻至環境溫度（大約22t)。將生成之固體分離， 如實施例17中之說明洗滌及乾燥，僅除了在洗滌步驟中使 用700¾升之一甲豕。生成粉末之總重量為622克。煤焦粉 末上之沈澱瀝青之量為約13.2重量％。 將乾燥粉末輕輕篩過120網目（125微米）之篩子。稱重1〇〇 克之過篩的粉末，並將其置於不銹鋼實驗室流體化床反應 器[自設設計，反應器室尺寸：5英吋（12·7公分）直徑及4.5 英对（11.4公分）高]中。將反應器置於經預熱至ι5〇^之經加 熱的砂浴中。將入口空氣及砂浴溫度在yc/分鐘之速率下 提高至275°C，及在275°C下停留15分鐘。接著將反應器自 砂浴移出，及將入口氣體改變為氮氣，以使經穩定化之粉 86864.DOC -72- 1302761 末及反應器可冷卻至環境溫度（大約22°C )。 將50克之經穩定化的粉末置於鋁氧坩堝中。將掛禍置於 管式爐中，及於純氮中在5°C/分鐘之速率下加熱至85〇^， 於850°C下停留2小時，然後再在5°C/分鐘之速率下冷卻至 環境溫度（大約22°C )。將粉末轉移至石墨掛禍，並在如备 施例17中說明之感應爐中石墨化。使用電化學試驗程序測 試經石墨化之粉末，結果示於表1 5。 實施例36-3 8 此等實施例顯示不同穩定化溫度分佈的影響。在各會施 例中使用100克利用實施例35說明之程序製得之經塗覆瀝 青之粉末。 在實施例36中，在使反應器掉入至砂浴中之前，將砂浴 預熱至200°C。將砂浴及入口空氣在6t/分鐘之速率下加熱 至 275〇C。 在實施例37中，在使反應器掉入至砂浴中之前，將砂浴 預熱至230°C。將砂浴及入口空氣在6。(〕/分鐘之速率下加熱 至300°C並停留15分鐘。在實施例38中，將砂浴預熱至28〇。〇 。於反應為掉入至砂浴中之後，使氣體出口之溫度快速提 鬲至400 C。將入口氣體快速轉變為氮氣，及將反應器自砂 浴拉出，並使其冷卻至環境溫度。 將50克之各經空氣穩定化之粉末轉移至個別的石墨坩 堝，並如實施例17中之說明碳化及石墨化。使用電化學試 驗程序測試經石墨化之粉末，結果示於表15。 實施例39-4286864.DOC -71- 1302761 Example 35 This is an illustration showing the use of a fluidized bed reactor in a stabilization step and the use of two gases as oxidation/stabilization reagents. By dissolving 320 grams of the low melting point asphalt (i93t METTLER softening point, 75% Alecco carbon residue, low ash isotropic petroleum pitch) used in Example 17 in a 500 ml glass flask at 100° A first solution was prepared by treating 320 grams of xylene under C. At the same time, 54 g of the pulverized mother-made needle-shaped coal char powder and 12 § mM of xylene used in Example 8 were heated to 12 (rc) while continuously stirring in a 6-liter stainless steel container. While continuously stirring the mixture, the asphalt/xylene solution was gradually poured into the coal char powder suspension. The mixture was then heated to 1 601: at ambient pressure and stirred for 15 minutes. Then the heat source was removed. And the mixture was allowed to cool to ambient temperature (approximately 22 t) while maintaining continuous agitation. The resulting solid was separated and washed and dried as described in Example 17, except that one of the 7003⁄4 liters of formazan was used in the washing step. The total weight of the powder was 622 g. The amount of precipitated bitumen on the coal coke powder was about 13.2% by weight. The dry powder was gently sieved through a sieve of 120 mesh (125 micrometers). The sieved powder was weighed by 1 gram. And placed in a stainless steel laboratory fluidized bed reactor [self-designed, reactor chamber size: 5 inches (12. 7 cm) diameter and 4.5 inches (11.4 cm) high]. Place the reactor Preheated to ι5〇^ In a hot sand bath, the inlet air and sand bath temperatures were increased to 275 ° C at a rate of yc / min and at 275 ° C for 15 minutes. The reactor was then removed from the sand bath and the inlet gas was changed. Nitrogen gas, so that the stabilized powder 86864.DOC -72- 1302761 and the reactor can be cooled to ambient temperature (about 22 ° C). 50 grams of stabilized powder is placed in the aluminum oxime. The scourge was placed in a tube furnace and heated to 85 〇 in pure nitrogen at a rate of 5 ° C / min, at 850 ° C for 2 hours, and then cooled to a rate of 5 ° C / min to Ambient temperature (approximately 22 ° C.) The powder was transferred to graphite and graphitized in an induction furnace as described in Example 17. The graphitized powder was tested using an electrochemical test procedure and the results are shown in Table 1. 5. Examples 36-3 8 These examples show the effect of different stabilization temperature profiles. 100 grams of coated asphalt powder prepared using the procedure described in Example 35 was used in each of the examples. In 36, the sand bath was preheated to 200 ° C before dropping the reactor into the sand bath. And the inlet air was heated to 275 ° C at a rate of 6 t / min. In Example 37, the sand bath was preheated to 230 ° C before dropping the reactor into the sand bath. Sand bath and inlet air Heated to 300 ° C at a rate of 6. (or / minute) and stayed for 15 minutes. In Example 38, the sand bath was preheated to 28 Torr. After the reaction was dropped into the sand bath, the gas was allowed to pass. The temperature at the outlet is quickly increased to 400 C. The inlet gas is quickly converted to nitrogen, and the reactor is pulled from the sand bath and allowed to cool to ambient temperature. 50 grams of each air stabilized powder is transferred to individual Graphite crucible and carbonization and graphitization as described in Example 17. The graphitized powder was tested using an electrochemical test procedure and the results are shown in Table 15. Examples 39-42

86864.DOC -73- 1302761 此等實施例顯示將在石墨化之前之將經穩定化之塗覆 顆粒碳化之步驟消除的影響。 土復 實施例3、42分別使用利用實施例35_38中說明之方去 得之經空氣穩定化之粉末。於穩定化之後，將粉末轉移二 個別的石墨坩堝中，並如實施例17中之說明石墨化。 兩^ 1 使用 兒化子試驗程序測試經石墨化之粉末，結果示於表1 $久 貫施例之數據顯示石墨粉末皆具有大於93%之充電效率 表15 ---- _5_施例 容量（mAh/g) 容量損耗（mAh/g) 效率（〇/、 35 330 17 1 \ /〇 ) ~~------ Q C 1 36 ------ 322 21 3 ) · 1 ~ 93 Q 37 ~_-— 331 17 乂 j，y ~~~~~~~—— 95 1 _38 338 16 ------ 95.6 39 327 24 1 40 328 23 ~~---—- 41 330 '----- 19 -------- L 94.6 42 339 16 -----J 95.6 實施例43-45 經由將65克之如實施例1中所使用之相同的石油、瀝青 (210°C梅特勒軟化點，75%亞爾可碳殘留物，&lt;1〇〇 ppm灰 分各向同性石油瀝青）溶解於100毫升玻璃燒瓶中之在1201 下之65克之二甲苯中，而製備得第一溶液。同時將1〇〇克之 86864.DOC -74- 1302761 400網目（38彳政米）天然石墨粉末（chuetsu Graphite w〇rks Co. Ltd，日本大阪）及4〇〇毫升二甲苯之混合物於5〇〇毫升之 破璃燒瓶中邊連續攪拌邊加熱至13代。邊將混合物連續擾 拌，邊如瀝青-二甲苯落液逐漸倒入至石墨粉末懸浮液中。 接著將混合物加熱至140X：並連續攪拌15分鐘。接著將熱源 移除，及邊維持連續攪拌邊使混合物冷卻至環境溫度（大約 22 C ) I由使用真空過濾漏斗過漉混合物而將生成之固體 自溶液分離。然後以200毫升二甲苯洗滌粉末，並於真空中 在120 c下乾：):呆約3小時。生成粉末之總重量為丨丨8克。計算 得石、I知末上之沈澱瀝青之量為總質量之約1 $重量％。將 經塗覆瀝青之顆粒轉移至不銹鋼盤内，並以如實施例26所 說明之相同方式於空氣中穩定化。 然後使經穩定化之塗覆顆粒直接於3〇〇(rCT石墨化（實 訑例43)，於1200 C下碳化（實施例44) ’或於9〇〇。(3下碳化 (實施例45)。 使用電化學試驗程序測試由實施例43_45製得之粉末，結 果示於表1 6。 亦對各此等材料測量對鋰之電池電壓成放電容量之函 數（圖1)。數據顯示雖然實施例43及實施例45之總容量在〇 土 2伏特足位能窗内幾乎相同，但在不同電極位能下之容量 分佈則相當不同。實施例43之位能於〇·5伏特之後陡增，而 實施例45於〇.5伏特之後則緩慢地增加，而有相當大的肩部 二貫施例4 3亦具有較實施例4 5高之實際容量及高之充電效 率。如陽極材料對！^之截止電位為〇·5伏特，則在實際的裝86864.DOC -73- 1302761 These examples show the effect of eliminating the step of carbonizing the stabilized coated particles prior to graphitization. The soil-resilient examples 3 and 42 respectively used the air-stabilized powder obtained by the method described in Example 35_38. After stabilization, the powder was transferred to two individual graphite crucibles and graphitized as described in Example 17. Two ^ 1 The graphitized powder was tested using the catalyzed test procedure. The results are shown in Table 1. The data for the long-term application shows that the graphite powder has a charging efficiency greater than 93%. Table 15 ---- _5_Example Capacity (mAh/g) Capacity loss (mAh/g) Efficiency (〇/, 35 330 17 1 \ /〇) ~~------ QC 1 36 ------ 322 21 3 ) · 1 ~ 93 Q 37 ~_-- 331 17 乂j,y ~~~~~~~—— 95 1 _38 338 16 ------ 95.6 39 327 24 1 40 328 23 ~~----- 41 330 ' ----- 19 -------- L 94.6 42 339 16 -----J 95.6 Examples 43-45 via 65 grams of the same petroleum, bitumen (210 used as in Example 1) °C Mettler softening point, 75% Alecco carbon residue, &lt;1〇〇ppm ash isotropic petroleum pitch) was dissolved in 65 g of xylene under 1201 in a 100 ml glass flask, and prepared The first solution was obtained. At the same time, 1 gram of 86864.DOC -74- 1302761 400 mesh (38 彳 米) natural graphite powder (chuetsu Graphite w〇rks Co. Ltd, Osaka, Japan) and 4 〇〇 ml of xylene mixture at 5 〇〇 The ML flask was heated to 13 generations with continuous stirring. While continuously mixing the mixture, the asphalt-xylene falling liquid was gradually poured into the graphite powder suspension. The mixture was then heated to 140X: and stirred continuously for 15 minutes. The heat source was then removed and the mixture was allowed to cool to ambient temperature (approximately 22 C) while maintaining continuous agitation. The resulting solid was separated from the solution by passing the mixture through a vacuum filter funnel. The powder was then washed with 200 ml of xylene and dried under vacuum at 120 c:): for about 3 hours. The total weight of the resulting powder was 8 g. Calculate the amount of precipitated bitumen on the stone and I know about 1% by weight of the total mass. The pitch-coated granules were transferred to a stainless steel pan and stabilized in air in the same manner as described in Example 26. The stabilized coated particles were then carbonized directly at 3 Torr (rCT graphitization (Example 43), carbonized at 1200 C (Example 44) ' or at 9 Torr. (3 under carbonization (Example 45) The powders prepared in Example 43_45 were tested using an electrochemical test procedure and the results are shown in Table 16. The values of the lithium battery voltage as a discharge capacity were also measured for each of these materials (Fig. 1). The total capacity of Example 43 and Example 45 is almost the same in the 2 volt foot energy window of the alumina, but the capacity distribution at different electrode potentials is quite different. The position of Example 43 can be sharply increased after 〇·5 volts. While Example 45 is slowly increasing after 〇5 volts, there is a considerable shoulder second embodiment 3-4 which also has a higher actual capacity and higher charging efficiency than Example 45. For example, anode material pair !^ The cut-off potential is 〇·5 volts, then the actual loading

86864.DOC -75- 1302761 置中將不會看到在高於0.5伏特之位能下的其餘容量。 圖2說明於實施例43-45中製備得之材料之在起始充電效 率與截止電位之間的關係。數據顯示實施例4 5之起始充電 效率係強烈地視截止電位而定。關於實施例45，在〇.5伏特 截止電位下之充電效率為82%，而實施例43自〇 5至2伏特 之充電效率則增加低於2%。 實施例43-45說明碳化/石墨化溫度對經塗覆瀝青之石墨 顆粒粉末之容量及效率兩者具有顯著的影響。在諸如9〇〇它 (&lt;1000°C)之低溫下，第一循環效率低，及如截止電位低於 1伏特則將再更低。當碳化溫度提高時，如實施例44所顯示 ，容量減小，但效率增加。當碳化/石墨化溫度增加至高於 2200°C時，如實施例45所顯示，容量及效率兩者增加。因 此，希望將複合顆粒粉末在高於22〇(rc之溫度下石墨化。 -----___ 表 1 6 實施例 塗覆之瀝青 容量 不可逆的 效率 (%) —------ (mAh/g) 容量損耗 (m Ah / (%) 43 15 - ---- 347 17 95.2 44 15 —_335 42 88.8 45 15 —&gt;—.— 344 31 91.7 卞夕具晅貝施例。然而，當明瞭可不脫 , ^~_ 3 1 91.7 已說明本發明之許多且两曲每 離本發明之精神及 圍而進行各種修改。因此，其他且體 實施例係在以下申嗜I剎#闽 八 τ明寻利軌圍之範圍内。86864.DOC -75- 1302761 will not see the remaining capacity at a potential above 0.5 volts. Figure 2 illustrates the relationship between the initial charge efficiency and the cut-off potential of the materials prepared in Examples 43-45. The data shows that the initial charging efficiency of Example 4 is strongly dependent on the cut-off potential. With respect to Example 45, the charging efficiency at the cutoff potential of 〇5 volt was 82%, and the charging efficiency of Example 43 from 〇 5 to 2 volts was increased by less than 2%. Examples 43-45 illustrate that the carbonization/graphitization temperature has a significant effect on both the capacity and efficiency of the coated pitch graphite particle powder. At low temperatures such as 9 〇〇 (&lt;1000 °C), the first cycle is inefficient and will be lower if the cutoff potential is below 1 volt. As the carbonization temperature increases, as shown in Example 44, the capacity decreases, but the efficiency increases. When the carbonization/graphitization temperature was increased above 2200 ° C, both capacity and efficiency increased as shown in Example 45. Therefore, it is desirable to graphitize the composite particle powder at a temperature higher than 22 〇 (rc). -----___ Table 16 The irreversible efficiency (%) of the asphalt capacity coated in the example - ( mAh/g) Capacity loss (m Ah / (%) 43 15 - ---- 347 17 95.2 44 15 —_335 42 88.8 45 15 —&gt; —. — 344 31 91.7 卞 晅 晅 。. 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 τ is clearly within the scope of the track.

86864.DOC -76- 1302761 【圖式簡單說明】 圖1顯示於實施例43-45中製備得之材料之電位成放電容 量之函數的圖。 圖2顯示於實施例43-45中製備得之材料之庫侖效率對截 止電壓之圖。 在各個圖示中之類似的元件符號指示類似的元件。 86864.DOC -77-86864.DOC -76- 1302761 BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a graph showing the potential of a material prepared in Examples 43-45 as a function of discharge capacity. Figure 2 is a graph showing the coulombic efficiency vs. cutoff voltage for the materials prepared in Examples 43-45. Similar element symbols in the various figures indicate similar elements. 86864.DOC -77-

Claims (1)

130236^119978號專利申請案 中文申請專利範圍替換本(97 拾、申請專利範圍·· 日Patent Application No. 130236^119978 Replacement of Chinese Patent Application Range (97 Pickup, Patent Application Range··Day 一種製造塗覆之碳質顆粒之方法，包括·· 提供一碳殘留物形成材料，其係選自當經氧化然後 再於惰性大氣中熱分解至至少85〇。〇之碳化溫度時，形 成至少90重量％碳之殘留物之材料； 提供碳質材料之顆粒； 將该奴殘留物形成材料及該碳質材料之顆粒在足以 使碳殘留物形成材料之均勻塗層沈積於碳質顆粒之表 面上之條件下混合；及 經由使該塗覆之顆粒進行氧化反應，而使塗覆之顆 粒穩定化。 2· —種製造塗覆之碳質顆粒之方法，包括： 提供碳殘留物形成材料之第一溶液，其中該第一溶 液包含一或多種溶劑及選自當經氧化然後再於惰性大 氣中熱分解至至少85(rc之碳化溫度時，形成至少9〇重 里之殘留物之材料的碳殘留物形成材料； 提供碳質材料之顆粒； 將该碳殘留物形成材料之第一溶液及該碳質材料之 顆粒在高溫下混合； 使石反殘留物形成材料之塗層沈積於碳質顆粒之表面 上；及 ‘由使4塗覆之顆粒進行氧化反應，而使塗覆之顆 粒穩定化。 3.如申請專利範圍第2項之方法，其中該碳f材料之顆粒 86864-970411.DOC 1302761 係以在與第一溶液混合之前在包含一或多種溶劑之第 二溶液中之分散液提供。 4·如申请專利範圍第2項之方法，其進一步包括將一或多 種’谷劑加至第一溶液及顆粒之混合物中。 5·如申請專利範圍第丨或2項之方法，其進一步包括將塗 覆之顆粒碳化。 6·如申凊專利範圍第5項之方法，其中該塗覆之顆粒係於 h〖生大氣中在大於約4〇〇。〇之溫度下碳化。 如申明專利範圍第5項之方法，其中該塗覆之顆粒係於 h性大氣中在約400°C至約2000°C之間之溫度下碳化。 8.如申凊專利範圍第5項之方法，其進一步包括將塗覆之 顆粒石墨化。 9·如申請專利範圍第丨或2項之方法，其進一步包括將塗 覆之顆粒石墨化。 10·如申印專利範圍第9項之方法，其中該塗覆之顆粒係在 大於約200(TC之溫度下石墨化。 11.如申明專利範圍第9項之方法，其中該塗覆之顆粒係在 大於約2200。(：之溫度下石墨化。 12·如申請專利範圍第2項之方法，其中該塗覆之顆粒係自 4石反殘邊物形成材料之第一溶液及該碳質材料之顆粒 之混合物分離出。 13·如申請專利範圍第12項之方法，彡中將該塗覆之顆粒 洗務及乾燥。 14.如申請專利範圍第12項之方法，彡進―步包括自該混 86864-970411.DOC _ 2 - 1302761 合物回收一或多種溶劑。 15·如申請專利範圍第14項之方法，#中該-或多種溶劑 係利用選自由蒸餾或蒸發所組成之群之一或多個步驟 回收。 16.如申請專利範圍第14項之方法，丨中將該回收溶劑再 利用於該碳殘留物形成材料之第一溶液中。 17·:申請專利範圍第2項之方法，其中該溶劑係選自由甲 苯苯—甲苯”奎琳、四氯咬喃、四氯茶、茶、甲 醇、丙酉同、1-甲基峨洛.定酉同及水所組成之群。 •如申明專利fe圍第2項之方法，其中該第一溶液係於高 /見下此口，以使该石反殘留物形成材料溶解於一或多種 溶劑中。 19.如申請專利範圍第3項之方法，其中該第二溶液係於高 溫下混合。 2〇·如申請專利範圍第2項之方法，其中該第—溶液中之一 或多種溶劑對碳殘留物形成材料之比係為1:1以下。 2!•如申請專利範圍第3項之方法，其中該第一及第二溶液 之混合物中之一或多種溶劑對碳殘留物形成材料之比 係大於約2 : 1。 22.如申請專利範圍第3項之方法，其中該第—及第二溶液 之此合物中之一或多種溶劑對碳殘留物形成材料之比 係大於約5 : 1。 23 ·如申明專利範圍第！項之方法，其中該碳殘留物形成材 料之塗層係於環境或較高壓力下沈積。 86864-970411.DOC 1302761 24·如中請專利範圍第23項之方法，其中該碳殘留物形成 材料之塗層係於約-5t至約4〇(rC2溫度下沈積。 25·如申請專利範圍第旧之方法，其中該碳質顆粒包括選 自由石油瀝青、烺製石油煤焦、未烺製石油煤焦、高 度結晶煤焦、煤塔煤焦、合成石墨、天然石墨了衍生 自有機聚合物之軟碳、及衍生自天然聚合物之軟碳所 組成之群之粉狀碳質材料。 26.如申請專利範圍第1項之方法，其中該顆粒具有至多約 150微米之平均顆粒大小。 2 7 ·如申請專利範圍第1項 貝之方法，其中該顆粒具有在約5 微米至約70微米之間之平均顆粒大小。 28·如申請專利範圍第1 貝之方法，其中該顆粒具有在約5 微米及約45微米之間之平均顆粒大小。 29·如申請專利範圍第2jg _ 項之方法，其中該碳殘留物形成材 係左由使石反殘留物形成材料選擇性沈澱於顆粒上， 而沈積於顆粒之表面上。 3 0 ·如申請專利範圍第1 、之方法，其中該碳殘留物形成材 料係選自由來自化學邀 + ^ 予I轾之石油及煤之重芳族殘留物 、來自紙漿工業之太暂I ^ 資素、酚系樹脂、及碳水化合物 材料所組成之群之聚合材料。 3 1 ·如申請專利範圍第1 ^ ώ ^ 、之方法，其中該碳殘留物形成材 枓係選自由石油瀝音 〜 月及煤哈瀝青或利用化學製程製得 之瀝s所組成之群。 32.如申請專利範圍第丨 、之方法，其中該碳殘留物形成材 86864-970411.DOC 1302761 料係以在約1%及约50重量％之間之量沈積於顆粒之表 面上。 33.如申請專利範圍第！項之方法，其中該碳殘留物形成材 料係以在約2.5%及25重量％之間之量沈積於顆粒之表 面上。 如申請專利範圍第旧之方法，其中該氧化反應係於氧 化劑之存在下進行。 此如申請專利範圍第34項之方法，其中該氧化劑係選自 由無機及有機氧化劑所組成之群之@態氧化劑。 从如申請專利範圍第35項之方法，丨中該固態氧化劑係 選自由鹼硝酸鹽及鹼硫酸鹽所組成之群。 37·如申請專利範圍第35項之方法，丨中該固態氧化劑係 選自無機鹽、有機鹽及具化學式Μ，〇χ之化合物，里中 Μ,係一或多個過渡金屬，及其中X為卜2、3或4,、 38·如申請專利範圍第34項 態氧化劑。 &lt;方法，其中该乳化劑係為液 39. 如申請專利範圍第38項之方法，其中該液態氧 選自由氧化酸、含氧化鹽之水溶液、含氧化鹽之非水 溶液、過氧化物及芳基醌所組成之群。 40. 如申請專利範圍第34項 p — 万去其中该氧化劑係選自 由乳、硫煙、氣態氧化物、氮氧化物氣體 、及鹵素所組成之群之氣態氧化劑^ 一 41. 如申請專利範圍第34項之 高溫下進行。 上亥乳化作用係於 86864-970411.DOC 1302761 42. 如申請專利範圍第41項之方法，#中該高溫係以具有 升溫及停留期間之受控制的方式提供。 43. =申請專利範圍第34項之方法，#中該氧化作用係於 減壓下進行。 # ±覆之碳質顆粒’其包括由經氧化之可炼解碳殘 留物形成材料形成之塗層。 45·如中請專利範圍第44項之塗覆之碳f顆粒，其中該塗 層係由經石墨化之可熔解經氧化碳殘留物形成材料所 形成。 46. 如申請專利範圍第44項之塗覆之碳質顆粒，其中該顆 粒包含實質上平滑的塗層。 47. 如申請專利範圍第44項之塗覆之碳質顆粒，其中該碳 質顆粒包括選自由石油瀝青、娘製石油煤焦、未娘製 石油煤焦、高度結晶煤焦、煤塔煤焦、合成石墨、天 然石墨、衍生自有機聚合物之軟碳、及衍生自天然聚 合物之軟碳所組成之群之粉狀碳質材料。 48·如申請專利範圍第44項之塗覆之碳質顆粒，其中該碳 質顆粒係選自由烺製石油煤焦、未煅製石油煤焦、= 度結晶煤焦、合成石墨、及天然石墨所組成之群之粉 狀碳質材料。 77 49·如申請專利範圍第44項之塗覆之碳質顆粒，其中該碳 質顆粒及該塗層皆為石墨。 50· —種製造U-離子電池之方法，其中將如申請專利範圍 第44項之塗覆之碳質顆粒使用作為陽極材料，及其中 86864-970411.DOC 1302761 、1、1離子電池當利用不含碳酸丙二酯溶劑之電解質 ’則4時’在對以1伏特之截止電位下展現大於90%之第 一楯環充電效率。 5 I種蓄電池，其包含如申請專利範圍第44項之塗覆之 碳質顆粒。 52·如申請專利範圍第51項之f電池，其中該蓄電池係可 再充電之蓄電池。 種製xe蓄電池之方法，其包括將如申請專利範圍第 44項之塗覆之碳質顆粒加入至蓄電池之陽極中。 54·種製造具有由經氧化之碳殘留物形成材料形成之實 質上平滑塗層之塗覆之碳質顆粒之方法，包括·· 提供選自由石油瀝青及煤塔瀝青所組成之群之碳殘 召物形成材料之第一溶液，其中該第一溶液包含選自 由甲笨、二甲苯、喳啉、四氫呋喃、四氫萘、及莕所 組成之群之一或多種溶劑； 提供選自由烺製或未烺製石油煤焦、天然石墨及合 成石墨所組成之群之碳質材料之顆粒，其中該顆粒係 提供於包含一或多種溶劑之第二溶液中； 將該第一溶液及第二溶液在高溫下混合； 使該碳殘留物形成材料之塗層沈積於該顆粒之表面 上；及 經由使該顆粒進行氧化反應，而使塗覆之顆粒穩定 化；及 將該塗覆之顆粒碳化。 86864-970411.DOC 1302761 55. 如申請專利範圍第54項之方法，其中該碳質材料係選 自烺製或未煅製石油煤焦，其進一步包括將該塗覆之 顆粒石墨化。 56. 如申請專利範圍第54項之方法，丨中該塗覆之顆粒係 於惰性大氣中在大於約4〇〇〇c之溫度下碳化。 57·如申請專利範圍第54項之m中該塗覆之顆粒係 於惰性大氣中在約55(rc至約150(rc之間之溫度下碳 %如申請專利範圍第55項之方法，其中該塗覆之顆心 於惰性大氣中在大於約㈣代之溫度下石墨化。 59·-種包含塗層之塗覆碳質顆粒，該塗層包含塗覆碳， 材料之經氧化碳㈣物，該碳質㈣係衍生自由石、、, :青、娘製石油煤焦、未娘製石油煤焦、高度結“ …煤苍煤焦、合成石墨、 ^ 人 …、墨、何生自有機5 軟奴、及衍生自天然聚合物之軟碳所組成之琴 :塗覆顆粒具有小於約150微米之平均顆粒大小，兮 碳殘留物係選自當經氧化鈇 ^ 至至少· ” 再於惰性大氣中熱分解 主至夕850 C之石反化溫度睥 料。 寻形成至少9〇重量〇/〇碳之材 各菊 1之塗覆碳質顆粒，該塗芦句 塗覆碳質材科之經氧化碳 θ ^ 自由馈製石油煤焦、二材料係衍 之群;該石墨…=煤焦及其組合所组 旅立大，丨、，兮*、 土覆顆粒具有小於150微米之平均 ’、’、，“碳殘留物係選自當經氧化然後再於惰性 86864-970411.DOC 1302761 氣中熱分解至至少85(rc之碳化溫度時，形成至少9〇重 量％碳之材料；塗覆顆粒表現規則的石墨化晶體晶格， 其係來自至少部分石墨化該塗覆碳質顆粒。 61· —種蓄電池，其包含如申請專利範圍第6〇項之石墨化 之塗覆碳質顆粒。 62,如申請專利範圍第61項之蓄電池，其中該蓄電池係可 再充電之蓄電池。 63. —種蓄電池之陽極，其包含如申請專利範圍第6〇項之 石墨化之塗覆碳質顆粒。 64.如申請專利範圍第63項之蓄電池之陽極，其中該蓄電 池係可再充電之蓄電池。A method of making coated carbonaceous particles comprising: providing a carbon residue forming material selected from the group consisting of oxidizing and then thermally decomposing to at least 85 Torr in an inert atmosphere. a material that forms a residue of at least 90% by weight of carbon at a carbonization temperature; a particle of a carbonaceous material is provided; and the residue-forming material and particles of the carbonaceous material are uniformly coated in a material sufficient to form a carbon residue The layer is mixed under conditions of depositing on the surface of the carbonaceous particles; and the coated particles are stabilized by subjecting the coated particles to an oxidation reaction. 2. A method of making coated carbonaceous particles, comprising: providing a first solution of a carbon residue forming material, wherein the first solution comprises one or more solvents and is selected from the group consisting of oxidized and then heated in an inert atmosphere a carbon residue forming material that decomposes to a material of at least 85 (the carbonization temperature of rc, forming a residue of at least 9 mils; providing particles of a carbonaceous material; forming a first solution of the carbon residue into the material and the carbonaceous material The particles of the material are mixed at a high temperature; a coating of the stone anti-residue forming material is deposited on the surface of the carbonaceous particles; and 'the particles coated by the 4 are subjected to an oxidation reaction to stabilize the coated particles. The method of claim 2, wherein the particles of the carbon f material 86864-970411.DOC 1302761 are provided in a dispersion in a second solution comprising one or more solvents prior to mixing with the first solution. The method of claim 2, further comprising adding one or more 'valleys to the first solution and the mixture of particles. 5. If the method of claim 2 or 2 is applied, The method further comprises carbonizing the coated particles. The method of claim 5, wherein the coated particles are carbonized at a temperature greater than about 4 Torr in the living atmosphere. The method of claim 5, wherein the coated particles are carbonized in a h atmosphere at a temperature between about 400 ° C and about 2000 ° C. 8. The method of claim 5 And further comprising: graphitizing the coated particles. 9. The method of claim 2 or 2, further comprising graphitizing the coated particles. 10. The method of claim 9 of the scope of the patent application, Wherein the coated particles are graphitized at a temperature greater than about 200 (TC). 11. The method of claim 9, wherein the coated particles are at a temperature greater than about 2200. 12. The method of claim 2, wherein the coated particles are separated from a mixture of a first solution of the 4 stone anti-residue forming material and a particle of the carbonaceous material. The method of item 12, the coated particles Washing and drying. 14. As in the method of claim 12, the step-by-step includes recovering one or more solvents from the mixed 86864-970411.DOC _ 2 - 1302761 compound. In the method of claim, the solvent or the solvent is recovered by one or more steps selected from the group consisting of distillation or evaporation. 16. The method of claim 14 is used in the process, and the recovered solvent is reused. In the first solution of the carbon residue forming material. The method of claim 2, wherein the solvent is selected from the group consisting of toluene benzene-toluene, quinine, tetrachloroethylene, tetrachloroethylene, tea, Methanol, propyl hydrazine, 1-methyl valerol. Groups composed of water and water. • The method of claim 2, wherein the first solution is at a height/lower to allow the stone anti-residue forming material to be dissolved in one or more solvents. 19. The method of claim 3, wherein the second solution is mixed at a high temperature. 2. The method of claim 2, wherein the ratio of one or more solvents to carbon residue forming materials in the first solution is 1:1 or less. The method of claim 3, wherein the ratio of one or more solvents to the carbon residue forming material in the mixture of the first and second solutions is greater than about 2:1. 22. The method of claim 3, wherein the ratio of the one or more solvents of the first and second solutions to the carbon residue forming material is greater than about 5:1. 23 · As stated in the scope of patents! The method of the present invention, wherein the coating of the carbon residue forming material is deposited under ambient or higher pressure. The method of claim 23, wherein the carbon residue forming material is coated at a temperature of from about -5 to about 4 Torr (rC2 temperature is deposited. 25) The first method, wherein the carbonaceous particles comprise an organic polymer selected from the group consisting of petroleum pitch, tantalum petroleum coal char, untanned petroleum coal char, highly crystalline coal char, coal tower coal char, synthetic graphite, natural graphite A powdered carbonaceous material of the group consisting of soft carbon and soft carbon derived from a natural polymer. 26. The method of claim 1, wherein the particles have an average particle size of up to about 150 microns. 7. The method of claim 1, wherein the particles have an average particle size of between about 5 microns and about 70 microns. 28. The method of claim 1 wherein the particles have a An average particle size between 5 microns and about 45 microns. 29. The method of claim 2, wherein the carbon residue is formed by selectively depositing a stone anti-residue material onto the particles. And deposited on the surface of the granules. The method of claim 1, wherein the carbon residue forming material is selected from the group consisting of heavy aromatic residues from petroleum and coal from the chemical industry. a polymeric material from the pulp industry that is composed of a group of phenolic resins, phenolic resins, and carbohydrate materials. 3 1 · The method of applying the patent scope 1 ^ ώ ^, wherein the carbon residue is formed The material is selected from the group consisting of petroleum liquefied ~ month and coal tar pitch or s s obtained by a chemical process. 32. The method of claim 丨, the carbon residue forming material 86864-970411 The DOC 1302761 is deposited on the surface of the granules in an amount between about 1% and about 50% by weight. 33. The method of claim 2, wherein the carbon residue forming material is at about 2.5 An amount of between 5% and 25% by weight is deposited on the surface of the granule. The method of claim </ RTI> wherein the oxidizing reaction is carried out in the presence of an oxidizing agent. The oxidizing agent is selected from the group consisting of inorganic and organic oxidizing agents. From the method of claim 35, the solid oxidizing agent is selected from the group consisting of alkali nitrates and alkali sulfates. 37. The method of claim 35, wherein the solid oxidant is selected from the group consisting of inorganic salts, organic salts, and compounds of the formula Μ, 〇χ, 里, which are one or more transition metals, and X thereof The method of claim 3, wherein the liquid oxygen is selected from the group consisting of the method of claim 34, wherein the emulsifier is a liquid. a group consisting of an oxidizing acid, an aqueous solution containing an oxidizing salt, a non-aqueous solution containing an oxidized salt, a peroxide, and an aryl hydrazine. 40. For example, in the scope of patent application, item 34, the oxidant is selected from the group consisting of milk, sulfur, gaseous oxides, nitrogen oxide gases, and halogens. Under the high temperature of item 34. The emulsification effect is on 86864-970411.DOC 1302761 42. As in the method of claim 41, the high temperature is provided in a controlled manner having a temperature rise and a residence period. 43. = The method of claim 34, the oxidation in # is carried out under reduced pressure. #±覆的碳质颗粒' includes a coating formed of a oxidized refinable carbon residue forming material. 45. The coated carbon f particle of claim 44, wherein the coating is formed from a graphitized fusible carbon oxide residue forming material. 46. The coated carbonaceous particle of claim 44, wherein the particle comprises a substantially smooth coating. 47. The coated carbonaceous particle of claim 44, wherein the carbonaceous particle comprises a petroleum charcoal selected from the group consisting of petroleum pitch, mother petroleum char, coke coal char, highly crystalline coal char, coal charcoal A powdery carbonaceous material composed of synthetic graphite, natural graphite, soft carbon derived from an organic polymer, and soft carbon derived from a natural polymer. 48. The coated carbonaceous particle of claim 44, wherein the carbonaceous particle is selected from the group consisting of tantalum petroleum coal char, uncalcined petroleum coal char, = degree crystalline coal char, synthetic graphite, and natural graphite. A group of powdery carbonaceous materials. 77. The coated carbonaceous particles of claim 44, wherein the carbonaceous particles and the coating are both graphite. 50. A method for manufacturing a U-ion battery, wherein a coated carbonaceous particle as claimed in claim 44 is used as an anode material, and wherein the ion source of 86864-970411.DOC 1302761, 1, 1 is used The electrolyte containing propylene carbonate solvent 'at 4 o' exhibited a first anthraquinone charging efficiency of greater than 90% at a cutoff potential of 1 volt. A lithium battery comprising the coated carbonaceous particles as in claim 44 of the patent application. 52. The battery of claim 51, wherein the battery is a rechargeable battery. A method of producing a xe battery comprising adding a coated carbonaceous particle as in claim 44 of the patent application to an anode of a battery. 54. A method of making coated carbonaceous particles having a substantially smooth coating formed from a oxidized carbon residue forming material, comprising: providing a carbon residue selected from the group consisting of petroleum pitch and coal pitch asphalt a first solution of the material forming material, wherein the first solution comprises one or more solvents selected from the group consisting of methyl, xylene, porphyrin, tetrahydrofuran, tetrahydronaphthalene, and anthracene; a particle of a carbonaceous material of a group consisting of petroleum coal char, natural graphite, and synthetic graphite, wherein the particle is provided in a second solution comprising one or more solvents; the first solution and the second solution are Mixing at a high temperature; depositing a coating of the carbon residue forming material on the surface of the particles; and stabilizing the coated particles by subjecting the particles to an oxidation reaction; and carbonizing the coated particles. The method of claim 54, wherein the carbonaceous material is selected from tantalum or uncalcined petroleum char, further comprising graphitizing the coated particles. 56. The method of claim 54, wherein the coated particles are carbonized in an inert atmosphere at a temperature greater than about 4 〇〇〇c. 57. The coated granules in the m of claim 54 are in an inert atmosphere at a temperature of from about 55 (rc to about 150 (the temperature between rc is carbon as in the method of claim 55, wherein The coated core is graphitized in an inert atmosphere at a temperature greater than about (iv). 59. A coated carbonaceous particle comprising a coating comprising coated carbon, a carbon monoxide (tetra) of the material , the carbonaceous (four) is derived from free stone,,,: Qing, Niang petroleum coal char, unmature petroleum coal char, high knot "... coal coal char, synthetic graphite, ^ people..., ink, Hesheng from organic a soft slave, and a soft carbon derived from a natural polymer: the coated particles have an average particle size of less than about 150 microns, and the ruthenium carbon residue is selected from the group consisting of ruthenium oxide to at least ” In the atmosphere, the thermal decomposition of the main eve 850 C stone reversal temperature dip. Find at least 9 〇 weight 〇 / 〇 carbon material of each chrysanthemum 1 coated carbon particles, the coating of the refining coated carbon material section The carbon θ ^ freely fed petroleum coal char, two materials are Yan Zhiqun; the graphite...=coal and its group The group of Lizhan, Bengbu, 兮*, and earth-coated granules have an average of ',', and the carbon residue is selected from the group consisting of oxidized and then inert in inert gas 86864-970411.DOC 1302761 Decomposed to at least 85 (the carbonization temperature of rc, a material that forms at least 9% by weight of carbon; the coated particles exhibit a regular graphitized crystal lattice from at least partially graphitizing the coated carbonaceous particles. 61· A storage battery comprising the graphitized coated carbonaceous particles according to claim 6 of the patent application. 62. The battery of claim 61, wherein the battery is a rechargeable battery. 63. An anode comprising a graphitized coated carbonaceous particle according to claim 6 of the patent application. 64. The anode of a battery according to claim 63, wherein the battery is a rechargeable battery. 之塗覆之碳質顆粒。Coated carbonaceous particles. 而產生。 67·如申請專利範圍第66項之方法 其中該部分沈澱係經 或多種相同或不同溶劑稀釋碳殘留物形成材 料之濃溶液而產生。 68·如申請專利範圍第π項之方法，其 劑對碳殘留物形成材料之比係為2 ·· 溶液中之溶劑對碳殘留物形成材料二 69·如申請專利範圍第67項之方法， 其中該濃溶液中之溶 2 ·· 1以下，及該稀釋 料之比係大於2 : 1。 ’其中該濃溶液中之溶 86864-970411.DOC 1302761 70. 71. 72. f對碳殘留物形成材料之比係為2: i以下，及該稀釋 〆合液中之溶劑對碳殘留物形成材料之比係大於5 : 1。 如=明專利範圍第66項之方法，其中該碳殘留物形成 材料之部分沈澱係經由在塗覆步驟中使碳質顆粒及碳 殘留物形成材料之混合物冷卻而產生。 如申請專利範圍第2項之方法，其中該碳殘留物形成材 料之塗層係於環境或較高壓力下沈積。 如申請專利範圍第55項之塗覆之碳質材料，其當於鋰 離子電池中使用作為陽極材料時，在對鋰金屬〇.5伏特 之截止電位下顯現大於90%之第一循環充電效率。 86864-970411.DOC 10-And produced. 67. The method of claim 66, wherein the partial precipitation is produced by diluting a concentrated solution of the carbon residue forming material with the same or different solvents. 68. As claimed in the method of claim π, the ratio of the agent to the carbon residue forming material is 2·· the solvent in the solution to the carbon residue forming material. 69. The method of claim 67, Wherein the concentration in the concentrated solution is less than 2··1, and the ratio of the diluted material is greater than 2:1. 'The ratio of the dissolved solution in the concentrated solution 86864-970411.DOC 1302761 70. 71. 72. f to the carbon residue forming material is 2: i or less, and the solvent in the diluted chelating solution forms a carbon residue. The ratio of materials is greater than 5:1. The method of claim 66, wherein the partial precipitation of the carbon residue forming material is produced by cooling a mixture of carbonaceous particles and a carbon residue forming material in a coating step. The method of claim 2, wherein the coating of the carbon residue forming material is deposited under ambient or higher pressure. The coated carbonaceous material as claimed in claim 55, when used as an anode material in a lithium ion battery, exhibits a first cycle charging efficiency of greater than 90% at an off potential of lithium metal 〇5 volts. . 86864-970411.DOC 10-