TW201213365A

TW201213365A - Method for making sulfurized polyacrylonitrile

Info

Publication number: TW201213365A
Application number: TW99131775A
Authority: TW
Inventors: xiang-ming He; Li Wang; wei-hua Pu; wen-ting Sun; Jian-Jun Li
Original assignee: Hon Hai Prec Ind Co Ltd
Priority date: 2010-09-20
Filing date: 2010-09-20
Publication date: 2012-04-01
Also published as: TWI425016B

Abstract

The present invention relates to a method for making a sulfurized polyacrylonitrile. In the method, polyacrylonitrile, a first solvent, a catalyst, and sulfur or sodium thiosulfate are provided. The polyacrylonitrile is completely dissolved in the first solvent to form a polyacrylonitrile solution. The catalyst is uniformly dispersed in the polyacrylonitrile solution. The polyacrylonitrile solution with the catalyst is heated to form a conjugated polymer solution with dissolved conjugated polymer. The conjugated polymer solution is uniformly mixed with the sulfur or sodium thiosulfate to form a mixture. The mixture is heated, thereby forming a sulfurized polyacrylonitrile.

Description

201213365 六、發明說明：【發明所屬之技術領域】 [0001] 本發明涉及一種硫化聚丙烯腈製備方法。 [先前技術] [0002]聚丙烯腈（PAN)係由交替碳原子上帶有氰基之飽和碳骨架構成之高聚物’其自身並無導電性，但研究發現若將聚丙烯腈粉末與硫混合並加熱可使聚丙烯腈發生硫化，並 Ο201213365 VI. Description of the Invention: [Technical Field of the Invention] [0001] The present invention relates to a method for preparing a sulfurized polyacrylonitrile. [Prior Art] [0002] Polyacrylonitrile (PAN) is a polymer composed of a saturated carbon skeleton having a cyano group on an alternate carbon atom, which itself has no conductivity, but it has been found that if polyacrylonitrile powder is used together with Sulfur is mixed and heated to vulcanize polyacrylonitrile, and Ο

製備出具有化學活性之可導電之硫化聚丙烯腈’請參閱 “硫化聚丙烯腈鋰離子電池之製備”，任建國等，BAT- TERY BIMONTHLY，Vol. 38，No. 2，P73〜74 (2008)。Preparation of chemically active electrically conductive vulcanized polyacrylonitriles. Please refer to "Preparation of Vulcanized Polyacrylonitrile Lithium Ion Batteries", Ren Jianguo et al., BAT-TERY BIMONTHLY, Vol. 38, No. 2, P73~74 (2008) .

該文獻揭示：以聚丙烯腈為前驅體，用單質硫在3〇OtT 進行徹底硫化，便可獲得硫化聚丙烯腈，該硫化聚丙烯腈可作為鋰離子電池之正極材料。在上述聚丙烯腈與硫反應之過程中，聚丙烯腈可能發生了環化反應，從而使形成之硫化聚丙烯腈為—種具有長程疋鍵共軛體系之共輕聚〇物，該共軛聚合物作為鋰離子電池正極材料具有較高之比容量。 []’、、、*於上述製備硫化聚丙稀腈之方法係通過直接將聚丙缔腈與硫所形成之混合物加熱㈣的，容易使所形之硫化聚丙烯腈之觀妓不高，即卿狀共輕續較乂從而使硫化聚丙締腈之電導率較低。【發明内容】 [0004] 有馨於此’提供-種具有較之製備方法實為必要。高環化程度之硫化聚丙締猜 [0005] 099131775 一種硫化聚丙烯腈表單編號Α0101 之製傷方法第3頁/共42頁其包括以下步驟：提供 0992055686-0 201213365 一聚丙稀腈、-第—溶劑及—催化劑，將該聚丙缚睛加入該第-溶劑中完全溶解形成—聚丙烯腈溶液，並將議催化劑均勻分散於該聚㈣腈溶液中；加熱上述分散^ 催化劑之聚丙晞腈溶液，形成—溶解有共㈣合物之第 /、軛聚合物溶液，提供_單質硫或硫代硫酸鈉，並將該單質硫或硫㈣酸納與上述共輛聚合物均勻混合以形成一混合物；及加熱上述混合物從而製備獲得硫化聚丙烯腈。 [0006] [0007] [0008] 相較於先前技術，本發明與單質硫或硫代硫酸鈉直接反應之為一種通過聚丙稀腈形成之已環化之共軛聚合物，之後，通過加熱該由單質硫或硫代硫酸鈉與該共軛聚合物形成之混合物，不僅使共輛聚合物發生了硫化反應形成了硫化聚丙烯腈，且在該過程中進〆步使該硫化聚丙烯腈發生環化，從而大大提高了該硫化聚丙烯腈之環化程度，並提高了該硫化聚丙烯腈之導電率。【實施方式】以下將結合附圖詳細說明本發姻實施例中用於製備硫化聚丙烯腈之一共軛聚合物之製備方法，硫化聚丙烯腈之製備方法，及應用該硫化聚丙埽腈之錄離子電池正極材料。以下將首先介紹用於製備所述硫化聚丙烯腈之—共軛聚合物之製備方法。請參閱圖1，本發明提供一種共軛聚合物之製備方法，該方法包括以下步驟： 099131775 表單編號A0】01 第4頁/共42頁 0992055686-0 [0009] 201213365 IWIUJ [0011] [0012] [0013] Ο [0014] Ο 步驟-，提供-聚丙炼腈、-第-溶劑及_催化劑，將該聚丙烯腈溶於所述第一溶劑中形成一聚丙烯浐☆ 並將該催化劑均勻分散於該聚丙烯腈溶液中.、及步驟二，加熱上述分散有催化劑之聚丙埽腈溶液，以形成一溶解有共軛聚合物之第一共概聚合物溶液。 7This document discloses that vulcanized polyacrylonitrile can be obtained by using polyacrylonitrile as a precursor and thoroughly vulcanizing with elemental sulfur at 3 〇 OtT, which can be used as a positive electrode material for lithium ion batteries. During the reaction of the above polyacrylonitrile with sulfur, the polyacrylonitrile may undergo a cyclization reaction, so that the formed sulfurized polyacrylonitrile is a kind of light-weight polythene having a long-range fluorene bond conjugate system, and the conjugate is conjugated. The polymer has a high specific capacity as a positive electrode material for lithium ion batteries. []',,, * The above method for preparing a vulcanized polyacrylonitrile is carried out by directly heating a mixture of polyacrylonitrile and sulfur (IV), so that the shape of the vulcanized polyacrylonitrile is not so high, that is, The shape is lighter than that of the crucible so that the conductivity of the vulcanized polyacrylonitrile is lower. SUMMARY OF THE INVENTION [0004] It is necessary to have a preparation in this case. Vulcanization of high degree of cyclization Polypropylene susceptibility [0005] 099131775 A sulphurized polyacrylonitrile form number Α 0101 method of injury, page 3 of 42 including the following steps: provide 0992055686-0 201213365 a polyacrylonitrile, - the first a solvent and a catalyst, the polyacrylic acid is added to the first solvent to completely dissolve to form a polyacrylonitrile solution, and the catalyst is uniformly dispersed in the poly(tetra)nitrile solution; and the polyacrylonitrile solution of the dispersion catalyst is heated. Forming a conjugated polymer solution of the co-(tetra) compound, providing _ elemental sulfur or sodium thiosulfate, and uniformly mixing the elemental sulfur or sulfur (tetra) acid with the above-mentioned co-polymer to form a mixture; And heating the above mixture to prepare a vulcanized polyacrylonitrile. [0008] [0008] Compared to the prior art, the present invention directly reacts with elemental sulfur or sodium thiosulfate as a cyclized conjugated polymer formed by polyacrylonitrile, and then by heating A mixture of elemental sulfur or sodium thiosulfate and the conjugated polymer not only causes a vulcanization reaction of the co-polymer to form a vulcanized polyacrylonitrile, but also causes the vulcanized polyacrylonitrile to occur during the process. Cyclization greatly increases the degree of cyclization of the vulcanized polyacrylonitrile and increases the conductivity of the vulcanized polyacrylonitrile. [Embodiment] Hereinafter, a preparation method for preparing a conjugated polymer of sulfurized polyacrylonitrile, a method for preparing a sulfurized polyacrylonitrile, and a recording method using the sulfurized polyacrylonitrile in the present embodiment will be described in detail with reference to the accompanying drawings. Ion battery cathode material. The preparation method of the conjugated polymer for preparing the sulfurized polyacrylonitrile will be first described below. Referring to FIG. 1, the present invention provides a method for preparing a conjugated polymer, which comprises the following steps: 099131775 Form No. A0] 01 Page 4 / Total 42 Page 0992055686-0 [0009] 201213365 IWIUJ [0012] Ο [0014] Ο Step - providing - polyacrylonitrile, - solvent - and - catalyst, dissolving the polyacrylonitrile in the first solvent to form a polypropylene crucible ☆ and uniformly dispersing the catalyst The polyacrylonitrile solution in which the catalyst is dispersed is heated in the polyacrylonitrile solution and in the second step to form a first copolymer solution in which the conjugated polymer is dissolved. 7

以下將對上述各步驟進行詳細描述D 在步驟-中，所述第-溶劑之種類不限，僅需使所述聚丙烯腈完全溶解於所述溶劑中即可。該第一溶劑優選為極性有機溶劑，所述極性有機溶劑可為二甲基甲醯胺、二甲基乙醯胺、二甲基亞颯、丙二腈、環丁砜或确酸亞乙基醋等。所述聚丙烯腈之分子量不限，㈣為】剛〜 1 00000。所述聚丙烯腈溶液之質量百分比濃度不限優選為0.1%〜1〇%。所述催化劑可為金屬粉、金屬氧化物粉、金屬鹽及單質硫粉中之-種或多種β所述金屬粉、金屬氡化物粉及金屬鹽中之金屬元素可以選自過渡元素、第iva族及va族金屬几素中之—種或多種。所述催化劑可溶或不溶於上述聚丙稀腈溶液巾，其巾所述金騎可為銀粉、銅粉、錫粉、鐵粉、⑽或錄粉等，㈣氧化物粉為二氧化鈦粉、氧化銅粉或氧化鐵粉等，所述金屬鹽可為鈷鹽、錫鹽銅鹽、錄鹽或鋅鹽等，如硝酸靴。（⑽A)、氣化辞 nC12)或氯化娣（SbCl3)等。若所述催化劑不能溶於上述聚㈣腈溶液巾，職催化叙純越小，越容易均勻分散於所述聚丙婦腈溶液卜從而使步驟二中聚丙 099131775 表單編號A0101 第5頁/共42頁 0992055686-0 201213365 烯腈之環化速度越快，即形成共軛聚合物之速度越快。該催化劑之粒徑可為50奈米至500微米，優選為1〇〇奈米至100微米。另，該催化劑之加入量越多，聚丙烯腈之環化速度也越快，該催化劑與所述聚丙烯腈之質量比可為 1 : 0. 2 〜1 : 6。 [0015]在步驟二中，所述加熱方式可為水浴加熱或者油浴加熱。該加熱溫度可為8 0 C ~ 3 0 〇，該加熱溫度可確保使聚丙烯腈發生環化反應或者發生環化反應所需時間較短，同時，不會形成不溶性共轆聚合物從所述溶液中析出。 5玄加熱時間只要使所述聚丙烯翁充分形成可溶性之共軛聚合物即可，具體可通過觀察所述分散有催化劑之聚丙烯腈溶液之顏色變化以判斷是否已形成可溶性之共軛聚合物，當溶液之顏色變黑時，代表已形成了共輛聚合物，且溶液之顏色越深，共軛聚合物之環化程度越高，該加熱時間可為5分鐘〜20天。 : 卜....... . 在忒加熱過程中，為使所述摧化和和所述聚丙烯腈在所述溶劑中充分混合，從而教快形祕耗聚合物，可進— 步攪拌上述分散有催化劑之料烯腈溶液。所述授摔之方式不限，可為磁力㈣、超聲分散或機械挽拌等。採用機械_時，賴拌之速度不限，優選為⑽轉/每分鐘至1 000轉/每分鐘。通過上述步驟—和步驟二形成之第二共魏聚合物溶㈣上述聚㈣腈通過環化反應形成之 4聚合物、催化劑及第-溶劑組成， Γ解於第—溶劑中，催化劑根㈣同二擇;溶料第—溶劑中或以顆粒形式存在。 099131775 表單，編號A0101 第6頁/共42頁 0992055686-0 201213365 LUU1M 可進一步包括去除所述第一共軛聚合物溶液中之催化劑與第一溶劑之步驟： [0018] 步驟三··去除所述第一共軛聚合物溶液中之催化劑。 [0019] 步驟四··去除所述第一共輛聚合物溶液中之第一溶劑。 [0020] 其中在步驟三中，當所述催化劑不溶於上述第一溶劑中時，可採用一網孔直徑小於催化劑之顆粒直徑之濾網將溶液中之催化劑過濾出，當所述催化劑溶於上述第一溶〇 [0021] 劑中時，可通過步驟四抽濾出。在步驟四中，採用一溶劑過濾器同時將所述第一共軛聚合物溶液中之第一溶劑和溶解於其中之催化劑抽濾出，從而僅剩呈黑色粉末狀之纯淨之共軛聚合物；或者直接在一較低溫度下如低於80 °C之溫度下繼續緩慢加熱所述第一共軏聚合物溶液，使其中之第一溶劑逐漸揮發，僅剩所述固態之共軛聚合物及催化劑，此時，為將該催化劑與所述共軛聚合物分離，可根據二者之比重不同，採用共振篩或離心機將二者分離，或者根據二者之電磁特性不同，採用電磁分離器將二者分離。 [0022] 第一實施例 [0023] S11，提供一質量百分比濃度為5%之聚丙烯腈溶液，和一粒徑為100微米之銀粉作為催化劑，將該銀粉按照與聚丙烯腈之質量比為1 : 2. 5之比例均勻分散於所述聚丙烯腈溶液中；S12，在150°C之温度下油浴加熱並以500轉/分鐘之攪拌速度攪拌所述分散有銀粉之聚丙烯腈溶液。 099131775 表單編號A0101 第7頁/共42頁 0992055686-0 201213365 [0024] 其中，在步驟S1 1中，所述聚丙烯腈溶液中之第一溶劑為二曱基甲醯胺。在步驟S12中，當加熱時間達到12小時，所述溶液已變成黑色，表明所述聚丙烯腈已發生環化反應並形成共耗聚合物，之後停止加熱，過濾出所述催化劑銀粉，並通過一溶劑過濾器將該溶液中之聚丙烯腈濾出。 [0025] 請參閱圖2，圖2為本實施例所獲得之共軛聚合物之紅外光譜測定曲線。從該曲線可以看出，特徵吸收峰分別為 2242CHT1(對應C三N)，2938 cnf1(對應CH2)，1387 cnT1(對應CH)，和 1670 cm—1 (對應C = N或C = C)等，由於在1 670 cnT1處出現了 C = N或C = C鍵之特徵吸收峰，證明經過上述方法之處理，所述聚丙烯腈發生了環化反應〇 [0026] 另，非共輛之不飽和聚合物僅對波長很短之紫外光具有吸收作用，而當聚合物中之雙鍵以共軛形式存在時，對波長較長之紫外光甚至可見光仍具有較強之吸收作用，且隨著共輛度之增加，對波長較長之波之吸收越強烈。根據該原理，本實施例進一步對所獲得之共軛聚合物進行紫外-可見光吸收光譜分析。請參閱圖3，可以看出該共軛聚合物對波長為300奈米〜400奈米範圍内之紫外光具有較強之吸收作用，對波長為400奈米〜600奈米範圍之紫外光波長也具有一定之吸收作用，但吸收減弱，而對波長為600奈米左右之可見光仍有少量之吸收。據此可知，該共輛聚合物中存在有共扼雙鍵。 [0027] 綜合上述圖2和圖3之分析可進一步證明通過本實施例之 099131775 表單編號A0101 第8頁/共42頁 0992055686-0 201213365 [0028] [0029] Ο [0030] [0031] Ο [0032] 製備方法獲得了可溶之共1¾聚合物β 第二實施例板;胃里百分比濃度為3%之聚丙稀腈溶液，和-:為100奈米之硫粉作為催 η I亥硫叔按照與聚丙液中.sr 例均句分散於所述聚丙烯腈溶轉/分鐘述刀散有硫粉之聚丙烯腈溶液。 =甚在步驟S21中，所述聚丙烯腈溶液中之第—溶劑為 _。在步驟繼中，當加熱剩吨溶液已變成黑色，厂吁所聚合物，之^ 所林㈣时反應形成共概劑喊㈣料粉，並通過一溶 :她將該溶液中之聚丙烯腈渡出。圖4為本實施例所獲得之共軛聚合物之紅外光譜測 '田深。從該曲姑 c=c)附近出以看出，在1668 cra_1(對應㈣或中有C=N或C=C鍵 ' 特徵吸收峰’即證實了該共輛聚合物述聚丙稀腈發生^出現’證明經過上述方法之處理，所了環化反應。請參閱圖5，同樣太止★ E > °以看出該共扼聚合物對400奈米〜600 布木波長範圍之势有少量之吸收。據此光及波長為6〇0奈米左右之可見光仍雙鍵。匕可知’該共軛聚合物中存在有共軛 [0033] 综合上述圖4和圖製備方法獲得了 5之分析可進一步證明通過本實施例之可溶之共軛聚合物 099131775 表單編號Α0101 第9頁/共42頁 0992055686-0 201213365 [0034] 第三實施例 [0035] S31，提供一質量百分比濃度為1 %之聚丙烯腈溶液，和氯化辞（ZnCl2)作為催化劑，將該氯化鋅按照與聚丙烯腈之質量比為2. 44: 1之比例均勻分散於所述聚丙烯腈溶液中 ;S32，在150°C之溫度下油浴加熱並以500轉/分鐘之攪拌速度攪拌所述分散有氣化鋅之聚丙烯腈溶液。 [0036] 其中，在步驟S31中，所述聚丙烯腈溶液中之第一溶劑為二曱基甲醯胺。在步驟S32中，當加熱時間達到24小時，所述溶液已變成黑色，表明所述聚丙烯腈已反應形成共輛聚合物，之後停止加熱，並通過一溶劑過濾器將該溶液中之共輛聚合物濾出。 [0037] 請參閱圖6為本實施例所獲得之共軛聚合物之紅外光譜測定曲線。從該曲線可以看出，在1655 cm 1 (對應C = N或 C = C)附近出現一組特徵吸收峰，即證實了該共軛聚合物中有C = N或C=C鍵之出現，證明經過上述方法之處理，所述聚丙烯腈發生了環化反應。 [0038] 請參閱圖7，可以看出該共輛聚合物對400奈米〜600奈米波長範圍之紫外光和600奈米〜800奈米波長範圍之可見光均具有一定之吸收，且在可見光段具有均一之吸收特性。據此可知，該共輛聚合物中存在有共輛雙鍵，且共輛程度較大。 [0039] 綜合上述圖6和圖7之分析可進一步證明通過本實施例之製備方法獲得了可溶之共軛聚合物。 [0040] 第四實施例 099131775 表單編號A0101 第10頁/共42頁 0992055686-0 201213365 LUU41J S41 r is. &供-質量百分比濃度細之聚丙稀腈溶液，和石肖 :C〇(N〇3)2)作為催化劑’將該硝酸鈷按照與聚丙烯 =之質量比為27:5之比例均勻分散於所述聚丙稀猜溶液、S42，在丨^^之溫度下油浴加熱並以託〇轉/分鐘之攪拌逮度_所述分散有觀狀聚㈣骑溶液。 [0042]The above respective steps will be described in detail below. In the step - the type of the first solvent is not limited, and it is only necessary to completely dissolve the polyacrylonitrile in the solvent. The first solvent is preferably a polar organic solvent, and the polar organic solvent may be dimethylformamide, dimethylacetamide, dimethyl hydrazine, malononitrile, sulfolane or acid vinegar. . The molecular weight of the polyacrylonitrile is not limited, and (4) is just ~1 00000. The mass percentage concentration of the polyacrylonitrile solution is not particularly limited to 0.1% to 1% by weight. The catalyst may be one or more of metal powder, metal oxide powder, metal salt and elemental sulfur powder. The metal element in the metal powder, metal halide powder and metal salt may be selected from transition elements, iva One or more of the family and va metal. The catalyst is soluble or insoluble in the above-mentioned polyacrylonitrile solution towel, and the gold can be silver powder, copper powder, tin powder, iron powder, (10) or recorded powder, and (4) the oxide powder is titanium dioxide powder or copper oxide. Powder or iron oxide powder, etc., the metal salt may be a cobalt salt, a tin salt copper salt, a salt or a zinc salt, such as a nitrate shoe. ((10)A), gasification word nC12) or barium chloride (SbCl3). If the catalyst is insoluble in the poly(tetra)nitrile solution, the smaller the catalytic catalysis is, the easier it is to uniformly disperse in the polyacrylonitrile solution, so that the second step is a polypropene 099131775. Form No. A0101 Page 5 of 42 0992055686-0 201213365 The faster the cyclization rate of the nitrile, the faster the conjugated polymer is formed. The catalyst may have a particle diameter of from 50 nm to 500 μm, preferably from 1 nm to 100 μm. Further, the mass ratio of the polyacrylonitrile to the polyacrylonitrile is as high as possible, and the mass ratio of the catalyst to the polyacrylonitrile may be 1:0. 2 to 1:6. [0015] In the second step, the heating mode may be water bath heating or oil bath heating. The heating temperature may be 80 C to 30 〇, and the heating temperature ensures a short time required for the cyclization reaction or the cyclization reaction of the polyacrylonitrile, and at the same time, no insoluble conjugated polymer is formed from the Precipitated in the solution. 5 玄 heating time as long as the polypropylene fiber fully forms a soluble conjugated polymer, specifically by observing the color change of the catalyst-dispersed polyacrylonitrile solution to determine whether a soluble conjugated polymer has been formed When the color of the solution turns black, it means that a total of a polymer has been formed, and the deeper the color of the solution, the higher the degree of cyclization of the conjugated polymer, and the heating time may be from 5 minutes to 20 days. : 卜....... In the heating process of hydrazine, in order to make the catalyzed and fully mixed with the polyacrylonitrile in the solvent, thereby teaching the fast-cutting polymer, it can be further advanced. The above-mentioned catalyst-dispersed acrylonitrile solution was stirred. The manner of the drop is not limited, and may be magnetic force (four), ultrasonic dispersion or mechanical mixing. When the machine is used, the speed of the mashing is not limited, and it is preferably (10) revolutions per minute to 1,000 revolutions per minute. The second co-polymer obtained by the above steps - and the second step is dissolved. (4) The poly(tetra)nitrile is formed by the cyclization reaction, the polymer, the catalyst and the first solvent are dissolved in the first solvent, and the catalyst root (four) is the same. The second choice; the solvent is present in the solvent or in the form of particles. 099131775 Form, No. A0101 Page 6 of 42 0992055686-0 201213365 The LUU1M may further comprise the step of removing the catalyst and the first solvent in the first conjugated polymer solution: [0018] Step 3·Removing the a catalyst in the first conjugated polymer solution. [0019] Step 4: removing the first solvent in the first total polymer solution. [0020] wherein in step three, when the catalyst is insoluble in the first solvent, a catalyst having a mesh diameter smaller than the particle diameter of the catalyst may be used to filter out the catalyst in the solution when the catalyst is dissolved. In the above first solvent [0021], it can be filtered out by step four. In the fourth step, the first solvent in the first conjugated polymer solution and the catalyst dissolved therein are simultaneously filtered by using a solvent filter, so that only the pure conjugated polymerization in the form of a black powder remains. Or continuing to slowly heat the first conjugated polymer solution directly at a lower temperature, such as less than 80 ° C, such that the first solvent is gradually volatilized, leaving only the solid conjugated polymerization And the catalyst, in this case, in order to separate the catalyst from the conjugated polymer, the resonance can be separated by a resonance sieve or a centrifuge according to the specific gravity of the two, or the electromagnetic characteristics are different according to the electromagnetic properties of the two. The separator separates the two. [0022] The first embodiment [0023] S11, providing a 5% by weight concentration of a polyacrylonitrile solution, and a particle size of 100 microns of silver powder as a catalyst, the silver powder according to the mass ratio of polyacrylonitrile 1 : 2. The ratio of 5 is uniformly dispersed in the polyacrylonitrile solution; S12, heating in an oil bath at a temperature of 150 ° C and stirring the polyacrylonitrile solution in which the silver powder is dispersed at a stirring speed of 500 rpm . 099131775 Form No. A0101 Page 7 of 42 0992055686-0 201213365 [0024] wherein, in step S11, the first solvent in the polyacrylonitrile solution is dimethylformamide. In step S12, when the heating time reaches 12 hours, the solution has turned black, indicating that the polyacrylonitrile has undergone a cyclization reaction and forms a covalent polymer, after which heating is stopped, the catalyst silver powder is filtered, and passed. A solvent filter filters out the polyacrylonitrile in the solution. [0025] Please refer to FIG. 2. FIG. 2 is an infrared spectrum measurement curve of the conjugated polymer obtained in the present embodiment. It can be seen from the curve that the characteristic absorption peaks are 2242 CHT1 (corresponding to C three N), 2938 cnf1 (corresponding to CH2), 1387 cnT1 (corresponding to CH), and 1670 cm-1 (corresponding to C = N or C = C), etc. Since the characteristic absorption peak of C = N or C = C bond appears at 1 670 cnT1, it is proved that the polyacrylonitrile undergoes a cyclization reaction after the above method [0026] A saturated polymer absorbs only ultraviolet light of a very short wavelength, and when a double bond in a polymer exists in a conjugated form, it has a strong absorption effect on a longer wavelength ultraviolet light or even visible light, and The increase in the total vehicle degree is more intense for the absorption of longer wavelength waves. According to this principle, the obtained conjugated polymer was further subjected to ultraviolet-visible absorption spectrum analysis. Referring to Figure 3, it can be seen that the conjugated polymer has a strong absorption effect on ultraviolet light having a wavelength in the range of 300 nm to 400 nm, and a wavelength of ultraviolet light having a wavelength in the range of 400 nm to 600 nm. It also has a certain absorption effect, but the absorption is weakened, and there is still a small amount of absorption for visible light having a wavelength of about 600 nm. According to this, it is known that a conjugated double bond exists in the total polymer. [0027] The analysis of the above FIG. 2 and FIG. 3 can further prove that the form number A0101 through the present embodiment is 8th/total 42 page 0992055686-0 201213365 [0028] [0029] [0030] [0031] Ο [ 0032] The preparation method obtained a soluble total of 12⁄4 polymer β second embodiment plate; a polyacrylonitrile solution having a percentage concentration of 3% in the stomach, and -: a sulfur powder of 100 nm as a nucleus According to the polystyrene solution, the polystyrene solution is dispersed in the polyacrylonitrile solution. = In step S21, the first solvent in the polyacrylonitrile solution is _. In the following step, when the heating remaining ton solution has turned black, the factory calls the polymer, and the chemistry (4) reacts to form a common agent shouting (four) powder, and through a solution: she polyacrylonitrile in the solution Get out. Fig. 4 is an infrared spectrum measurement of the conjugated polymer obtained in the present example. From the vicinity of the Quku c=c), it can be seen that in 1668 cra_1 (corresponding to (four) or in the C=N or C=C bond ' characteristic absorption peak', it is confirmed that the co-polymer is polyacrylonitrile generated ^ The cyclization reaction has been demonstrated to demonstrate the treatment by the above method. Please refer to Figure 5, too. ★ E > ° to see that the conjugated polymer has a small potential in the wavelength range of 400 nm to 600. According to this, the visible light of the light and the wavelength of about 0.6 nm is still double-bonded. It is known that there is a conjugate in the conjugated polymer [0033] The synthesis of the above-mentioned Figure 4 and the preparation method is obtained. The soluble conjugated polymer of this embodiment can be further proved to be 099131775. Form No. 1010101 Page 9/Total 42 Page 0992055686-0 201213365 [0034] Third Embodiment [0035] S31, providing a mass concentration of 1% a polyacrylonitrile solution, and a chlorinated product (ZnCl2) as a catalyst, the zinc chloride is uniformly dispersed in the polyacrylonitrile solution in a ratio of 2.44:1 by mass ratio to polyacrylonitrile; S32, The oil bath was heated at a temperature of 150 ° C and stirred at a stirring speed of 500 rpm. The polyacrylonitrile solution in which zinc sulfide is dispersed is described. [0036] wherein, in step S31, the first solvent in the polyacrylonitrile solution is dimethylformamide. In step S32, when the heating time is reached At 24 hours, the solution has turned black, indicating that the polyacrylonitrile has reacted to form a co-host polymer, after which heating is stopped and the co-polymer in the solution is filtered through a solvent filter. Referring to Fig. 6 is an infrared spectrum measurement curve of the conjugated polymer obtained in the present embodiment. It can be seen from the curve that a characteristic absorption peak appears in the vicinity of 1655 cm 1 (corresponding to C = N or C = C), that is, It was confirmed that there was a C=N or C=C bond in the conjugated polymer, and it was confirmed that the polyacrylonitrile was subjected to a cyclization reaction by the above method. [0038] Referring to FIG. 7, it can be seen that The total polymer has a certain absorption of ultraviolet light in the wavelength range of 400 nm to 600 nm and visible light in the wavelength range of 600 nm to 800 nm, and has uniform absorption characteristics in the visible light range. There are a total of double bonds in the total polymer. The degree of total vehicle is relatively large. [0039] The analysis of the above-mentioned Figures 6 and 7 can further prove that a soluble conjugated polymer is obtained by the preparation method of the present embodiment. [0040] Fourth Embodiment 099131775 Form No. A0101 10 pages / total 42 pages 0992055686-0 201213365 LUU41J S41 r is. & for the concentration-concentration of fine polyacrylonitrile solution, and Shi Sha: C〇 (N〇3) 2) as a catalyst 'the cobalt nitrate according to a ratio of mass ratio of polypropylene = 27:5 is uniformly dispersed in the polypropylene solution, S42, and the oil bath is heated at a temperature of 丨^^ and the stirring degree is Torr/min. There is a viewing poly (four) riding solution. [0042]

其中’在步驟S射，所述聚丙稀腈溶液中之第一溶劑為 —甲基甲酿胺。在步驟S42中，當加熱時間達到48小時， :述溶液已變成黑色，表明所述聚丙烯腈已反應形成共物’之後停止加熱，顧過，溶劑過遽器將該溶、之聚丙稀腈漆Jrw'… [0043] [0044]Wherein 'in the step S, the first solvent in the polyacrylonitrile solution is - methylcarbachol. In step S42, when the heating time reaches 48 hours, the solution has turned black, indicating that the polyacrylonitrile has reacted to form a complex, and then the heating is stopped, and the solvent is passed through the solvent to dissolve the polyacrylonitrile. Paint Jrw'... [0043] [0044]

:參_8為本實施觸獲得之聽料物之紅外光譜測定曲線。從該曲線可以看出特徵吸收峰完全消失在1661 cm 1 (對應C=N或C=c)附近出現一組特徵吸收峰’即證實了該共輛聚合物中有c = _c=(：鍵之出現，且通過上述方法’整個共輛聚合物已基本完全環化。請參閲圖9 ’可以看出該共梃聚合物對彻奈米〜_奈米波長範圍之紫外光和刚奈米〜8叫米波長範圍之可見光具有均-之吸收特性，且基本具有75%吸收率，即吸收強度較高。據此可知，該共減合物中存在有共輛雙鍵 ’且共軛程度很大。 []#合上述圖8和圖9之分析可進—步證明通過本實施例之製傷方法獲得了共輕程度很大之可溶之共輕聚合物。 [_]帛五實施例 099131775 S51，提供一質量百表單鵠號A0101 $ 分比濃度為4%之聚丙烯腈溶液，和二 11頁/共42頁 0992055686-0 [0047] 201213365 [0048] [0049] [0050] [0051] [0052] 099131775 第12頁/共42頁氧化鈦（Ti〇、 1C)2)粉作為催化劑知聚丙烯腈之質量比為將°"—孔化鈦粉按照與溶液令；S52，在15〇。^之^例均勻分散於所述聚丙烯腈鐘之攪拌速度攪拌浴加熱並以500轉/分。一乳化鈦之聚丙烯腈溶液其中，在步驟S51中，所二甲基甲醯胺。在+ :丙烯腈溶液中之第-溶劑為述溶液已變成黑色二8 2令，當加熱時間達到16天，所聚合物，之後停止加埶==㈣猜已反應形成縣 —溶劑過遽器將K 遽所述二氧化鈦，並通過將该溶液争之共乾聚合物遽出。請參閱圖1〇為本實施得測定曲線。從該曲線…、軛聚合物之紅外光譜: _8 is the infrared spectrum measurement curve of the listen material obtained by the implementation. It can be seen from the curve that the characteristic absorption peak completely disappears at 1661 cm 1 (corresponding to a set of characteristic absorption peaks near C=N or C=c), which confirms that there is c = _c=(: bond in the total polymer). The appearance, and through the above method 'the entire co-polymer has been substantially completely cyclized. Please refer to Figure 9 'can be seen that the conjugated polymer to the Chennai ~ _ nanometer wavelength range of ultraviolet light and just nano The visible light having a wavelength range of ~8 m has a uniform absorption characteristic, and has a basic absorption rate of 75%, that is, a higher absorption intensity. According to this, there is a common double bond in the co-compliment and a degree of conjugation []# The analysis of Figures 8 and 9 above can further demonstrate that a total light-weight soluble total light polymer is obtained by the method of the present invention. [_] Example 099131775 S51, providing a mass 100 form nickname A0101 $ 4% polyacrylonitrile solution, and 2 11 pages / a total of 42 pages 0992055686-0 [0047] 201213365 [0048] [0050] [0050] 0051] [0052] 099131775 Page 12 of 42 Titanium oxide (Ti〇, 1C) 2) powder as a catalyst to know the quality of polyacrylonitrile The ratio ° " - aperture of the titanium powder with the solution according to the order; S52, in 15〇. The example was uniformly dispersed in the stirring speed of the polyacrylonitrile clock and heated at 500 rpm. A polyacrylonitrile solution of emulsified titanium, wherein, in step S51, dimethylformamide is used. In the +: acrylonitrile solution, the first solvent is said to have become black 2 8 2, when the heating time reaches 16 days, the polymer is stopped, then the twisting is stopped == (4) Guess has reacted to form a county-solvent passurizer The titanium dioxide is K , and the solution is quenched by the solution. Please refer to Figure 1 for the measurement curve of this implementation. From the curve..., the infrared spectrum of the yoke polymer

Mr、線看出’在1589 cm'1 (對應C-NMr, line sees ' at 1589 cm'1 (corresponding to C-N

或C=C)附近出現— （對應C-M 物令购购鍵之㈣卩證實了該共輛聚合所述聚丙稀腈發生了環化及過上述方法之處理， ·. .... 請參閱圖11，可以看屮4 米波長筋圚夕物〜、軛聚合物對400奈米〜600奈 1=Γ 600奈米〜_奈米波長範圍之可有共輛雙鍵，且共挺程度^知，該共輛聚合物中存在 :==1。和圖u之分析可進—步證明通過本之製備方法獲得了可溶之共概聚合物。域各實施例製備之共缺合物對紫外光或可見光具有 3之= 作用。同時，由於該共絲合物中存在共概之厌~兔雙鍵和碳—I螫縫鍵’使得該共軛聚合物具有了較表單蝙號A0101 201213365 導電性和離子傳導性，因此等領域。B A也了用於鐘離子電池且由於该共輕聚合物可溶於此’在實際應㈣財，便 ☆劑中，因應用範圍。便於加工成獏，從而可擴大其 [0053] 本發明提供—種硫化聚㈣腈之製備方法下步驟：具體包括以剛Μ卜提供硫或硫代硫賴，並㈣單質硫或硫代硫酸納與上述共扼聚合物均勻滿合以形成-混合物；闕M2，加熱上述混合·，從而製備獲得硫化聚丙稀猜。闕好觀巾，所述單質硫或硫代硫⑽與職共輕聚合物可進行固固混合或固液混合。所謂固液混合可以係直接將所述單質硫或硫代硫酸鈉均勻分散於上述通過步驟一和步驟二形成之第一共軛聚合物溶液中，也可以係首先將上述通過步驟三和步驟四分離出之純之共軛聚合物溶於一第二溶劑中形成一第二兵軛聚合物溶液，之後再將所述單質硫或硫代硫酸納均勻分散於所述第二共輪聚合物溶液中。其中，當直接將所述單質硫或硫代碗峻辦均勻分散於上述通過步驟一和少驟一形成之第一共輕聚合物溶液中時，若所述第一共觯聚合物溶液中分散有不溶之催化劑，可在步驟Ml之前首先將催化劑過濾出，若所述催化劑溶於該第一共軛聚合物溶液，則無需分離讀催化劑，待步驟M2結束之後，I接將形成之硫化聚丙烯腈通過溶劑過濾器過濾出即町。所述第二溶劑與上迷第一溶劑可以相同或不同，具體該第二溶劑可為二甲基曱 099131775 表單編號A0101 第13頁/共42真 °"2〇556 201213365 醯胺、二甲基乙醯胺、二甲基亞砜或丙二腈、環丁砜或硝酸亞乙基酯等。所述共軛聚合物與單質硫或硫代硫酸鈉按照摩爾比為1 :1〜1 : 6之比例混合。當將所述單質硫或硫代硫酸鈉均勻分散於所述共軛聚合物溶液中時，該溶質之質量百分比濃度為5%〜50%，所述溶質為單質硫或硫代硫酸鈉與共軛聚合物。另，可進一步攪拌上述分散有單質硫或硫代硫酸鈉之聚丙烯腈溶液，該攪拌方式可為機械攪拌、磁力攪拌或超聲分散等。當二者為固固混合時，為使二者均勻混合，可進一步球磨所述混合物。 [0057] 在步驟M2中，當上述二者為固固混合時，所述加熱溫度為200°C〜600°C，加熱時間為5分鐘〜10小時。當上述二者為固液混合時，所述加熱溫度為60°C〜150°C，加熱時間為5分鐘〜10天。所述加熱方式可為水浴加熱或油浴加熱。進一步地，上述加熱所述固固混合或固液混合之混合物可在一惰性氣氛下，所述惰性氣氛可為氮氣或氬氣氛圍。 [0058] 在該方法中，與硫或硫代硫酸鈉直接反應之為一種通過聚丙稀腈形成之已環化之共耗聚合物，之後，通過加熱該由硫或硫代硫酸鈉與該共軛聚合物形成之混合物，不僅使共輛聚合物發生了硫化反應形成了硫化聚丙烯腈，且在該過程中進一步使該硫化聚丙烯腈發生環化，從而大大提高了該硫化聚丙烯腈之環化程度，並提高了該硫化聚丙浠腈之導電率。 [0059] 第六實施例 099131775 表單編號A0101 第14頁/共42頁 0992055686-0 201213365 LU刪j 將單質碟與上述共軛聚合物分別按照1 :4與1 之比例均勻混人 ^ Q ’並球磨半個小時使其均勻混合；之後再在氮氣保護氣氛下’在300°C之溫度下油浴加熱該混合物2小時 <而獲得了疏化聚丙浠腈。 [0061] °月參閱圖12，圖12對本實施例中單質硫和共軛聚合物八別按昭1 n 〜1 : 4與1 : 6之比例均勻混合並加熱形成之硫化聚丙 @以及共扼聚合物之紅外光譜測定曲線，其中，a曲線 “執聚合物之紅外光譜測定曲線，b曲線代表單質碎 Ο 和共軛聚合物按照1 :4之比例均句混合並加熱形成之硫化聚内'埽腈之紅外光譜測定曲線，c曲線代表單質硫和共輕聚合物按照1: 6之比例均勻混合並加熱形成之硫化聚丙稀猜之紅外光譜測定曲線。從該曲線可以看出，與共概聚合物之红外光譜測定曲線相比，該兩種硫化聚丙烯猜之紅外光譜測定曲線中在25〇〇cm-i(CsN)附近之特徵吸收蜂’肖失’而在15〇〇 cm-1 (c=N或C=C)附近仍存在一組特徵吸收峰等。表明經過上述製備方法所獲得之硫化聚 ❹ [0062] 丙烯腈已環化完全（：i 凊參閱圖13和圖14，為對本實施例中單質硫和共軛聚合物按照1 .4之比例均勻混合並加熱形成之硫化聚丙烯腈之硫元素和氮元素之X射線能譜分析曲線圖。從該曲線圖可以看出，該硫化聚丙烯腈中存在還原態之硫和氧化態之氮，從而表明該硫化聚丙烯腈中之氰基（(：ξΝ)中之氮疋素得到電子，而硫單質則失去電子，進而形成了 N=S雙鍵。 099131775 可見，通過上述方法可獲得一種硫化聚丙烯腈表單編號第15頁/共42頁該硫化 0992055686-0 [0063] 201213365 聚丙烯腈包括一結構單元，該結構單元之分子通式為 [CQHNS] (n = l，2, 3…），該結構單元之結構式為 ό ηOr appears near C=C)—(corresponding to the CM order purchase key (4)卩, it is confirmed that the co-polymerization of the polyacrylonitrile has been cyclized and processed by the above method, ..... 11, you can see 屮 4 m wavelength 圚圚〜 ~ ~, yoke polymer to 400 nm ~ 600 Nai 1 = Γ 600 nm ~ _ nanometer wavelength range can have a total of double-key, and a total degree of knowledge There is: ==1 in the total polymer. The analysis of Fig. u can further prove that a soluble copolymer is obtained by the preparation method of the present invention. Light or visible light has a function of 3. At the same time, due to the existence of a common anaerobic-rabbit double bond and a carbon-I quilting bond in the co-filament, the conjugated polymer has a conductivity of the form tar number A0101 201213365. Sex and ionic conductivity, and so on. BA is also used in clock-ion batteries and because the co-light polymer is soluble in this 'in practical (four), ☆ agent, due to the scope of application. Therefore, it can be expanded [0053] The present invention provides a step of preparing a vulcanized poly(tetra)nitrile: Providing sulfur or thiosulfate, and (iv) elemental sulfur or sodium thiosulfate uniformly mixed with the above conjugated polymer to form a mixture; 阙M2, heating the above mixture, thereby preparing a sulfided polypropylene In the case of a good towel, the elemental sulfur or thiosulfur (10) and the co-copolymer light polymer may be solid-solid mixed or solid-liquid mixed. The so-called solid-liquid mixing may directly disperse the elemental sulfur or sodium thiosulfate directly. In the first conjugated polymer solution formed by the first step and the second step, the first conjugated polymer separated by the third step and the fourth step may be first dissolved in a second solvent to form a first a second yoke polymer solution, and then uniformly dispersing the elemental sulfur or sodium thiosulfate in the second co-round polymer solution, wherein when the elemental sulfur or thiophene is directly dispersed uniformly In the first co-light polymer solution formed by the first step and the lesser step, if the insoluble catalyst is dispersed in the first conjugated polymer solution, the catalyst may be first filtered out before the step M1. Place If the catalyst is dissolved in the first conjugated polymer solution, the read catalyst is not required to be separated, and after the end of the step M2, the formed fluorinated polyacrylonitrile is filtered through a solvent filter to remove the sol. The first solvent may be the same or different, and the second solvent may be dimethyl hydrazine 099131775 Form No. A0101 Page 13 / Total 42 true ° " 2 〇 556 201213365 decylamine, dimethyl acetamide, dimethyl a sulfoxide or malononitrile, sulfolane or ethylene nitrate, etc. The conjugated polymer is mixed with elemental sulfur or sodium thiosulfate in a molar ratio of 1:1 to 1:6. When the elemental sulfur or sodium thiosulfate is uniformly dispersed in the conjugated polymer solution, the mass percentage of the solute is 5% to 50%, and the solute is elemental sulfur or sodium thiosulfate and a conjugated polymer. Further, the above polyacrylonitrile solution in which the elemental sulfur or sodium thiosulfate is dispersed may be further stirred, and the stirring may be mechanical stirring, magnetic stirring or ultrasonic dispersion. When the two are solid-solid mixed, the mixture may be further ball milled in order to uniformly mix the two. [0057] In the step M2, when the two are solid-solid mixing, the heating temperature is 200 ° C to 600 ° C, and the heating time is 5 minutes to 10 hours. When the above two are solid-liquid mixed, the heating temperature is 60 ° C to 150 ° C, and the heating time is 5 minutes to 10 days. The heating method may be water bath heating or oil bath heating. Further, the above-mentioned mixture for heating the solid-solid or solid-liquid mixture may be under an inert atmosphere which may be a nitrogen or argon atmosphere. [0058] In the method, directly reacting with sulfur or sodium thiosulfate is a cyclized co-consumption polymer formed by polyacrylonitrile, and then heating the sulfur or sodium thiosulfate by heating The mixture formed by the conjugated polymer not only causes the vulcanization reaction of the co-polymer to form a vulcanized polyacrylonitrile, but further cyclizes the vulcanized polyacrylonitrile in the process, thereby greatly improving the vulcanized polyacrylonitrile. The degree of cyclization increases the conductivity of the vulcanized polyacrylonitrile. [0059] Sixth Embodiment 099131775 Form No. A0101 Page 14 / Total 42 Page 0992055686-0 201213365 LU Delete j The uniform disc and the above conjugated polymer are uniformly mixed in a ratio of 1:4 and 1 respectively. The mixture was ball milled for half an hour to make it uniformly mixed; then, the mixture was heated in an oil bath at a temperature of 300 ° C for 2 hours under a nitrogen atmosphere to obtain a thinned polyacrylonitrile. [0061] Referring to FIG. 12, FIG. 12 shows that in the present embodiment, the elemental sulfur and the conjugated polymer are uniformly mixed and heated in the ratio of 1 n to 1:4 and 1:6 to form a vulcanized polypropylene@@ The infrared spectroscopy curve of the polymer, wherein the a curve "the infrared spectroscopy curve of the polymer, the b curve represents the vulcanization of the elemental mash and the conjugated polymer in a ratio of 1:4. Infrared spectroscopy curve of phthalonitrile, c curve represents the infrared spectroscopy curve of sulfurized polypropylene formed by uniform mixing and heating of elemental sulphur and co-light polymer in a ratio of 1:6. From the curve, it can be seen that Compared with the infrared spectroscopy curve of the polymer, the characteristics of the two kinds of vulcanized polypropylene guessed in the infrared spectroscopy curve near the 25 〇〇 cm-i (CsN) absorption of the bee 'Xiao lost' at 15 〇〇 cm-1 There is still a set of characteristic absorption peaks and the like in the vicinity of (c=N or C=C), indicating that the fluorinated polyfluorene obtained by the above preparation method [0062] acrylonitrile has been cyclized completely ( :i 凊 see FIGS. 13 and 14 , For the elemental sulfur and conjugated polymer in this example The X-ray energy spectrum analysis curve of the sulfur element and the nitrogen element of the vulcanized polyacrylonitrile formed by uniformly mixing and heating in the ratio of 1.4. From the graph, it can be seen that the sulfur in the reduced state exists in the sulfurized polyacrylonitrile. And the nitrogen in the oxidation state, indicating that the cyano group in the fluorinated polyacrylonitrile (the azinin in (: ξΝ) gets electrons, while the elemental sulphur loses electrons, thereby forming a N=S double bond. 099131775 The above method can obtain a vulcanized polyacrylonitrile form No. 15 / total 42 vulcanization 0992055686-0 [0063] 201213365 Polyacrylonitrile comprises a structural unit having a molecular formula of [CQHNS] (n = l , 2, 3...), the structural formula of the structural unit is ό η

(η=1，2,3…）。另，該結構單元可以係該硫化聚丙烯腈之主要結構單元，該硫化聚丙烯腈之分子式中還可以存在其他未發生環化之結構單元。 [0064] 該硫化聚丙烯腈可以作為一鋰離子電池正極活性物質材料使用。與該正極活性物質對應之負極活性物質可以係金屬裡、天然石墨、有機裂解碳或金屬合金。另，如果負極活性物質係天然石墨、有機裂解碳或金屬合金等無鋰材料，上述正極或負極在組裝成鋰離子電池之前需首先進行嵌鋰。 [0065] 在不同電壓下，該硫化聚丙烯腈嵌鋰過程之反應式為：(η=1, 2, 3...). Alternatively, the structural unit may be the main structural unit of the fluorinated polyacrylonitrile, and other structural units which are not cyclized may be present in the molecular formula of the fluorinated polyacrylonitrile. [0064] The sulfurized polyacrylonitrile can be used as a positive electrode active material material for a lithium ion battery. The negative electrode active material corresponding to the positive electrode active material may be a metal, natural graphite, organic cracked carbon or a metal alloy. Further, if the negative electrode active material is a lithium-free material such as natural graphite, organic cracked carbon or a metal alloy, the above positive electrode or negative electrode needs to be first intercalated before being assembled into a lithium ion battery. [0065] The reaction formula of the lithium intercalation process of the vulcanized polyacrylonitrile at different voltages is:

[0066][0066]

201213365 LUUbYJ 上述嵌鋰或未嵌鋰之硫化聚丙烯腈均可直接用於鋰離子電池正極活性材料。在欲链後，對應上述兩個反應式，該正極活性材料包括一結構單元，該結構單元之分子通式為[C HNSLi] (n = l，2,3…），該結構單元之結構通 ο η 式為「 ] (η = 1，2, 3…）；或者該結構單元之分201213365 LUUbYJ The above-mentioned lithium-encapsulated or non-lithium-doped fluorinated polyacrylonitrile can be directly used as a positive active material for lithium ion batteries. After the chain is desired, the positive electrode active material includes a structural unit having a molecular formula of [C HNSLi] (n = 1 , 2, 3...) corresponding to the above two reaction formulas, and the structure of the structural unit is ο η is " ] (η = 1,2, 3...); or the division of the structural unit

f ϋ 〇子通式為[CQHNSLiq] (η = 1，2,3…），該結構單元之結〇 ο η 構通式為 ϋ (η=1，2, 3…）。f ϋ 〇 Subclass is [CQHNSLiq] (η = 1, 2, 3...), and the structure 结 ο η of the structural unit is ϋ (η = 1, 2, 3...).

[0068] 本實施例採用所述硫化聚丙烯腈作為正極活性材料，製備鋰離子電池並對該鋰離子電池之電化學性能進行了測試。具體地，將質量百分含量為85%~98%之上述硫化聚丙烯腈、1%~10%之導電劑及1%〜5%之粘結劑混合並塗覆於鋁集流體表面形成一正極，負極為金屬鋰，電解液由濃度為lmol/L之六氟磷酸鋰（LiPFe)溶於體積比為1:1之In the present embodiment, the vulcanized polyacrylonitrile was used as a positive electrode active material, a lithium ion battery was prepared, and the electrochemical performance of the lithium ion battery was tested. Specifically, the above-mentioned vulcanized polyacrylonitrile, 1% to 10% of a conductive agent and 1% to 5% of a binder having a mass percentage of 85% to 98% are mixed and coated on the surface of the aluminum current collector to form a The positive electrode and the negative electrode are metallic lithium, and the electrolyte is dissolved in a volume ratio of 1:1 by a lithium hexafluorophosphate (LiPFe) having a concentration of 1 mol/L.

D 碳酸乙烯酯（EC)及碳酸甲基乙基酯（EMC)混合形成之溶劑得到。 [0069] 請參閱圖15，對該鋰離子電池在0〜3伏之電壓範圍内，且在0. 2C倍率下進行充放電性能測試，測得在0. 2C倍率 099131775 表單編號A0101 第17頁/共42頁 0992055686-0 201213365 下’其充電比容量為1271毫安時/克（mAh/g)，放電比谷量為 1 502 mAh/g。 [0070] 請參閱圖16和圖17，圖16為將上述鋰離子電池先以0. 25 毫安（mA)之電流恒流充電至3. 7伏，並在3. 7伏恒壓充電至電流為〇，最後恒流放電至1伏，從圖16可以看出，此條件下，該電池僅能反復充放電3次。圖17為將該鋰離子電池先以0. 25 mA之電流恒流充電至3. 6伏，並在3. 6伏恒·壓充電至電流為〇，最後恒流放電至1伏，從圖17可以看出’此條件下，該電池能反復充放電多次，即具有較好之循環性能。因此，奸款讀定該鋰離子電池充電截止電壓應小於等於3. 6伏。陳1]請參閱圖18，對上述鋰離子電池在-3(TC，-20°C，-10 C ’ 〇°C ’ l〇°c，25°C，60°C時進行放電之比容量測試曲線’從圖18可以看出，隨著溫度之降低，該電池之放電比容量降低，其中在—2(TC時，放電比容f為632 mAh/g 在6〇Ί〇時，其放電比容量為854 ®At]iVg，因此，該链離子電池可在-2(TC至60°C之溫摩範圍内正常工作。陳2]請參閱圖19，對上述鋰離子電池在667毫安/克（mA/g)， mA/g，l67 mA/g及55.6 mA/g之電流密度下進行玫電之比容量測試，從該圖可以看出隨著電流密度之降低’該鋰離子電池之放電比容量降低，當電流密度為 55· 6mA/g時，其放電比容量為792mAh/g，當電流密度為667mA/g時，其放電比容量為667mAh/g。 [〇〇73] 综上所述，本發明確已符合發明專利之要件，遂依法提 099131775 表單編號A0101 第18頁/共42頁 0992055686-0 201213365 [0074] [0075] Ο [0076] [0077] ❹ [0078] [0079] [0080] 099131775 出專利申明。惟，以上所述者僅為本發明之較佳實施方式’自不能以此限制本案之巾請專利範圍。舉凡熟悉本案技藝之人士援依本發明之精神所作之等效修飾或變化，皆應涵蓋於以下申請專利範圍内。【圖式簡單說明】圖1為本發明實施例提供之用於製備硫化聚丙稀腈之_共軛聚合物之製備方法流程圖。圖2，圖4，圖6 ’圖8及圖10分別為本發明第—實施例至第五實施例所獲得的共軛聚合物本紅外光譜測定曲線圖〇 . 圖3，圖5，圖7，圖9及圖11分別岛本發明第—實施例至第五實施例所獲得的共軛聚合物之紫外-可見光吸收光譜分析曲線圖》圖12為本發明第六實施例中單質硫和共軛聚合物分別按照1 : 4與1: 6的比例均勻混合並加熱形成的硫化聚丙烯腈以及共輛聚合物之紅鄭光譜測定曲線。 - 乂 - . '：：! 11 圖13為本發明第六實施例中單質硫和共軛聚合物按照工^ 之比例均勻混合並加熱形成的硫化聚丙稀腈中之硫元素之X射線能譜分析曲線圖。圖14為本發明第六實施例中單質硫和共軛聚合物按照i 之比例均勻混合並加熱形成的硫化聚丙烯腈中之氮元素之X射線能譜分析曲線圖。圖1 5為本發明第六實施例所製備獲得的硫化聚丙稀猜作為鋰離子電池正極材料在0.2C倍率下之充放電曲線圖。表單編號A0101 第19買/共42頁 201213365 [0081] 圖1 6為本發明第六實施例所製備獲得的硫化聚丙烯腈作為鋰離子電池正極材料在1伏至3.7伏電壓範圍内之充放電循環測試曲線圖。 [0082] 圖1 7為本發明第六實施例所製備獲得的硫化聚丙烯腈作為鋰離子電池正極材料在1伏至3. 6伏電壓範圍内之充放電循環測試曲線圖。 [0083] 圖18為本發明第六實施例所製備獲得的硫化聚丙烯腈作為鋰離子電池正極材料在不同溫度下之放電曲線圖。 [0084] 圖1 9為本發明第六實施例所製備獲得的硫化聚丙烯腈作為鋰離子電池正極材料在不同電流密度下之放電曲線圖〇【主要元件符號說明】 [0085] 無： 099131775 表單編號A0101 第20頁/共42頁 0992055686-0D A solvent obtained by mixing ethylene carbonate (EC) and methyl ethyl carbonate (EMC). [0069] Please refer to FIG. 15, the lithium ion battery in the voltage range of 0 to 3 volts, and the charge and discharge performance test at 0. 2C rate, measured at 0. 2C rate 099131775 Form No. A0101 page 17 / Total 42 pages 0992055686-0 201213365 'The charging specific capacity is 1271 mAh / gram (mAh / g), the discharge ratio is 1 502 mAh / g. The volts are charged to a constant current of 3.7 mA to 3.7 volts and charged at a constant voltage of 3.7 volts to a voltage of 0.25 mA (mA). The current is 〇, and finally the constant current discharge is 1 volt. As can be seen from Fig. 16, under this condition, the battery can only be repeatedly charged and discharged 3 times. Figure 17 is a diagram showing that the lithium ion battery is firstly charged at a constant current of 0.25 mA to 3. 6 volts, and charged at a constant voltage of 3.6 volts to a current of 〇, and finally a constant current discharge to 1 volt. 17 It can be seen that under this condition, the battery can be repeatedly charged and discharged multiple times, that is, it has better cycle performance. Therefore, the charge cutoff voltage of the lithium ion battery should be less than or equal to 3.6 volts. Chen 1] Please refer to Figure 18 for the specific capacity of the above lithium-ion battery discharged at -3 (TC, -20 ° C, -10 C ' 〇 ° C ' l ° ° C, 25 ° C, 60 ° C Test curve 'As can be seen from Figure 18, as the temperature decreases, the discharge specific capacity of the battery decreases, where at -2 (TC, the discharge specific volume f is 632 mAh / g at 6 ,, its discharge The specific capacity is 854 ® At]iVg, therefore, the chain ion battery can work normally in the temperature range of -2 (TC to 60 ° C. Chen 2), please refer to Figure 19, the above lithium-ion battery at 667 mAh / gram (mA / g), mA / g, l67 mA / g and 55.6 mA / g current density of the specific capacity test of the rose, from the figure can be seen with the decrease in current density 'the lithium-ion battery The discharge specific capacity is reduced. When the current density is 55·6 mA/g, the discharge specific capacity is 792 mAh/g, and when the current density is 667 mA/g, the discharge specific capacity is 667 mAh/g. [〇〇73] As described above, the present invention has indeed met the requirements of the invention patent, and is pursuant to the law. 099131775 Form No. A0101 Page 18 / Total 42 Page 0992055686-0 201213365 [0074] 007 [0076] [0077] ❹ [0078] 00 [0080] 099131775 Patent declaration. However, the above description is only a preferred embodiment of the present invention, which can not limit the scope of the patent application of the present invention. Those who are familiar with the skill of the present invention are in accordance with the spirit of the present invention. The equivalent modifications or variations are to be included in the following claims. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flow chart of a method for preparing a conjugated polymer for preparing a sulfided polyacrylonitrile according to an embodiment of the present invention. Figure 2, Figure 4, Figure 6 'Figure 8 and Figure 10 are the infrared spectroscopy curves of the conjugated polymers obtained in the first to fifth embodiments of the present invention. Figure 3, Figure 5, Fig. 7, Fig. 9 and Fig. 11 are graphs showing ultraviolet-visible absorption spectrum analysis of the conjugated polymer obtained in the first to fifth embodiments of the present invention, respectively. Fig. 12 is a view showing the elemental sulfur in the sixth embodiment of the present invention. And the conjugated polymer are uniformly mixed and heated in a ratio of 1:4 to 1:6, respectively, and the formed chemi-polyacrylonitrile and the composite polymer are determined by the red Zheng spectrum. - 乂- . ': :! 11 Figure 13 Single in the sixth embodiment of the present invention The X-ray energy spectrum analysis curve of the sulfur element in the sulfurized polyacrylonitrile formed by uniformly mixing and heating the sulfur and the conjugated polymer according to the ratio of the working composition. Fig. 14 is a view showing the elemental sulfur and the conjugated polymerization in the sixth embodiment of the present invention. The X-ray energy spectrum analysis curve of the nitrogen element in the vulcanized polyacrylonitrile formed by uniformly mixing and heating according to the ratio of i. Fig. 15 is a lithium ion battery which is obtained by the sixth embodiment of the present invention. Charge and discharge graph of the cathode material at 0.2 C rate. Form No. A0101 19th Buy/Total 42 Page 201213365 [0081] FIG. 16 is a charge and discharge of a vulcanized polyacrylonitrile prepared as a positive electrode material for a lithium ion battery in a voltage range of 1 volt to 3.7 volts according to a sixth embodiment of the present invention. Cycle test curve. Figure 7 is a graph showing the charging and discharging cycle test of the vulcanized polyacrylonitrile obtained in the sixth embodiment of the present invention as a positive electrode material of a lithium ion battery in a voltage range of 1 volt to 3.6 volt. 18 is a graph showing discharge curves of a sulfide polyacrylonitrile prepared as a positive electrode material of a lithium ion battery at different temperatures according to a sixth embodiment of the present invention. FIG. 19 is a discharge curve diagram of a sulfurized polyacrylonitrile prepared as a positive electrode material for a lithium ion battery at different current densities according to a sixth embodiment of the present invention. [Main component symbol description] [0085] None: 099131775 Form No. A0101 Page 20 of 42 0992055686-0

Claims

201213365 七申請專利範圍： =硫:聚丙稀腈之製備方法，其如供—聚丙烯腈、一第— ^ 加入該第-溶劑中完全.、容:开:及―催化劑，將該聚丙稀腈催化劑均句分散於該聚丙歸腈溶液令；婦猜冷液，並將该力口熱上述分时催化狀w制雜，使聚丙烯赌發生 ^化反應’以形成-溶解有共輕聚合物之第—共輛聚合物溶液；201213365 Seven patent application scope: = sulfur: preparation method of polyacrylonitrile, such as - polyacrylonitrile, a - ^ added to the first solvent - complete, capacity: open: and - catalyst, the polyacrylonitrile The catalyst is uniformly dispersed in the polyacrylonitrile solution; the woman guesses the cold liquid, and the heat is catalyzed by the above-mentioned time-sharing catalytic w, so that the polypropylene gambling reaction is formed to form - dissolve the co-light polymer The first - a total of polymer solution;

提供-單質硫或硫代硫酸納，戴將該單質硫或硫代硫酸納與上述共輕聚合物均句激合以形成一混合物；及加熱上述混合物，從而製備獲得硫化聚丙烯腈。 2 .如申請專利範圍第1項所述之硫化聚丙烯腈之製備方法，其中，所述第一溶劑為二甲基曱醯胺、二甲基乙醯胺、二甲基亞砜、丙二腈、環丁颯或硝酸亞乙基醋。 3 .如申請專利範圍第丨項所述之硫化聚丙烯腈之製備方去，其中’所述催化劑與所述聚丙烯腈之質量比為1.〇 2 1 6 o t ❹ 4 .如申請專利範圍第1項所述之硫化聚丙烯腈之製傷方去其中’所述催化劑為金屬粉’該金屬粉為銀粉、網粉、錫粉、鐵粉、鈷粉或鎳粉。如申請專利範圍第1項所述之硫化聚丙烯腈之製備方去其中’所述催化劑為金屬氧化物，該金屬氡化物化鈦、氧化銅或氧化鐵。粉為二氧如申請專利範圍第4或5項所述之硫化聚丙烯腈之製備、，其中，所述金屬粉或金屬氧化物粉之粒徑範圍两& Q奈米 099131775 表單編號A0101 第21買/共42頁 0992055686-0 201213365 至500微米。 7 .如申請專利範圍第1項所述之硫化聚丙烯腈之製備方法，其中，所述催化劑為金屬鹽，該金屬鹽為钻鹽、錫鹽、銅鹽、鎳鹽或鋅鹽。 8 .如申請專利範圍第1項所述之硫化聚丙烯腈之製備方法，其中，所述加熱上述分散有催化劑之聚丙烯腈溶液之溫度為80°C~300°C。 9 .如申請專利範圍第1項所述之硫化聚丙烯腈之製備方法，其中，在加熱上述分散有催化劑之聚丙烯腈溶液之過程中，進一步攪拌上述分散有催化劑之聚丙烯腈溶液，所述攪拌速度為100轉/每分鐘至1 000轉/每分鐘。 10 .如申請專利範圍第1項所述之硫化聚丙烯腈之製備方法，其中，在形成所述第一共軛聚合物溶液之後，進一步將所述催化劑過濾出，並通過一溶劑過濾器將所述共輛聚合物抽濾出。 11 .如申請專利範圍第10項所述之硫化聚丙烯腈之製備方法，其中，所述混合物為單質硫或硫代硫酸鈉與所述共軛聚合物直接混合之固固混合物，所述加熱上述混合物之溫度為 200°C〜600°C，加熱時間為5分鐘〜10小時。 12 .如申請專利範圍第10項所述之硫化聚丙烯腈之製備方法，其中，所述混合物為固液混合物，所述形成混合物之步驟進一步包括以下次步驟：將所述共軛聚合物溶於一第二溶劑中以形成一第二共軛聚合物溶液；將所述單質硫或硫代硫酸鈉均勻分散於所述第二共軛聚合物溶液中。 13 .如申請專利範圍第12項所述之硫化聚丙烯腈之製備方法，其中，所述第二溶劑可為二曱基曱醢胺、二甲基乙醯胺、 099131775 表單編號A0101 第22頁/共42頁 0992055686-0 201213365 14 . 15 . 16 . Ο 二曱基亞砜或丙二腈。如申請專利範圍第1項所述之硫化聚丙烯腈之製備方法，其中，所述混合物為固液混合物，所述形成混合物之步驟為將所述單質硫或硫代硫酸鈉均勻分散於所述第一共輛聚合物溶液中。如申請專利範圍第12或14項所述之硫化聚丙烯腈之製備方法，其中，所述加熱上述混合物之溫度為60°C〜150°C ，加熱時間為5分鐘〜1 0天。如申請專利範圍第1項所述之硫化聚丙烯腈之製備方法，其中，所述共輛聚合物與單質硫或硫代硫酸鈉按照摩爾比為1:1 ~ 1 : 6之比例混合。 099131775 表單編號A0101 第23頁/共42頁 0992055686-0Providing - elemental sulfur or sodium thiosulfate, the elemental sulfur or sodium thiosulfate is mixed with the above-mentioned co-light polymer to form a mixture; and the above mixture is heated to prepare a vulcanized polyacrylonitrile. 2. The method for preparing a sulfurized polyacrylonitrile according to claim 1, wherein the first solvent is dimethyl decylamine, dimethyl acetamide, dimethyl sulfoxide, and propylene. Nitrile, cyclobutyl hydrazine or ethyl vinegar nitrate. 3. The preparation of the vulcanized polyacrylonitrile according to the scope of the patent application, wherein the mass ratio of the catalyst to the polyacrylonitrile is 1. 〇 2 16 ot ❹ 4 . The sulphurized polyacrylonitrile according to the first aspect is in which the 'the catalyst is a metal powder'. The metal powder is silver powder, mesh powder, tin powder, iron powder, cobalt powder or nickel powder. The preparation of the vulcanized polyacrylonitrile described in claim 1 is wherein the catalyst is a metal oxide, the metal telluride titanium, copper oxide or iron oxide. The powder is dioxane, as described in claim 4 or 5, wherein the metal powder or metal oxide powder has a particle size range of two & Q Nano 099131775 Form No. A0101 21 buy / a total of 42 pages 0992055686-0 201213365 to 500 microns. The method for producing a sulfurized polyacrylonitrile according to claim 1, wherein the catalyst is a metal salt, and the metal salt is a drill salt, a tin salt, a copper salt, a nickel salt or a zinc salt. The method for producing a vulcanized polyacrylonitrile according to claim 1, wherein the heating of the polyacrylonitrile solution in which the catalyst is dispersed is from 80 ° C to 300 ° C. 9. The method for preparing a vulcanized polyacrylonitrile according to claim 1, wherein the polyacrylonitrile solution in which the catalyst is dispersed is further stirred during heating of the polyacrylonitrile solution in which the catalyst is dispersed. The stirring speed is from 100 rpm to 1 000 rpm. 10. The method for preparing a vulcanized polyacrylonitrile according to claim 1, wherein after the first conjugated polymer solution is formed, the catalyst is further filtered and passed through a solvent filter. The co-polymer is filtered off by suction. The method for producing a sulfurized polyacrylonitrile according to claim 10, wherein the mixture is a solid mixture of elemental sulfur or sodium thiosulfate directly mixed with the conjugated polymer, the heating The temperature of the above mixture is from 200 ° C to 600 ° C, and the heating time is from 5 minutes to 10 hours. 12. The method for producing a vulcanized polyacrylonitrile according to claim 10, wherein the mixture is a solid-liquid mixture, and the step of forming the mixture further comprises the step of: dissolving the conjugated polymer Forming a second conjugated polymer solution in a second solvent; uniformly dispersing the elemental sulfur or sodium thiosulfate in the second conjugated polymer solution. The method for producing a sulfurized polyacrylonitrile according to claim 12, wherein the second solvent is dinonyl decylamine, dimethylacetamide, 099131775, Form No. A0101, page 22 / Total 42 pages 0992055686-0 201213365 14 . 15 . 16 . Ο Dimercapto sulfoxide or malononitrile. The method for preparing a sulfurized polyacrylonitrile according to claim 1, wherein the mixture is a solid-liquid mixture, and the step of forming the mixture is to uniformly disperse the elemental sulfur or sodium thiosulfate in the The first total polymer solution. The method for producing a sulfurized polyacrylonitrile according to claim 12, wherein the temperature of the mixture is from 60 ° C to 150 ° C and the heating time is from 5 minutes to 10 days. The method for preparing a vulcanized polyacrylonitrile according to claim 1, wherein the co-polymer is mixed with elemental sulfur or sodium thiosulfate in a molar ratio of 1:1 to 1:6. 099131775 Form No. A0101 Page 23 of 42 0992055686-0