TW201213366A - Sulfurized polyacrylonitrile and lithium-ion battery cathode material using the same - Google Patents

Abstract

The present invention provides a sulfurized polyacrylonitrile containing a structural unit, wherein general molecular formula of the structural unit is [C3HNS]n (n = 1, 2, 3..), and general structural formula of the structural unit is described in the specification. This invention also provides a lithium-ion battery cathode material contains a sulfurized polyacrylonitrile or a lithium ion-inserted sulfurized polyacrylonitrile.

Description

201213366 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 homopolymer composed of a saturated carbon skeleton with a cyano group on an alternate carbon atom. It has no conductivity itself, but it has been found that if it is a polyacrylonitrile The powder is mixed with sulfur and heated to vulcanize the polyacrylonitrile, and a chemically active conductive polyacrylonitrile is prepared. Please refer to “Preparation of Sulfurized Polyacrylonitrile Lithium Ion Battery”, Ren Jianguo et al., BAT_TERY BIMONTHLY , Vol.38, No. 2, p73~74 (2〇〇8). This document discloses that a polyacrylonitrile can be obtained as a precursor of a lithium ion battery by using polyacrylonitrile as a precursor and thoroughly vulcanizing with elemental sulfur at 3 Torr (rc). During the reaction of the above polyacrylonitrile with sulfur, the polyacrylonitrile may undergo a cyclization reaction such that the formed sulfurized poly(tetra)nitrile is a conjugated polymer having a residual π bond conjugated system, the conjugated polymer As a positive electrode material Q of a lithium ion battery, it has a high specific capacity. [0003] However, since the above method for preparing a vulcanized polyacrylonitrile is formed by directly heating a mixture of polyacrylonitrile and sulfur, it is easy to form the formed. The degree of cyclization of the vulcanized polyacrylonitrile is not high, that is, the total light π bond formed is less, so that the conductivity of the vulcanized polyacrylonitrile is lower. [Summary of the invention] It is indeed necessary to provide Highly cyclic bismuth vulcanized polyacrylonitrile and an ion battery positive electrode material used therein. [0005] A vulcanized polyacrylonitrile, the vulcanized polyacrylonitrile comprises a structural unit, 0992055688-0 099131777 Form No. 0101 Page 3 of 42 201213366 The molecular formula of the structural unit is [C HNS] (1,2,3...), ^ η The structural unit of the structural unit is

[0006] A positive electrode material for a clock ion battery, comprising a structural unit having a molecular formula of [C3HNS]n (n = 1, 2, 3...')

(n= 1,2,3 ...) 〇

[0007] A positive electrode material for a clock ion battery, comprising a lithium intercalated vulcanized polyacrylonitrile, wherein the lithium intercalated vulcanized polyacrylonitrile comprises a structural unit, and the molecular formula of the structural unit is [C^ bribe isn ] l(1(nm··), 〇ny

[0008] A positive electrode material for a lithium ion battery, comprising a lithium intercalated polyacrylonitrile, wherein the lithium intercalated vulcanized polyacrylonitrile comprises a structural unit, and the molecular formula of the 3 metameric unit is [(^HNSLiJ) (n=l,2,3...), 〇3 η 099131777 Form No.Α0101 Page 4/Total 42 Page 0992055688-0 201213366

Li

Li (n=l, 2, 3...)〇 [0009] Compared with the prior art, the present invention synthesizes a new vulcanized polyacrylonitrile which has a higher degree of cyclization and has Good conductivity. [Embodiment] Hereinafter, a vulcanized polyacrylonitrile according to an embodiment of the present invention and a preparation method thereof, a positive electrode material of a lithium ion battery using the vulcanized polyacrylonitrile, and a preparation of the vulcanized polyacrylonitrile are described in detail with reference to the accompanying drawings. A method of preparing a conjugated polymer. [0011] A method of preparing a conjugated polymer for preparing the sulfurized polyacrylonitrile will be first described below. [0012] Please refer to FIG. 1 , the present invention provides a method for preparing a conjugated polymer, the method comprising the following steps: [0013] Step one, providing a polyacrylonitrile, a first solvent and a catalyst, the poly Acrylonitrile is dissolved in the first solvent to form a polyacrylonitrile solution, and the catalyst is uniformly dispersed in the polyacrylonitrile solution; and [0014] Step 2, heating the above-mentioned catalyst-dispersed polyacrylonitrile solution, To form a first co-roll polymer solution in which a co-polymer is dissolved. [0015] The above steps will be described in detail below. 099131777 Form No. A0101 Page 5 / Total 42 Page 0992055688-0 201213366 [0016] 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 such as methylformamide, dimethylacetamide, dimethyl sulfoxide, malononitrile, cyclobutyl hydrazine or ethylene nitrate. The molecular weight of the polyacrylonitrile is not limited, and is preferably from 1,000 to 10,000. 1%〜10百分比。 The polyacrylonitrile solution is not limited by the mass ratio, preferably 0. 1% ~ 10%. [0017] 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, the metal oxide powder and the metal salt may be selected from one or more of a transition element, a Group IVA and a Group VA metal element. The catalyst is soluble or insoluble in the above polyacrylonitrile solution, wherein the metal powder may be silver powder, copper powder, tin sulphide, iron powder, cobalt powder or nickel powder, etc., the metal oxide powder is titanium dioxide powder, bismuth Copper powder or bismuth iron powder, etc., the metal salt may be a cobalt salt, a tin salt, a steel salt, a nickel salt or a zinc salt, such as cobalt nitrate (C 〇 (NO; 3) 2), zinc hydride (ZnCip) Or gasified bismuth (SbCl) or the like; if the catalyst is insoluble in the above-mentioned polyacrylonitrile solution, the smaller the particle size of the catalyst, the easier it is to be uniformly dispersed in the polyacrylonitrile solution, thereby making the step The faster the cyclization rate of the second polypropylene is, the faster the conjugated polymer is formed. The catalyst may have a particle diameter of 50 nm to 500 μm, preferably 100 nm to 100 μm. The more the amount of addition, the faster the cyclization rate of polyacrylonitrile, and the mass ratio of the catalyst to the polyacrylonitrile may be 1:0.2 to 1:6. In the second step, the heating method may be a water bath. Heating or oil bath heating ° The heating temperature can be 8G ° C ~ 3G (TC, the heating temperature can be mixed to make the 099131777 table A0101 Page number 6/42 co 0992055688-0 [0018] 201 213 366

[0020] 〇 Acrylonitrile undergoes a cyclization reaction or a cyclization reaction takes a short time, and at the same time, an insoluble co-polymer is not formed to precipitate from the solution. The heating time may be such that the polyacrylonitrile sufficiently forms a soluble covalent polymer, and specifically, by observing the color change of the catalyst-dispersed polyacrylonitrile solution to determine whether a soluble covalent polymer has been formed, When the color of the solution turns black, it means that the conjugated polymer has been formed and the darker 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. In the heating process, in order to accelerate the formation of the conjugated polymer by allowing the catalyst and the polypropylene to be sufficiently mixed in the solvent, the above-mentioned catalyst-dispersed polyacrylonitrile solution can be further stirred. The manner of granting is not limited to magnetic stirring, ultrasonic dispersion or mechanical mixing. When the mechanical agitation is employed, the stirring speed is not limited, and is preferably from 1 rpm to from 1 000 rpm. The first conjugated polymer solution formed by the above steps 1 and 2 is composed of a conjugated polymer formed by the above polyacrylonitrile by a cyclization reaction, a catalyst, and a first solvent, wherein the conjugated polymer is dissolved in the first * Agent, the catalyst may be dissolved in the first solvent or in the form of beads depending on the choice " [0021] may further include the step of removing the first solvent from the first conjugated polymer solution: [0024] [0024] 099131777 Step 3 in the solvent: removing the catalyst in the first total polymer solution Step 4: removing the first in the first conjugated polymer solution. In the third step, when the catalyst is insoluble in the above-mentioned first form, the nickname A0101, page 7 / total page 42 ° " 2〇55688-| 201213366, a filter having a mesh diameter smaller than the particle diameter of the catalyst can be used. The net filters the catalyst in the solution, and when the catalyst is dissolved in the first solvent, it can be filtered off through the fourth step. [0025] In the fourth step, the first solvent in the first conjugated polymer solution and the catalyst dissolved therein are simultaneously filtered by a solvent filter, so that only the black powder remains pure. Co-hosting the polymer; or continuing to slowly heat the first total polymer solution directly at a lower temperature, such as below 80 ° C, such that the first solvent is gradually volatilized, leaving only the solid state a conjugated polymer and a catalyst. In this case, in order to separate the catalyst from the conjugated polymer, the two may be separated by a resonator or a centrifuge according to the specific gravity of the two. Different characteristics, using an electromagnetic separator to separate the two. [0026] The first embodiment [0027] 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, heated in an oil bath at a temperature of 150 ° C and stirred at a stirring speed of 500 rpm, the polyacrylonitrile solution in which the silver powder is dispersed . [0028] wherein, in step S11, the first solvent in the polyacrylonitrile solution is decyl decylamine. 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 conjugated polymer, after which the heating is stopped, the catalyst silver powder is filtered, and passed. A solvent filter filters out the polyacrylonitrile in the solution. 099131777 Form No. A0101 Page 8 of 42 0992055688-0 201213366 [0029] Please refer to FIG. 2, which shows the extra-spectral measurement curve of the co-light polymer obtained in the present example. It can be seen from the curve that the characteristic absorption peaks are

2242cm-1 (corresponding to CeN), 2938 cm-1 (corresponding to CH n2; * 1387 cnT1 (corresponding to CH), and 1670 cm_i (corresponding to Ci or c==c), etc. • appeared at 1670 cm-1 = characteristic absorption peak of N or C=C bond, it is proved that the polyacrylonitrile has undergone cyclization reaction by the above method [0030] In addition, the non-consumable unsaturated polymer only has a short wavelength Ultraviolet light has a 〇 absorption effect'. When the double bond in the polymer exists in a conjugated form, it has a strong absorption effect on the longer wavelength ultraviolet light or even visible light, and increases with the commonality. The stronger the absorption of longer waves. According to this principle, the obtained conjugated polymer is further subjected to ultraviolet-visible absorption spectroscopy according to the principle. Please refer to Fig. 3 to show that the total bowl polymer has a wavelength of The ultraviolet light in the range of 300 nm to 4 〇〇 nanometer has a strong absorption effect, and the ultraviolet light wavelength of the range of 400 nm to 6 〇〇 nanometer has a certain absorption, but the absorption is weakened. And 仍有 there is still a small amount of absorption for visible light with a wavelength of about 600 nm. It is known that a co-peach double bond is present in the co-light polymer. [0031] The analysis of the above-mentioned FIG. 2 and FIG. 3 can further prove that a soluble conjugated polymer is obtained by the production method of the present embodiment. Second Embodiment [0033] S21 'provides a mass percentage concentration of 3% polyacrylonitrile solution, and a particle size of 100 nm sulfur powder as a catalyst 'the mass ratio of the sulfur powder to polyacrylonitrile is 1: The ratio of 〇. 5 is uniformly dispersed in the polyacrylonitrile solution 099131777 Form No. A0101 Page 9 / Total 42 Page 0992055688-0 201213366 [0034] [0036] [0039] [0039] S22, at the temperature of ^^, ^ and the oil bath is heated and mixed with the sulfur powder-dispersed polypropylene solution at a speed of 500 rpm. The second step of the polyacrylonitrile solution The first solvent in the solution is methyl sub-grinding. The solution has turned black in step S22, indicating that the heating time reaches 24 hours, the polymer, and then the polyacrylonitrile has reacted to form a conjugate agent. The polyacrylonitrile in the solution is derivatized. See Figure 4 for the total of the obtained ^^ & Infrared spectroscopy of the polymer. It can be seen from the curve that the in-situ peak confirms that there is a CN or C = C bond in the covalent polymer, and the polypropylene is treated by the above method. The nitrile undergoes a cyclization reaction. It can be seen from Figure 5 (5) that the conjugated polymer has a small amount of absorption in the ultraviolet light of the wavelength range of ~6 〇〇 nanometer and the visible light of the wavelength of about 6 〇〇 nanometer. . According to this, it can be seen that there is a common light double bond in the co-polymerization. The analysis of Figs. 4 and 5 above can further demonstrate that a soluble conjugated polymer is obtained by the production method of this embodiment. The ratio of the ratio of the weight of the zinc oxide to the polyacrylonitrile is 2.44:1. The ratio of the mass ratio of the zinc oxide to the polyacrylonitrile is 2.44:1. The homogenous sentence was dispersed in the polyacrylonitrile solution; S32, the oil bath was heated at a temperature of 15 °C and the polyacrylonitrile solution in which the vaporized zinc was dispersed was stirred at a stirring speed of 5 Torr. Form No. A0101 Page 10/Total 42 Page 0992055688-0 201213366 [0040] wherein, in step S31, +. is taken as _φ. ^ The first solvent of the acrylonitrile solution t is monomethylformamide. In step 3, 'When the heating time reaches 24 hours, the solution has turned black, 矣", JJ ^ ^ The polyacrylonitrile has reacted to form a conjugated polymer, and then stops adding, the total of the liquid The object "I35 over-solvent" will dissolve the solution - [0041] ❹ Refer to Figure 6 for the infrared spectrum measurement curve of the total polymer of the embodiment. From this curve, it can be (iv) A group of features in the vicinity of 1655(10)-^ correspondence (3) or C2C) confirms that the hills are concentrated The presence of a C=N or C=C bond in the compound indicates that the yoke mouthpiece appeared, which proves that the polyacrylonitrile has undergone a cyclization reaction by the above method. [0042] Please refer to FIG. 7 , it can be seen that the ruthenium, yoke poly σ object has a wavelength range of 40Q nanometer ~ 6 〇〇 nanometer wavelength and a wavelength range of 600 nm ~ 8 〇〇 nanometer is visible first. Each has an absorption of 1 and has a uniform absorption characteristic at the visible level. From this, it can be seen that there are a total of 16 double bonds in the co-tetra compound, and the degree of the yoke is large. [0043] The analysis of the above-described FIGS. 6 and 7 can further demonstrate that a soluble conjugated polymer is obtained by the production method of this embodiment. [0044] Fourth Embodiment [0045] (4), providing a poly-propion_concentration concentration of 6%, (4) acid drill (Co (N〇3) 2) as a catalyst, the acid is in accordance with the polypropylene a ratio of mass ratio of 27:5 is uniformly dispersed in the polypropylene solution; S42' is heated in an oil bath at a temperature of 15 G ° C and the polycobalt dispersed with cobalt nitrate is stirred at a stirring speed of coffee/min. Nitrile solution. 099131777 wherein, in step S41, the agent in the polyacrylonitrile solution Form No. A0101 Page 11 of 42 7 0992055688-0 201213366 — Mercaptocarboxamide. In step S42, when the heating time reaches 48 hours, the solution has turned black, indicating that the polyacrylonitrile has reacted to form a conjugated polymer, then the heating is stopped, and the polypropylene in the solution is passed through a solvent filter. The nitrile was filtered off. [0047] Month > FIG. 8 is an infrared spectrum measurement curve of the conjugated polymer obtained in the present example. It can be seen from the curve that a characteristic absorption peak of C 3 N characteristic absorption peak disappears completely at 1661 cm (corresponding to C=N or C=C), which confirms that C=N or The occurrence of the c=c bond, and by the above method, the entire conjugated polymer has been substantially completely cyclized. [0048] Referring to FIG. 9, it can be seen that the conjugated polymer has a uniform absorption of ultraviolet light in the wavelength range of 4 〇〇 nanometers to 6 〇〇 nanometers and visible light in the wavelength range of 600 nm to 800 nm. Characteristics, and basically has a 75% absorption rate, that is, a higher absorption intensity. From this, it is understood that the co-reducing towel has a conjugated double bond' and a large degree of conjugation. [0049] The synthesis of the above-mentioned FIG. 8 and FIG. 9 can be further improved. "The preparation method of the present embodiment obtains a large soluble organic polymer. [0050] The fifth embodiment [ 0051] S5 provides a 4% poly(10) nitrile solution with a percentage of -f content, and titanium dioxide (TiG2) powder as a catalyst, and the titanium dioxide powder is uniformly dispersed in a ratio of 1:5 by mass ratio to polyacrylonitrile. In the solution of polypropylene guess; S52, the temperature of the oil bath is heated at the temperature of (4) and then the velocity of the pottery/minutes (4). The polytetrazide dispersed (4) guess solution 0 [0052] 099131777 wherein, in step S51, The first form in the polypropylene guess solution A0101 page 2 / total 42 page 0992055688-0 201213366 dimethyl decylamine. In step s52 'when the heating time reaches the post, the solution has turned black, indicating The poly-nitrile has reacted to form a co-light polymer, after which the heating is stopped, the dioxide drink is filtered out, and the conjugated polymer in the solution is spattered through a solvent filter. '[_请参_1G Infrared spectrum of the polymer obtained in this example

- Measurement curve. It can be seen from the curve that a characteristic absorption peak appears in the vicinity of 1589 cra-i (corresponding to the C=N tree), which confirms that the conjugated polymer has (3) or appears, which proves that after the above method is processed, 0 The polyacrylonitrile undergoes a cyclization reaction. Just refer to Figure η, it can be seen that the total polymer has absorption in the ultraviolet range of 4 〇〇 nanometer ~ 6 〇〇 〇〇 波长 wavelength range and the wavelength of 600 nm ~ 8 〇〇 nanometer wavelength characteristic. From this, it is known that there is a conjugated double bond in the co-polymer, and the degree of conjugation is large. [_Integration of the above-mentioned and the analysis of Figure U can be carried out - step (4) A soluble conjugated polymer is obtained by the production method of this embodiment.共 闺_L The co-round polymer prepared in each of the examples has a certain absorption effect on ultraviolet light or visible light. At the same time, since the conjugated carbon-carbon double bond and the carbon-nitrogen double bond are present in the co-light polymer, the co-roll polymer has good conductivity and ion transmission (4), and therefore, a sub-battery, etc. field. Moreover, since the conjugated polymer is soluble in a certain solvent, it can be easily processed into a film during practical application, thereby expanding its application range. The invention provides a method for preparing a polysulfide poly(tetra)nitrile, which comprises the following steps: 099131777 Form No. 1010101 Page 13 / Total 42 Page 0992055688-0 201213366 [0058] Ml provides a simple sulfur or sodium thiosulfate, and The elemental sulfur or sodium thiosulfate is uniformly mixed with the above-mentioned co-polymer to form a mixture; [0059] M2, the above mixture is heated to prepare a vulcanized polyacrylonitrile. [0060] In step M1, the elemental sulfur or sodium thiosulfate may be subjected to solid-solid mixing or solid-liquid mixing with the conjugated polymer. The so-called solid-liquid mixing may directly disperse the elemental sulfur or sodium thiosulfate uniformly in the first conjugated polymer solution formed by the first step and the second step, or may first pass the above steps 3 and 4. The separated pure co-polymer is dissolved in a second solvent to form a second co-polymer solution, and then the elemental sulfur or sodium thiosulfate is uniformly dispersed in the second co-polymer solution. in. Wherein, when the elemental sulfur or sodium thiosulfate is directly dispersed in the first co-bowl polymer solution formed by the first step and the second step, if the first conjugated polymer solution is insoluble in dispersion The catalyst may be first filtered out before the step M1. If the catalyst is dissolved in the first conjugated polymer solution, the catalyst does not need to be separated, and after the end of the step M2, the formed sulfide polyacrylonitrile is directly passed. The solvent filter can be filtered out. The second solvent may be the same as or different from the first solvent, and the second solvent may be dimethylformamide, dimethylacetamide, dimethyl sulfoxide or malononitrile, sulfolane or nitrate. Ethyl ester and the like. The co-polymer is mixed with elemental sulfur or sodium thiosulfate in a molar ratio of 6. When the elemental sulfur or sodium thiosulfate is uniformly dispersed in the co-polymer solution, the mass percentage of the solute is 5% to 50%, and the solute is a single substance of sulfur or sodium thiosulfate. Yoke polymer. In addition, the polyacrylonitrile solution in which the elemental sulfur or sodium thiosulfate is dispersed may be further stirred, and the stirring method may be 099131777. Form No. A0101 Page 14 / Total 42 page 0992055688-0 201213366 Mechanical stirring, magnetic stirring or ultrasonic dispersion, etc. . When the two are solid-solid mixed, the mixture may be further ball milled in order to uniformly mix the two. [0061] 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 of heating or solid-liquid mixing may be heated under an inert atmosphere which may be a nitrogen or argon atmosphere. [0062] In the method, directly reacting with sulfur or sodium thiosulfate is a cyclized copolymerized polymer formed by polyacrylonitrile, and then heated by the sulfur or sodium thiosulfate The mixture formed by the conjugated polymer not only causes the conjugated polymer to undergo a vulcanization reaction to form a vulcanized polyacrylonitrile, but further cyclizes the vulcanized polyacrylonitrile in the process, thereby greatly increasing the vulcanized polyacrylonitrile. The degree of cyclization increases the conductivity of the sulfurized polyacrylonitrile.第六 [0063] [0064] The elemental sulfur and the above-mentioned co-polymer are uniformly mixed in a ratio of 1 · 4 and 1: 6 respectively, and ball-milled for half an hour to uniformly mix; and then protected by nitrogen The mixture was heated in an oil bath at a temperature of 300 ° C for 2 hours under an atmosphere to obtain a vulcanized polyacrylonitrile. [0065] Please refer to FIG. 12, FIG. 12 is an infrared diagram of the sulfurized polyacrylonitrile and the conjugated polymer formed by uniformly mixing and heating the elemental sulfur and the conjugated polymer in the ratio of 1:4 to 1:6 in the present embodiment. Spectral measurement curve, wherein, a curve 099131777 Form No. A0101 Page 15 / Total 42 page 0992055688-0 201213366 红外 Table of the infrared spectrum of the total light polymer curve, b curve represents the elemental sulfur conjugated polymer according to 1: 4 The infrared spectrometric curve of the sulfide polyacrylonitrile formed by uniformly mixing and heating, and the c curve represents the infrared spectrum measurement curve of the sulfurized polyacrylonitrile uniformly formed by mixing and heating the elemental sulfur and the conjugated poly-σ in a ratio of 1:6. . It can be seen from the curve that the characteristic absorption peaks in the infrared spectrum measurement curve of the two fluorinated polyacrylonitriles in the vicinity of 2500 cm-i (c = N) disappeared compared with the infrared spectrum measurement curve of the conjugated poly-sigma. There is still a set of characteristic absorption peaks around 1500 cnfi (〇N4C = C). It is shown that the vulcanized polyacrylonitrile obtained by the above preparation method has been cyclized completely .... . . . . . . . .

[0067] m Refer to m3 and FIG. 14' is the sulfur element and nitrogen element of the argon-like acrylonitrile formed by self-mixing and heating in the ratio of 1:4 to the simple sulfur and the common polymer of the present embodiment. The ray can be analyzed and analyzed. It can be seen from the graph that 'the sulfur in the reduced state and the nitrogen in the sulfonated state are present in the sulfurized polyacrylonitrile, thereby indicating that the cyano group in the poly(tetra)nitrile (the diazo element in ((:)) is electron- The elemental element of sulfur loses electrons and forms a double bond of N = s. A vulcanized polyacrylonitrile can be obtained by the above method - 咏 L L1匕 polyacrylonitrile includes a structural unit, and the molecular unit of the structural unit The formula is [C3HNS]n (n = l, 2,3..·), and the structural formula of the structural unit is

(n = l, 2'3...). In addition, the structural unit may be 099131777. The main structural unit of the vulcanized polyacrylonitrile is shown in Form No. A0101. Page 16 of 42 Shai Sulfurized Polyacrylonitrile (0992055688-0 201213366) There may be other non-circularization in the subform. The structural unit. The vulcanized 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. [0069] The reaction formula of the lithium intercalation process of the vulcanized polyacrylonitrile is different at different voltages:

[0070]

as well as

Li

[0071] The above-mentioned lithium-encapsulated or non-lithium-doped fluorinated polyacrylonitrile can be directly used for a positive electrode active material of a lithium ion battery. After lithium intercalation, corresponding to the above two reaction formulas, the positive active material comprises a structural unit, and the molecular unit of the structural unit is 099131777. Form No. A0101 Page 17 / Total 42 Page 0992055688-0 201213366 Formula [CQHNSLi] (n= l, 3 η [0072 ] 2, 3...), the structural unit of the structural unit is "1"

n = l, 2, 3...); or the molecular formula of the structural unit is [CJNSLi. ] (n = l, 2, 3...), the structural unit of this structural unit is 6 ο η LL (η = 1, 2, 3 -).

[0073] In this 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 metal lithium, and the electrolyte is dissolved in a solvent having a concentration of 1 mol/L of lithium hexafluorophosphate (LiPFe) dissolved in a volume ratio of 1:1, ethylene carbonate (EC) and decyl ethyl carbonate (EMC). get. The charging capacity is measured at a rate of 0. 2C. The charging capacity is measured at a rate of 0. 2C. 1271 mAh/g (mAh/g) with a specific discharge capacity of 1 502 mAh/g. 099131777 Form No. A0101 Page 18 of 42 0992055688-0 201213366 [0075] Please refer to FIG. 16 and FIG. 17, FIG. 16 is a current of the above lithium-ion battery with 0.25 〇 [0076] mA (mA) The constant current is charged to 3.7 volts, and is charged at a constant voltage of 3.7 volts until the current is 0, and finally the constant current is discharged to 1 volt. As can be seen from Fig. 16, under this condition, the battery can only be repeatedly charged and discharged. Times. Figure 17 shows the lithium ion battery charged to 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 0, and finally a constant current discharge to 1 volt, from Figure 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. 5伏。 Therefore, the lithium ion battery charge cutoff voltage should be less than or equal to 3. 6 volts. Please refer to Figure 18 for the above-mentioned lithium-ion battery at -3〇r, -201, -10 °C, 0 °C '10 °C '25 °C, 6 (TC when discharging the specific capacity test curve 'from the figure 18 It can be seen that as the temperature decreases, the discharge specific capacity of the battery decreases, wherein at -2 (TC, the discharge specific capacity is 632 mAh / g, and at 60 ° C, its discharge specific capacity is 854 mAh / g, therefore, the lithium ion battery can operate normally in the temperature range of -20 ° C to 6 (TC). [0077] Please refer to Figure 19 'for the above clock ion battery, at 667 mA / g (mA / g ), 333 mA / g, 167 mA / g and 55. 比 mA / g current density discharge capacity test, from the figure can be seen that with the reduction of current density, the discharge specific capacity of the cesium ion battery 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. [0078] In summary, the present invention It is clear that the requirements of the invention patent have been met, and the patent application is filed according to law. However, the above description is only a preferred embodiment of the present invention, and the present invention cannot be limited thereby. The scope of the patent application is to be understood by those skilled in the art of the present invention. The equivalent modification or variation form number A0101, page 19/42, 0992055688-0 201213366, which is based on the spirit of the present invention, should be covered by the following patents. BRIEF DESCRIPTION OF THE DRAWINGS [0079] FIG. 1 is a flow chart of a method for preparing a conjugated polymer for preparing a vulcanized polyacrylonitrile according to an embodiment of the present invention. [0080] FIG. 2, FIG. 4, FIG. 10 is a graph showing infrared spectrum measurement of a common polymer obtained in the first to fifth embodiments of the present invention. [0081] FIG. 3, FIG. 5, FIG. 7, FIG. 9 and FIG. FIG. 12 is a graph showing the ultraviolet-visible absorption spectrum analysis of the common polymer obtained in the first to fifth embodiments. [0082] FIG. 12 is a sixth embodiment of the present invention, in which the elemental sulfur and the conjugated polymer are respectively according to 1: The infrared spectrometric curve of the vulcanized polyacrylonitrile and the co-polymer formed by uniformly mixing and heating the ratio of 4 to 1: 6. [0083] FIG. 13 is a sixth embodiment of the present invention, the elemental sulfur and the conjugated polymer are in accordance with 1 : 4 ratio is evenly mixed and added Figure 14 is a graph showing the X-ray energy spectrum analysis of the sulfur element in the thermally formed sulfurized polyacrylonitrile. [0084] Figure 14 is a sixth embodiment of the present invention, in which the elemental sulfur and the conjugated polymer are uniformly mixed and heated in a ratio of 1:4. The X-ray energy spectrum analysis curve of the nitrogen element in the formed sulfurized polyacrylonitrile. [0085] FIG. 15 is a sulfurized polyacrylonitrile obtained by the sixth embodiment of the present invention as a cathode material of a lithium ion battery at a 0.2 C rate. The charging and discharging curve below. 16 is a sulphurized polyacrylonitrile prepared according to a sixth embodiment of the present invention as a positive electrode material for a lithium ion battery in a voltage range of 1 volt to 3.7 volts. 099131777 Form No. A0101 Page 20 of 42 Page 0992055688-0 201213366 [0089] [0090] [0090] Electrical loop test curve β FIG. 17 is a sulfurized polyacrylonitrile prepared as a positive electrode material for a clock ion battery according to a sixth embodiment of the present invention. A charge-discharge loop test curve in the range of 3.6 volts. Fig. 18 is a graph showing the discharge curves of the obtained vulcanized polyacrylonitrile as a positive electrode material for a plasma ion battery at different temperatures according to a sixth embodiment of the present invention. Figure 19 is a graph showing the discharge curves of the obtained polyacrylonitrile obtained as a positive electrode material for a clock ion battery at different current densities according to a sixth embodiment of the present invention; ::. :::.;::..: ... ... [Main component symbol description] None: ❹

099131777 Form number Α0101 Page 21 of 42 0992055688-0

Claims (1)

201213366 VII. Patent application scope: A vulcanized polyacrylonitrile comprising a structural unit, the improvement being that the molecular formula of the structural unit is [CQHNS] ( ό η η = 1, 2, 3...), the structural unit of the structural unit is (n = 1, 2, 3...). An ion battery positive electrode material, the improvement comprising the vulcanized polyacrylonitrile as described in claim 1 of the patent application. 6V。 The charging voltage range of the vulcanized polyacrylonitrile is 0V~3. 6V. The lithium ion battery cathode material according to claim 2, wherein the vulcanized polyacrylonitrile has an operating temperature of -20 ° C to 60 ° C. A positive electrode material for an ion battery, comprising an embedded sulfurized polyacrylonitrile, wherein the lithium-incorporated sulfurized polyacrylonitrile comprises a structural unit having a molecular formula of [C^HNSLi] ( n = l,2, 3...) (n:l,2,3...) The structural unit of the structural unit is Li 6 . A lithium ion battery cathode material comprising a lithium intercalated polyacrylonitrile. The improvement is that the lithium-incorporated vulcanized polyacrylonitrile comprises a structural unit 099131777, Form No. A0101, and the molecular formula of the structural unit is [CQHNSLiQ] (n = l, 2, 3...) ο ο Π , the structural unit of this structural unit is ϋ (η = 1, 2, 3···) 099131777 Form number A0101 Μ Page 23 of 42 0992055688-0