TW200945651A - Method for preparing a negative electrode material for lithium ion batteries and the products thereof - Google Patents

Abstract

A method for preparing a negative electrode material for lithium ion batteries comprises the following steps: preparing a modifying solution containing a carbonaceous material; treating the modifying solution with a mixing treatment to obtain a modified carbonaceous material; and subsequently drying the solution in a non-oxidizing atmosphere to obtain the negative electrode material; wherein the modifying solution contains a first component or a second component, and a polar solvent, and the first component comprises Sn(BF4)2, HBF4, and (NH2)2CS, and the second component comprises SnCl2, K3C6H5O7, and at least one alkali selected from the group consisting of KOH, LiOH, and NaOH. The negative electrode material can be produced fast, safely, and easily. The present invention also discloses a negative electrode material for lithium ion batteries comprising an attachment having an atom number ratio of sulfur to stannum from 0.8 to 12.

Description

200945651 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a method for preparing a battery material, and more particularly to a method for preparing a negative electrode material for a lithium ion battery. The invention also relates to the product of the preparation process. [Prior Art] Lithium ion battery has been widely used in communication and electronic equipment because of its small size and high storage capacity and high discharge capacity for a long time. "Carbonous material" (carbon substrate) has become the mainstream material of the anode material of lithium ion battery based on its safety and cost considerations; and various lithium ion battery anode materials using carbon substrate as raw material, and related preparation methods It has also been gradually developed. Paper Jowma/〇/Power Sowrces, 102 (2001) 60-67. The technique disclosed is a hydrothermal hydrogen-reduction method; it is mixed with a carbon substrate at 150 ° C. Sulfuric acid. Ammonium nickel [Ni(NH4)nS04] aqueous solution is passed through high-pressure hydrogen) to prepare a lithium ion tantalum battery anode material comprising the carbon substrate and the nickel metal modified thereon; however, the method is at a high temperature The use of high pressure hydrogen is dangerous to operate. Paper Electrochemistry Communications, 5 (2003) 65. The technique disclosed is to add Mesocarbon Microbeads (MCMB) to an aqueous solution in which SnCh, NiCl2, and sodium citrate are dissolved, and then apply ultrasonic vibration. After the next hour, NaBH4 was slowly added to the solution while stirring the solution to deposit the tin-nickel alloy on the surface of the MCMB, and finally filtered, filtered, and dried for 5 hours to complete the 200945651 process. The entire preparation process; from the above, this method has the disadvantages of complicated operation procedures (especially NaBH4 is poor in stability, easy to react with air), and long operation time. 〇... Paper 41 (2〇〇3) 959. Yes to contain

The suspension water of SnCh, SbCh, and carb〇n nanotube is added to kbh4 as a metal reducing agent in a small amount of multiple additions, and then obtained by filtration, washing and drying. A negative electrode material for a lithium ion battery, comprising the carbon nanotube and the tin metal and the ruthenium ruthenium modified thereon; wherein the KBH4 is added in a small amount, the method is troublesome in the operation step. The two methods described above are suitable for, for example, a small amount of preparation in a laboratory, which is not conducive to mass production processes in the industry. The preparation method proposed in the paper Jcia, 50 (2004) 517. is 55. °C is the operating temperature, and the MCMB is suspended in a modification liquid containing 'SnCl2, Na0H, Na3C6H5〇7, NaH2P〇2, and then filtered, washed and dried to obtain a lithium ion battery anode material® It contains MCMB and a tin-phosphor compound modified on its surface; this method uses up to four kinds of chemical materials, and the battery produced by the anode material of the clock ion battery has a short life and no capacity. High, not conducive to use. SUMMARY OF THE INVENTION One object of the present invention is to provide a high-safety, simple operation, and a small variety of materials to be used, which is advantageous for the low-cost planning and laying of production lines in the industry, thereby mass-making a lithium ion battery anode material. Preparation method 6 200945651 The preparation method of the anode material of the lithium ion battery of the present invention comprises: preparing - : * substrate "* liquid, which is subjected to - mixing treatment to thereby form the carbon substrate of (4), Then, it is placed in a non-oxidizing gas atmosphere to obtain a negative electrode material of the ion battery, wherein the modification liquid contains a polar solvent and a first group or a group of & The first component is tin stannous I borate, citric acid and thiourea'. The second component has vaporized stannous, potassium citrate and at least ❹ A underneath - assay: hydrazine, hydrogen and oxygen And the sodium hydroxide hydroxide. The above-mentioned dried "modified carbon substrate" can be used to prepare the (tetra) ion battery for normal operation, and thus can be used as a negative electrode material for a clock ion battery. The preparation method of the invention does not need to use a large amount of hydrogen, so there is no safety concern; in addition, when it is carried out, the kind of materials that must be used is small, and the modification of the carbon substrate is also carried out in the stage of the mixing treatment. #液中再'Additional materials, but most of the previous cases require a small amount and continuous addition of human NaBH4, KBH4'. The method of the present invention is safer and more convenient to operate. Further, in terms of composition, the negative electrode material of the lithium ion battery of the present invention comprises a carbon substrate 'and a bonding material attached to the surface of the carbon substrate. In the repeated test of the applicant's multiple times, it was found that when the preparation method of the present invention is carried out by using a modification liquid containing the first component, the adhesion material is analyzed by an Energy Dispersive Spectrometer (EDS). The ratio of the number of atoms of S to Sn is close to 1, and this result is also unseen in the skill 7 200945651; the applicant speculates that the attachment (four) is SnS. Negative Electrode 2 'The other object of the present invention is to provide - (iv) ion battery t - carbon substrate, and - attachment material attached to the surface of the carbon substrate, and the number of sulfur and kick atoms in the attachment material The ratio is between the ancient: 1.2; and the novel clock ion battery negative electrode material can be produced by the above preparation method containing the first component. [Embodiment] The basic operational requirements of the method for preparing the negative electrode material of the sub-battery of the present invention are as set forth above, and preferred and preferred embodiments of the respective operational requirements are as follows. There is basically no limit to the amount of each material used in the method of the invention. The relevant description of the amount of each material is calculated on the basis of the modification liquid per liter. As far as the carbon substrate is concerned, as long as it is incorporated, the higher the amount of the change, the larger the total surface area, and naturally the relative surface area is formed to be less. Preferably, the amount incorporated is between 0.1 g and 600 g ©, more preferably between 0.1 g and 450 g. 3, the type of the carbon substrate is not limited, but it is recommended to use a large surface area, such as a powder, in order to facilitate attachment of the attachment material to the surface of the carbon substrate ◎ preferably the carbon substrate is selected from graphite Mesophase graphite p〇wder (MGp), MCMB, carb〇n capsuie, artificial graphite, natural graphite, carbon nanotubes, hard hydrazine Hard carbon) 'or a combination of them. As shown in the following examples, the amount of the carbon substrate pushed in per liter of the modification liquid is from 250 g to 416 200945651 v g, and the selected type is powdered natural graphite (referred to as "NG toner" for short). Ο 3 It should be noted that the method of the present invention may also use a carbon substrate which is already present on the surface thereof, such as those exemplified in the following embodiments, and such an implementation is similar to that of a surface thereof. i A carbon substrate without any adhering matter is modified in stages by repeated operations of the method of the present invention. Applicants speculate that the carbon substrate which can be finally obtained when further controlling the components of the modifying liquid used each time On the surface, there are a plurality of types of attachment materials #', and the applicant has also confirmed by the following examples that such a product of the method of the present invention can make the subsequently produced battery operate normally, and can be used as a negative electrode material for lithium ion batteries. The method for carrying out the method of the present invention may correspondingly select the use of the modifying liquid containing the first component or the second component, and the polar solvent used is in principle only The first component, or each of the materials in the second component, can be dissolved. Therefore, the polar solvent can be water, an alcohol, an aldehyde, a ketone, or a combination thereof. Ground, the alcohols are methanol (methan〇i), ® ethanol (ethano1), propanol (Propanol), butanol (butanol), pentanol (pentanol), isopropanol (isopropanol); ketones are acetone (acet〇) Ne), methyl ethyl ketone, N-methyl-2-pyrrolidcme (NMP; CsI^NO); aldehydes are butyraldehyde. As exemplified in the examples, the polar solvent is water. The upper limit of the amount of each material in the first component or the second component is to be saturated with the concentration of the modified solution, and the modification liquid is dissolved in the first group. The content of each material is considered to be the content of each material, and the stannous fluoroborate is preferably dissolved. 〇1 9 200945651 Moer ~ 2 Moule, more preferably μ (4) 7 2 Acid is preferably dissolved in bismuth, 〇1莫耳蝶,斗2莫耳' is better to dissolve 0.1 moles 1 mole; sulfur glands are better from dissolved GG1 moles ~5 moles more preferably 疋♦ have 0.5 moles~ 4 Mo As exemplified in the following examples, the modification liquid containing the first component is dissolved in stannous fluoroborate with 〇15 moles to 0.75 moles, 〇21 moles to 〇273 Mohr's fluoroboric acid, and h39 mol ~ 2.78 mol of thiourea. Another test case is the dissolution of the second component

The content of each material 'gasified stannous is preferably dissolved in Q. (8) 5 moles to 3 moles, more preferably 'four (5) 5 moles to 2 moles; the test is preferably dissolved in G .GG5 Moule ~ 8 Moule, more preferably dissolved in G.5 Moer ~ 2 5 Moule; Molybdenum acid is preferably dissolved (4) 5 Molar ~ 3 Mo, more preferably dissolved (d) Moer ~ i Moer potassium citrate. As exemplified in the following examples, the liquid containing the second component is dissolved in a solution containing 5 moles to (four) moles of stannous chloride, 〇·9 moles to 195 moles (K〇 H or LiOH), as well as 〇.1 摩尔~ 〇·2 molar potassium citrate. The mixing treatment can be performed by means of scrambling, ultrasonic vibration, etc., for the purpose of causing the carbon substrate and the materials of the modified liquid towel to contact each other as much as possible to promote the formation of the adhesive material on the surface of the carbon substrate. . The operation technique of increasing the temperature of the mixing treatment, introducing a current into the modification liquid during the mixing treatment, etc., is advantageous for the purpose. Preferably, the mixing treatment is carried out at a temperature ranging from 60 ° C to boiling. For the convenience of operation, it is more preferably carried out in a temperature range of 60 ° C to 100 t. As exemplified in the following examples, the mixing treatment is carried out in a temperature range of 7 (rc to 95 t. 10 200945651 It is found in practice that if only the length of the mixing process is only _ the cause is longer ( The surface of the carbon substrate can be modified with more adhesive materials), and the subsequent battery does not necessarily have a stronger effect or a longer service life. Therefore, the preferred execution time of the mixing process is based on the case. As exemplified in the following examples, the mixing treatment time varies from 3 sec to 3 hr. After the modified carbon substrate formed by the mixing treatment is taken out from the modification liquid, the drying treatment is performed. However, it is dried; the temperature and pressure of the drying treatment are not substantially limited, but it is preferably as long as the modified carbon substrate can be dried, and the drying treatment is carried out at a temperature range of 20. 〇 150 ° C The pressure is not higher than 1 〇·2 。. The non-oxidizing gas atmosphere used in the drying treatment is to prevent the modified carbon substrate from being oxidized during the drying process, which affects subsequent production. Lithium The efficiency or service life of the sub-battery, so the non-oxidizing gas atmosphere - basically as long as it does not contain any gas having oxidizing ability (for example, oxygen), preferably, the non-oxidizing gas atmosphere is nitrogen, indirect gas, carbon dioxide © Or a combination of the above. On the other hand, the non-oxidizing gas atmosphere may further contain a small amount of hydrogen as a reducing agent, and the safety is considered to be less than 5 v〇l%. In the following examples, the crucible is dried in a nitrogen atmosphere of 90 C, 10 2 Torr. The lithium ion battery anode material obtained by the method of the present invention comprises a carbon substrate and a surface attached to the carbon substrate. The attached material is in the form of particles which are discontinuous and non-woven; the size of the attached material is preferably between 3 nm and 200 nm, and more preferably between 3 nm and 1 nm. Between 11 and 200945651 ♦ exemplified in the following examples, the size of the adhesive material is between nm and 100 nm. In addition, the present invention is carried out with a modifying liquid containing only the first component. Method, this The ratio of the atomic number of sulfur to tin in the material is substantially between 〇.8 and 1.2, and is exemplified in the following examples, between 0.8667 and 1.0588. The following will be the embodiment/application example. The embodiments and the effects of the various objects of the present invention are explained. The chemicals and equipment used in the embodiments/application examples are as follows. It should be noted that the embodiments/applications are for illustrative purposes only. It should not be construed as limiting the implementation of the invention. Unless otherwise specified, temperature, pressure, application or application of the examples/applications, and subsequent tests and evaluations are in a normal temperature and atmospheric environment. Go on.

[Example I <Chemicals> - L NG Toner: supplied by Taiwan Sinosteel Carbon Chemical Company. 2. Stannous fluoroborate [Sn(BF4)2]: Made by Belgian Α_ Company, the purity is 50%. 3. Fluoroboric acid (HBF4): Made by Spanish company Panreac with a purity of 35%. 4. Thiourea [(NHzhCS]. Made by WWako, purity 99% ° 5. SnCh · 2H2 〇. Made by Spanish company Panreac, purity 98% ° - 6. KOH: manufactured by Panreac, Spain Purity is 99%. 12 200945651 贽7. Ll〇H ··Made by Taiwan Merck, purity 98% 8. Potassium citrate (Κ3〇:6Η5〇7·η20): Made by Spanish panreac company, purity is 99.5%. <Examples 1 to 5 > Dissolving thiourea, fluoroboric acid, stannous fluoroborate (the above two materials of "first component") in the same order with secondary deionized water as a solvent To prepare a volume of 600 ml of the modification liquid; then, the temperature is raised to 8 〇 to 95 〇c and 25 gram of NG toner is added, and a mixing treatment is performed by stirring with a magnet, thereby using NG toner It can be modified. The modified NG toner (which contains an attached matter attached to the surface of the original NG toner) is filtered out and washed with a small amount of secondary deionized water several times. Move into an oven with a nitrogen atmosphere and a pressure of 1〇_2 Torr, and dry at 9CTC. After the treatment, the dried modified NG toner is taken out after 8 minutes. The operating conditions of the examples 1 to 5 are as shown in Table 1; the amount of each material in the first group _ is meaning " The number of moles per liter of the modification solution is expressed in terms of molar concentration (M). Table 1 Example - Mixing of the first component __Sn(BF4)2 hbf4 ^thiourea temperature time 1 0-611M 0.273M 1.39M 80°C 30 seconds 2 0.375M 0.21M 1.39M 95 °C 30 seconds 3 0.375M 0.21M 1.39M 95 °C 30 minutes 4 0.75M 0.42M 2.78M 95 °C 30 seconds 5 0.75 M 0.42M 2.78 M 95 ° C 30 minutes 13 200945651 SEM analysis of the products of Examples 1 to 5 using a scanning electron microscope/energy dispersive spectrometer manufactured by FEI Corporation, model number Quanta 400 F Hereinafter, the surface of the products of Example 1 to 5 (dried modified NG toner) was observed at a specific magnification. The SEM of the surface of the NG toner (Comparative Example) without any treatment was observed. The analysis results are shown in Fig. 1, and at the same magnification, Example 1 The surface morphology of the dried NG toner obtained by 0 is shown in Fig. 2. The difference between the two figures clearly confirms that the embodiment 1 contains, in addition to the NG toner as in Fig. 1, a substance attached to the surface thereof (hereinafter referred to as "attachment"). Upon magnification observation, it is known that the size range of the attachment is between 1 〇 nm and 100 nm, and most of the attachments have a size ranging from 1 〜 nm to 40 nm. Further, as shown in Fig. 3, the surface of the dried NG toner obtained in Example 2 was observed by a transmission electron micrograph (hereinafter referred to as FTEM), and the size of the attached matter was observed. There are as small as 2 nm. The EDS analysis of the products of Examples 1 to 5 was further carried out by using the EDS function in the above SEM/EDS apparatus to conduct EDS analysis on the attachments of Examples 1 to 5, so as to know the elements and the elements contained therein. The proportion of the operation; the operating parameters are as follows: the scanning surface area is 3.5 μ m X 3.5 /X m, and the electron beam intensity is 25 KeV. 14 200945651 Beta, screaming, there are no carbon, oxygen, sulfur, tin four elements detected, where the atomic ratio of s 冉T b to Sn is 44: 48, examples 2~5 The attached EDS splitting ply 4 is also very similar to the one in the first example. 'The above four elements are also tested and tested. The only difference is that the atomic number ratio of each element is slightly different, so s盥c α The atomic numbers of J彳-S and Sn are still extremely the same.

The proportion of the number of EDS sub-assemblies of Examples 1 to 5 is compiled in Table 2 below.

As can be seen from Table 2, the number of atoms of S and Sn in the adhering materials is almost equal, and it is presumed that the adhering materials may be SnS. <Application Examples 1 to 5 >

J 5 dry modified NO carbon powder, with a conductive material (carbon black; manufactured by MMM Carbon (Belgium), model super-s), a binder (PVDF; manufactured by s〇lef company 6020, molecular weight is about 3〇4 〇〇〇), and oxalic acid (made by the company 'purity is 99.0%) by weight ratio 9〇: 3 ·· 6 9 : 〇丨 ratio is doped into a solid composition' and then taken 51 wt% of the composition of the composition [NMP 15 200945651 %; manufactured by Aldrich, purity 99 5%] was uniformly mixed with the solid composition to form a paste; the paste was applied to a paste The negative electrode tab was formed by a sheet-like current collector (copper foil; manufactured by Nippon Foil, thickness 15 μm), dried, and then pressed and cut. Thereafter, a battery component and an electrolyte as described later are separately prepared for each of the negative electrode tabs, and a glove box having a water oxygen content of 10 ppm or less and provided with a battery capping machine [Haoju Industrial Co., Ltd.] is provided. Unilab Mbraum, model Ργο』·4189] is assembled internally, and the battery capping machine is used to cover (to ensure its sealing), and a coin-type lithium ion battery to be tested is obtained respectively (ie Application example 匀~ uniform; Comparative example (using unmodified NG breaking powder as clock electronic negative electrode material) is to produce a lithium ion secondary battery in the same manner. The relevant information of the battery component and electrolyte is as follows - <Electrolyte> 1. Electrolyte: LiPF6' is manufactured by Ferro Company with a purity of 99%. 2_Solvent: equal weight of ethylene carbonate and dinonyl carbonate, all manufactured by Merck, Germany, with a purity of 99 <Battery Parts> 1·Upper cover and lower cover: manufactured by Taiwan Haoju Industrial Co., Ltd., model number is 2032. 2. Spring 塾片, 不钱钢圆片: Taiwan Haoju Industrial Co., Ltd. Manufacturing 3. Separator: manufactured by Celgard, model celgard 2300. 4. Positive electrode: Lithium foil, manufactured by FMC, is a purity of 99.9%, straight 16 200945651 diameter 1.65 cm. <Efficacy test> [Charge/Discharge Test] With a charge and discharge tester (manufactured by Taiwan Jiayou Technology Co., Ltd., model BAT-700S), with a current of 0.326 mAcm-2 (about 〇lc), application examples 1 to 5 and comparative examples Each battery is charged at a constant current until the voltage of the battery circuit reaches 0.01 V, and the first charge capacity value of the battery is obtained; after 10 minutes, the current is performed at a current of 0·326 mAcmd. The constant current is discharged until the circuit voltage reaches 2·0 V, and the first discharge capacity value thereof is obtained, and then the above charging and discharging steps are repeated a plurality of times, and the discharge electric power measured at each discharge is synchronously synchronized. The capacity value 'finished as shown in FIG. 5' can also be used to understand the development trend of the capacitance of each battery in the case of repeated charging/discharging; and the application examples corresponding to the respective symbols in FIG. / comparison The following Table 3 - in: Table 3 represents the application example Comparative Example 1 2 3 4 5 Mark ▲ △ □ • 〇 Figure 5 shows the dried modified NG obtained by Examples 1 to 5 The lithium ion battery (i.e., application examples ～5) prepared by the carbon powder can be operated normally. Thus, it is proved that the products prepared in the examples 1 to 5 can be used as the negative electrode material of the lithium ion battery; further, only after 1 〇 After the repeated charge and discharge, the capacitances of the application examples 1 to 5 are obviously higher than those of the comparative example, and the more the number of charge and discharge times of 17 200945651 times, the difference between the capacitances of the comparative example and the application example 丨 5 The larger, the comparison, it is obvious that the service life of the application example 丨5 is much longer than that of the comparative example, and it can also be proved that the examples 丨~5 can actually produce a lithium ion battery anode material with good quality. Referring to Table 1, in the embodiment 丨~5, after the preparation of the modification liquid, it is only necessary to carry out the mixing treatment for 30 minutes or even 30 seconds, and it is obvious that the preparation method of the example 〖~5 has an advantage in time cost, and is advantageous. A large number of lithium ion battery anode materials are manufactured in the industry. ❹ <Examples 6 to 1 〇> Dissolve hydrazine, potassium citrate, and stannous vaporized gas (the above two materials of "second component") in the same order with secondary deionized water as a solvent. A modification liquid was prepared; after that, the temperature was raised to 75 to 8 (TC and added with NG, and a mixing treatment was carried out by stirring with a magnet for 15 hours to 3 hours, whereby the NG toner was modified. • After filtering the modified NG toner, wash the crucible with a small amount of secondary deionized water several times until the water after washing is instilled with Ag(NO). Then, the modified NG toner is transferred into a 1-gas atmosphere, the pressure value is controlled to be 10-2 Torr in the water tank, and the (4) treatment is performed under _, and the dried modified NG toner is taken out after 180 minutes. The operating conditions of Examples 6 to 10 are shown in Table 4; the amount of each material in the second component is "the number of moles dissolved per liter of the solution and directly in the molars." The concentration (M) is expressed. 18 200945651 Table 4 Example NG toner second component modification liquid mixed treatment SnCl2 KOH rod-like acid _ Volume temperature time 6 70 g 0.089M 0.9M 0.1M 300 ml 80°C 3hr 7 250 g 0.089M 0.9M 0.1M 600 ml 75 °C 1.5hr 8 250 g 0.089M 0.9M 0.1M 600 ml 75 °C 3hr 9 250 g 0.18M 1.8M 0.2M 600 ml 75 °C 1.5hr 10 250 g 0.18M 1.8M 0.2 M 600 ml 75 °C 3hr SEM analysis of the product of the 6~10 product 舆EDS tiller

干燥 The dried modified NG toner obtained in Examples 6 to 10 was subjected to SEM analysis in the manner described above. The surface profile of Example 6 is shown in Fig. 6; it is apparent that the NG toner does have some deposits on its surface due to the operation of Example 6. The results of the SEM analysis of the products of Examples 7 to 10 were also the same. The EDS analysis results of the deposits of the products of Example 6 were as shown in Fig. 7; the results of EDS analysis similar to the products of Examples 1 to 5, Example 7 The attachments were also analyzed for carbon, oxygen, sulfur and tin. According to the results of EDS analysis, together with the various materials used in Example 6, the applicant speculated that the deposits should be oxidized. Stannous (Sn〇) and tin. The EDS analysis results of Examples 7 to 10 are also very similar to those of Example 6, and will not be repeated. &lt;Application Examples 6 to 10&gt; Using the dried modified carbon powder obtained in Example 6 10, respectively, the application example 1 (4) was used, and each of the coin-type clock ion batteries produced by the test was produced (i.e., application example 6). ~1〇); Also, Yun, also / } ^ The charge/discharge test accepted in Application Example 1 was also performed. 19 200945651 Application Example 6~1 The values of the discharge capacity measured at each discharge in this test are as shown in Fig. 8. It can also be seen that in the case of repeated charge/discharge of each battery, The development trend of the capacitance; and the corresponding examples/comparative examples corresponding to the symbols in Fig. 8 are illustrated in the following Table 5: Table 5 represents the application 1 (column comparison example 6 7 8 9 10 mark □ ▲ Δ • The results of FIG. 8 confirmed that the lithium ion batteries (ie, Application Examples 6 to 10) prepared by the modified NG toners obtained in Examples 6 to 10 were sure to operate normally, thus demonstrating the examples. The products prepared in 6 to 10 can be used as the negative electrode material of the lithium ion battery; in addition, under the multiple charge and discharge tests, the capacitance performance of the application examples 6 to 10 is almost superior to the comparative example, and thus the example 6 is confirmed. The method of ～10 can indeed produce a negative electrode material of lithium ion battery with good quality. <Examples 11 to 19 &gt; Examples 11 to 19 are similar to those described in Examples 6 to 1 ,, but The carbon substrate used is connected in advance The NG toner thus treated was previously treated (this pretreatment was similar to the procedure described in Examples 1 to 5, but was not subjected to drying treatment), and thus the surface of the NG toner was applied before Examples 11 to 19 were carried out. That is, there is already an attachment. The pretreatment uses 75 g of NG toner, and the pretreatment and the operating conditions of Examples 11 to 19 are as shown in Table 6. The volume is 300 ml; and the amount of each material of the first component and the second component of 20 200945651 means "the number of moles per liter of the modification liquid", and directly to the molar concentration (M) Table 6 NG toner pre-treatment example Operation example First component mixing treatment Second component mixing treatment Sn(BF4)2 hbf4 Thiourea temperature_Time SnCl2 Alkali agent potassium citrate temperature time 11 0.611M 0.273M 1.39M 80°C 30 seconds 0.089M KOH/0.9M 0.1M 80°C 3hr 12 0.15M 0.273M 2.0M 80°C 30 seconds 0.075M LiOH/0.9M 0.1M 70 °C lhr 13 0.15M 0.273M 2*0M 80°C 3 0 seconds 0.15M KOH/0.9M 0.2M 80°C 3hr 14 0.15M 0.273M 2.0M 80°C 2min 0.075M LiOH/0 .975M 0.1M 80°C 3hr 15 0.15M 0.273M 2.0M 80°C 2min 0.15M KOH/1.95M 0.2M 70°C lhr 16 0.611M 0.273M 1.39M 80. . 30 seconds 0.15M LiOH/1.95M 0.2M 80 °C lhr 17 0.611M 0.273M 1.39M 80°C 30 seconds 0.075M KOH/0.975M 0.1M 70 °C 3hr 18 0.611M 0.273M 1.39M 80°C 2min 0.15 M Li〇H/0.9M 0.2M 70°C 3hr 19 0.611M 0.273M 1.39M 80° C. 2min ] 0.075M KOH/0.9M 0.1M 80° C. lhr &lt;Application Examples 11 to 19&gt; From Example 11~ The dried modified NG toner obtained in 19 was separately subjected to the operation mode of Application Example 1, and each of the coin-type lithium ion batteries to be tested (ie, Application Examples 11 to 19) was produced; Example i 充 Accepted charge/discharge test. The discharge capacity values measured in each of the discharges of the application examples 11 to 19 in the test are as shown in FIG. 9, and it is also understood that the respective batteries are in the case of repeated charge/discharge. Development trend; and the examples/comparative examples corresponding to the representative symbols in Fig. 9 are illustrated in the following Table 7: 21 200945651 Table 7

The results of Fig. 9 confirmed that the lithium ion batteries (i.e., application examples u to l9) obtained by the modified carbon substrates obtained in Examples u to 19 were sure to operate normally' thus demonstrating Examples u to 19 The product produced by the household can be used as a negative electrode material for the ion battery. In addition, under the multiple charge and discharge tests, the capacitance performance of the application example u 19 is almost superior to that of the comparative example, especially in the case where the number of charge and discharge times exceeds 35 times, the capacitance of the application examples and the comparative examples. The difference was more pronounced 'it is clear that the service life of the application examples u to 19 is longer than that of the comparative example; thus, it was confirmed that the methods of the examples U to 19 can actually produce a negative electrode material of a lithium ion battery having good quality. ❹ Combining the results of the above examples and application examples, it is apparent that the method of the present invention can pass the mixing treatment and drying treatment only by the modification liquid containing the first component or the second component without additional addition. (especially in a small amount and continuously) under other materials, it is possible to safely prepare a lithium ion battery anode material; further, when the modification liquid contains the first component, only a short 3G is required. The mixing process of the second can produce the (four) ion battery anode material, so the method of the invention is indeed very suitable for the industry, in order to manufacture the lithium ion battery anode material in a large amount and quickly, the production line can also be dry and dry. Pay attention to safety and management convenience. However, the above is only the preferred embodiment of the present invention, and the scope of the invention is not limited thereto, that is, the simple equivalent change and modification of the patent scope and the description of the invention according to the invention. , are still 22 200945651

V is within the scope of the invention patent. [Simple description of the diagram] ® 1 is -SEM ®, indicating the shape of the surface of an untreated NG toner at a magnification of 40,000 times; Figure 2 is a SEMS, illustrated by the embodiment! The obtained battery negative electrode material has a shape exhibited by the surface at a magnification of 40,000 times; and FIG. 3 is - TEM ® , indicating that the surface of the negative electrode material of the clock battery obtained in Example 2 is presented under magnification The type of the product is the EDS analysis result of the adhesive material on the anode material of the battery of the example i; the weight percentage of the four elements c, 〇, s, and Sn is 91.09%, respectively. 3.36%, 1.11%, 4.45%, the percentage of atomic percentage is 96.42%, 26.7%, 〇44%, 〇48%; Figure 5疋 Cycle life diagram, showing application examples 1 to 5 and comparative examples Charge/discharge test result; 'Figure 6 is an SEM image showing the shape of the surface of the lithium battery anode material obtained by the Example 在 at a magnification of 80,000 times; ® Figure 7 Figure ' is the EDS analysis result of the adhesive material on the negative electrode material of the battery of Example 6; the weight percentages of the three elements of C, 〇 and Sn are 52.09% '26.31% and 21.60%, respectively, and the percentage of atomic percentage respectively 70.37%, 26.68%, 2.95%; Figure 8 is a cycle life diagram, indicating that Example Comparative Example 6~10 of the charge / discharge test results; FIG. 9 is - FIG cycle life, charge-described Comparative Examples 11~19 and Example of Application / discharge test results. 23 200945651

V [Main component symbol description] None

twenty four

Claims (1)

200945651 X. Patent application scope: 1. A method for preparing a lithium ion battery anode material comprises: preparing a modification liquid mixed with a carbon substrate, and subjecting the mixture to a mixture treatment to thereby form a modified carbon substrate a carbon substrate, which is then subjected to a drying treatment in a non-oxidizing gas atmosphere to obtain the lithium ion battery anode material; wherein the modifying liquid contains a polar solvent and a first component or - The second component 'the first component has stannous fluoroborate, _acid' and the second component has vaporized stannous, lemon® (four)' and at least the following: test agent: potassium hydroxide, hydrogen peroxide With sodium hydroxide. 2. The preparation method according to the invention of claim 2, wherein the carbon substrate is incorporated in an amount of between gram and 6 gram per liter of the modifying liquid. 3. The preparation method according to claim 2, wherein the carbon substrate is incorporated in an amount of from gram to 450 g per liter of the modifying liquid. ❹ 4. The preparation method according to claim 1, wherein the carbon substrate is selected from graphitized mesophase green powder, mesocarbon carbon sphere, spherical carbon material, artificial graphite, natural graphite, A combination of carbon nanotubes, hard carbon, or the like. 5. The preparation method according to claim 1, wherein the modifying liquid contains the first component. 6. The preparation method according to the fifth aspect of the invention, wherein the modification liquid is stannous fluoroacetate dissolved in 2009·01 mol to 2 mol per liter of the modification liquid. 7. The preparation method according to claim 6, wherein the modification liquid is stannous fluoroborate dissolved in 0.075 mol to 1.25 mol per liter of the modifying liquid. 8. The preparation method according to claim 5, wherein the modification liquid is dissolved in 0.01 mol to 2 mol% of fluoroboric acid per liter of the modifying liquid. The preparation method according to the invention of claim 8, wherein the modification liquid is I boric acid dissolved in 0.1 mol to 1 mol per liter of the modification liquid. The preparation method according to claim 5, wherein the modification liquid is a sulfur vein dissolved in 〇〇1 mol to 5 mol per liter of the modification liquid. 11. The preparation method according to claim 10, wherein the modification liquid is thiourea dissolved in 0 5 mol to 4 mol per liter of the modification liquid. The preparation method according to the invention of claim 1, wherein the modifying liquid contains the second component. The preparation method according to the cap patent of claim 12, wherein the modification liquid is dissolved in 0.005 mol to 3 mol of stannous chloride per liter of the modifying liquid. The preparation method according to claim 13, wherein the senna solution is dissolved in 0.05 mol to 2 mol of stannous chloride per liter of the modifying liquid. 26 200945651 15. According to the modification liquid of the patent application range, the alkali preparation method according to the item 12, wherein each of the modification liquids is dissolved in 〇〇mol 8-8 m. According to the preparation liquid of the preparation liter of the above-mentioned patent scope, the modification liquid is dissolved in the 'in' of each test. The preparation method according to the invention of claim 12, wherein the modification liquid is dissolved in 莫5 moles per mole of the modification liquid per liter. Potassium citrate. The preparation method according to claim 17, wherein the modification liquid is potassium citrate dissolved in 〇 杲 〜 〜 1 1 1 每 每 每 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The preparation method according to claim 1, wherein the polar solvent is selected from the group consisting of water, alcohols, aldehydes, anthraquinones, or the like. The preparation method according to claim 1, wherein the mixing treatment is carried out at a temperature ranging from 60 ° C to boiling. 21. The preparation method according to claim 20, wherein the mixing treatment is at 60 ° C to 90 °. The method according to the first aspect of the invention, wherein the non-oxidizing gas atmosphere is nitrogen, indirect gas, carbon dioxide, or a combination thereof. The preparation method according to the above aspect, wherein the non-oxidizing gas atmosphere further contains 5 vol% or less of hydrogen. 27 200945651 24. The preparation method according to the invention, wherein The drying treatment is carried out at a pressure value not higher than 10·2. 25. The preparation method according to the scope of the patent application, wherein the drying treatment is at 2 〇. (: 〜15 〇. The temperature range is: X dry 26. A lithium ion battery anode material, comprising a carbon _* ', attached to the surface of the carbon substrate, the attachment material is a discontinuous distribution of particles, And the ratio of the atomic quantity of sulfur to tin is between ~. 〜1·2 ❹ The anode material of the cesium ion battery according to claim 26 of the patent scope, wherein the atom of sulfur and tin in the additive material The quantity ratio is 〇~1.0588. 67 28· According to the scope of patent application No. 26, the size of the attached material is in the range of the size of the attached material. a material, wherein the size of the adhesive material is in the range of 3 nm to 1 〇〇 n 〇 ", the negative electrode material of the series of batteries described in the scope of the patent scope", and the preparation method as described in claim 5 And made. 28