WO2015010437A1 - A nano silicon/graphene lithium ion battery cathode material and preparation method thereof - Google Patents
A nano silicon/graphene lithium ion battery cathode material and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 101
- 239000005543 nano-size silicon particle Substances 0.000 title claims abstract description 73
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000010406 cathode material Substances 0.000 title abstract 4
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- 238000000034 method Methods 0.000 claims abstract description 21
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims abstract description 13
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- 229910052744 lithium Inorganic materials 0.000 claims description 18
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 16
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- 229910052684 Cerium Inorganic materials 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the invention belongs to the field of electrochemical and new energy materials, and particularly relates to a nano silicon/graphene lithium ion battery anode material and a preparation method thereof.
- lithium ion batteries Since the first launch of commercial lithium-ion battery products by SONY Corporation in Japan in 1991, lithium ion batteries have been developed for more than 20 years. Lithium-ion batteries have a unique charge/discharge mechanism for inserting/extracting lithium ions. Therefore, compared with similar battery products, it has the advantages of large specific capacity, high operating voltage, high safety, and low environmental pollution. The development of a negative electrode material for a lithium ion battery lithium storage body has become a key point for improving the total specific capacity, charge and discharge, and cycle performance of a lithium ion battery.
- lithium-ion batteries were mainly made of lithium alloys.
- the main problem was poor cycle performance and large irreversible capacity for the first time.
- the fundamental reason is that the anode material has a crystal structure recombination during charge and discharge, resulting in a large volume expansion; in addition, there is also a phase-to-volume change that causes loss of lithium intercalation. Therefore, in the commercial battery after industrialization, the alloy material having a high theoretical specific capacity is discarded, and the graphite-based carbon material which forms a layer compound with lithium ions is used instead. Since the graphite-based carbon material can accommodate lithium ions through its graphite gap, the problem of volume expansion is solved.
- Such graphite-based carbon materials with excellent electrochemical properties have become the most common anode materials in commercial lithium-ion batteries.
- silicon-based anode materials in non-carbon anode materials is more advantageous. It has the highest theoretical capacity ratio (forming Li4.4Si, theoretical capacity up to 4200 mAh/g) and relatively low lithium insertion potential. It has better stability and safety than other metal materials, and the source of raw materials is also richer. Therefore, research on silicon-based anode materials has been ongoing. However, it also has a volume effect during charge and discharge (volume expansion rate > 300%), which leads to structural collapse, gradual pulverization, loss of electrical contact between active materials and current collectors, and electrical conductivity during charge and discharge. The loss eventually leads to a loss of reversible capacity.
- the theoretical capacity ratio can reach 744 mAh/g, and the reported graphene anode material can have a first discharge capacity of 650 mAh/g, after 100 cycles. Its capacity remains at 460 mAh/g. Therefore, although the theoretical capacity of graphene is weaker than some metal and silicon-based materials, if it can be combined with the high capacity of silicon-based materials, the cycle performance of silicon-based materials can be improved.
- silicon powder ( ⁇ 40 nm ) and graphene were mechanically mixed and ground at a mass ratio of 1:1. The first discharge specific capacity was 2158 mAh/g, and the discharge specific capacity after 30 cycles was also At 1168 mAh/g, it is still three times the specific capacity of existing carbon materials.
- the combination of nano-silicon and graphene with a high theoretical capacity ratio is the focus of research on non-carbon negative materials.
- the main combination method is always on the mechanical scale.
- the main method is to combine graphene and nano-silicon by ball milling. Although it can achieve certain effects, due to the uneven mixing of mechanical scales, it is impossible to make graphene. Performance is fully utilized.
- the heat treatment method capable of achieving molecular-scale combination has high energy consumption, and the COD chemical vapor deposition method is expensive and unsuitable for industrial development. Therefore, it is very necessary and far-reaching to develop an effective combination of graphene and nano-silicon.
- the higher the level of this combination the more the performance of the new silicon-carbon matrix pole piece material can be improved.
- nano-silicon/graphene lithium ion battery anode material which is excellent in electrical conductivity and stable in cycle performance.
- Another object of the present invention is to provide a method for preparing a nano silicon/graphene lithium ion battery anode material.
- a nano silicon/graphene lithium ion battery anode material comprising nano silicon and graphene, wherein the nano silicon particle size is 10 ⁇ 100 nm, and the mass ratio of nano silicon to graphene is 1: 5 ⁇ 10.
- a preparation method of a nano silicon/graphene lithium ion battery anode material comprising the following steps:
- the graphene oxide gel-like solution is supported on the nano-silicon: the nano-silica suspension in the electron solution in the step (2) is stirred at a high speed until the hook is added, and the electronic solution is added as a reducing agent to be diluted, and then started.
- the graphene oxide gel-like solution prepared in the step (3) is slowly added dropwise, and the amount of the graphene solution is determined according to the mass ratio of the nano silicon to the graphene, and stirred, and gradually precipitated with the mixing of the first solvent and the second solvent.
- Graphene after the addition of the graphene solution is completed, and then ultrasonically treated to disperse the nano-silicon and graphene, preferably, the stirring speed is 150-300 rpm;
- the mixed solution obtained in the step (4) is subjected to differential centrifugation separation, vacuum-filtered and dried, placed in a quartz boat, and placed in an argon-protected tube furnace. The gas flow rate was controlled, calcined, and the obtained product was pulverized and sieved to obtain a composite electrode material.
- the first type of solvent is an ether or an amine organic compound
- the second type of solvent described in the step (3) is an amine or an alcohol solvent.
- the polycyclic aromatic hydrocarbon as a co-solvent allows lithium ions formed by dissolving lithium metal to be embedded in the aromatic layer, thereby shifting the dissolution equilibrium and further promoting the formation of solvated electrons in the solvent. Since amines and ethers do not contain active hydrogen, solvated electrons have a long life and are sufficient to complete the reduction process. Therefore, amines and ethers are selected as the first type of solvent. Since amines or alcohols can form ⁇ -hydrogen bonds with graphite and graphene, they can also form conventional hydrogen bonds with the partially oxidized sites on graphite and graphene, thereby effectively assisting the dissolution of graphite and graphene, thus selecting alcohol. Class or amine as a second type of solvent.
- the co-solvent according to the step (1) is biphenyl, 4,4'-diaminobiphenyl, 4,4'-dimethoxybiphenyl and the like, ruthenium, naphthalene, phenanthrene and graphene. One or two or more.
- the first solvent is one or more of ethylenediamine, tripropylamine, morpholine, dicyclohexyl ether, ethylene glycol dioxime ether and diethyl ether.
- the second type of solvent described in the step (3) is one or more selected from the group consisting of ethanol, ethylenediamine, tripropylamine, cyclohexanol and ethylene glycol.
- the amount of the metal lithium in the step (1) is 1% to 5% of the total weight of the electronic solution, and the amount of the auxiliary solvent is 0% to 5% of the total weight of the electronic solution.
- the absence of cosolvents also leads to the formation of solvated electrons, but the reaction proceeds slowly.
- the mass fraction of the aqueous graphite oxide solution or the graphene suspension in the step (3) is 0.5 to 1.5 g/L, and the mass concentration of the nitric acid is 60% to 70%, graphite oxide.
- the volume ratio of the aqueous solution or graphene suspension to nitric acid is 1:2 to 10.
- the mass fraction of the gel sample solution in the step (3) is 0.1 ⁇
- the mass ratio of nano silicon to graphene oxide in step (4) is 1: 5-10.
- the mass percentage of the additional electron solution in the step (4) is 0% - 5%, and the frequency of the ultrasonic treatment is 40 ⁇ 80 Hz.
- the gas flow rate in the step (5) is 20 to 100 mL/min
- the sintering temperature is 500 ° C to 800 ° C
- calcination is performed for 2 to 5 hours.
- the silicon-carbon composite electrode material prepared by the invention obtains the nano-silicon particles with more controllable particle size by liquid phase reduction, and then forms a rubber layer by reducing the solvent by precipitating the colloid, and adsorbing on the same.
- the silicon-carbon composite is brought to the molecular level, and the silicon-carbon composite obtained by the method has stable cycle performance, which is 1 times compared with the conventional graphite and pure graphene materials.
- the above specific capacity, and the reaction is completed in the same phase, the operation is simple, and it can be completed without special equipment.
- the invention reduces liquid phase of silicon tetrachloride into nano silicon, and then partially deposits part of graphene oxide on the nano silicon in the liquid phase, and further reduces partial graphene oxide to graphene in a reducing environment, Efficiently combine graphene and nano-silicon on a molecular scale to provide a graphene-nanosilicon anode material with better performance.
- the liquid phase reduction technique used in the present invention reduces the liquid phase of silicon tetrachloride to nano-silicon, and the obtained nano-silicon has a better scale and structure.
- the invention utilizes nano silicon to have the highest theoretical specific capacity in the material of the same period of time, and uses graphene as a carrier to load at the molecular level, which can effectively reduce the volume effect of the material and further improve the overall cycle performance.
- the graphene in the composite material of the invention can effectively inhibit the volume expansion of the silicon negative electrode, so the prepared nano silicon/graphene lithium ion battery anode material has excellent electrical conductivity, and the corresponding lithium ion battery has large specific capacity and circulation. Good performance.
- the addition is complete.
- the centrifugal speed was 16000 rpm, and the centrifugation was 0.5 h.
- the addition is complete.
- the centrifugal speed was 16000 rpm and centrifuged for 0.5 h.
- the metal lithium with a mass percentage of 5% is directly dissolved in the solvent without adding a co-solvent.
- the addition is complete.
- the centrifugal speed was 30,000 rpm and centrifuged for 1 h.
- the composite electrode material of Example 4 was obtained.
- the metal lithium with a mass percentage of 5% was directly dissolved in 1 kg of tripropylamine without adding a co-solvent, dissolved by magnetic stirring, and the solution was metallic black after dissolution. Then add the shield ratio to the solution?.0% ⁇
- Fossils 1 1 ⁇ inside, Si plus ⁇ the same day ten magnetic stirring, WO / Minutes, stop stirring after lh.
- Comparative Example 1916 mAh/g 645 mAh/g As seen from the above table, the preparation method of the present invention has a significant difference compared with the comparative example, and the negative electrode material of the present invention can effectively retain the capacity.
- the existing graphite carbon negative electrode material has a first discharge specific capacity of 350 mAh/g and a retention capacity of 320 to 340 mAh/g. Therefore, the specific capacity of the negative electrode material of the present invention is far superior to the existing graphite carbon negative electrode.
- Properties of materials and similar silicon carbon anode materials This is because the new loading method and reduction method can effectively control the close combination between nano-silicon and graphene, and graphene acts as a buffer material to prevent volume change caused by structural damage, thereby eliminating the problem of poor cycle performance.
Abstract
A nano silicon/graphene lithium ion battery cathode material and preparation method thereof. The cathode material comprises nano silicon and graphene, wherein the granularity of nano silicon granules is 10-100nm, and the mass ratio of nano silicon to graphene is 1:(5-10). The preparation method of the nano silicon/graphene lithium ion battery cathode material comprises the following steps: preparing an electron solution; reducing a silicon tetrachloride liquid phase into nano silicon; preparing a graphene oxide glue sample solution; loading the graphene oxide glue sample solution on nano silicon; and drying and sintering the semi-finished product of the composite electrode material. After the nano silicon granules with more controllable granularity are obtained through a liquid phase reducing method; in a mode that a glue body is separated out through replacing a solvent, the graphene is reduced and a glue layer is formed at the same time, and moreover the glue layer is adsorbed on an existing nano silicon glue nucleus; the obtained nano silicon has a better size and a better structure, can combine graphene and nano silicon efficiently at molecular scale, and has stable circulation performance and excellent electric conducting performance.
Description
说 明 书 一种纳米硅 /石墨烯锂离子电池负极材料及其制备方法 技术领域 Nano silicon/graphene lithium ion battery anode material and preparation method thereof
本发明属于电化学和新能源材料领域， 具体涉及一种纳米硅 /石墨烯锂离子 电池负极材料及其制备方法。 The invention belongs to the field of electrochemical and new energy materials, and particularly relates to a nano silicon/graphene lithium ion battery anode material and a preparation method thereof.
背景技术 Background technique
自从 1991年日本 SONY公司首次推出商品化的锂离子电池产品以来，锂离 子电池发展至今， 已历经 20余年之久。锂离子电池有着独特的嵌入 /脱出锂离子 的充放电机理， 因而较同类电池产品而言， 它具有比容量大、 工作电压高、 安 全性高、 环境污染小等优点。 作为锂离子电池储锂主体的负极材料的开发， 就 变成了提高锂离子电池总比容量、 充放电及循环性能的关键点。 Since the first launch of commercial lithium-ion battery products by SONY Corporation in Japan in 1991, lithium ion batteries have been developed for more than 20 years. Lithium-ion batteries have a unique charge/discharge mechanism for inserting/extracting lithium ions. Therefore, compared with similar battery products, it has the advantages of large specific capacity, high operating voltage, high safety, and low environmental pollution. The development of a negative electrode material for a lithium ion battery lithium storage body has become a key point for improving the total specific capacity, charge and discharge, and cycle performance of a lithium ion battery.
早期， 锂离子电池的负极材料以锂合金为主， 主要的问题在于循环性能差 及首次不可逆容量大。 其根本原因在于负极材料在充放电过程中存在晶体结构 的重组， 导致较大的体积膨胀； 另外， 也有相间体积变化造成嵌锂物质的损失。 所以， 在产业化后的商用电池中， 摒弃了理论比容量高的合金材料而改用和锂 离子形成层插化合物的石墨类碳材料。 由于石墨类碳材料可以通过其石墨间隙 容纳锂离子， 从而解决了体积膨胀的问题。 而这类电化学性能优良的石墨类碳 材料， 也就变成了现在商品锂离子电池中最常见的负极材料。 In the early days, lithium-ion batteries were mainly made of lithium alloys. The main problem was poor cycle performance and large irreversible capacity for the first time. The fundamental reason is that the anode material has a crystal structure recombination during charge and discharge, resulting in a large volume expansion; in addition, there is also a phase-to-volume change that causes loss of lithium intercalation. Therefore, in the commercial battery after industrialization, the alloy material having a high theoretical specific capacity is discarded, and the graphite-based carbon material which forms a layer compound with lithium ions is used instead. Since the graphite-based carbon material can accommodate lithium ions through its graphite gap, the problem of volume expansion is solved. Such graphite-based carbon materials with excellent electrochemical properties have become the most common anode materials in commercial lithium-ion batteries.
然而， 石墨类碳材料储锂理论容量低， 始终是一个根本性的问题。 一般的 石墨类碳材料的理论比容量仅为 372 mAh/g,而实际应用中已达到了 370 mAh/g, 已基本接近理论水平。 即使是改性的石墨类碳材料， 其容量也才 450 mAh/g。 因 此， 石墨虽然保证了锂离子电池的循环性能， 但也大大限制了它的总比容量， 而这远远跟不上现在对于锂离子电池的功能要求。 所以， 具有高容量的、 石墨
类碳材料以外的锂离子电池负极材料的开发， 已经成为当务之急。 However, the low theoretical capacity of graphite-based carbon materials for storage is always a fundamental problem. The theoretical specific capacity of general graphite-based carbon materials is only 372 mAh/g, but in practice it has reached 370 mAh/g, which is almost close to the theoretical level. Even the modified graphite-based carbon material has a capacity of 450 mAh/g. Therefore, although graphite ensures the cycle performance of a lithium-ion battery, it also greatly limits its total specific capacity, which is far behind the current functional requirements for lithium-ion batteries. Therefore, graphite with high capacity The development of anode materials for lithium ion batteries other than carbon-based materials has become a top priority.
相比较之下， 硅基负极材料在非碳类负极材料中， 其性能则显得更有优势。 它具有最高的理论容量比（形成 Li4.4Si, 理论容量高达 4200 mAh/g )和相对较 低的嵌锂电位， 较其他金属材料也有更好的稳定性及安全性， 原料的来源也更 丰富， 因此， 对硅基负极材料的研究始终在进行。 但它也存在着充放电过程中 的体积效应（体积膨胀率 > 300% ),而导致充放电过程中材料本身发生结构垮塌、 逐渐粉化、 活性物质和集流体的电接触丧失、 电传导能力的丧失， 最终导致了 可逆容量的损失。 In comparison, the performance of silicon-based anode materials in non-carbon anode materials is more advantageous. It has the highest theoretical capacity ratio (forming Li4.4Si, theoretical capacity up to 4200 mAh/g) and relatively low lithium insertion potential. It has better stability and safety than other metal materials, and the source of raw materials is also richer. Therefore, research on silicon-based anode materials has been ongoing. However, it also has a volume effect during charge and discharge (volume expansion rate > 300%), which leads to structural collapse, gradual pulverization, loss of electrical contact between active materials and current collectors, and electrical conductivity during charge and discharge. The loss eventually leads to a loss of reversible capacity.
不过， 目前对于硅基材料存在的技术问题也有了一定的解决方案。 通过将 硅处理到纳米尺度， 可使其绝对体积变化大大下降， 或釆用表面改性、 掺杂、 复合等方法形成包覆或高度分散的体系， 从而提高材料的力学性能， 以緩解脱 嵌锂过程中体积膨胀产生的内应力对材料结构的破坏， 这就可以消除体积效应 的影响， 从而达到提高其电化学循环稳定性的目的。 但另一方面， 纯纳米硅又 易团聚， 而利用现有的表面改性及掺杂技术修饰过的硅基材料， 又存在高成本、 或掺杂水平不好、 产品不均一的新问题。 因此， 以纯纳米硅或修饰过的硅基材 料为负极材料的锂离子电池， 始终只能躺在实验室里， 而不能成功的工业化。 However, there are certain solutions to the technical problems existing in silicon-based materials. By treating silicon to the nanometer scale, the absolute volume change can be greatly reduced, or the surface modification, doping, recombination, etc. can be used to form a coated or highly dispersed system, thereby improving the mechanical properties of the material to alleviate the deintercalation. The internal stress generated by the volume expansion in the lithium process destroys the structure of the material, which can eliminate the influence of the volume effect, thereby achieving the purpose of improving the stability of the electrochemical cycle. On the other hand, pure nano-silicon is easy to agglomerate, and the silicon-based materials modified by the existing surface modification and doping techniques have new problems of high cost, poor doping level and product inconsistency. Therefore, a lithium-ion battery using pure nano-silicon or a modified silicon substrate as a negative electrode material can only lie in the laboratory and cannot be industrialized successfully.
另外， 电化学性能较好的碳类材料的研发也有所突破。 改用单层石墨烯作 为锂离子电池的负极材料后， 其理论容量比可达 744 mAh/g, 而有报道的石墨烯 负极材料， 其首次放电容量可以达到 650 mAh/g, 100次循环后， 其容量依然保 持在 460 mAh/g的水平。 因此， 石墨烯虽然理论容量比较一些金属及硅基材料 更弱， 但如果能将它和硅基材料的高容量紧密相结合， 便能提高硅基材料的循 环性能。 在研究报道中， 将硅粉 ( ~ 40 nm )与石墨烯按照质量比 1 :1的比例机 械混合研磨， 首次放电比容量为 2158 mAh/g, 30次循环之后的放电比容量亦可
达到 1168 mAh/g, 依然是现有碳材料比容量的三倍。 In addition, the development of carbon materials with better electrochemical performance has also made breakthroughs. When the single-layer graphene is used as the anode material of the lithium ion battery, the theoretical capacity ratio can reach 744 mAh/g, and the reported graphene anode material can have a first discharge capacity of 650 mAh/g, after 100 cycles. Its capacity remains at 460 mAh/g. Therefore, although the theoretical capacity of graphene is weaker than some metal and silicon-based materials, if it can be combined with the high capacity of silicon-based materials, the cycle performance of silicon-based materials can be improved. In the research report, silicon powder ( ~ 40 nm ) and graphene were mechanically mixed and ground at a mass ratio of 1:1. The first discharge specific capacity was 2158 mAh/g, and the discharge specific capacity after 30 cycles was also At 1168 mAh/g, it is still three times the specific capacity of existing carbon materials.
因此， 将高理论容量比的纳米硅和石墨烯结合起来， 就是现在对于非碳负 极材料研究的重点。 现在主要的结合方式始终还是机械尺度上的， 主要是用球 磨法将石墨烯和纳米硅结合在一起， 虽然能够起到一定的效果， 但是由于机械 尺度混合不均勾， 始终无法让石墨烯的性能充分发挥。 而能达到分子尺度结合 的热处理法能耗高， COD化学气相沉积法又造价昂贵， 不适合工业开发。 因此， 开展一种有效地石墨烯和纳米硅的结合技术是非常有必要和具有深远意义的。 这种结合的水平越高， 越能够提高新的硅-碳基质的极片材料的性能。 原材料及 制备方法越廉价， 越容易进行工业化推广。 Therefore, the combination of nano-silicon and graphene with a high theoretical capacity ratio is the focus of research on non-carbon negative materials. At present, the main combination method is always on the mechanical scale. The main method is to combine graphene and nano-silicon by ball milling. Although it can achieve certain effects, due to the uneven mixing of mechanical scales, it is impossible to make graphene. Performance is fully utilized. The heat treatment method capable of achieving molecular-scale combination has high energy consumption, and the COD chemical vapor deposition method is expensive and unsuitable for industrial development. Therefore, it is very necessary and far-reaching to develop an effective combination of graphene and nano-silicon. The higher the level of this combination, the more the performance of the new silicon-carbon matrix pole piece material can be improved. The cheaper the raw materials and preparation methods, the easier it is to promote industrialization.
发明内容 Summary of the invention
为了克服现有技术的不足， 本发明的目的在于提供一种导电性能优异、 循 环性能稳定的纳米硅 /石墨烯锂离子电池负极材料。 In order to overcome the deficiencies of the prior art, it is an object of the present invention to provide a nano-silicon/graphene lithium ion battery anode material which is excellent in electrical conductivity and stable in cycle performance.
本发明的另一目的在于提供一种纳米硅 /石墨烯锂离子电池负极材料的制备 方法。 Another object of the present invention is to provide a method for preparing a nano silicon/graphene lithium ion battery anode material.
为解决上述问题， 本发明所釆用的技术方案如下： In order to solve the above problems, the technical solutions adopted by the present invention are as follows:
一种纳米硅 /石墨烯锂离子电池负极材料， 其包括纳米硅和石墨烯， 其中， 纳米硅粒子粒度为 10 ~ 100 nm, 纳米硅与石墨烯的质量比 1 : 5 ~ 10。 A nano silicon/graphene lithium ion battery anode material comprising nano silicon and graphene, wherein the nano silicon particle size is 10 ~ 100 nm, and the mass ratio of nano silicon to graphene is 1: 5 ~ 10.
由于石墨烯的理论比容量 ( ~ 700 mAh/g )相较纳米硅而言较小， 过量的石 墨烯会导致材料整体的平均比容量下降， 因此， 当纳米硅与石墨烯的比例大于 1:10 时， 材料整体的比容量就开始出现了衰减。 另外， 若纳米硅与石墨烯的含 量不足 1 :5, 会导致石墨烯无法完全覆盖纳米硅， 使纳米硅粒子间依然存在团聚 并丧失电接触的可能， 从而进一步导致材料的循环性能受到影响。
一种纳米硅 /石墨烯锂离子电池负极材料的制备方法， 包括下列步骤：Since the theoretical specific capacity of graphene (~700 mAh/g) is smaller than that of nano-silicon, excessive graphene will cause the average specific capacity of the material to decrease. Therefore, when the ratio of nano-silicon to graphene is greater than 1: At 10 o'clock, the specific capacity of the material begins to decay. In addition, if the content of nano-silicon and graphene is less than 1:5, the graphene can not completely cover the nano-silicon, so that there is still a possibility of agglomeration and loss of electrical contact between the nano-silicon particles, which further affects the cycle performance of the material. A preparation method of a nano silicon/graphene lithium ion battery anode material, comprising the following steps:
(1 ) 电子溶液的制备： 在氩气保护下， 将金属锂和助溶剂溶解在去水的第 一类溶剂中， 磁力搅拌溶解， 待溶解完成后， 溶液中含有与金属锂等计量比的 电子时， 保存在氩气环境下待用； (1) Preparation of electronic solution: Under the protection of argon, the lithium metal and the co-solvent are dissolved in the first type of solvent to be dehydrated, and dissolved by magnetic stirring. After the dissolution is completed, the solution contains a ratio of metal lithium to the like. In the case of electrons, it is stored in an argon atmosphere for use;
(2) 四氯化硅液相还原成纳米硅： 在氩气保护下， 向装有步骤（1 )制得 的电子溶液的反应器中， 逐滴加入占电子溶液总重量为 5%~20%的四氯化硅， 同时伴随磁力搅拌或电动搅拌， 待四氯化硅滴加完毕后， 获得处在电子溶液中 的粒度为 10 ~ 100 nm的纳米硅粒子的悬浊液，优选的，搅拌的转速维持在 100 ~ 300转 /分钟； (2) Liquid phase reduction of silicon tetrachloride into nano-silicon: Under the protection of argon, to the reactor containing the electron solution prepared in step (1), the total weight of the electron-containing solution is added dropwise to 5%~20 % of silicon tetrachloride, accompanied by magnetic stirring or electric stirring, after the completion of the dropwise addition of silicon tetrachloride, a suspension of nano silicon particles having a particle size of 10 to 100 nm in an electron solution is obtained, preferably, The stirring speed is maintained at 100 ~ 300 rev / min;
(3)氧化石墨烯胶样溶液的制备： 以水作为分散剂， 配置氧化石墨水溶液 或石墨烯悬浊液， 再加入硝酸， 将氧化石墨水溶液或石墨烯悬浊液与硝酸混合， 超声处理溶液后， 反复离心洗涤， 将体系洗到 pH接近中性后， 真空干燥， 再将 得到的干燥产物与第二类溶剂超声处理， 配成胶样溶液； (3) Preparation of graphene oxide gel-like solution: Dissolve graphite oxide aqueous solution or graphene suspension with water as dispersing agent, add nitric acid, mix graphite oxide aqueous solution or graphene suspension with nitric acid, and sonicate solution After repeated centrifugal washing, the system is washed until the pH is close to neutral, vacuum dried, and the obtained dried product is sonicated with the second type of solvent to prepare a gel-like solution;
(4) 氧化石墨烯胶样溶液负载于纳米硅： 将步骤（2) 中处在电子溶液中 的纳米硅悬浊液高速搅拌至均勾， 并补加电子溶液作为还原剂进行稀释， 再开 始緩慢滴加入步骤（3)制得的氧化石墨烯胶样溶液， 按纳米硅与石墨烯的质量 比决定石墨烯溶液的添加量， 搅拌， 伴随第一类溶剂与第二类溶剂的混合逐渐 析出石墨烯， 待石墨烯溶液滴加完成后， 再经过超声处理， 分散纳米硅和石墨 烯， 优选的， 搅拌的转速为 150 ~ 300转 /分钟； (4) The graphene oxide gel-like solution is supported on the nano-silicon: the nano-silica suspension in the electron solution in the step (2) is stirred at a high speed until the hook is added, and the electronic solution is added as a reducing agent to be diluted, and then started. The graphene oxide gel-like solution prepared in the step (3) is slowly added dropwise, and the amount of the graphene solution is determined according to the mass ratio of the nano silicon to the graphene, and stirred, and gradually precipitated with the mixing of the first solvent and the second solvent. Graphene, after the addition of the graphene solution is completed, and then ultrasonically treated to disperse the nano-silicon and graphene, preferably, the stirring speed is 150-300 rpm;
(5) 复合电极材料半成品的干燥及烧结： 步骤（4)得到的混合溶液经过 差速离心分离， 真空抽滤及干燥后， 放置在石英舟中， 放置于氩气保护的管式 炉内， 控制气体流速， 煅烧， 将得到的产品粉碎后过筛， 得到复合电极材料。 (5) Drying and sintering of the semi-finished product of the composite electrode material: the mixed solution obtained in the step (4) is subjected to differential centrifugation separation, vacuum-filtered and dried, placed in a quartz boat, and placed in an argon-protected tube furnace. The gas flow rate was controlled, calcined, and the obtained product was pulverized and sieved to obtain a composite electrode material.
太 明 0 i井一舟 太古奮， ^ l ( 1 ) 所^ ？助 剂 % 、苦烃恭 ό 右
机化合物， 所述的第一类溶剂为醚类或胺类有机化合物， 步骤（3 )所述的第二 类溶剂为胺类或醇类溶剂。 Tai Ming 0 i well a boat too ancient, ^ l ( 1 ) ^ ^ ? Additive %, bitter hydrocarbons, respectful right The first type of solvent is an ether or an amine organic compound, and the second type of solvent described in the step (3) is an amine or an alcohol solvent.
多环芳烃作为助溶剂可以使金属锂在溶解后形成的锂离子被嵌入芳香层 内， 从而使溶解平衡移动， 进一步促进溶剂中溶剂化电子的形成。 由于胺类及 醚类不存在活泼氢， 溶剂化电子有较长寿命， 足以完成还原过程， 因此选择胺 类及醚类化合物作为第一类溶剂。 由于胺类或醇类可以和石墨及石墨烯形成 π - 氢键， 也能和石墨及石墨烯上部分氧化的位点形成传统氢键， 从而能有效协助 石墨和石墨烯的溶解， 因此选择醇类或胺类作为第二类溶剂。 The polycyclic aromatic hydrocarbon as a co-solvent allows lithium ions formed by dissolving lithium metal to be embedded in the aromatic layer, thereby shifting the dissolution equilibrium and further promoting the formation of solvated electrons in the solvent. Since amines and ethers do not contain active hydrogen, solvated electrons have a long life and are sufficient to complete the reduction process. Therefore, amines and ethers are selected as the first type of solvent. Since amines or alcohols can form π-hydrogen bonds with graphite and graphene, they can also form conventional hydrogen bonds with the partially oxidized sites on graphite and graphene, thereby effectively assisting the dissolution of graphite and graphene, thus selecting alcohol. Class or amine as a second type of solvent.
优选地， 步骤（1 ) 所述的助溶剂为联苯、 4,4'-二氨基联苯、 4,4'-二曱氧基 联苯及类似物， 蒽、 萘、 菲和石墨烯中的一种或者两种以上。 Preferably, the co-solvent according to the step (1) is biphenyl, 4,4'-diaminobiphenyl, 4,4'-dimethoxybiphenyl and the like, ruthenium, naphthalene, phenanthrene and graphene. One or two or more.
优选地， 所述的第一类溶剂为乙二胺、 三丙胺、 吗啉、 二环己基醚、 乙二 醇二曱醚和***中的一种或者两种以上。 Preferably, the first solvent is one or more of ethylenediamine, tripropylamine, morpholine, dicyclohexyl ether, ethylene glycol dioxime ether and diethyl ether.
优选地， 步骤（3 )所述的第二类溶剂为乙醇、 乙二胺、 三丙胺、 环己醇和 乙二醇中的一种或者两种以上。 作为本发明的进一步技术方案， 步骤（1 ) 中所述金属锂的用量为电子溶液 总重量的 1% ~ 5%,助溶剂的用量为电子溶液总重量的 0% ~ 5%。 不加入助溶剂 亦会导致溶剂化电子的形成， 只是反应进行得较慢。 Preferably, the second type of solvent described in the step (3) is one or more selected from the group consisting of ethanol, ethylenediamine, tripropylamine, cyclohexanol and ethylene glycol. As a further technical solution of the present invention, the amount of the metal lithium in the step (1) is 1% to 5% of the total weight of the electronic solution, and the amount of the auxiliary solvent is 0% to 5% of the total weight of the electronic solution. The absence of cosolvents also leads to the formation of solvated electrons, but the reaction proceeds slowly.
作为本发明的进一步技术方案， 步骤（3 ) 中所述氧化石墨水溶液或石墨烯 悬浊液的质量分数为 0.5 ~ 1.5 g/L, 所述硝酸的质量浓度为 60% ~ 70%, 氧化石 墨水溶液或石墨烯悬浊液与硝酸的体积比为 1 : 2 ~ 10。 As a further technical solution of the present invention, the mass fraction of the aqueous graphite oxide solution or the graphene suspension in the step (3) is 0.5 to 1.5 g/L, and the mass concentration of the nitric acid is 60% to 70%, graphite oxide. The volume ratio of the aqueous solution or graphene suspension to nitric acid is 1:2 to 10.
作为本发明的进一步技术方案，步骤（ 3 )中所述胶样溶液的质量分数为 0.1 ~
作为本发明的进一步技术方案， 步骤（4) 中纳米硅与氧化石墨烯的质量比 1: 5~10。 As a further technical solution of the present invention, the mass fraction of the gel sample solution in the step (3) is 0.1 ~ As a further technical solution of the present invention, the mass ratio of nano silicon to graphene oxide in step (4) is 1: 5-10.
作为本发明的进一步技术方案， 步骤（4) 中补加电子溶液的质量百分比为 0% - 5%, 超声处理的频率为 40 ~ 80 Hz。 As a further technical solution of the present invention, the mass percentage of the additional electron solution in the step (4) is 0% - 5%, and the frequency of the ultrasonic treatment is 40 ~ 80 Hz.
作为本发明的进一步技术方案，步骤（5)中的气体流速为 20 ~ 100 mL/min, 烧结温度为 500°C ~800°C, 煅烧 2~5h。 As a further technical solution of the present invention, the gas flow rate in the step (5) is 20 to 100 mL/min, the sintering temperature is 500 ° C to 800 ° C, and calcination is performed for 2 to 5 hours.
相比现有技术， 本发明的有益效果在于： Compared with the prior art, the beneficial effects of the present invention are:
1 )本发明制备的硅碳复合电极材料， 通过液相还原的方式获得粒度更可控 的纳米硅粒子后， 再通过更换溶剂析出胶体的方式使石墨烯被还原的同时形成 胶层， 吸附在已有的纳米硅胶核上， 从而使硅碳间达到分子层面的结合， 由该 方法得到的硅碳复合材料， 其循环性能稳定， 相对传统石墨类及纯石墨烯类材 料而言， 具有 1 倍以上的比容量， 而且反应同相内完成， 操作简单， 不需特种 设备即可完成。 1) The silicon-carbon composite electrode material prepared by the invention obtains the nano-silicon particles with more controllable particle size by liquid phase reduction, and then forms a rubber layer by reducing the solvent by precipitating the colloid, and adsorbing on the same. On the existing nano-silica core, the silicon-carbon composite is brought to the molecular level, and the silicon-carbon composite obtained by the method has stable cycle performance, which is 1 times compared with the conventional graphite and pure graphene materials. The above specific capacity, and the reaction is completed in the same phase, the operation is simple, and it can be completed without special equipment.
2)本发明将四氯化硅液相还原成纳米硅， 再于液相中原位将部分氧化石墨 烯负载于纳米硅上， 进一步在还原性环境下将部分氧化石墨烯还原为石墨烯， 可以高效地在分子尺度上将石墨烯和纳米硅结合， 从而提供一种性能更好的石 墨烯 -纳米硅负极材料。 2) The invention reduces liquid phase of silicon tetrachloride into nano silicon, and then partially deposits part of graphene oxide on the nano silicon in the liquid phase, and further reduces partial graphene oxide to graphene in a reducing environment, Efficiently combine graphene and nano-silicon on a molecular scale to provide a graphene-nanosilicon anode material with better performance.
3)本发明釆用的液相还原技术将四氯化硅液相还原成纳米硅， 得到的纳米 硅具有更好的尺度和结构。 3) The liquid phase reduction technique used in the present invention reduces the liquid phase of silicon tetrachloride to nano-silicon, and the obtained nano-silicon has a better scale and structure.
4)本发明利用纳米硅在同比材料内具有最高理论比容量的同时， 以石墨烯 作为载体， 在分子水平上加以负载， 能有效地降低材料的体积效应， 使整体循 环性能进一步提高。
5 )本发明的复合材料中的石墨烯能有效抑制硅负极的体积膨胀， 因此制备 得到的纳米硅 /石墨烯锂离子电池负极材料具有优异的导电性能， 对应的锂离子 电池比容量大、 循环性能好。 4) The invention utilizes nano silicon to have the highest theoretical specific capacity in the material of the same period of time, and uses graphene as a carrier to load at the molecular level, which can effectively reduce the volume effect of the material and further improve the overall cycle performance. 5) The graphene in the composite material of the invention can effectively inhibit the volume expansion of the silicon negative electrode, so the prepared nano silicon/graphene lithium ion battery anode material has excellent electrical conductivity, and the corresponding lithium ion battery has large specific capacity and circulation. Good performance.
具体实施方式 detailed description
实施例 1 : Example 1
在氩气保护下， 将质量百分比为 1%的金属锂和 1%的联苯溶解于 1 kg的乙 二醇二曱醚中， 磁力搅拌溶解， 溶解后溶液呈墨绿色。 再向该溶液中滴加质量 比为 5%的四氯化硅， l h内滴加完， 同时加以磁力搅拌， 维持在 100转 /分钟， 1 h后停止搅拌。 Under argon protection, 1% by mass of metallic lithium and 1% of biphenyl were dissolved in 1 kg of ethylene glycol dioxime ether, dissolved by magnetic stirring, and the solution was dark green after dissolution. Further, silicon tetrachloride having a mass ratio of 5% was added dropwise to the solution, and the dropwise addition was carried out in 1 h, and magnetic stirring was carried out at 100 rpm, and stirring was stopped after 1 hour.
以水作为分散剂， 配置 0.5 g/L的石墨烯悬浊液，加入体积比为 1： 2的 60% 浓度的硝酸后用超声处理 0.5 h。处理后，将得到的溶液反复离心洗涤，洗至 pH=7 时结束。真空干燥后重新用超声处理 0.5 h,使其溶解于环己醇中，配置成 0.1 g/L 的氧化石墨烯胶样溶液。 Using water as a dispersing agent, a 0.5 g/L graphene suspension was placed, and 60% of the nitric acid having a volume ratio of 1:2 was added and then sonicated for 0.5 h. After the treatment, the obtained solution was repeatedly washed by centrifugation and washed until pH = 7 to end. After vacuum drying, it was again sonicated for 0.5 h, dissolved in cyclohexanol, and placed into a 0.1 g/L graphene oxide gel-like solution.
将纳米硅悬浊液以 200转 /分钟的转速搅拌， 并在搅拌过程中， 按质量比为 纳米硅： 石墨烯 =1 : 8滴加上述 1 g/L的氧化石墨烯溶液， 1 h内滴加完毕。 1 h 后， 再用 40 Hz的超声分散 0.5 h, 分散完成后， 离心转速为 16000转 /分钟， 离 心 0.5 h。 离心完成后真空抽滤， 干燥， 再放置于石英舟中， 放置于氩气保护的 管式炉内， 保持 20 mL/min的气体流速， 在 500°C下煅烧 2 h, 将得到的产品粉 碎后过 ， 得到实施例 1的复合电极材料。 The nano silicon suspension was stirred at 200 rpm, and during the stirring process, the mass ratio was nano silicon: graphene = 1: 8 drops of the above 1 g / L graphene oxide solution, within 1 h The addition is complete. After 1 h, it was dispersed by ultrasonic at 40 Hz for 0.5 h. After the dispersion was completed, the centrifugal speed was 16000 rpm, and the centrifugation was 0.5 h. After centrifugation, vacuum filtration, drying, placing in a quartz boat, placing in an argon-protected tube furnace, maintaining a gas flow rate of 20 mL/min, calcining at 500 ° C for 2 h, crushing the obtained product. Thereafter, the composite electrode material of Example 1 was obtained.
实施例 2: Example 2:
在氩气保护下， 将质量百分比为 3%的金属锂和 5%的 4,4'-二曱氧基联苯溶 解于 l kg的三丙胺中， 磁力搅拌溶解， 溶解后溶液接近深蓝色。 再向该溶液中
滴加质量比为 20%的四氯化硅， 3 h内滴加完， 同时加以磁力搅拌， 维持在 150 转 /分钟， l h后停止搅拌。 Under argon protection, 3% by mass of metallic lithium and 5% of 4,4'-dimethoxyoxybiphenyl were dissolved in 1 kg of tripropylamine, dissolved by magnetic stirring, and the solution was nearly dark blue after dissolution. Again in the solution Add silicon tetrachloride with a mass ratio of 20%, add it dropwise within 3 h, and stir it magnetically at 150 rpm. Stop stirring after lh.
以水作为分散剂， 配置 0.5 g/L的氧化石墨水溶液， 加入体积比为 1 : 5的 60%浓度的硝酸后， 用超声处理 0.5 h。 处理后， 将得到的溶液反复离心洗涤， 洗至 pH=7时结束。 真空干燥后重新用超声处理 3 h, 使其溶解于乙醇中， 配置 成 5 g/L的氧化石墨烯胶样溶液。 Using water as a dispersing agent, a 0.5 g/L aqueous solution of graphite oxide was placed, and 60% by weight of nitric acid having a volume ratio of 1:5 was added, and sonicated for 0.5 h. After the treatment, the obtained solution was repeatedly washed by centrifugation, and washed until pH = 7 to end. After vacuum drying, it was again sonicated for 3 h, dissolved in ethanol, and placed into a 5 g/L graphene oxide gel-like solution.
将纳米硅悬浊液以 150转 /分钟的转速搅拌， 并在搅拌过程中， 按质量比为 纳米硅： 石墨烯 =1 : 5滴加上述 5 g/L的氧化石墨烯溶液， 2 h内滴加完毕。 2 h 后， 再用 40 Hz超声分散 1 h, 分散完成后， 离心转速为 16000转 /分钟， 离心 0.5 h。 离心完成后真空抽滤， 干燥， 再放置于石英舟中， 放置于氩气保护的管 式炉内， 保持 30 mL/min的气体流速， 在 600 °C下煅烧 5 h, 将得到的产品粉碎 后过 ， 得到实施例 2的复合电极材料。 The nano silicon suspension was stirred at 150 rpm, and during the stirring process, the mass ratio was nano silicon: graphene = 1: 5 drops of the above 5 g / L graphene oxide solution, within 2 h The addition is complete. After 2 h, it was dispersed by ultrasonic at 40 Hz for 1 h. After the dispersion was completed, the centrifugal speed was 16000 rpm and centrifuged for 0.5 h. After centrifugation, vacuum filtration, drying, placing in a quartz boat, placing in an argon-protected tube furnace, maintaining a gas flow rate of 30 mL/min, calcining at 600 °C for 5 h, crushing the obtained product. Thereafter, the composite electrode material of Example 2 was obtained.
实施例 3 : Example 3:
在氩气保护下， 将质量百分比为 5%的金属锂和 5%的蒽溶解于 1 kg的吗啉 中，磁力搅拌溶解，溶解后溶液接近金属黑色。再向该溶液中滴加质量比为 20% 的四氯化硅， 3 h内滴加完， 同时加以磁力搅拌， 维持在 150转 /分钟， l h后停 止搅拌。 Under argon protection, 5% by mass of metallic lithium and 5% of cerium were dissolved in 1 kg of morpholine, dissolved by magnetic stirring, and the solution was close to metallic black after dissolution. Further, silicon tetrachloride having a mass ratio of 20% was added dropwise to the solution, and the mixture was added dropwise over 3 hours while being magnetically stirred, maintained at 150 rpm, and the stirring was stopped after 1 h.
以水作为分散剂，配置 0.5 g/L的石墨烯悬浊液，加入体积比为 1 : 10的 60% 浓度的硝酸后， 用 60 Hz超声处理 0.5 h。 处理后， 将得到的溶液反复离心洗涤， 洗至 pH=7时结束。 真空干燥后重新用超声处理 3 h, 使其溶解于乙二醇中， 配 置成 1 g/L的氧化石墨烯胶样溶液。 Using water as a dispersing agent, 0.5 g/L of graphene suspension was placed, and 60% of nitric acid having a volume ratio of 1:10 was added, and then ultrasonically treated at 60 Hz for 0.5 h. After the treatment, the obtained solution was repeatedly washed by centrifugation, and washed until pH = 7 to end. After vacuum drying, it was again sonicated for 3 h, dissolved in ethylene glycol, and formulated into a 1 g/L graphene oxide gel-like solution.
将纳米硅悬浊液以 200转 /分钟的转速搅拌， 并在搅拌过程中， 按质量比为 纳失石 · 石, ¥、 =1 · 1 0 ¾加 hi# 5 ίτ/Τ , ό 氳化石, 、烯 ¾ , ?. 1ι 内'; ϋ加^ „ 7 h
后， 再用超声分散 l h, 分散完成后， 离心转速为 16000转 /分钟， 离心 0.5 h。 离心完成后真空抽滤， 干燥， 再放置于石英舟中， 放置于氩气保护的管式炉内， 保持 50 mL/min的气体流速， 在 800 °C下煅烧 3 h, 将得到的产品粉碎后过筛， 得到实施例 3的复合电极材料。 The nano silicon suspension was stirred at 200 rpm, and during the stirring process, the mass ratio was 纳石石·石, ¥, =1 · 1 0 3⁄4 plus hi# 5 ίτ/Τ , ό 氲 fossil , 烯3⁄4, ?. 1ι内'; ϋ加^ „ 7 h After that, it was dispersed by ultrasonic for 1 hour. After the dispersion was completed, the centrifugal speed was 16,000 rpm, and the mixture was centrifuged for 0.5 h. After centrifugation, vacuum filtration, drying, placing in a quartz boat, placing in an argon-protected tube furnace, maintaining a gas flow rate of 50 mL/min, calcining at 800 °C for 3 h, crushing the obtained product. After sieving, the composite electrode material of Example 3 was obtained.
实施例 4: Example 4:
在氩气保护下， 将质量百分比为 5%的金属锂， 不加入助溶剂， 直接溶解于 Under the protection of argon, the metal lithium with a mass percentage of 5% is directly dissolved in the solvent without adding a co-solvent.
1 kg的乙二胺中， 磁力搅拌溶解， 溶解后溶液呈深蓝色。 再向该溶液中滴加质 量比为 15%的四氯化硅， 2 h内滴加完， 同时加以磁力搅拌，维持在 200转 /分钟， l h后停止搅拌。 1 kg of ethylenediamine was dissolved by magnetic stirring, and the solution was dark blue after dissolution. Further, silicon tetrachloride having a mass ratio of 15% was added dropwise to the solution, and the addition was completed within 2 hours, and magnetic stirring was carried out at 200 rpm, and stirring was stopped after 1 h.
以水作为分散剂， 配置 0.5 g/L的氧化石墨水溶液， 加入体积比为 1 : 2的 60%浓度的硝酸后用超声处理 0.5 h。 处理后， 将得到的溶液反复离心洗涤， 洗 至 pH=7时结束。 真空干燥后重新用超声处理 1 h, 使其溶解于乙醇中， 配置成 Using water as a dispersing agent, a 0.5 g/L aqueous solution of graphite oxide was placed, and a 60% strength nitric acid having a volume ratio of 1:2 was added and then ultrasonically treated for 0.5 h. After the treatment, the obtained solution was repeatedly washed by centrifugation, and washed until pH = 7 to end. After vacuum drying, re-sonicize for 1 h, dissolve it in ethanol, and configure
2 g/L的氧化石墨烯胶样溶液。 2 g/L graphene oxide gel solution.
将纳米硅悬浊液以 300转 /分钟的转速搅拌， 并在搅拌过程中， 按质量比为 纳米硅： 石墨烯 =1 : 9滴加上述 2 g/L的氧化石墨烯溶液， 2 h内滴加完毕。 2 h 后， 再用 60 Hz超声分散 l h, 分散完成后， 离心转速为 30000转 /分钟， 离心 1 h。 离心完成后真空抽滤， 干燥， 再放置于石英舟中， 放置于氩气保护的管式炉 内， 保持 70 mL/min的气体流速， 在 800 °C下煅烧 2 h, 将得到的产品粉碎后过 筛， 得到实施例 4的复合电极材料。 The nano silicon suspension was stirred at 300 rpm, and during the stirring process, the mass ratio was nano silicon: graphene = 1: 9 drops of the above 2 g / L graphene oxide solution, within 2 h The addition is complete. After 2 h, it was dispersed by ultrasonic wave at 60 Hz for 1 h. After the dispersion was completed, the centrifugal speed was 30,000 rpm and centrifuged for 1 h. After centrifugation, vacuum filtration, drying, placing in a quartz boat, placing in an argon-protected tube furnace, maintaining a gas flow rate of 70 mL/min, calcining at 800 °C for 2 h, crushing the obtained product. After sieving, the composite electrode material of Example 4 was obtained.
实施例 5 : Example 5:
在氩气保护下， 将质量百分比为 5%的金属锂， 不加入助溶剂， 直接溶解于 1 kg的三丙胺中， 磁力搅拌溶解， 溶解后溶液呈金属黑色。 再向该溶液中滴加 盾音比 ?.0%ό 四教.化石 1 1ι 内、; Si加^ , 同日十加以磁力搅棘， WO /
分钟， l h后停止搅拌。 Under the protection of argon, the metal lithium with a mass percentage of 5% was directly dissolved in 1 kg of tripropylamine without adding a co-solvent, dissolved by magnetic stirring, and the solution was metallic black after dissolution. Then add the shield ratio to the solution?.0%ό Four teachings. Fossils 1 1ι inside, Si plus ^, the same day ten magnetic stirring, WO / Minutes, stop stirring after lh.
以水作为分散剂， 配置 0.5 g/L的石墨烯悬浊液，加入体积比为 1： 2的 60% 浓度的硝酸后用超声处理 0.5 h。处理后，将得到的溶液反复离心洗涤，洗至 pH=7 时结束。 真空干燥后重新用超声处理 1 h, 使其溶解于环己醇中， 配置成 5 g/L 的氧化石墨烯胶样溶液。 Using water as a dispersing agent, a 0.5 g/L graphene suspension was placed, and 60% of the nitric acid having a volume ratio of 1:2 was added and then sonicated for 0.5 h. After the treatment, the obtained solution was repeatedly washed by centrifugation and washed until pH = 7 to end. After vacuum drying, it was again sonicated for 1 h, dissolved in cyclohexanol, and placed into a 5 g/L graphene oxide gel-like solution.
将纳米硅悬浊液以 300转 /分钟的转速搅拌， 并在搅拌过程中， 按质量比为 纳米硅： 石墨烯 =1 : 9滴加上述 5 g/L的氧化石墨烯溶液， 2 h内滴加完。 2 h后， 再用 80 Hz超声分散 l h, 分散完成后， 离心转速为 30000 转 /分钟， 离心 l h。 离心完成后真空抽滤， 干燥， 再放置于石英舟中， 放置于氩气保护的管式炉内， 保持 lOO mL/min的气体流速， 在 500°C下煅烧 5 h, 将得到的产品粉碎后过筛， 得到实施例 5的复合电极材料。 The nano silicon suspension was stirred at 300 rpm, and during the stirring process, the mass ratio was nano silicon: graphene = 1: 9 drops plus the above 5 g / L graphene oxide solution, within 2 h Add the drop. After 2 h, it was dispersed by ultrasonic wave at 80 Hz for 1 h. After the dispersion was completed, the centrifugal speed was 30,000 rpm, and it was centrifuged for 1 h. After centrifugation, vacuum filtration, drying, and placed in a quartz boat, placed in an argon-protected tube furnace, maintaining a gas flow rate of 100 mL/min, calcined at 500 ° C for 5 h, and pulverizing the obtained product. After sieving, the composite electrode material of Example 5 was obtained.
对比实施例： Comparative example:
以水作为分散剂， 配置 0.4 g/L的石墨烯悬浊液，加入体积比为 1： 2的 60% 浓度的硝酸后用超声处理 0.5 h。处理后，将得到的溶液反复离心洗涤，洗至 pH=7 时结束。 真空干燥后重新用超声处理 1 h, 使其溶解于水中， 配置成 0.4 g/L的氧 化石墨烯胶样溶液。 Using water as a dispersing agent, 0.4 g/L of graphene suspension was placed, and 60% of nitric acid having a volume ratio of 1:2 was added and then sonicated for 0.5 h. After the treatment, the obtained solution was repeatedly washed by centrifugation and washed until pH = 7 to end. After vacuum drying, it was again sonicated for 1 h, dissolved in water, and placed into a 0.4 g/L oxy graphene gel-like solution.
取一定量的市售的粒径尺寸为 20 ~ 50 nm纳米硅， 暴露于空气中 16 h, 再 将上述纳米硅加入水中， 超声分散 l h后， 按质量比为纳米硅： 石墨烯 =1 : 2滴 加上述 0.4 g/L的氧化石墨烯溶液， 2 h内滴加完毕。 2 h后， 再用 40 Hz超声分 散 1.5 h, 分散完成后真空抽滤， 干燥， 再放置于石英舟中， 放置于氢氩混合气 体（氢： 氩 =6%: 94% )保护的管式炉内，保持 70 mL/min的气体流速， 在 800°C 下煅烧 l h, 将得到的产品粉碎后过筛， 得到比较例的复合电极材料。 Take a certain amount of commercially available nano-silicone with a particle size of 20 ~ 50 nm, expose it to air for 16 h, then add the above-mentioned nano-silicon into water. After ultrasonic dispersion for 1 h, the mass ratio is nano-silicon: graphene = 1: 2 0.4 g/L of the graphene oxide solution was added dropwise, and the addition was completed within 2 h. After 2 h, it was dispersed by ultrasonic at 40 Hz for 1.5 h. After the dispersion was completed, it was vacuum filtered, dried, placed in a quartz boat, and placed in a tube of hydrogen-argon mixed gas (hydrogen: argon = 6%: 94%). In the furnace, a gas flow rate of 70 mL/min was maintained, and calcination was carried out at 800 ° C for 1 h, and the obtained product was pulverized and sieved to obtain a composite electrode material of a comparative example.
hi# Φ 1 ~ 4；及 比 Φ ¼ Φ, -1-4能 »\ i^,古法 · Κ異 )1 ¼ Φ,极
放置在铜箔上制成负极极片， 和金属锂片组装成 2016型纽扣电池， 电解液为 1 mol/L的 LiPF6溶解于 DMC中， 在 0.02 ~ 1.5V的电压范围内， 室温下， 以 100 mAh/g 的电流进行充放电循环测试， 循环 100次。 上述实施例 1 ' 5及对比实施例的电学性能测试的结果列表如下： Hi# Φ 1 ~ 4 ; and ratio Φ 1⁄4 Φ, -1-4 can »\ i^, ancient method · strange) 1 1⁄4 Φ, pole Placed on a copper foil to form a negative electrode piece, and a metal lithium piece is assembled into a 2016 type button battery, and an electrolyte solution of 1 mol/L of LiPF 6 is dissolved in DMC, in a voltage range of 0.02 to 1.5 V, at room temperature, The charge and discharge cycle test was performed at a current of 100 mAh/g, and the cycle was performed 100 times. The results of the electrical performance tests of the above Example 1 '5 and the comparative examples are as follows:
项目 首次放电比容量 循环 100次后的保留容量 实施例 1 1807 mAh/g 1019 mAh/g Item First discharge specific capacity reserved capacity after 100 cycles Example 1 1807 mAh/g 1019 mAh/g
实施例 2 1643 mAh/g 859 mAh/g Example 2 1643 mAh/g 859 mAh/g
实施例 3 2036 mAh/g 870 mAh/g Example 3 2036 mAh/g 870 mAh/g
实施例 4 1915 mAh/g 961 mAh/g Example 4 1915 mAh/g 961 mAh/g
实施例 5 1751 mAh/g 1123 mAh/g Example 5 1751 mAh/g 1123 mAh/g
对比实施例 1916 mAh/g 645 mAh/g 由上表可见， 本发明的制备方法与对比实施例相比， 具有显著性的差异， 本发明的负极材料可以有效地保留容量。 然而， 目前现有的石墨碳负极材料的 首次放电比容量为 350 mAh/g, 保留容量为 320 ~ 340 mAh/g, 因此， 本发明的 负极材料的比容量远远优于现有石墨碳负极材料及类似硅碳负极材料的性能。 这是由于新的负载方法和还原方法都能有效地控制纳米硅和石墨烯间的紧密结 合， 石墨烯作为緩冲物质， 防止结构破坏而造成的体积变化， 从而消除了循环 性能差的问题。 Comparative Example 1916 mAh/g 645 mAh/g As seen from the above table, the preparation method of the present invention has a significant difference compared with the comparative example, and the negative electrode material of the present invention can effectively retain the capacity. However, the existing graphite carbon negative electrode material has a first discharge specific capacity of 350 mAh/g and a retention capacity of 320 to 340 mAh/g. Therefore, the specific capacity of the negative electrode material of the present invention is far superior to the existing graphite carbon negative electrode. Properties of materials and similar silicon carbon anode materials. This is because the new loading method and reduction method can effectively control the close combination between nano-silicon and graphene, and graphene acts as a buffer material to prevent volume change caused by structural damage, thereby eliminating the problem of poor cycle performance.
上述实施方式仅为本发明的优选实施方式， 不能以此来限定本发明保护的 范围， 本领域的技术人员在本发明的基础上所做的任何非实质性的变化及替换 均属于本发明所要求保护的范围。
The above embodiments are merely preferred embodiments of the present invention, and the scope of the present invention is not limited thereto, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention belong to the present invention. The scope of the claim.
Claims
1. 一种纳米硅 /石墨烯锂离子电池负极材料， 其特征在于： 其包括纳米硅和 石墨烯，其中，纳米硅粒子粒度为 10~100nm,纳米硅与石墨烯的质量比 1: 5~ 10。 1. A nano-silicon/graphene lithium-ion battery negative electrode material, characterized by: It includes nano-silicon and graphene, wherein the nano-silicon particle size is 10~100nm, and the mass ratio of nano-silicon to graphene is 1: 5~ 10.
2. 一种如权利要求 1 所述的纳米硅 /石墨烯锂离子电池负极材料的制备方 法， 其特征在于包括下列步骤： 2. A method for preparing nano-silicon/graphene lithium-ion battery negative electrode material as claimed in claim 1, characterized by comprising the following steps:
(1 ) 电子溶液的制备： 在氩气保护下， 将金属锂和助溶剂溶解在去水的第 一类溶剂中， 磁力搅拌溶解， 待溶解完成后， 溶液中含有与金属锂等计量比的 电子时， 保存在氩气环境下待用； (1) Preparation of electronic solution: Under the protection of argon gas, dissolve metallic lithium and co-solvent in the first type of solvent that removes water, and magnetically stir to dissolve. After the dissolution is completed, the solution will contain the same metric ratio as metallic lithium. When using electrons, store them in an argon environment for later use;
(2) 四氯化硅液相还原成纳米硅： 在氩气保护下， 向装有步骤（1 )制得 的电子溶液的反应器中， 逐滴加入占电子溶液总重量 5% ~ 20%的四氯化硅， 同 时伴随磁力搅拌或电动搅拌， 待四氯化硅滴加完毕后， 获得处在电子溶液中的 粒度为 10 ~ 100 nm的纳米硅粒子的悬浊液； (2) Liquid-phase reduction of silicon tetrachloride into nano-silicon: Under argon protection, add 5% to 20% of the total weight of the electron solution dropwise into the reactor containing the electron solution prepared in step (1). of silicon tetrachloride, accompanied by magnetic stirring or electric stirring. After the dropwise addition of silicon tetrachloride is completed, a suspension of nanometer silicon particles with a particle size of 10 to 100 nm in the electron solution is obtained;
(3)氧化石墨烯胶样溶液的制备： 以水作为分散剂， 配置氧化石墨水溶液 或石墨烯悬浊液， 再加入硝酸， 将氧化石墨水溶液或石墨烯悬浊液与硝酸混合， 超声处理溶液后， 反复离心洗涤， 将体系洗到 pH接近中性后， 真空干燥， 再将 得到的干燥产物与第二类溶剂超声处理， 配成胶样溶液； (3) Preparation of graphene oxide colloidal solution: Use water as the dispersant, prepare a graphite oxide aqueous solution or graphene suspension, then add nitric acid, mix the graphite oxide aqueous solution or graphene suspension with nitric acid, and ultrasonicate the solution Afterwards, the system is centrifuged and washed repeatedly until the pH is close to neutral, and then dried in a vacuum, and then the obtained dry product is ultrasonically treated with a second type solvent to prepare a gel-like solution;
(4) 氧化石墨烯胶样溶液负载于纳米硅： 将步骤（2) 中处在电子溶液中 的纳米硅悬浊液高速搅拌至均勾， 并补加电子溶液作为还原剂进行稀释， 再开 始緩慢滴加入步骤（3)制得的氧化石墨烯胶样溶液， 按纳米硅与石墨烯的质量 比决定石墨烯溶液的添加量， 搅拌， 伴随第一类溶剂与第二类溶剂的混合逐渐 析出石墨烯， 待石墨烯溶液滴加完成后， 再经过超声处理， 分散纳米硅和石墨
( 5 ) 复合电极材料半成品的干燥及烧结： 步骤（4 )得到的混合溶液经过 差速离心分离， 真空抽滤及干燥后， 放置在石英舟中， 放置于氩气保护的管式 炉内， 控制气体流速， 煅烧， 将得到的产品粉碎后过筛， 得到复合电极材料。 (4) Graphene oxide colloidal solution is loaded on nano-silica: Stir the nano-silica suspension in the electron solution in step (2) at high speed until homogeneous, and add the electron solution as a reducing agent to dilute, and then start. Slowly add the graphene oxide colloidal solution prepared in step (3) dropwise, determine the amount of graphene solution added according to the mass ratio of nano-silicon to graphene, stir, and gradually precipitate as the first type of solvent and the second type of solvent are mixed. Graphene, after the graphene solution is added dropwise, it is then subjected to ultrasonic treatment to disperse nano silicon and graphite. (5) Drying and sintering of composite electrode material semi-finished products: The mixed solution obtained in step (4) is separated by differential centrifugation, vacuum filtered and dried, then placed in a quartz boat and placed in an argon-protected tube furnace. The gas flow rate is controlled, the product is calcined, and the obtained product is crushed and screened to obtain a composite electrode material.
3. 根据权利要求 2所述的纳米硅 /石墨烯锂离子电池负极材料的制备方法， 其特征在于： 步骤（1 )所述的助溶剂为多环芳烃类的有机化合物， 所述的第一 类溶剂为醚类或胺类有机化合物， 步骤（3 )所述的第二类溶剂为胺类或醇类溶 剂。 3. The preparation method of nano silicon/graphene lithium ion battery negative electrode material according to claim 2, characterized in that: the co-solvent in step (1) is an organic compound of polycyclic aromatic hydrocarbons, and the first The first type of solvent is an ether or amine type organic compound, and the second type of solvent described in step (3) is an amine or alcohol type solvent.
4. 根据权利要求 3所述的纳米硅 /石墨烯锂离子电池负极材料的制备方法， 其特征在于： 步骤（1 ) 所述的助溶剂为联苯、 4,4'-二氨基联苯、 4,4'-二曱氧基 联苯及类似物， 蒽、 萘、 菲和石墨烯中的一种或者两种以上， 所述的第一类溶 剂为乙二胺、 三丙胺、 吗啉、 二环己基醚、 乙二醇二曱醚和***中的一种或者 两种以上， 步骤（3 )所述的第二类溶剂为乙醇、 乙二胺、 三丙胺、 环己醇和乙 二醇中的一种或者两种以上。 4. The preparation method of nano silicon/graphene lithium ion battery negative electrode material according to claim 3, characterized in that: the co-solvent in step (1) is biphenyl, 4,4'-diaminobiphenyl, 4,4'-dimethoxybiphenyl and the like, one or more of anthracene, naphthalene, phenanthrene and graphene, the first type of solvent is ethylenediamine, tripropylamine, morpholine, One or more of dicyclohexyl ether, ethylene glycol dimethyl ether and diethyl ether, the second type of solvent described in step (3) is ethanol, ethylenediamine, tripropylamine, cyclohexanol and ethylene glycol. One or more than two kinds.
5. 根据权利要求 2所述的纳米硅 /石墨烯锂离子电池负极材料的制备方法， 其特征在于： 步骤（1 ) 中所述金属锂的用量为电子溶液总重量的 1% ~ 5%, 助 溶剂的用量为电子溶液总重量的 0% ~ 5%。 5. The preparation method of nano silicon/graphene lithium ion battery negative electrode material according to claim 2, characterized in that: the amount of metallic lithium described in step (1) is 1% ~ 5% of the total weight of the electron solution, The dosage of co-solvent is 0% ~ 5% of the total weight of the electronic solution.
6. 根据权利要求 2所述的纳米硅 /石墨烯锂离子电池负极材料的制备方法， 其特征在于：步骤（ 3 )中所述氧化石墨水溶液或石墨烯悬浊液的质量分数为 0.5 ~ 1.5 g/L, 所述硝酸的质量浓度为 60% ~ 70%, 氧化石墨水溶液或石墨烯悬浊液与 硝酸的体积比为 1 : 2 ~ 10。 6. The preparation method of nano silicon/graphene lithium ion battery negative electrode material according to claim 2, characterized in that: the mass fraction of the graphite oxide aqueous solution or graphene suspension described in step (3) is 0.5 ~ 1.5 g/L, the mass concentration of the nitric acid is 60% ~ 70%, and the volume ratio of the graphite oxide aqueous solution or graphene suspension to the nitric acid is 1: 2 ~ 10.
7. 根据权利要求 2所述的纳米硅 /石墨烯锂离子电池负极材料的制备方法， 其特征在于： 步骤（ 3 ) 中所述胶样溶液的质量分数为 0.1 ~ 5 g/L。 7. The method for preparing nano-silicon/graphene lithium-ion battery negative electrode material according to claim 2, characterized in that: the mass fraction of the colloidal solution described in step (3) is 0.1 ~ 5 g/L.
8 报圾奴剎要炎 )所^ ό^ι纳失砝 /石 ,雾、烯锂惠子 Φ,池 极封舛 ό 法，
其特征在于： 步骤（4) 中纳米硅与氧化石墨烯的质量比 1: 5~10。 8 The report of the garbage slave is to be ignited) so^ ό^ιNalos weight/stone, mist, ene lithium Huizi Φ, Chi Ji Feng Shu ό method, It is characterized in that: in step (4), the mass ratio of nanometer silicon to graphene oxide is 1: 5~10.
9. 根据权利要求 2所述的纳米硅 /石墨烯锂离子电池负极材料的制备方法， 其特征在于： 步骤（4) 中补加电子溶液的质量百分比为 0%~ 5%, 超声处理的 频率为 40~80Hz。 9. The preparation method of nano silicon/graphene lithium ion battery negative electrode material according to claim 2, characterized in that: the mass percentage of the electronic solution added in step (4) is 0% ~ 5%, the frequency of ultrasonic treatment is 40~80Hz.
10. 根据权利要求 2所述的纳米硅 /石墨烯锂离子电池负极材料的制备方法， 其特征在于：步骤（ 5 )中的气体流速 20 - 100 mL/min,烧结温度为 500 °C ~ 800 °C , 煅烧 2 ~ 5 h。
10. The preparation method of nano silicon/graphene lithium ion battery negative electrode material according to claim 2, characterized in that: the gas flow rate in step (5) is 20-100 mL/min, and the sintering temperature is 500 °C ~ 800 °C, calcined for 2 to 5 hours.
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| CN115215341A (en) * | 2021-04-19 | 2022-10-21 | 四川物科金硅新材料科技有限责任公司 | Preparation method of nano silicon |
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