WO2022007402A1 - Silicon-containing powder for lithium ion battery negative eletrode material and preparation method therefor - Google Patents

Silicon-containing powder for lithium ion battery negative eletrode material and preparation method therefor Download PDF

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WO2022007402A1
WO2022007402A1 PCT/CN2021/075669 CN2021075669W WO2022007402A1 WO 2022007402 A1 WO2022007402 A1 WO 2022007402A1 CN 2021075669 W CN2021075669 W CN 2021075669W WO 2022007402 A1 WO2022007402 A1 WO 2022007402A1
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silicon
containing powder
negative electrode
powder
lithium ion
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French (fr)
Chinese (zh)
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胡亮
张少波
方伟
曹德福
夏永生
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马鞍山科达普锐能源科技有限公司
安徽科达铂锐能源科技有限公司
安徽科达新材料有限公司
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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 technical field of lithium ion batteries, and in particular relates to a silicon-containing powder for a negative electrode material of a lithium ion battery and a preparation method thereof.
  • the conventional lithium ion anode materials are mainly graphite anodes, but the theoretical specific capacity of graphite anodes is only 372mAh/g, which can no longer meet the urgent needs of users.
  • the theoretical capacity of silicon is as high as 4200mAh/g, which is more than 10 times that of the graphite anode material.
  • the coulombic efficiency of the silicon-carbon composite product is also close to that of the graphite anode, and it is cheap, environmentally friendly, and rich in earth reserves. It is a new generation of high-capacity products. The best choice for negative electrode materials.
  • silicon carbon material has many advantages as the negative electrode material of battery, silicon carbon material inevitably has a certain volume expansion effect during the charging and discharging process, which affects the initial efficiency and cycle performance of the battery. Therefore, there is still a need to find a silicon-containing powder for lithium-ion battery negative electrode materials that can alleviate the volume expansion during charging and discharging, and at the same time achieve the effect of improving electrochemical performance.
  • silicon carbon anode material The most important component of silicon carbon anode material is silicon. Silicon is not only related to the volume expansion coefficient of the anode material during the charge and discharge process, but also greatly affects the electrochemical performance of the anode material. In order to optimize the performance of the anode material, this paper The invention provides a silicon-containing powder for a negative electrode material of a lithium ion battery.
  • the silicon-containing powder contains 50-90 wt.% silicon, 5-30 wt.% oxygen and 5-20 wt.% zirconium.
  • the grain size is below 12nm.
  • the silicon-containing powder is detected by a field emission scanning electron microscope, and it can be observed that the silicon particles and zirconium particles in the silicon-containing powder are irregular in shape, and some zirconium particles have sharp edges and corners and are uniformly dispersed in the silicon particles.
  • the silicon-containing powder contains 55-85 wt.% silicon, and more preferably, the silicon-containing powder contains 65-75 wt.% silicon.
  • the silicon-containing powder is detected by an oxygen, nitrogen and hydrogen analyzer, and the oxygen content can be obtained to be 5-30 wt.%, preferably 10-25 wt.%, more preferably 15-20%.
  • part of the oxygen element exists on the surface of the silicon particles.
  • the part of the oxygen element forms silicon oxide on the surface of the silicon particles.
  • the silicon-containing powder is detected by an inductively coupled plasma emission spectrometer, and it is obtained that the zirconium content is 5-20 wt.%, preferably 10-15 wt.%.
  • the zirconium particles are in the form of zirconium oxide.
  • the silicon-containing powder has a true density of 1.2-2.6 g/cm 3 and a specific surface area of 2-300 m 2 /g.
  • the present invention also relates to a method for preparing the silicon-containing powder for lithium ion battery negative electrode material described in any one of the above, characterized in that:
  • micron silicon powder to the mixing tank matched with the sand mill.
  • the median particle size D50 of the micron silicon powder is 1-1000 ⁇ m, and the purity of the micron silicon powder is ⁇ 99%.
  • solvent to the mixing tank for wet grinding to control the stirring.
  • the solid content of the mixed solution in the tank is 5-40%, start slow stirring, fill the sand mill with 0.05-0.5mm zirconia balls, and control the mass ratio of zirconia beads to silicon powder to be 15:1 ⁇ 20:1, the main engine speed of the sand mill is 900-1000rpm, the grinding time is 10-90h, preferably 35-60h, and the obtained silicon slurry is heated and dried to obtain silicon-containing powder;
  • the structure and shape of the sand mill stirring shaft is a disc type, a rod type or a rod disc type;
  • the grinding solvent is pure water, methanol, toluene, benzyl alcohol, ethanol, ethylene glycol, chlorinated ethanol, propanol, isopropanol, propylene glycol, butanol, n-butanol, isobutanol, amyl alcohol, neopentyl alcohol One or more of alcohol, octanol, acetone or cyclohexanone.
  • the viscosity of the slurry after wet grinding is 0-100 Pa ⁇ s.
  • the solid content of the wet-milled slurry is 5-40%, preferably 10-25%.
  • the present invention also relates to a negative electrode material for a lithium ion battery, which is characterized in that it comprises the silicon-containing powder described in any one of the above in combination with a carbon-based material, wherein the carbon-based material is artificial graphite, natural graphite, porous One or more of layered graphite sheets, soft carbon, hard carbon, graphene, carbon nanotubes, carbon nanofibers, porous carbon, and cracked carbon.
  • the silicon-containing powder prepared by wet grinding of the present invention can significantly reduce its absolute volume expansion during charging and discharging due to the large reduction in macroscopic and microscopic dimensions;
  • the silicon-containing powder prepared by wet grinding of the present invention contains 5-30 wt.% oxygen, which partially exists on the surface of nano-silicon to form silicon oxide, which can reduce the surface activation energy of nano-silicon and form
  • the protective layer on the one hand, can reduce the risk of spontaneous combustion of nanoparticles in the production process and improve the safety factor; on the other hand, silicon oxide can inhibit the volume expansion of nano-silicon during the charging and discharging process, and improve the cycle performance of the negative electrode material;
  • the silicon-containing powder prepared by wet grinding in the present invention contains 5-20 wt.% zirconium.
  • Zirconium is an electrochemically inert component, which will not intercalate and delithiate, and can stabilize the powder structure and further inhibit nano The expansion effect of silicon;
  • the silicon-containing powder prepared by the present invention when used in a negative electrode material, it can provide high specific capacity and excellent cycle performance.
  • Example 1 is a field emission scanning electron microscope image of the silicon-containing powder prepared in Example 1 of the present invention.
  • Example 3 is the XRD data of the silicon-containing powder prepared in Example 1 of the present invention.
  • FIG. 4 is a buckling charge-discharge curve of the negative electrode material prepared in Example 1 of the present invention.
  • a preparation method of a lithium ion battery negative electrode material containing silicon powder comprising the following steps:
  • Preparation of silicon-containing powder Add 1000 g of silicon powder with a median particle size of 1 ⁇ m to the stirring tank equipped with the sand mill, and the purity of the silicon powder is 99.92%, and then add methanol into the stirring tank to control the stirring tank.
  • the solid content of the mixed solution is 10%, start slow stirring, fill the sand mill with 0.3mm zirconia beads, control the mass ratio of zirconia beads to silicon powder to be 15:1, and the speed of the main machine of the sand mill is 1000rpm, grinding for 60h, the obtained silicon slurry, and then the silicon slurry is heated and dried to obtain a silicon-containing powder.
  • the median particle size D50 of the silicon-containing powder is 56nm, and the grain size of silicon is 7.9nm.
  • the silicon powder contained 65.6 wt.% silicon, 26.3 wt.% oxygen and 8.1 wt.% zirconium.
  • Step (2) Preparation of negative electrode material for lithium ion battery:
  • the silicon-containing powder obtained in step (1) is mixed with artificial graphite in a mass ratio of 7:3 to obtain the negative electrode material.
  • a preparation method of a lithium ion battery negative electrode material containing silicon powder comprising the following steps:
  • Preparation of silicon-containing powder Add 1000 g of silicon powder with a median particle size of 50 ⁇ m to the stirring tank matched with the sand mill, and the purity of the silicon powder is 99.53%. Then add propanol to the stirring tank to control the stirring tank. The solid content of the mixed solution is 15%, start slow stirring, fill the sand mill with 0.05mm zirconia beads, control the mass ratio of zirconia beads to silicon powder to be 18:1, and the main engine speed of the sand mill.
  • the median particle size D50 of the silicon-containing powder is 71 nm
  • the grain size of silicon is 8.5 nm
  • the silicon-containing powder is contains 74.4 wt.% silicon, 19.4 wt.% oxygen and 6.2 wt.% zirconium;
  • Step (2) Preparation of negative electrode material for lithium ion battery:
  • the silicon-containing powder obtained in step (1) is mixed with natural graphite and graphene in a ratio of 7:2:1 to obtain the negative electrode material.
  • a preparation method of a lithium ion battery negative electrode material containing silicon powder comprising the following steps:
  • Preparation of silicon-containing powder Add 1000 g of silicon powder with a median particle size of 500 ⁇ m to the stirring tank matched with the sand mill, and the purity of the silicon powder is 99.67%. Then add butanol to the stirring tank to control the stirring tank.
  • the solid content of the mixed solution is 10%, start slow stirring, fill the sand mill with 0.2mm zirconia beads, control the mass ratio of zirconia beads to silicon powder to be 20:1, and the speed of the main machine of the sand mill.
  • the median particle size D50 of the silicon-containing powder is 86 nm
  • the grain size of silicon is 10.3 nm
  • the silicon-containing powder is contains 57.6 wt.% silicon, 24.1 wt.% oxygen and 18.3 wt.% zirconium;
  • Step (2) Preparation of negative electrode material for lithium ion battery:
  • the silicon-containing powder obtained in step (1) is mixed with soft carbon at a ratio of 7:3 to obtain the negative electrode material.
  • a preparation method of a lithium ion battery negative electrode material containing silicon powder comprising the following steps:
  • Preparation of silicon-containing powder Add 1000 g of silicon powder with a median particle size of 1000 ⁇ m to the stirring tank equipped with the sand mill, and the purity of the silicon powder is 99.29%, and then add absolute ethanol to the stirring tank to control the stirring.
  • the solid content of the mixed solution in the tank is 25%, start slow stirring, fill the sand mill with 0.5mm zirconia beads, control the mass ratio of zirconia beads and silicon powder to 20:1, and the host of the sand mill
  • the rotating speed is 950 rpm, grinding is performed for 60 hours, and the obtained silicon slurry is heated and dried to obtain silicon-containing powder.
  • the silicon-containing powder has a median particle size D50 of 102 nm, a grain size of silicon of 11.6 nm, and the silicon-containing powder contains 83.5 wt. % silicon, 5.3 wt. % oxygen and 11.2 wt. % zirconium;
  • step (1) Preparation of negative electrode material for lithium ion battery:
  • the silicon-containing powder obtained in step (1) is mixed with hard carbon and carbon nanometers at a ratio of 7:2:1 to obtain the negative electrode material.
  • step (2) the silicon-containing powder obtained in step (1) is mixed with natural graphite in a mass ratio of 7:3, and the rest are the same as in Example 1, and will not be repeated here.
  • step (2) the silicon-containing powder obtained in step (1) is mixed with soft carbon in a mass ratio of 7:3, and the rest are the same as in Example 1, and are not repeated here.
  • step (2) the silicon-containing powder obtained in step (1) and carbon nanotubes are mixed at a mass ratio of 7:3, and the rest are the same as those in Example 1, which will not be repeated here.
  • Example 1 The difference from Example 1 is that the silicon powder raw material is not nano-sized, and the rest are the same as in Example 1, and will not be repeated here.
  • Example 1 The difference from Example 1 is that the grinding time is adjusted to 10h, and the rest are the same as those in Example 1, which will not be repeated here.
  • Example 1 The difference from Example 1 is that the grinding time is adjusted to 30h, and the rest are the same as those in Example 1, which will not be repeated here.
  • Example 1 The difference from Example 1 is that the grinding time is adjusted to 90h, and the rest are the same as those in Example 1, which will not be repeated here.
  • Example 1 The difference from Example 1 is that zirconia beads are not used, but cemented carbide beads of the same size are used, so that there is no zirconium element in the obtained silicon-containing powder.
  • Example 1 The difference from Example 1 is that dry grinding is performed without adding a grinding solvent, and the rest are the same as in Example 1, and will not be repeated here.
  • the particle size range of the material was tested with a Malvern Mastersizer 3000.
  • the morphology and patterning of the materials were analyzed by field emission scanning electron microscopy (SEM) (JSM-7160).
  • the oxygen, nitrogen and hydrogen analyzer (ONH) is used to accurately and quickly determine the oxygen content in materials.
  • XRD diffractometer (X'Pert3 Powder) was used to analyze the phase of the material to determine the grain size of the material.
  • the true density of the powder was tested by the American Mack true density tester (AccuPyc II 1340).
  • the viscosity of the slurry was measured using a digital display viscometer (NDJ-5S type).
  • the silicon-containing powders described in Examples 1-7 all had a true density of 1.2-2.6 g/cm 3 and a specific surface area of 2-300 m 2 /g; The viscosity is 0 to 100 Pa ⁇ s.
  • the field emission scanning electron microscope image of the silicon-containing powder prepared in Example 1 is shown in Figure 1; the particle size detection data of the silicon-containing powder is shown in Figure 2; the XRD data of the silicon-containing powder is shown in Figure 3; the negative electrode prepared in Example 1 is shown in Figure 2.
  • the charge-discharge curve of the material is shown in Figure 4.
  • the silicon-containing negative electrode materials obtained in Examples 1 to 7 and Comparative Examples 1 to 6 were mixed with negative electrode material, conductive agent carbon black (Super P), carbon nanotubes and LA133 glue in a mass ratio of 91:2:2:5. Solvent pure water, homogenize, control the solid content at 45%, coat on copper foil current collector, vacuum dry to prepare negative pole piece.
  • a button cell was assembled in an argon atmosphere glove box.
  • the charge and discharge test of the button battery is carried out, the voltage range is 5mV ⁇ 1.5V, and the current density is 80mA/g.
  • the first reversible capacity and efficiency of the silicon-containing anode materials in Examples and Comparative Examples were measured.
  • the test equipment of the button battery adopts the LAND battery test system of Wuhan Jinnuo Electronics Co., Ltd.
  • Table 1 is the performance test results of the silicon carbon anode materials in Examples 1-7 and Comparative Examples 1-6
  • the median particle size, silicon grain size, oxygen content and zirconium content of the silicon-containing powder can be adjusted to obtain the negative electrode material with the best comprehensive performance.
  • the first 50-week cycle capacity retention rate of the battery prepared with silicon-containing powder in Example 1 is the best, which is 91.7%, but due to the high oxygen content, the first Coulomb efficiency has a certain loss, which is only 80.4%; in Examples 2-4
  • the oxygen content of the silicon-containing powder gradually decreases, and the first coulombic efficiency of the prepared battery is high, ranging from 81.2 to 84.7%, but its cycle performance has a decreasing trend.
  • the zirconium content of the silicon-containing powder in Example 3 is high, it is beneficial to improve the cycle performance, and the cycle capacity retention rate for the first 50 weeks is 90.2%.
  • the obtained silicon-containing powder when the obtained silicon-containing powder was mixed with natural graphite, soft carbon and carbon nanotubes at a mass ratio of 7:3, respectively, the obtained silicon-carbon negative electrode material had the first capacity and the first Coulomb efficiency.
  • the cycle performance is basically the same as the first 50 weeks. It can be seen that the performance of the silicon carbon anode material is mainly affected by the performance indicators of nano-silicon.
  • Comparative Example 6 when dry grinding was performed without adding an organic solvent, the temperature of the material was too high, and there was agglomeration. The grinding was carried out for only 1 hour, and the material was taken out. The performance of the test was close to that of the silicon powder raw material.
  • the present invention illustrates the detailed process equipment and process flow of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned detailed process equipment and process flow, that is, it does not mean that the present invention must rely on the above-mentioned detailed process equipment and process flow. Process flow can be implemented. Those skilled in the art should understand that any improvement of the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Abstract

The present invention belongs to the technical field of lithium ion batteries, and specifically relates to a silicon-containing powder for a lithium ion battery negative electrode material and a preparation method therefor. The silicon-containing powder contains 50-90 wt.% silicon, 5-30 wt.%. oxygen, and 5-20 wt.% zirconium. The median particle size D50 of the silicon-containing powder is 110 nm or less. The silicon-containing powder is analyzed by means of X-ray diffraction patterns according to the half-peak width of diffraction peaks attributed to Si (111) near 2θ=28.4°, and the grain size of silicon calculated by the Scherrer formula is below 12 nm. Compared to the existing technology, the silicon-containing powder prepared by the present invention can provide a high specific capacity and excellent cyclic performance when used in a negative electrode material.

Description

一种锂离子电池负极材料用含硅粉末及其制备方法A kind of silicon-containing powder for negative electrode material of lithium ion battery and preparation method thereof 技术领域technical field
本发明属于锂离子电池技术领域，具体涉及一种锂离子电池负极材料用含硅粉末及其制备方法。The invention belongs to the technical field of lithium ion batteries, and in particular relates to a silicon-containing powder for a negative electrode material of a lithium ion battery and a preparation method thereof.
背景技术Background technique
目前常规的锂离子负极材料以石墨负极为主，但石墨负极的理论比容量仅为372mAh/g，已无法满足用户的迫切需求。硅的理论容量高达4200mAh/g，是石墨负极材料容量的10倍以上，同时，硅碳复合品的库伦效率也和石墨负极接近，且价格便宜、环境友好、地球储量丰富，是新一代高容量负极材料的最优选择。但由于硅材料本身导电性差，且硅在充电时体积膨胀高达300％，充放电过程中的体积膨胀容易导致材料结构的崩塌和电极的剥落、粉化，造成活性材料损失，进而导致电池容量锐减，循环性能严重恶化。为了克服这一困难，科研人员通过掺杂、纳米化等方法来解决这个问题。硅碳材料、硅氧材料、硅合金、多孔硅等材料在解决该问题方面取得了一定的进展，特别是硅碳材料，已经实现商业化生产。At present, the conventional lithium ion anode materials are mainly graphite anodes, but the theoretical specific capacity of graphite anodes is only 372mAh/g, which can no longer meet the urgent needs of users. The theoretical capacity of silicon is as high as 4200mAh/g, which is more than 10 times that of the graphite anode material. At the same time, the coulombic efficiency of the silicon-carbon composite product is also close to that of the graphite anode, and it is cheap, environmentally friendly, and rich in earth reserves. It is a new generation of high-capacity products. The best choice for negative electrode materials. However, due to the poor conductivity of the silicon material itself, and the volume expansion of silicon during charging is as high as 300%, the volume expansion during charging and discharging can easily lead to the collapse of the material structure and the peeling and pulverization of the electrodes, resulting in the loss of active materials, which in turn leads to sharp battery capacity. decrease, the cycle performance is seriously deteriorated. In order to overcome this difficulty, researchers have solved this problem by doping, nanoscale and other methods. Materials such as silicon-carbon materials, silicon-oxygen materials, silicon alloys, and porous silicon have made some progress in solving this problem, especially silicon-carbon materials, which have been commercially produced.
尽管硅碳材料作为电池的负极材料时具有很多优点，但是硅碳材料在充放电过程中不可避免的具有一定的体积膨胀效应，从而影响电池的首次效率发挥和循环性能。因此，仍需寻找一种能够缓解充放电过程中的体积膨胀，同时达到改善电化学性能效果的锂离子电池负极材料用含硅粉末。Although silicon carbon material has many advantages as the negative electrode material of battery, silicon carbon material inevitably has a certain volume expansion effect during the charging and discharging process, which affects the initial efficiency and cycle performance of the battery. Therefore, there is still a need to find a silicon-containing powder for lithium-ion battery negative electrode materials that can alleviate the volume expansion during charging and discharging, and at the same time achieve the effect of improving electrochemical performance.
发明内容SUMMARY OF THE INVENTION
硅碳负极材料中最重要的组成部分为硅，硅不仅关系到负极材料在充放电过程中的体积膨胀系数，也极大的影响着负极材料的电化学性能，为了优化负极材料的性能，本发明提供了一种锂离子电池负极材料用含硅粉末，该含硅粉末中有50～90wt.％的硅、5～30wt.％的氧和5～20wt.％的锆，所述含硅粉末的中值粒度D50在110nm以下；所述含硅粉末通过X射线衍射图案分析，根据2θ＝28.4°附近的归属于Si(111)的衍射峰的半峰宽值，由Scherrer公式计算出硅的晶粒尺寸在12nm以下。The most important component of silicon carbon anode material is silicon. Silicon is not only related to the volume expansion coefficient of the anode material during the charge and discharge process, but also greatly affects the electrochemical performance of the anode material. In order to optimize the performance of the anode material, this paper The invention provides a silicon-containing powder for a negative electrode material of a lithium ion battery. The silicon-containing powder contains 50-90 wt.% silicon, 5-30 wt.% oxygen and 5-20 wt.% zirconium. The silicon-containing powder The median particle size D50 is below 110 nm; the silicon-containing powder is analyzed by X-ray diffraction pattern, according to the half width value of the diffraction peak attributed to Si(111) in the vicinity of 2θ=28.4°, and the Scherrer formula calculates the value of silicon The grain size is below 12nm.
优选的，所述含硅粉末通过场发射扫描电镜进行检测，可观察到含硅粉末中的硅颗粒和锆颗粒都呈不规则形状，部分锆颗粒具有尖锐的棱角，均匀分散在硅颗粒中。Preferably, the silicon-containing powder is detected by a field emission scanning electron microscope, and it can be observed that the silicon particles and zirconium particles in the silicon-containing powder are irregular in shape, and some zirconium particles have sharp edges and corners and are uniformly dispersed in the silicon particles.
优选的，该含硅粉末中有55～85wt.％的硅，更优选的，该含硅粉末中有65～75wt.％的硅。Preferably, the silicon-containing powder contains 55-85 wt.% silicon, and more preferably, the silicon-containing powder contains 65-75 wt.% silicon.
优选的，所述含硅粉末通过氧氮氢分析仪检测，可得到氧含量为5～30wt.％，优选为10～25wt.％，更优选为15～20％。Preferably, the silicon-containing powder is detected by an oxygen, nitrogen and hydrogen analyzer, and the oxygen content can be obtained to be 5-30 wt.%, preferably 10-25 wt.%, more preferably 15-20%.
优选的，所述部分氧元素存在于硅颗粒的表面。优选的，所述部分氧元素在硅颗粒的表面形成硅氧化物。Preferably, part of the oxygen element exists on the surface of the silicon particles. Preferably, the part of the oxygen element forms silicon oxide on the surface of the silicon particles.
优选的，所述含硅粉末通过电感耦合等离子体发射光谱仪检测，得到锆含量为5～20wt.％，优选为10～15wt.％。Preferably, the silicon-containing powder is detected by an inductively coupled plasma emission spectrometer, and it is obtained that the zirconium content is 5-20 wt.%, preferably 10-15 wt.%.
优选的，所述锆颗粒以锆氧化物形式存在。Preferably, the zirconium particles are in the form of zirconium oxide.
优选的，所述含硅粉末具有1.2～2.6g/cm 3的真密度，具有2～300m 2/g的比表面积。 Preferably, the silicon-containing powder has a true density of 1.2-2.6 g/cm 3 and a specific surface area of 2-300 m 2 /g.
本发明还涉及一种制备上述任一项所述的锂离子电池负极材料用含硅粉末的方法，其特征在于：The present invention also relates to a method for preparing the silicon-containing powder for lithium ion battery negative electrode material described in any one of the above, characterized in that:
在砂磨机配套的搅拌罐中加入微米硅粉，微米硅粉的中值粒径D50为1～1000μm，微米硅粉的纯度≥99％，再在搅拌罐中加入溶剂湿法研磨，控制搅拌罐中的混合溶液的固含量为5～40％，开启慢速搅拌，砂磨机中填入0.05～0.5mm的氧化锆球磨珠，控制氧化锆珠与硅粉的质量比为15:1～20:1，砂磨机的主机转速为900～1000rpm，研磨时间为10-90h，优选为35～60h，得到的硅浆料，再将硅浆料进行加热干燥，得到含硅粉末；Add micron silicon powder to the mixing tank matched with the sand mill. The median particle size D50 of the micron silicon powder is 1-1000 μm, and the purity of the micron silicon powder is ≥99%. Then add solvent to the mixing tank for wet grinding to control the stirring. The solid content of the mixed solution in the tank is 5-40%, start slow stirring, fill the sand mill with 0.05-0.5mm zirconia balls, and control the mass ratio of zirconia beads to silicon powder to be 15:1～ 20:1, the main engine speed of the sand mill is 900-1000rpm, the grinding time is 10-90h, preferably 35-60h, and the obtained silicon slurry is heated and dried to obtain silicon-containing powder;
所述砂磨机搅拌轴的结构形状为盘式，棒式或棒盘式中的一种；The structure and shape of the sand mill stirring shaft is a disc type, a rod type or a rod disc type;
所述研磨溶剂为纯水、甲醇、甲苯、苯甲醇、乙醇、乙二醇、氯化乙醇、丙醇、异丙醇、丙二醇、丁醇、正丁醇、异丁醇、戊醇、新戊醇、辛醇、丙酮或环已酮的一种或多种。The grinding solvent is pure water, methanol, toluene, benzyl alcohol, ethanol, ethylene glycol, chlorinated ethanol, propanol, isopropanol, propylene glycol, butanol, n-butanol, isobutanol, amyl alcohol, neopentyl alcohol One or more of alcohol, octanol, acetone or cyclohexanone.
优选的，所述湿法研磨后的浆液的粘度为0～100Pa·s。Preferably, the viscosity of the slurry after wet grinding is 0-100 Pa·s.
优选的，所述湿法研磨后的浆液的固含量为5～40％，优选10～25％。Preferably, the solid content of the wet-milled slurry is 5-40%, preferably 10-25%.
本发明还涉及一种锂离子电池负极材料，其特征在于，其包含上述任一项所述的含硅粉末与碳类材料结合，所述碳类材料为人造石墨、天然石墨、多孔石墨、多层石墨片、软碳、硬碳、石墨烯、碳纳米管、碳纳米纤维、多孔碳、裂解碳中的一种或多种。The present invention also relates to a negative electrode material for a lithium ion battery, which is characterized in that it comprises the silicon-containing powder described in any one of the above in combination with a carbon-based material, wherein the carbon-based material is artificial graphite, natural graphite, porous One or more of layered graphite sheets, soft carbon, hard carbon, graphene, carbon nanotubes, carbon nanofibers, porous carbon, and cracked carbon.
本发明制备的锂离子电池负极材料用含硅粉末的优点在于：The advantages of the silicon-containing powder for the lithium ion battery negative electrode material prepared by the present invention are:
(1)本发明通过湿法研磨制备的含硅粉末，由于宏观和微观尺寸的大幅度降低，能明显降低其在充放电过程中的绝对体积膨胀；(1) The silicon-containing powder prepared by wet grinding of the present invention can significantly reduce its absolute volume expansion during charging and discharging due to the large reduction in macroscopic and microscopic dimensions;
(2)本发明通过湿法研磨制备的含硅粉末，含有5～30wt.％的氧，部分存在于纳米硅的表面，形成硅氧化物，硅氧化物能降低纳米硅的表面活化能，形成保护层，一方面能降低纳米颗粒在生产过程中的自燃风险，提升安全系数，另一方面硅氧化物能抑制纳米硅在充放电过程中的体积膨胀，提升负极材料的循环性能；(2) The silicon-containing powder prepared by wet grinding of the present invention contains 5-30 wt.% oxygen, which partially exists on the surface of nano-silicon to form silicon oxide, which can reduce the surface activation energy of nano-silicon and form The protective layer, on the one hand, can reduce the risk of spontaneous combustion of nanoparticles in the production process and improve the safety factor; on the other hand, silicon oxide can inhibit the volume expansion of nano-silicon during the charging and discharging process, and improve the cycle performance of the negative electrode material;
(3)本发明通过湿法研磨制备的含硅粉末，含有5～20wt.％的锆，锆为电化学惰性组分，不会嵌锂和脱锂，且能稳定粉体结构，进一步抑制纳米硅的膨胀效应；(3) The silicon-containing powder prepared by wet grinding in the present invention contains 5-20 wt.% zirconium. Zirconium is an electrochemically inert component, which will not intercalate and delithiate, and can stabilize the powder structure and further inhibit nano The expansion effect of silicon;
(4)相比于现有技术，本发明制备的含硅粉末用在负极材料中时，能提供高比容量和优秀的循环性能。(4) Compared with the prior art, when the silicon-containing powder prepared by the present invention is used in a negative electrode material, it can provide high specific capacity and excellent cycle performance.
附图说明Description of drawings
下面结合附图对本发明进一步说明。The present invention will be further described below with reference to the accompanying drawings.
图1是本发明实施例1制得的含硅粉末的场发射扫描电镜图；1 is a field emission scanning electron microscope image of the silicon-containing powder prepared in Example 1 of the present invention;
图2是本发明实施例1制得的含硅粉末的粒度检测数据；2 is the particle size detection data of the silicon-containing powder prepared in Example 1 of the present invention;
图3是本发明实施例1制得的含硅粉末的XRD数据；3 is the XRD data of the silicon-containing powder prepared in Example 1 of the present invention;
图4是本发明实施例1制得的负极材料的扣电充放电曲线。FIG. 4 is a buckling charge-discharge curve of the negative electrode material prepared in Example 1 of the present invention.
具体实施方式detailed description
为便于理解本发明，本发明列举实施例如下。本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应视为对本发明的具体限制。In order to facilitate the understanding of the present invention, examples of the present invention are as follows. It should be understood by those skilled in the art that the embodiments are only for helping the understanding of the present invention, and should not be regarded as a specific limitation of the present invention.
实施例1Example 1
一种含硅粉末的锂离子电池负极材料的制备方法，包括如下步骤：A preparation method of a lithium ion battery negative electrode material containing silicon powder, comprising the following steps:
(1)含硅粉末的制备：在砂磨机配套的搅拌罐中加入中值粒径为1μm的硅粉1000g，硅粉的纯度为99.92％，再在搅拌罐中加入甲醇，控制搅拌罐中的混合溶液的固含量为10％，开启慢速搅拌，砂磨机中填入0.3mm的氧化锆珠，控制氧化锆珠与硅粉的质量比为15：1，砂磨机的主机转速为1000rpm，研磨60h，得到的硅浆料，再将硅浆料进行加热干燥，得到含硅粉末，通过检测，该含硅粉末的中值粒度D50为56nm，硅的晶粒尺寸为7.9nm，含硅粉末中含有65.6wt.％的硅、26.3wt.％的氧和8.1wt.％的锆。(1) Preparation of silicon-containing powder: Add 1000 g of silicon powder with a median particle size of 1 μm to the stirring tank equipped with the sand mill, and the purity of the silicon powder is 99.92%, and then add methanol into the stirring tank to control the stirring tank. The solid content of the mixed solution is 10%, start slow stirring, fill the sand mill with 0.3mm zirconia beads, control the mass ratio of zirconia beads to silicon powder to be 15:1, and the speed of the main machine of the sand mill is 1000rpm, grinding for 60h, the obtained silicon slurry, and then the silicon slurry is heated and dried to obtain a silicon-containing powder. Through testing, the median particle size D50 of the silicon-containing powder is 56nm, and the grain size of silicon is 7.9nm. The silicon powder contained 65.6 wt.% silicon, 26.3 wt.% oxygen and 8.1 wt.% zirconium.
(2)锂离子电池负极材料的制备：将步骤(1)所得的含硅粉末与人造石墨按质量比7:3进行混合，得到所述负极材料。(2) Preparation of negative electrode material for lithium ion battery: The silicon-containing powder obtained in step (1) is mixed with artificial graphite in a mass ratio of 7:3 to obtain the negative electrode material.
实施例2Example 2
一种含硅粉末的锂离子电池负极材料的制备方法，包括如下步骤：A preparation method of a lithium ion battery negative electrode material containing silicon powder, comprising the following steps:
(1)含硅粉末的制备：在砂磨机配套的搅拌罐中加入中值粒径为50μm的硅粉1000g，硅粉的纯度为99.53％，再在搅拌罐中加入丙醇，控制搅拌罐中的混合溶液的固含量为15％，开启慢速搅拌，砂磨机中填入0.05mm的氧化锆珠，控制氧化锆珠与硅粉的质量比为18:1，砂磨 机的主机转速为950rpm，研磨35h，得到的硅浆料，再将硅浆料进行加热干燥，得到含硅粉末，该含硅粉末的中值粒度D50为71nm，硅的晶粒尺寸为8.5nm，含硅粉末中含有74.4wt.％的硅、19.4wt.％的氧和6.2wt.％的锆；(1) Preparation of silicon-containing powder: Add 1000 g of silicon powder with a median particle size of 50 μm to the stirring tank matched with the sand mill, and the purity of the silicon powder is 99.53%. Then add propanol to the stirring tank to control the stirring tank. The solid content of the mixed solution is 15%, start slow stirring, fill the sand mill with 0.05mm zirconia beads, control the mass ratio of zirconia beads to silicon powder to be 18:1, and the main engine speed of the sand mill. 950 rpm, grinding for 35 hours, the obtained silicon slurry, and then heating and drying the silicon slurry to obtain silicon-containing powder, the median particle size D50 of the silicon-containing powder is 71 nm, the grain size of silicon is 8.5 nm, and the silicon-containing powder is contains 74.4 wt.% silicon, 19.4 wt.% oxygen and 6.2 wt.% zirconium;
(2)锂离子电池负极材料的制备：将步骤(1)所得的含硅粉末与天然造石墨、石墨烯按7:2:1进行混合，得到所述负极材料。(2) Preparation of negative electrode material for lithium ion battery: The silicon-containing powder obtained in step (1) is mixed with natural graphite and graphene in a ratio of 7:2:1 to obtain the negative electrode material.
实施例3Example 3
一种含硅粉末的锂离子电池负极材料的制备方法，包括如下步骤：A preparation method of a lithium ion battery negative electrode material containing silicon powder, comprising the following steps:
(1)含硅粉末的制备：在砂磨机配套的搅拌罐中加入中值粒径为500μm的硅粉1000g，硅粉的纯度为99.67％，再在搅拌罐中加入丁醇，控制搅拌罐中的混合溶液的固含量为10％，开启慢速搅拌，砂磨机中填入0.2mm的氧化锆珠，控制氧化锆珠与硅粉的质量比为20：1，砂磨机的主机转速为900rpm，研磨50h，得到的硅浆料，再将硅浆料进行加热干燥，得到含硅粉末，该含硅粉末的中值粒度D50为86nm，硅的晶粒尺寸为10.3nm，含硅粉末中含有57.6wt.％的硅、24.1wt.％的氧和18.3wt.％的锆；(1) Preparation of silicon-containing powder: Add 1000 g of silicon powder with a median particle size of 500 μm to the stirring tank matched with the sand mill, and the purity of the silicon powder is 99.67%. Then add butanol to the stirring tank to control the stirring tank. The solid content of the mixed solution is 10%, start slow stirring, fill the sand mill with 0.2mm zirconia beads, control the mass ratio of zirconia beads to silicon powder to be 20:1, and the speed of the main machine of the sand mill. 900 rpm, grinding for 50 hours, the obtained silicon slurry, and then heating and drying the silicon slurry to obtain silicon-containing powder, the median particle size D50 of the silicon-containing powder is 86 nm, the grain size of silicon is 10.3 nm, and the silicon-containing powder is contains 57.6 wt.% silicon, 24.1 wt.% oxygen and 18.3 wt.% zirconium;
(2)锂离子电池负极材料的制备：将步骤(1)所得的含硅粉末与软碳按7:3进行混合，得到所述负极材料。(2) Preparation of negative electrode material for lithium ion battery: The silicon-containing powder obtained in step (1) is mixed with soft carbon at a ratio of 7:3 to obtain the negative electrode material.
实施例4Example 4
一种含硅粉末的锂离子电池负极材料的制备方法，包括如下步骤：A preparation method of a lithium ion battery negative electrode material containing silicon powder, comprising the following steps:
(1)含硅粉末的制备：在砂磨机配套的搅拌罐中加入中值粒径为1000μm的硅粉1000g，硅粉的纯度为99.29％，再在搅拌罐中加入无水乙醇，控制搅拌罐中的混合溶液的固含量为25％，开启慢速搅拌，砂磨机中填入0.5mm的氧化锆珠，控制氧化锆珠与硅粉的质量比为20：1，砂磨机的主机转速为950rpm，研磨60h，得到的硅浆料，再将硅浆料进行加热干燥，得到含硅粉末。该含硅粉末的中值粒度D50为102nm，硅的晶粒尺寸为11.6nm，含硅粉末中含有83.5wt.％的硅、5.3wt.％的氧和11.2wt.％的锆；(1) Preparation of silicon-containing powder: Add 1000 g of silicon powder with a median particle size of 1000 μm to the stirring tank equipped with the sand mill, and the purity of the silicon powder is 99.29%, and then add absolute ethanol to the stirring tank to control the stirring. The solid content of the mixed solution in the tank is 25%, start slow stirring, fill the sand mill with 0.5mm zirconia beads, control the mass ratio of zirconia beads and silicon powder to 20:1, and the host of the sand mill The rotating speed is 950 rpm, grinding is performed for 60 hours, and the obtained silicon slurry is heated and dried to obtain silicon-containing powder. The silicon-containing powder has a median particle size D50 of 102 nm, a grain size of silicon of 11.6 nm, and the silicon-containing powder contains 83.5 wt. % silicon, 5.3 wt. % oxygen and 11.2 wt. % zirconium;
(2)锂离子电池负极材料的制备：将步骤(1)所得的含硅粉末与硬碳、碳纳米按7:2:1进行混合，得到所述负极材料。(2) Preparation of negative electrode material for lithium ion battery: The silicon-containing powder obtained in step (1) is mixed with hard carbon and carbon nanometers at a ratio of 7:2:1 to obtain the negative electrode material.
实施例5Example 5
与实施例1的区别在于步骤(2)中，将步骤(1)所得的含硅粉末与天然石墨按质量比7:3进行混合，其余同实施例1，这里不再赘述。The difference from Example 1 is that in step (2), the silicon-containing powder obtained in step (1) is mixed with natural graphite in a mass ratio of 7:3, and the rest are the same as in Example 1, and will not be repeated here.
实施例6Example 6
与实施例1的区别在于步骤(2)中，将步骤(1)所得的含硅粉末与软碳按质量比7:3 进行混合，其余同实施例1，这里不再赘述。The difference from Example 1 is that in step (2), the silicon-containing powder obtained in step (1) is mixed with soft carbon in a mass ratio of 7:3, and the rest are the same as in Example 1, and are not repeated here.
实施例7Example 7
与实施例1的区别在于步骤(2)中，将步骤(1)所得的含硅粉末与碳纳米管按质量比7:3进行混合，其余同实施例1，这里不再赘述。The difference from Example 1 is that in step (2), the silicon-containing powder obtained in step (1) and carbon nanotubes are mixed at a mass ratio of 7:3, and the rest are the same as those in Example 1, which will not be repeated here.
对比例1Comparative Example 1
与实施例1的区别在于，即硅粉原料不进行纳米化，其余同实施例1，这里不再赘述。The difference from Example 1 is that the silicon powder raw material is not nano-sized, and the rest are the same as in Example 1, and will not be repeated here.
对比例2Comparative Example 2
与实施例1的区别在于，将研磨时间调整为10h，其余同实施例1，这里不再赘述。The difference from Example 1 is that the grinding time is adjusted to 10h, and the rest are the same as those in Example 1, which will not be repeated here.
对比例3Comparative Example 3
与实施例1的区别在于，将研磨时间调整为30h，其余同实施例1，这里不再赘述。The difference from Example 1 is that the grinding time is adjusted to 30h, and the rest are the same as those in Example 1, which will not be repeated here.
对比例4Comparative Example 4
与实施例1的区别在于，将研磨时间调整为90h，其余同实施例1，这里不再赘述。The difference from Example 1 is that the grinding time is adjusted to 90h, and the rest are the same as those in Example 1, which will not be repeated here.
对比例5Comparative Example 5
与实施例1的区别在于，不使用氧化锆珠，而是同样尺寸的硬质合金珠，使所得含硅粉末中没有锆元素，其余同实施例1，这里不再赘述。The difference from Example 1 is that zirconia beads are not used, but cemented carbide beads of the same size are used, so that there is no zirconium element in the obtained silicon-containing powder.
对比例6Comparative Example 6
与实施例1的区别在于，不加入研磨溶剂，进行干法研磨，其余同实施例1，这里不再赘述。The difference from Example 1 is that dry grinding is performed without adding a grinding solvent, and the rest are the same as in Example 1, and will not be repeated here.
采用以下方法对实施例1至7和对比例1至6中含硅负极材料进行测试：The silicon-containing anode materials in Examples 1 to 7 and Comparative Examples 1 to 6 were tested by the following methods:
采用马尔文激光粒度仪Mastersizer 3000测试材料粒度范围。The particle size range of the material was tested with a Malvern Mastersizer 3000.
采用场发射扫描电镜(SEM)(JSM-7160)分析材料的形貌和图形处理。The morphology and patterning of the materials were analyzed by field emission scanning electron microscopy (SEM) (JSM-7160).
采用氧氮氢分析仪(ONH)精准、快速的测定材料中的氧元素含量。The oxygen, nitrogen and hydrogen analyzer (ONH) is used to accurately and quickly determine the oxygen content in materials.
采用XRD衍射仪(X’Pert3 Powder)对材料进行物相分析，确定材料的晶粒尺寸。XRD diffractometer (X'Pert3 Powder) was used to analyze the phase of the material to determine the grain size of the material.
采用美国麦克真密度仪(AccuPyc II 1340)测试粉末的真密度。The true density of the powder was tested by the American Mack true density tester (AccuPyc II 1340).
采用数字显示粘度计(NDJ-5S型)测试浆液的粘度。The viscosity of the slurry was measured using a digital display viscometer (NDJ-5S type).
检测到实施例1-7所述含硅粉末均具有1.2～2.6g/cm 3的真密度，具有2～300m 2/g的比表面积；实施例1-7所述湿法研磨后的浆液的粘度为0～100Pa·s。 It was detected that the silicon-containing powders described in Examples 1-7 all had a true density of 1.2-2.6 g/cm 3 and a specific surface area of 2-300 m 2 /g; The viscosity is 0 to 100 Pa·s.
实施例1制得的含硅粉末的场发射扫描电镜图见附图1；含硅粉末的粒度检测数据见附图2；含硅粉末的XRD数据见附图3；实施例1制得的负极材料的扣电充放电曲线见附图4。The field emission scanning electron microscope image of the silicon-containing powder prepared in Example 1 is shown in Figure 1; the particle size detection data of the silicon-containing powder is shown in Figure 2; the XRD data of the silicon-containing powder is shown in Figure 3; the negative electrode prepared in Example 1 is shown in Figure 2. The charge-discharge curve of the material is shown in Figure 4.
将实施例1至7和对比例1至6中得到含硅负极材料，按负极材料、导电剂炭黑(Super P)、 碳纳米管和LA133胶按质量比91:2:2:5混合在溶剂纯水中，进行匀浆，控制固含量在45％，涂覆于铜箔集流体上，真空烘干、制得负极极片。在氩气气氛手套箱中组装扣式电池，所用隔膜为Celgard2400，电解液为1mol/L的LiPF6/EC+DMC+EMC(v/v＝1:1:1)，对电极是金属锂片。对扣式电池进行充放电测试，电压区间是5mV～1.5V，电流密度为80mA/g。测得实施例和对比例中含硅负极材料的首次可逆容量和效率。The silicon-containing negative electrode materials obtained in Examples 1 to 7 and Comparative Examples 1 to 6 were mixed with negative electrode material, conductive agent carbon black (Super P), carbon nanotubes and LA133 glue in a mass ratio of 91:2:2:5. Solvent pure water, homogenize, control the solid content at 45%, coat on copper foil current collector, vacuum dry to prepare negative pole piece. A button cell was assembled in an argon atmosphere glove box. The separator used was Celgard2400, the electrolyte was 1 mol/L LiPF6/EC+DMC+EMC (v/v=1:1:1), and the counter electrode was a metal lithium sheet. The charge and discharge test of the button battery is carried out, the voltage range is 5mV ~ 1.5V, and the current density is 80mA/g. The first reversible capacity and efficiency of the silicon-containing anode materials in Examples and Comparative Examples were measured.
扣式电池的测试设备采用武汉金诺电子有限公司的LAND电池测试***。The test equipment of the button battery adopts the LAND battery test system of Wuhan Jinnuo Electronics Co., Ltd.
实施例与对比例的含硅粉末的性能测试结果见表1：The performance test results of the silicon-containing powders of Examples and Comparative Examples are shown in Table 1:
表1是实施例1-7与对比例1-6中的硅碳负极材料的性能测试结果Table 1 is the performance test results of the silicon carbon anode materials in Examples 1-7 and Comparative Examples 1-6
Figure PCTCN2021075669-appb-000001
Figure PCTCN2021075669-appb-000001
另外，由表1可见，采用本申请所述方法制备的含硅粉末，其中值粒度D50在110nm以下；所述纳米硅通过X射线衍射图案分析，根据2θ＝28.4°附近的归属于Si(111)的衍射峰的半峰宽值，由Scherrer式计算出纳米硅的晶粒在12nm以下。通过调整湿法研磨的工艺参数，可以调节含硅粉末的中值粒径、硅晶粒尺寸、氧含量和锆含量，以得到综合性能最优的负极材 料。实施例1中含硅粉末制备的电池的前50周循环容量保持率最优，为91.7％，但因氧含量较高，首次库伦效率有一定的损失，仅80.4％；实施例2-4中含硅粉末的氧含量逐渐降低，所制备的电池的首次库伦效率较高，为81.2～84.7％，但其循环性能有逐渐下降的趋势。因实施例3中含硅粉末的锆含量较高，有利于改善循环性能，前50周循环容量保持率为90.2％。In addition, it can be seen from Table 1 that the median particle size D50 of the silicon-containing powder prepared by the method described in the present application is below 110 nm; the nano-silicon is analyzed by X-ray diffraction pattern, according to the vicinity of 2θ=28.4° is attributed to Si (111 ) of the diffraction peak at half maximum width, calculated from the Scherrer formula, the crystal grains of nano-silicon are 12 nm or less. By adjusting the process parameters of wet grinding, the median particle size, silicon grain size, oxygen content and zirconium content of the silicon-containing powder can be adjusted to obtain the negative electrode material with the best comprehensive performance. The first 50-week cycle capacity retention rate of the battery prepared with silicon-containing powder in Example 1 is the best, which is 91.7%, but due to the high oxygen content, the first Coulomb efficiency has a certain loss, which is only 80.4%; in Examples 2-4 The oxygen content of the silicon-containing powder gradually decreases, and the first coulombic efficiency of the prepared battery is high, ranging from 81.2 to 84.7%, but its cycle performance has a decreasing trend. Because the zirconium content of the silicon-containing powder in Example 3 is high, it is beneficial to improve the cycle performance, and the cycle capacity retention rate for the first 50 weeks is 90.2%.
实施例5、6和7中，将所得的含硅粉末分别与天然石墨、软碳和碳纳米管按质量比7:3进行混合时，得到的硅碳负极材料的首次可以容量、首次库伦效率和前50周循环性能基本一致，由此可见，硅碳负极材料的性能主要受纳米硅性能指标的影响。In Examples 5, 6 and 7, when the obtained silicon-containing powder was mixed with natural graphite, soft carbon and carbon nanotubes at a mass ratio of 7:3, respectively, the obtained silicon-carbon negative electrode material had the first capacity and the first Coulomb efficiency. The cycle performance is basically the same as the first 50 weeks. It can be seen that the performance of the silicon carbon anode material is mainly affected by the performance indicators of nano-silicon.
对比例1中，硅粉原料不进行纳米化，电池的整体性能都很差；In Comparative Example 1, the silicon powder raw material is not nanosized, and the overall performance of the battery is very poor;
对比例2和对比3中，含硅粉末的研磨时间低于实施例1，虽首次可逆容量较高，但全电池的前50周循环容量保持率明显下降；In Comparative Example 2 and Comparative Example 3, the grinding time of the silicon-containing powder was lower than that of Example 1, and although the first reversible capacity was higher, the cycle capacity retention rate of the full battery decreased significantly in the first 50 weeks;
对比例4中将研磨时间调整为90h，所得含硅粉末中的氧含量和锆含量太高，使得电池的容量发挥大幅下降，仅912.6mAh/g，且首次库伦效率和循环性能也较差；In Comparative Example 4, the grinding time was adjusted to 90h, the oxygen content and zirconium content in the obtained silicon-containing powder were too high, so that the capacity of the battery was greatly reduced, only 912.6mAh/g, and the first Coulomb efficiency and cycle performance were also poor;
对比例5中使用硬质合金材质研磨珠，使所得含硅粉末中没有锆元素，电池的前50周循环容量保持率明显下降；In Comparative Example 5, cemented carbide grinding beads were used, so that there was no zirconium element in the obtained silicon-containing powder, and the cycle capacity retention rate of the battery decreased significantly in the first 50 weeks;
对比例6中，不加入有机溶剂，进行干法研磨时，物料的温升过高，且有结块的现象，研磨仅仅进行了1h，将物料取出，测试的性能与硅粉原料接近。In Comparative Example 6, when dry grinding was performed without adding an organic solvent, the temperature of the material was too high, and there was agglomeration. The grinding was carried out for only 1 hour, and the material was taken out. The performance of the test was close to that of the silicon powder raw material.
申请人声明，本发明通过上述实施例来说明本发明的详细工艺设备和工艺流程，但本发明并不局限于上述详细工艺设备和工艺流程，即不意味着本发明必须依赖上述详细工艺设备和工艺流程才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。The applicant declares that the present invention illustrates the detailed process equipment and process flow of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned detailed process equipment and process flow, that is, it does not mean that the present invention must rely on the above-mentioned detailed process equipment and process flow. Process flow can be implemented. Those skilled in the art should understand that any improvement of the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims (10)

  1. 一种锂离子电池负极材料用含硅粉末，该含硅粉末中有50～90wt.％的硅、5～30wt.％的氧和5～20wt.％的锆，所述含硅粉末的中值粒度D50在110nm以下；所述含硅粉末通过X射线衍射图案分析，根据2θ＝28.4°附近的归属于Si(111)的衍射峰的半峰宽值，由Scherrer公式计算出硅的晶粒尺寸在12nm以下。A silicon-containing powder for a negative electrode material of a lithium ion battery, the silicon-containing powder contains 50-90 wt.% silicon, 5-30 wt.% oxygen and 5-20 wt.% zirconium, and the median value of the silicon-containing powder is The particle size D50 is below 110 nm; the silicon-containing powder is analyzed by X-ray diffraction pattern, and the grain size of silicon is calculated by the Scherrer formula according to the half-peak width value of the diffraction peak attributable to Si(111) near 2θ=28.4° below 12nm.
  2. 根据权利要求1所述的一种锂离子电池负极材料用含硅粉末，其特征在于，所述含硅粉末通过场发射扫描电镜进行检测，可观察到含硅粉末中的硅颗粒和锆颗粒都呈不规则形状，部分锆颗粒具有尖锐的棱角，均匀分散在硅颗粒中。The silicon-containing powder for a negative electrode material for a lithium ion battery according to claim 1, wherein the silicon-containing powder is detected by a field emission scanning electron microscope, and it can be observed that both silicon particles and zirconium particles in the silicon-containing powder are It is irregular in shape, and some zirconium particles have sharp edges and corners, and are uniformly dispersed in the silicon particles.
  3. 根据权利要求1所述的一种锂离子电池负极材料用含硅粉末，其特征在于，该含硅粉末中有55～85wt.％的硅，更优选的，该含硅粉末中有65～75wt.％的硅。The silicon-containing powder for a negative electrode material for a lithium ion battery according to claim 1, wherein the silicon-containing powder contains 55-85 wt.% silicon, and more preferably, the silicon-containing powder contains 65-75 wt. % .% Silicon.
  4. 根据权利要求1所述的一种锂离子电池负极材料用含硅粉末，其特征在于，所述含硅粉末通过氧氮氢分析仪检测，可得到氧含量为5～30wt.％，优选为10～25wt.％，更优选为15～20％，所述部分氧元素存在于硅颗粒的表面。The silicon-containing powder for a negative electrode material of a lithium ion battery according to claim 1, wherein the silicon-containing powder is detected by an oxygen, nitrogen and hydrogen analyzer to obtain an oxygen content of 5-30 wt.%, preferably 10 wt.% ~25wt.%, more preferably 15~20%, part of the oxygen element is present on the surface of the silicon particles.
  5. 根据权利要求1所述的一种锂离子电池负极材料用含硅粉末，其特征在于，所述含硅粉末通过电感耦合等离子体发射光谱仪检测，得到锆含量为5～20wt.％，优选为10～15wt.％，优选的，所述锆颗粒以锆氧化物形式存在。The silicon-containing powder for a negative electrode material of a lithium ion battery according to claim 1, wherein the silicon-containing powder is detected by an inductively coupled plasma emission spectrometer, and the content of zirconium obtained is 5-20wt.%, preferably 10 ~15 wt.%, preferably, the zirconium particles are present in the form of zirconium oxide.
  6. 根据权利要求1所述的一种锂离子电池负极材料用含硅粉末，其特征在于，所述含硅粉末具有1.2～2.6g/cm 3的真密度，具有2～300m 2/g的比表面积。 The silicon-containing powder for a negative electrode material for a lithium ion battery according to claim 1, wherein the silicon-containing powder has a true density of 1.2-2.6 g/cm 3 and a specific surface area of 2-300 m 2 /g .
  7. 一种制备权利要求1-6任一项所述的锂离子电池负极材料用含硅粉末的方法，其特征在于：A method for preparing the silicon-containing powder for lithium ion battery negative electrode material according to any one of claims 1-6, characterized in that:
    在砂磨机配套的搅拌罐中加入微米硅粉，微米硅粉的中值粒径D50为1～1000μm，微米硅粉的纯度≥99％，再在搅拌罐中加入溶剂湿法研磨，控制搅拌罐中的混合溶液的固含量为5～40％，开启慢速搅拌，砂磨机中填入0.05～0.5mm的氧化锆球磨珠，控制氧化锆珠与硅粉的质量比为15:1～20:1，砂磨机的主机转速为900～1000rpm，研磨时间为10-90h，优选为35～60h，得到的硅浆料，再将硅浆料进行加热干燥，得到含硅粉末；Add micron silicon powder to the mixing tank matched with the sand mill. The median particle size D50 of the micron silicon powder is 1-1000μm, and the purity of the micron silicon powder is ≥99%. Then add solvent to the mixing tank for wet grinding to control the stirring. The solid content of the mixed solution in the tank is 5-40%, start slow stirring, fill the sand mill with 0.05-0.5mm zirconia balls, and control the mass ratio of zirconia beads to silicon powder to be 15:1～ 20:1, the main machine speed of the sand mill is 900-1000rpm, the grinding time is 10-90h, preferably 35-60h, and the obtained silicon slurry is heated and dried to obtain silicon-containing powder;
    所述砂磨机搅拌轴的结构形状为盘式，棒式或棒盘式中的一种；The structure and shape of the mixing shaft of the sand mill is one of a disc type, a rod type or a rod disc type;
    所述研磨溶剂为纯水、甲醇、甲苯、苯甲醇、乙醇、乙二醇、氯化乙醇、丙醇、异丙醇、丙二醇、丁醇、正丁醇、异丁醇、戊醇、新戊醇、辛醇、丙酮或环已酮的一种或多种。The grinding solvent is pure water, methanol, toluene, benzyl alcohol, ethanol, ethylene glycol, chlorinated ethanol, propanol, isopropanol, propylene glycol, butanol, n-butanol, isobutanol, amyl alcohol, neopentyl alcohol One or more of alcohol, octanol, acetone or cyclohexanone.
  8. 根据权利要求7所述的方法，其特征在于，所述湿法研磨后的浆液的粘度为0～100Pa·s。The method according to claim 7, wherein the viscosity of the slurry after wet grinding is 0-100 Pa·s.
  9. 根据权利要求7所述的方法，其特征在于，所述湿法研磨后的浆液的固含量为5～40％，优选10～25％。The method according to claim 7, wherein the solid content of the slurry after wet grinding is 5-40%, preferably 10-25%.
  10. 一种锂离子电池负极材料，其特征在于，其包含权利要求1至6中任一项所述的含硅粉末与碳类材料结合，所述碳类材料为人造石墨、天然石墨、多孔石墨、多层石墨片、软碳、硬碳、石墨烯、碳纳米管、碳纳米纤维、多孔碳、裂解碳中的一种或多种。A lithium-ion battery negative electrode material, characterized in that it comprises the silicon-containing powder described in any one of claims 1 to 6 in combination with a carbon-based material, wherein the carbon-based material is artificial graphite, natural graphite, porous graphite, One or more of multi-layer graphite sheets, soft carbon, hard carbon, graphene, carbon nanotubes, carbon nanofibers, porous carbon, and cracked carbon.
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