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WO2015010230A1 - Procédé de préparation de sphères de silicium creuses et sphères de silicium creuses ainsi préparées - Google Patents

Procédé de préparation de sphères de silicium creuses et sphères de silicium creuses ainsi préparées Download PDF

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Publication number
WO2015010230A1
WO2015010230A1 PCT/CN2013/079760 CN2013079760W WO2015010230A1 WO 2015010230 A1 WO2015010230 A1 WO 2015010230A1 CN 2013079760 W CN2013079760 W CN 2013079760W WO 2015010230 A1 WO2015010230 A1 WO 2015010230A1
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WO
WIPO (PCT)
Prior art keywords
silicon
hollow
hollow silicon
silicon spheres
anode material
Prior art date
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Ceased
Application number
PCT/CN2013/079760
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English (en)
Inventor
Yuqian DOU
Yuan Liu
Xinping Qiu
Jingjun Zhang
Longjie Zhou
Xun Guo
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tsinghua University
Robert Bosch GmbH
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Tsinghua University
Robert Bosch GmbH
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Publication date
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Priority to PCT/CN2013/079760 priority Critical patent/WO2015010230A1/fr
Priority to CN201380078422.4A priority patent/CN105705460A/zh
Publication of WO2015010230A1 publication Critical patent/WO2015010230A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0421—Methods of deposition of the material involving vapour deposition
    • H01M4/0428—Chemical vapour deposition
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C01P2004/34—Spheres hollow
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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 present invention generally relates to the field of lithium ion batteries. Particularly, the present invention relates to a method for preparing hollow silicon spheres, the obtained hollow silicon spheres and its application as anode materials for lithium ion batteries.
  • hollow porous Si0 2 nanoparticles were synthesized using cetyltrimethylammonium bromide (CTAB) as surfactant to produce pores and polystyrene (PS) nanoparticles as templates to generate hollow structures; the resulting hollow porous Si0 2 nanoparticles were reduced to porous hollow Si by magnesiothermic reduction, followed by Ag coating to reach certain conductivity.
  • CTAB cetyltrimethylammonium bromide
  • PS polystyrene
  • the vital process drop-casting is quite complex and low efficient.
  • the nano Si0 2 templates need to be dispersed into ethanol solvent and the substrates need to be 0 2 plasma-treated before coating; during drop-casting, the operation need to be strictly controlled and the evaporation of solvent is not environment friendly. Even though the drop-casting process is repeated several times, the final silicon mass loading is only 0.1-0.2 mg/cm , which is too low for commercial application.
  • hollow silicon spheres (named HSS) as a novel anode material with high capacity and good stability for Li-ion battery is synthesized by a simple and low cost method.
  • the method for preparing hollow silicon spheres of the present invention can be summarized as below:
  • a silicon coating layer is formed on the nano particles using a silicon source by means of chemical vapor deposition, followed by template removal and purification.
  • hollow silicon spheres obtained by the process according to the present invention.
  • an anode material comprising the hollow silicon spheres of the present invention.
  • a negative electrode for a lithium ion battery comprising the anode material.
  • a lithium ion battery comprising the negative electrode.
  • Figure 1 shows the typical synthesis process of the inventive hollow silicon spheres and the final product HSS.
  • Figure 2 shows the TEM image of commercially available nano-calcium carbonate particles (20-100 nm).
  • Figures 3a, 3b show TEM images of HSS-1 obtained in Example 1.
  • Figure 3c shows SAED pattern of HSS-1.
  • Figure 4 shows SEM images and EDS pattern of HSS-1.
  • Figure 5 shows nitrogen adsorption/desorption isotherms and pore size distribution of HSS-1.
  • Figure 6 shows an XRD pattern of HSS-1.
  • Figure 7 (a) shows an XPS pattern of HSS-1
  • Figure 7 (b) shows Si 2p spectra of HSS-1.
  • Figure 8 shows TEM images of HSS-2.
  • Figure 9 shows SEM images of HSS-2.
  • Figure 10 shows an XRD pattern of HSS-2.
  • Figure 11 shows the particle size distribution of HSS-2.
  • Figure 12 shows the cycling curve of HSS-1 at 400 mA/g between 0.02 and 1.5 V (100 m A/g in first 3 cycles).
  • Figure 13 shows the cycling curve of HSS-2 at 400 mA/g between 0.02 and 1.5 V (100 m A/g in first 3 cycles).
  • the invention describes a novel anode material of hollowed silicon spheres with good stability and capacity for lithium ion battery and its preparation method.
  • our HSS material shows high capacity and good stability due to the designed hollow structure.
  • the hollow structure leaves enough space for volume expansion during the lithium intercalation and the interconnection of silicon spheres provide a conductive network for the transference of electrons .
  • the present method is simple and easy to control.
  • the template nano particles are directly used for Si CVD without drop-casting onto a particular substrate. More importantly, compared with low active substance loading (0.1-0.2 mg/cm ) in Ref.l, an active substance loading between 0.2 to 1.5 2
  • mg/cm is achieved easily in the present method and the active substance loading can be further increased up to 3 mg/cm by controlling the coating process.
  • the method of the present invention is low cost and involves no expensive reactant (surfactant, Ag).
  • the template nano particles in present method are commercially available with a low cost. Therefore, the present method has great potential for practical application in industry.
  • the nano particles used as a template in the present invention are selected from carbonates and oxides.
  • the carbonate is preferably selected from the group consisting of calcium carbonate, magnesium carbonate, strontium carbonate, barium carbonate.
  • the oxides are preferably selected from the group consisting of AI2O3, MgO, ZnO and Si0 2 .
  • the size of the nano particles used as a template in the present invention is in a range of lO nm to 100 nm.
  • the silicon source used in the present invention is selected from the group consisting of high purity silane, chlorosilane and the like.
  • Various kinds of chlorosilane can be used in the present invention, preferably trichlorosilane.
  • the chemical vapor deposition (CVD) used in the present invention is a conventional technique.
  • CVD can be simply described as that a carrier gas is used to carry one or more source vapor gases into the reaction chamber, chemical reactions occur on the substrate surface, and the desired solid material is deposited onto the substrate.
  • a carrier gas is used to carry one or more source vapor gases into the reaction chamber, chemical reactions occur on the substrate surface, and the desired solid material is deposited onto the substrate.
  • nano particles as the substrate are placed in a horizontal tube furnace or a fluidized-bed furnace, and silicon is deposited onto the substrate.
  • the particle size of the nano particles used in the present invention lies in a range of 10 nm to 100 nm, preferably in a range of 40 nm to 80 nm.
  • a mixture of 5% H 2 and 95% inert gas such as Ar with a flow rate of 120 seem is introduced into the furnace before the temperature reaches 400-500 °C so as to form a reductive atmosphere.
  • high-purity silane with a purity of 99.999% carried by an inert gas such as Ar is introduced to the furnace which is at a temperature of 400-500°C at a flow rate of 80-120 seem for 1 to 3 hours.
  • the mixing weight ratio of silane and Ar is in a range of 10:80- 2:98, preferably 5:95.
  • silicon coating layers with different thicknesses can be obtained by controlling the time for deposition.
  • the time for deposition is 1.5 h, a silicon coating layer of about 10 nm is obtained; when the time for deposition is 2 h, a silicon coating layer of about 16 nm was obtained.
  • acid with a concentration of for example 2 wt% is used to remove the nano particles, so as to obtain a hollow structure material.
  • suitable acids for this treatment can choose suitable acids for this treatment, as long as the acid can react with the nano particles template to form a soluble salt or gas and does not impair the properties of silicon.
  • the acid can be suitably selected by a person skilled in the art from the group consisting of hydrochloric acid, sulfuric acid and hydrofluoric acid.
  • these acids may not be suitable for any kind of the template mentioned above.
  • hydrofluoric acid is suitable when Si0 2 is used as the template, but may not be suitable for other templates.
  • hydrofluoric acid with a concentration of for example 10 wt% is used to purify the product, so as to obtain the final product hollow silicon spheres.
  • the hollow part size of the hollow silicon spheres is in a range of 10 nm to 90 nm, the primary particle size is in a range of 80 nm to 100 nm, and the secondary particle size is in a range of 1 to 30 ⁇ , the thickness of the silicon wall is about 9-17 nm.
  • the term "primary particle” refers to the original particles of the hollow silicon spheres
  • the term “secondary particle” refers to the particles agglomerated by the original particles of the hollow silicon spheres.
  • an anode material for lithium ion batteries comprising hollow silicon spheres material, conductive agents and binders.
  • the anode material includes 50 wt%-80 wt% of hollow silicon spheres, 5 wt%-20 wt% of conductive agents and 5 wt%-30 wt% of binders, based on the total weight of the anode material.
  • the hollow silicon spheres are the hollow silicon spheres of the present invention.
  • the conductive agent can be selected by a person skilled in the art so as to improve the conductivity.
  • the conductive agent can be selected from the group consisting of conductive carbon black, carbon nanotubes and graphene.
  • the binder is preferably polyacrylic acid (PAA), and it can also be selected from the group consisting of sodium carboxymethylcellulose (CMC), a mixture of sodium carboxymethylcellulose and styrene-butadiene rubber (SB ), and sodium alginate (SA).
  • PAA polyacrylic acid
  • CMC sodium carboxymethylcellulose
  • SB styrene-butadiene rubber
  • SA sodium alginate
  • the anode material includes 60 wt% of the hollow silicon spheres of the present invention, 20 wt% of the conductive carbon black and 20 wt% of polyacrylic acid, based on the total weight of the anode material.
  • hollow silicon spheres of the present invention, conductive carbon black and polyacrylic acid in a weight ratio of 60:20:20 are dispersed in deioned water to form an anode material in the form of slurry.
  • the anode material in the form of slurry is poured onto a horizontally placed copper foil, preferably a wet film applicator of 150 ⁇ is used to coat a film to make an electrode. After coating, the electrode is left to dry. Then, the electrode is subjected to a tabletting process under a pressure of for example 8 MPa. After being tabletted, the electrode is placed preferably in a vacuum oven at a temperature of 80 °C to dry overnight, thus a negative electrode is produced.
  • the negative electrode formed as described above together with lithium foil may form counter electrodes of a lithium ion battery.
  • 1 mol/L of LiPF 6 /EC: DMC: EMC in the volume ratio of 1 : 1 : 1 with 2 wt% VC as an additive may be used as the electrolyte.
  • EC refers to allyl carbonate
  • DMC refers to dimethyl carbonate
  • EMC refers to ethyl methyl carbonate
  • VC vinylene carbonate.
  • the battery mold is for example a 2025 type coin cell. Coin cells are thus prepared.
  • the active substance loading is determined by the amount of anode materials coated onto the copper foil.
  • the coin cells are subjected to galvanostatic charge-discharge tests.
  • the current density is 100 mA/g (the first three cycles) and 400 mA/g (subsequent cycles), the voltage range is set to 0.02-1.5 V.
  • the capacity is calculated based on the weight of hollow silicon spheres in the anode.
  • EV-E-006 produced by Hefei EV NANO Technology Co., Ltd., China was used as the nano calcium carbonate template, its particle size is 50-80 nm.
  • Chemical vapor deposition was carried out in a horizontal tube furnace (its internal diameter is 60 mm) at a temperature of 450 °C. Before the temperature reached 450 °C, a mixture of 5% 3 ⁇ 4 and 95% Ar was introduced into the furnace to form a reductive atmosphere and remove the remaining oxygen. Then, high-purity silane with a purity of 99.999% carried by Ar was introduced to the horizontal tube furnace which was at a temperature of 450°C at a flow rate of 100 seem for 1.5 hours.
  • Silane was decomposed into silicon particles and 3 ⁇ 4, and silicon particles finally deposited onto the nano-calcium carbonate.
  • the mixing weight ratio of silane and Ar is 5:95.
  • a mixture of 5% 3 ⁇ 4 and 95% Ar was reintroduced into the furnace to accelerate the cooling and prevent oxidization of silicon particles.
  • 2 wt% of hydrochloric acid was used to remove the nano-calcium carbonate to obtain hollow structure materials.
  • 10 wt% of hydrofluoric acid was used to purify the product, so as to obtain the final product hollow silicon spheres HSS-1.
  • HSS-1 is consisted of interconnected hollow spheres with a narrow primary particle size distribution.
  • the wall thickness of the hollow silicon spheres is 9-12 nm.
  • the SAED pattern in Figure 3 c shows that HSS-1 is almost an amorphous material. This is also verified by the XRD pattern in Figure 6.
  • Figure 6 does not show obvious characteristic peaks of crystalline silicon.
  • Figure 5 shows nitrogen adsorption/desorption and pore size distribution of HSS-1. It can be seen that hollow silicon spheres HSS-1 has a specific surface area of 35.7 m /g and a pore volume of 0.274 cm /g. Pore size distribution corresponding to hollow part size of HSS-1 is mainly between 10 nm and 90 nm, which is identical to the size of the nano-calcium carbonate template.
  • Example 2 is almost the same with Example 1 , except that the time for CVD deposition is 2 hours. That is, during the chemical vapor deposition, high-purity silane with a purity of 99.999% carried by Ar was introduced to the horizontal tube furnace (with an internal diameter of 60 mm) at a temperature of 450 °C at a flow rate of 100 seem for 2 hours.
  • HSS-2 is consisted of mainly interconnected hollow spheres with a narrow primary particle size distribution.
  • the wall thickness of the hollow spheres is about 16 nm.
  • the X-ray diffraction pattern in Figure 10 verifies that HSS-2 is also amorphous, since no obvious characteristic peaks of crystalline silicon is shown.
  • the SEM images in Figure 9 show that HSS-2 has a secondary sphere structure.
  • the primary particle size is similar to that of the nano-calcium carbonate, and the secondary particle size is approximately 10 ⁇ , which is consistent with the measurement results of the particle size distribution shown in Figure 11.
  • Figure 11 shows that about 95% of the hollow silicon spheres have a size of 1-30 ⁇ .
  • Hollow silicon spheres HSS-1 prepared by Example 1 was used to prepare a negative electrode.
  • the anode material comprised 60 wt% of hollow silicon spheres, 20 wt% of conductive carbon black and 20 wt% binder, wherein the binder is polyacrylic acid (PAA).
  • PAA polyacrylic acid
  • the formed negative electrode together with lithium foil constituted counter electrodes of a lithium ion battery.
  • 1 mol/L of LiPF 6 /EC: DMC: EMC in the volume ratio of 1 : 1 : 1 with 2 wt% VC as an additive was used as the electrolyte.
  • the battery mold was a 2025 type coin cell, a coin cell was thus prepared.
  • the coin cell was subjected to galvanostatic charge-discharge tests.
  • the current density was 100 mA/g (the first three cycles) and 400 mA/g (subsequent cycles), the voltage range was set to 0.02-1.5 V.
  • Figure 12 shows the charge-discharge cycle performance curves.
  • the test results show that the initial discharge capacity of the coin cell is up to 3063 mAh/g, the first charge capacity can reach 2246 mAh/g.
  • the first columbic efficiency is 73%.
  • the reversible capacity still reached 1150 mAh/g. That is, after 160 cycles, the capacity retention ratio is 73%. From the 20 th to the 160 th cycle, the capacity loss was less than 2%.
  • Hollow silicon spheres HSS-2 prepared by Example 2 was used to prepare a negative electrode.
  • the anode material comprised 60 wt% of hollow silicon spheres material, 20% by weight of conductive carbon black and 20 wt% binder, wherein the binder is polyacrylic acid (PAA).
  • PAA polyacrylic acid
  • the formed negative electrode together with lithium foil constituted counter electrodes of a lithium ion battery.
  • 1 mol/L of LiPF 6 /EC: DMC: EMC in the volume ratio of 1 : 1 : 1 with 2 wt% VC as an additive was used as the electrolyte.
  • the battery mold was a 2025 type coin cell, a coin cell was thus prepared. 2
  • the coin cell was subjected to galvanostatic charge-discharge tests.
  • the current density was 100 mA/g (the first three cycles) and 400 mA/g (subsequent cycles), the voltage range was set to 0.02-1.5 V.
  • Figure 13 shows the charge-discharge cycle performance curves.
  • the test results show that the initial discharge capacity of the coin cell is up to 2547 mAh/g, the first charge capacity can reach 2093 mAh/g.
  • the initial columbic efficiency reaches 82%.
  • the capacity retention ratio is 44%.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

La présente invention concerne un procédé de préparation de sphères de silicium creuses, les sphères de silicium creuses ainsi préparées, ainsi qu'un matériau d'anode, une électrode négative et une batterie lithium-ion utilisant lesdites sphères de silicium creuses. Ledit procédé comprend les étapes consistant à utiliser des nanoparticules en tant que matrice, la couche de revêtement à base de silicium étant formée sur les nanoparticules au moyen d'une source de silicium par dépôt chimique en phase vapeur, cela étant suivi de l'élimination de la matrice et d'une purification.
PCT/CN2013/079760 2013-07-22 2013-07-22 Procédé de préparation de sphères de silicium creuses et sphères de silicium creuses ainsi préparées Ceased WO2015010230A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/CN2013/079760 WO2015010230A1 (fr) 2013-07-22 2013-07-22 Procédé de préparation de sphères de silicium creuses et sphères de silicium creuses ainsi préparées
CN201380078422.4A CN105705460A (zh) 2013-07-22 2013-07-22 制备中空硅球的方法及由该方法制备的中空硅球

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PCT/CN2013/079760 WO2015010230A1 (fr) 2013-07-22 2013-07-22 Procédé de préparation de sphères de silicium creuses et sphères de silicium creuses ainsi préparées

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CN105226260A (zh) * 2015-10-19 2016-01-06 中南大学 一种锂离子电池用硅基负极材料的制备方法
CN108439419A (zh) * 2018-04-02 2018-08-24 深圳元颉新材料科技有限公司 介孔二氧化硅纳米半球材料的制备方法
KR20190019652A (ko) * 2017-08-18 2019-02-27 한국기술교육대학교 산학협력단 그래핀 나노구체 제조방법
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CN110862089A (zh) * 2019-12-09 2020-03-06 徐少晨 一种介孔空心硅球的制备方法
CN111180713A (zh) * 2020-02-10 2020-05-19 马鞍山科达普锐能源科技有限公司 一种锂离子电池用硅碳负极材料及制备方法
CN112158846A (zh) * 2020-08-14 2021-01-01 安徽德亚电池有限公司 泡沫硅负极材料及其制备方法
CN116282044A (zh) * 2023-01-13 2023-06-23 浙江锂宸新材料科技有限公司 一种硅氧负极材料的制备方法及其产品

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CN109553107B (zh) * 2017-09-26 2021-03-23 清华大学 纳米颗粒材料的连续性、批量化的制备方法和制备装置
CN111072051B (zh) * 2018-10-19 2021-07-23 清华大学 一种生产纳米包覆材料的方法和装置
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