WO2002027822A1 - Metal nanometrique ou materiau composite alliage/carbone nanometrique, son procede de fabrication et ses applications dans un element secondaire - Google Patents

Metal nanometrique ou materiau composite alliage/carbone nanometrique, son procede de fabrication et ses applications dans un element secondaire Download PDF

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WO2002027822A1
WO2002027822A1 PCT/CN2001/000918 CN0100918W WO0227822A1 WO 2002027822 A1 WO2002027822 A1 WO 2002027822A1 CN 0100918 W CN0100918 W CN 0100918W WO 0227822 A1 WO0227822 A1 WO 0227822A1
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nano
alloy
composite material
carbon
metal
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PCT/CN2001/000918
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English (en)
Chinese (zh)
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Hong Li
Lihong Shi
Qing Wang
Xuejie Huang
Liquan Chen
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Institute Of Physics, Chinese Academy Of Sciences
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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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B22F1/056—Submicron particles having a size above 100 nm up to 300 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/14—Treatment of metallic powder
    • B22F1/148—Agglomerating
    • 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
    • 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
    • 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
    • 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
    • H01M4/58—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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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
    • 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
    • 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 relates to a metal or alloy / carbon composite material and a preparation method and application thereof, and particularly to a nano metal or nano alloy / carbon composite material, a preparation method thereof, and application in a secondary lithium battery.
  • Nano-metal / carbon composites Compared with general carbon materials, nano-metal / carbon composites have outstanding advantages in terms of magnetic properties, electrical properties and adsorption properties. Nano-metals are dispersed in the surface or internal pore structure of carbon materials, which can reduce the oxidation of nano-metals and improve the stability of nano-metals. Therefore, nano metal / carbon composite materials can combine the advantages of nano metal and carbon materials, and have broad application prospects. However, in the current nano-metal / carbon composite materials, most of the nano-metals are catalytically active metals such as Fe, Co, Ni, Pt or Pd, and other metals or alloys are reported less in patents and published literature.
  • the current methods for preparing metal / carbon composite materials mainly include (1) a liquid phase impregnation method, mixing carbon with a metal salt solution, then filtering, drying, and reducing; (2) a vapor deposition method, in which carbon particles are in contact with metal vapor; (3) Carbonization pyrolysis using an organometallic compound, a polymer metal complex or an organometallic polymer as a precursor; (4) A co-precipitation method in which carbon is mixed with an aqueous solution of a metal salt and reduced in a liquid phase.
  • methods (2) and (3) can obtain nanometer-scale metal particles (less than 100 nanometers) and carbon composite materials, but the load is lower and the cost is higher.
  • the nanometal / carbon composite material obtained by method (1) is mainly a composite material of noble metal with high melting point and carbon, and the load is low.
  • the metal particles obtained by method (4) are large in size and unevenly dispersed. The above is introduced in the review of Carbon Technology, Issue 5, 2000, published by Chen Xuegang et al.
  • Metals or alloys can be used as negative electrode active materials in secondary lithium batteries and have high lithium storage capacity. From the early 1970s to the end of the 1980s, lithium alloys such as lithium aluminum, lithium silicon, lithium lead, lithium tin, and lithium cadmium were used as negative electrode active materials for secondary lithium batteries. However, these alloys gradually pulverized due to volume expansion and contraction during repeated charge and discharge processes, resulting in poor electrical contact between alloy particles and current collectors and between alloy particles, and battery performance quickly deteriorated or even failed, such as KM Abraham As described in "Electrochemica. Acta.!, Vol. 138, 1233 (1993).
  • ultra-fine metal or alloy system as the negative electrode active material.
  • the ultra-fine alloy particles have good plasticity and can withstand band changes due to volume changes during the charge and discharge process.
  • the ability to change the stress in the future is stronger, so compared with the alloy material with larger size, its cyclicity is significantly improved, As described by Li Hong in Chinese Patent CN 97112460.4 (1997).
  • the object of the present invention is to overcome the shortcomings of the poor stability of existing nano-alloy materials and provide a new nano-metal or nano-alloy / carbon composite material with stable structure and chemical properties.
  • Another object of the present invention is to provide a simple process, Low cost, suitable for large-scale production, and the prepared nano-metal or nano-alloy particles are about 100 nanometers in size, uniformly dispersed, and good adhesion to carbon materials.
  • a further object of the present invention is to provide the use of such a nano-metal or nano-alloy / carbon composite material, in particular, this composite material solves the problem of electrochemical agglomeration of nano-metal or nano-alloy during charging and discharging
  • the application as a negative electrode material of a secondary lithium battery enables the lithium battery to have good cycle characteristics and safety, and has a high energy density.
  • the nano-metal or nano-alloy / carbon composite material provided by the present invention comprises: nano-metal or nano-alloy particles are deposited on the outer surface of the carbon particles and the pore cavity or pore wall (ie, the inner surface) of the inner pores contained in the carbon particles, wherein the nano-metal Or the average size of nano-alloy particles is 1 ⁇ 250nm, the average size of carbon particles is lum ⁇ 50um, and the weight percentage of nano-metal or nano-alloy particles and carbon particles is 10% -70%.
  • the nano metal is any one of Sn, Sb, In or Zn.
  • nanoalloys defined as M ⁇ M ⁇ .M 1 ⁇ , wherein MM 2 ... M n represent different elements, and containing at least any from among Sn, Sb, In or Zn one of It can also contain Mg, B, Al, Si in the main group elements, and Ti, V, Mn, Fe, Co, Ni, Cu, or Ag in the transition metal group; where the subscripts xl, ⁇ 2 ... ⁇ represent different elements
  • the sum of the mole percentages of the four elements is not less than 50%; where n is an integer from 1 to 16.
  • the carbon material may be graphite-based carbon or non-graphite-based carbon.
  • the nano-metal or nano-alloy / carbon composite material provided by the present invention further includes a small amount of oxygen in the nano-metal or nano-alloy / carbon composite material, and the weight percentage of oxygen element in the composite material is 0.001% -10%. This is because nanometals or nanoalloys are relatively active, and their surfaces inevitably undergo oxidation during preparation, storage, and transfer, so a small amount of oxygen can be allowed to exist.
  • the nano metal or nano alloy / carbon composite material of the present invention wherein the nano alloy is, for example, Sn. . ⁇ Sb ⁇ ⁇ Gold, Sn. S8 Sb Q 12 alloy, 8 44 813 ⁇ 4 16 . 3 ⁇ 44 alloy or 8 4 2 3 ⁇ 455 0. .. 5 alloy, nano metal Sb, In, Sn or Zn all meet the requirements of the present invention.
  • the actual composition of the 2 alloy can be S 3 ⁇ 476 / (SnSb).
  • the two-phase mixture of 12 can also be Sn. S8 / Sb. . 12 two-phase mixture.
  • nano alloys such as S3 ⁇ 4 49 C3 ⁇ 4 51 and nano metal Sn. . 88 0. , lj does not meet the requirements of the present invention.
  • the carbon material may be graphite-based carbon or non-graphite-based carbon, and is preferably natural graphite, graphitized mesophase carbon pellets, needle coke, carbon fiber, or microporous hard carbon pellets.
  • the average size of carbon particles is lum ⁇ 50um, which can be a non-porous carbon material, or it can contain a large number of micropores. These carbon particles are capable of reversibly inserting and extracting lithium ions.
  • the carbon material by Brunauer- Emmett-Teller (hereinafter referred to as BET method) Method of measuring specific surface area of 0.1-3000 m 2 / g, wherein the external surface area of 0.1-50m 2 / g, a surface area contained in the pores (the surface area) 0.1-
  • nano-metal or nano-alloy / carbon composite material of the present invention most of the nano-metal or nano-alloy particles are in direct contact with the outer surface of the carbon particles or the inner surface of the pores contained therein.
  • the proportion of the inner-outer surface nano-metal or nano-alloy Unlimited In nanometals or nanoalloys / carbon composites, the nanometals or nanoalloys in the free state do not directly contact the outer surface of the carbon particles, and they account for 0.1-30% of the total weight of the nanometals or alloys in the composite.
  • the nano metal or nano alloy / carbon composite material provided by the present invention can be prepared by a co-reduction technique in an organic solvent system, and the specific steps are as follows:
  • the chloride is a chloride of Sn, Sb, In, Zn or Mg, B, Al, Si in the main group element or Ti, V, Mn, Fe, Co, Ni, Cu, Ag in the transition metal group element, It contains at least one of the chlorides of Sn, Sb, In or Zn, and the sum of the molar percentages of the chlorides of Sn, Sb, In or Zn to all chlorides is not less than 50%.
  • step 2 Or add carbon powder to the reducing suspension prepared in step 1 above, and use the separatory funnel to mix the chloride prepared in step 1 at a temperature of -20 ° C ⁇ 200 ° C for 1min-24h. The entire solution was added dropwise to the reducing suspension, while stirring;
  • the weight ratio of cations to carbon powder in the chloride solution prepared in step 1 above is 10% to 70%.
  • the method for preparing a nano-metal or nano-alloy / carbon composite material provided in the present invention wherein the C1-C4 alcohol is a C1-C4 linear or branched mono- or polyhydric alcohol, such as methanol, ethanol, and ethyl alcohol. Diol, isopropanol, glycerol or butanol.
  • a reaction temperature for co-reduction in an organic solvent system should keep the reaction system from solidifying, and the co-reduction reaction is preferably performed at -10-50 C.
  • nano-metals or nano-alloys / carbon composites During the preparation of nano-metals or nano-alloys / carbon composites, and during the transfer and storage of nano-metals or nano-alloys / carbon composites, the surface of the nano-metals or nano-alloys is difficult to avoid oxidation, so in the described In nano-metal or nano-alloy / carbon composite materials, the presence of oxygen can generally be detected, and the weight percentage of oxygen element in the composite material is 0.001% to 10%.
  • the nano-metal or nano-alloy / carbon composite material of the present invention can also be obtained by the liquid phase impregnation reduction method, vapor deposition method, or carbonization pyrolysis method of organometallic compounds described above; it can also be obtained by hydrothermal, solvothermal, A sol-gel method is used to prepare a carbon composite material having a metal oxide deposited on the surface, and then the carbon composite material is reduced in a reducing atmosphere. These methods are either costly, or the products obtained cannot achieve the purpose of depositing and dispersing nano-sized metals or alloys on the inner and outer surfaces of carbon materials.
  • One of the uses of the nanometal or nanoalloy / carbon composite material of the present invention is as a negative electrode active material for a secondary hammer battery, the negative electrode and a lithium-containing transition metal oxide positive electrode, an organic electrolyte solution, a separator, a battery case, and a current collector. And the lead constitute the secondary lithium battery in the present invention.
  • leaching between the positive electrode and the negative electrode The separator or polymer electrolyte in which the organic electrolyte solution is bubbled is separated, and one end of the positive electrode and the negative electrode is respectively connected with a lead on the current collector and connected to two ends of the battery case which are mutually insulated.
  • a nano metal or a nano alloy / carbon composite material is used as a negative electrode active material of a secondary lithium battery.
  • the preparation method of the negative electrode is a general industrial preparation method, and the preparation method includes: (1) a nano metal or The nano-alloy / carbon composite material is evenly mixed with the conductive additive, and then mixed with the binder at room temperature and pressure to form a composite slurry.
  • the conductive additive refers to a substance commonly used in lithium ion batteries to increase the conductivity of the active material, such as carbon black, acetylene hafnium, graphite powder, metal powder or metal wire, etc., and the weight percentage of the additive with the nano metal or nano alloy / carbon composite material is 0% ⁇ 15%.
  • the adhesive includes a solution type or an emulsion type adhesive, for example, polytetrafluoroethylene is mixed with water to form an emulsion type adhesive, or polyvinylidene fluoride is dissolved in N-methyl Pyrrolidone forms a solution-type adhesive.
  • a solution type or an emulsion type adhesive for example, polytetrafluoroethylene is mixed with water to form an emulsion type adhesive, or polyvinylidene fluoride is dissolved in N-methyl Pyrrolidone forms a solution-type adhesive.
  • the thickness of the obtained film is about 10-150 ⁇ m, then it is dried at 100 ° C-150 ° C, compacted at a pressure of 1-60Kg / cm 2 and then continued at 100 ° Bake at C-150 ° C for 1-12 hours. After drying, the adhesive accounts for 2% -15% of the total weight of the film and the carrier. According to the specifications of the prepared secondary lithium battery, the negative electrode is cut into a required shape.
  • the positive electrode active material used in the secondary lithium battery of the present invention is a known positive electrode material for a secondary lithium battery, that is, a lithium-containing transition metal oxide capable of reversibly inserting and extracting lithium, such as lithium cobalt oxide. Materials, lithium nickel oxide or lithium manganese oxide.
  • the organic electrolyte solution used in the secondary lithium battery of the present invention is an electrolyte commonly used in secondary lithium batteries, and may be composed of one organic solvent or a mixed solvent composed of several organic solvents and one or more soluble lithium salts added .
  • Typical organic solvents are, for example, ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate or dimethoxyethane.
  • Typical soluble lithium salts are lithium perchlorate, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium trifluoromethanesulfonate or lithium hexafluoroarsenate.
  • a typical system is a 1 mol / liter lithium hexafluorophosphate solution, and the solvent used is a mixed solvent of ethylene carbonate and diethyl carbonate in a volume ratio of 1: 1; or a 1 mol / liter lithium hexafluorophosphate solution, the solvent used is 3: 7 volume ratio A mixed solvent of ethylene carbonate and dimethyl carbonate.
  • the separator used in the secondary lithium battery of the present invention is a separator commonly used in secondary lithium batteries, such as a porous polypropylene separator or a porous polyethylene separator.
  • the nano-metal or nano-alloy / carbon composite material provided by the present invention has good stability. Its nano-metal or nano-alloy particles are not easy to agglomerate, are uniformly dispersed on the carbon surface, have good adhesion, and have a relatively small particle size. small.
  • the preparation method of the nano-metal or nano-alloy / carbon composite material provided by the present invention has simple process, low cost, and is suitable for large-scale production, and the prepared nano-metal or nano-alloy particles have a size of about 100 nanometers, and they are on the surface of the carbon particles. Evenly dispersed, good adhesion to carbon materials, stable performance, and no environmental pollution caused by the preparation process.
  • the nano-metal or nano-alloy / carbon composite material provided by the present invention provides a rigid skeleton structure and the nano-metal or nano-alloy is dispersedly attached to the inner and outer surfaces of the carbon material, the nano-alloy is not easy to agglomerate, and the stability is greatly improved.
  • a composite material is used as a negative electrode material of a secondary lithium battery, the problem of electrochemical agglomeration of nano-metals or nano-alloys during charging and discharging can be greatly reduced.
  • the carbon materials and nano-metals or nano-alloy materials used in the present invention are active lithium storage materials.
  • This composite material has a high lithium storage capacity, and the secondary lithium battery using this composite material has a good performance. Cyclic characteristics and safety, as well as obvious advantages in dynamics. Therefore, the secondary lithium battery using the nano-metal or nano-alloy / carbon composite material of the present invention as a negative electrode active material has a high reversible capacity, good cycleability, safety and reliability, resistance to large current charge and discharge, cheap electrode materials, and easy Preparation and environmentally friendly and other significant advantages.
  • the secondary lithium battery using the nano-metal or nano-alloy / carbon composite material of the present invention as the negative electrode active material is suitable for various applications, such as mobile phones, notebook computers, portable video recorders, electronic toys, and cordless power tools.
  • nano-metal or nano-alloy / carbon composite materials provided by the present invention can also be used in other fields, such as catalysts, absorbing materials, and electronic composite materials.
  • FIG. 1 is a nano Sno. 5 Sb prepared in Examples 1, 2, and 3 of the present invention. . 5 alloy / spherical pyrolytic hard carbon, nano Sn 48 Sb. X-ray diffraction pattern of 52 alloy / graphitized mesophase carbon spheres, nano Sn ⁇ Sb ⁇ alloy / acicular coke composite;
  • FIG. 2 is nano-Sn prepared in Example 1 of the present invention.
  • 5 Sb Transmission electron micrograph of 5 alloy / spherical pyrolytic hard carbon composite material
  • Figures 4 (A) and (B) respectively show that the composite materials prepared in Examples 1 and 2 of the present invention are used as negative electrode active materials. Charge and discharge curve of a lithium button-type analog battery.
  • spherical pyrolytic hard carbon material 400 g of sucrose is dissolved in 600 ml of distilled water to prepare a homogeneous dispersion system, and the organic additive tetraethylamine hydroxide (TEA0H) is added to make the final concentration of 1M, and the mixture is stirred.
  • TAA0H organic additive tetraethylamine hydroxide
  • the temperature 200 ° C at a temperature rise rate of 30 "C / hour and hold for 24 hours.
  • the product was washed with distilled water, filtered until the filtrate was transparent, and then dried at 120 ° C to obtain an intermediate product.
  • the intermediate product was then placed in a tube furnace (furnace tube length 1000 mm, diameter 60 hidden), and heated to 1000 at a rate of 300 "C / hour under nitrogen protection, with a nitrogen flow rate of 25 ml / min, after a constant temperature of 6 hours Cool to room temperature at a rate of 20 "C / hour.
  • XRD X-ray diffraction
  • Co-reduction in an organic solvent system 72 g of spherical pyrolytic hard carbon having an average particle size of 10 um was added to the metal chloride solution prepared in step 1 above, and stirred well. At a temperature of 0.0 ⁇ 5.0 ° C, within 1 hour, the Zn powder reduction suspension was slowly added dropwise to the metal chloride solution containing HCS10 using a separatory funnel, and simultaneously stirred at high speed.
  • step 2 The black product obtained in step 2 was filtered and washed with ethanol until no Cl_ ions were detected in the filtrate with silver nitrate, and then the obtained powder was vacuumed at 0.1 mmHg, 80. After C was dried for 5 hours, nano-Sn was obtained. . 5 Sb. 5 alloy / HCS 10 composite samples. 2. Nano S 3 ⁇ 4 5 Sb. . Performance test and analysis of 5 alloy / spherical pyrolytic hard carbon composite material:
  • nano Sn in the nano S 5 Sb 5 alloy / HCS10 composite. . 5 Sb. 5 alloys account for 25% by weight of the composite.
  • the X-ray diffraction pattern of the 5 alloy / HCS10 composite is shown in Fig. 1A.
  • the results show that the nano-Sn deposited on the HCS10. . 5 Sb. 5 alloy is a pure phase of ⁇ -SnSb alloy, and its grain size is 25nm according to the calculation of Shelley's formula.
  • the scanning electron microscope photograph of the 5 alloy / HCS10 composite material is shown in Figure 3 (A), in Figure 3 (A), the magnification of a is 6000 times and the scale is 3um ; the magnification of b is 50,000 times, and the scale is 360nm; More than 99% of the nano-alloys are deposited on the surface of HCS10 particles and are evenly distributed. The average size of the alloy particles is 110 nm. Electron energy distribution X-ray absorption spectroscopy (EDAX) results show that oxygen in the composite material accounts for 0.5% of the total weight of the composite material, and it is inferred that carbon accounts for 74.5% of the weight of the composite material.
  • the transmission electron microscope photograph of the composite material is shown in FIG.
  • the BET method measures nano Sno. 5 Sb.
  • the 5 / HCS10 composite has a micropore specific surface area of 150m 2 / g, and the micropore volume is reduced by 60% compared to the raw spherical pyrolytic hard carbon material. Calculations show that the alloy in the pores accounts for 18% of the total amount of the nano-alloy. . Since the average pore diameter of the micropores in the HCS10 is 2 nm, and the pore distribution is from 1 nm to 10 nm, the alloy particle size in the pores is 1-10 nm.
  • Nano S 3 ⁇ 4 5 Sb. Application of 5 alloy / HCS10 composite material as the negative electrode active material of secondary lithium battery.
  • the preparation method of the electrode is similar to that used in the lithium ion battery industry. The steps are as follows: The nano alloy / carbon composite material prepared above is combined with The N-methylpyrrolidone solution of the binder polyvinylidene fluoride is mixed at normal temperature and pressure to form a slurry, and the slurry is uniformly coated on a copper foil substrate as a current collector. After the obtained film was dried at 150 ° C, it was compacted at 20Kg / cm 2 , and then dried at 150 ° C for 12 hours.
  • the weight percentage of the composite material and polyvinylidene fluoride is 95: 5.
  • the film was then cut into a round sheet with a diameter of 1.6 cm as a nano-alloy / carbon composite electrode.
  • a conventional The electrode experiment button battery 2016 type was studied.
  • the electrolyte is a 1 mol / liter lithium hexafluorophosphate (LiPF 6 ) solution, and the solvent used in the solution is a mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC) in a volume ratio of 1: 1;
  • the separator was a porous polypropylene separator Celgard 300 ; a metal lithium sheet with a diameter of 1.8 cm and a thickness of 1 mm was used as a counter electrode.
  • An argon-filled glove box H 2 0 ⁇ 5ppm, 0 2 ⁇ 5ppm) was assembled into an experimental battery. The experimental battery was charged and discharged by a computer-controlled automatic charge-discharge meter.
  • the current density is O.lmA / cm 2
  • the charge cut-off voltage is 2.0V
  • the discharge cut-off voltage is 0.00V.
  • the charge-discharge curve is shown in Figure 4 (A). From this curve, it can be seen that the reversible capacity of the composite material is 500mAh / g, which is much higher than the current commercial two.
  • the reversible capacity of the carbon material in the lithium secondary battery (330mAh / g), the battery has good cycle performance, and the shape of the charge-discharge curve is a typical nano-Sn. . 5 Sb. .
  • the charge and discharge efficiency in the first week was 84%
  • the charge and discharge efficiency in the tenth week was 99%. These two parameters reflect Coulomb efficiency and cyclicity and are listed in Table 1.
  • the graphitized mesophase carbon spheres are denoted as CMS28, manufactured by Anshan Thermal Energy Institute, with an average particle size of 15um, which is measured by XRD (1 ... 2 is 0.3351 ⁇ 1, La, Lc> 100nm.
  • the specific surface area measured by BET is lm 2 / g, There are almost no micropores.
  • nano-Sn Q. 48 Sb Nano S 48 Sb in 52 alloy / CMS28 composite.
  • the weight percentage of 52 alloy to the composite material is 29.5%.
  • the X-ray diffraction pattern of the composite material is shown as B in FIG. 1.
  • the result indicates that the alloy deposited on the CMS28 is a pure phase ⁇ -SnSb alloy.
  • the grain size is 34 nm.
  • the composite scanning electron microscope photograph is shown in Figure 3 (B), where the a scale is 100um and the b scale is 100nm.
  • the results show that more than 90% of the nano-alloys are deposited on the surface of the CMS28 particles, and the distribution is uniform.
  • the average size of the alloy particles 100nm.
  • the EDAX results show that the weight percentage of oxygen in the composite material is 0.2%, and the CMS28 accounted for The weight percentage is 70.3%.
  • Example 48 Sb ⁇ Using the same method as in Example 1, the nano Sno. 48 Sb. 52 alloy / CMS28 composite material was prepared into an electrode, and the two-electrode experimental button cell 2016 type described in Example 1 was used to study the electrochemical performance of the composite material as the negative electrode active material of a secondary lithium battery, as assembled in Example 1.
  • the test is performed by using the same test method as in Example 1.
  • the charge-discharge curve is shown in FIG. 4 (B), and the charge-discharge curve is a typical nano-Sn.
  • the charge and discharge curve of 48 Sb 52 alloy / graphite-based carbon has a reversible capacity of 450 mAh / g and good cycleability.
  • the electrochemical performance parameters are shown in Table 1.
  • nano S 3 ⁇ 4 4 Sb was prepared. . 6 alloy / petroleum coke composite.
  • the difference is that the alcohol used in step 1 is ethanol.
  • the raw material carbon powder used in step 2 is acicular petroleum coke, denoted as coke, provided by Anshan Coastal Chemical Plant, China, with an average particle size of 50um, and its d Q is measured by XRD. 2 is 0.35 nm, Lc is 5 nm, and its specific surface area is 4 m 2 / g as measured by BET, and it does not contain micropores.
  • the composite material is obtained after drying at 50 ° C. for 12 hours under a vacuum of 1 mmHg.
  • the results of chemical analysis of a conventional nano S n The percentage of nano-Sn 4 Sb 6 alloy in the 4 Sb 6 alloy / petroleum coke composite material to the total weight of the composite material is 30.1%.
  • the X-ray diffraction pattern of the composite material is shown as C in FIG. 1.
  • the result indicates that the alloy deposited on petroleum coke is a pure phase ⁇ -SnSb alloy, and its grain size is 36 nm according to the calculation of Xie Le formula.
  • the scanning electron microscope photograph of the composite material is shown in FIG. 3 (C), where the a scale is 50um and the b scale is lum.
  • the results show that more than 80% of the nano-alloys are deposited on the surface of petroleum coke particles, and the average size of the alloy particles is 150 nm.
  • the EDAX results show that the weight percentage of oxygen in the composite material is 5%.
  • Example 1 In the same manner as in Example 1, the composite material was prepared into an electrode, and the two-electrode experimental button cell 2016 as described in Example 1 was used to study the electrochemical performance of the composite material as the negative electrode active material of a secondary lithium battery. Assembled into an experimental battery as in Example 1. The test was performed using the same test method as in Example 1. The reversible capacity was 330 mAh / g, and the cycle was good. The electrochemical performance parameters are shown in Table 1. In addition, the high-current (1C) discharge of the analog battery can still maintain 90% of the reversible capacity.
  • step 1 SnCl 2 .2H 2 0 is replaced with InCl 3; the reducing agent is replaced with ultra-fine Fe powder (particle size is 50 nm), and the amount is 90% of the required stoichiometry.
  • the raw material carbon powder used in step 2 is HCS10E, HCS10E is HCS10 after C0 2 and water vapor reaming.
  • nanometer In. . 5 Sb. . Nano-In in 5 alloy / HCS 10E composites. . 5 Sb. 5 alloy accounts for 40% by weight of the composite material.
  • the average particle size of the alloy deposited on the outer surface of HCS10E was 90 nm, and the percentage of free alloy to the total weight of the alloy was 0.1%.
  • the alloy on the outer surface of HCS10E accounts for 49.9% of the total weight of the alloy
  • the alloy on the inner surface accounts for 50% of the total weight of the alloy
  • the size of the alloy in the filled hole ranges from 1nm to 50nm .
  • the EDAX results show that the weight percentage of oxygen in the composite material is 2%.
  • Example 1 Using the same method as in Example 1, the composite material was prepared into an electrode, and the two-electrode experimental button cell 2016 as described in Example 1 was used to study the electrochemical performance of the composite material as the negative electrode active material of a secondary lithium battery.
  • An experimental battery was assembled as in Example 1. The test was performed using the same test method as in Example 1. The experimental data are shown in Table 1.
  • a nano-Zn fl . 5 Sb fl 5 alloy / HCS10 composite material was prepared.
  • the differences are as follows:
  • the raw material SnCl 2 .2H 2 0 in step 1 is replaced by ZnCl 2 , the solvent used is isopropanol, the volume of the chloride solution is 8 liters, and 81 ⁇ 23 ⁇ 4 and 2! ⁇ 1 2 in the chloride solution
  • the concentration is 0.01M;
  • the reducing agent in step 1 is replaced with Mg powder (particle size is 10um), the amount of which is 90% of the required stoichiometry, and is formulated into a 40ml Mg powder isopropanol suspension.
  • the raw material carbon powder used in step 2 is HCS10, and the added amount is 16.5g; during the co-reduction reaction, the dropping time is 24 hours, and the reaction temperature is -10 ° C.
  • the composite material was obtained after drying at 120 ° C for 48 hours under a vacuum of 0.1 mmHg.
  • nanometer Z 3 ⁇ 4 5 Sb The percentage of nano-Zn ⁇ Sb ⁇ alloy in the 5 alloy / HCS10 composite material is 70% of the total weight of the composite material.
  • the average particle size of the alloy deposited on the outer surface of HCS10 was 250 nm, and the proportion of free alloy to the total weight of the alloy was 30%.
  • the proportion of the alloy on the outer surface of HCS10 to the total alloy weight is 65%, the proportion of the alloy on the inner surface to the total alloy weight is 5%, and the alloy size in the filled hole From 1 to 10mn.
  • EDAX results show that the weight percentage of oxygen in the composite material is 3%.
  • Example 6 Using the same method as in Example 1, the composite material was prepared into an electrode, and the two-electrode experimental button cell 2016 as described in Example 1 was used to study the electrochemical performance of the composite material as the negative electrode active material of a secondary lithium battery. Example 1 was assembled into an experimental battery. The test was performed using the same test method as in Example 1. The experimental data are shown in Table 1.
  • Example 6 Using the same method as in Example 1, the composite material was prepared into an electrode, and the two-electrode experimental button cell 2016 as described in Example 1 was used to study the electrochemical performance of the composite material as the negative electrode active material of a secondary lithium battery. Example 1 was assembled into an experimental battery. The test was performed using the same test method as in Example 1. The experimental data are shown in Table 1. Example 6
  • a nano Sb / HCS10 composite material is prepared.
  • the difference is that:
  • the metal chloride solution prepared in step 1 is 30 ml of 3M SbCl 3 methanol solution; 2 liters of Zn powder methanol suspension is prepared, and the amount of Zn powder added is 8.7 g.
  • the raw material carbon powder used in step 2 is HCS10, and the added amount of the carbon powder is 23g; during the co-reduction reaction, the dropping time is 1 minute, and the reaction temperature is -20 ° C.
  • the composite material is obtained after drying at 50 ° C. for 1 hour under a vacuum of 0.1 mmHg.
  • the percentage of nano-Sb in the total weight of the nano-Sb / HCS10 composite is 30%.
  • the average particle size of metal Sb deposited on the outer surface of HCS10 was 120 nm, and the proportion of free Sb to the total weight of metal Sb was 5%.
  • the proportion of Sb on the outer surface to the total weight of metal Sb is 90%, and the proportion of Sb on the inner surface to the total weight of metal Sb is 5%. Sizes range from l-10nm.
  • the EDAX results show that the weight percentage of oxygen in the composite material is 4%.
  • Example 1 Using the same method as in Example 1, the composite material was prepared into an electrode, and the two-electrode experimental button cell 2016 as described in Example 1 was used to study the electrochemical performance of the composite material as the negative electrode active material of a secondary lithium battery. Example 1 was assembled into an experimental battery. The test was performed using the same test method as in Example 1. The electrochemical performance parameters are shown in Table 1.
  • nano-Sn was prepared. 6 C U 4 alloy / CMS28 composite.
  • the raw material SbCl 3 in step 1 is replaced with CuCl 2
  • the alcohol used is butanol
  • the concentration of SnCl 2 in the prepared mixed metal chloride solution is 0.6M, and the concentration of 010 2 is 0.4M
  • the reducing agent used is ultra-fine Zn powder (particle size is 20nm), and its amount is 97% of the required stoichiometry.
  • the raw material carbon powder used in step 2 is CMS28 with a particle size of lum.
  • nano-Sn. 6 Cuo. 4 alloy / CMS28 composites. . 6 Cu The percentage of 4 alloy to the total weight of the composite is 20%.
  • the average particle size of the alloy deposited on the outer surface of CMS28 was 150 nm, and the proportion of free alloy to the total weight of the alloy was 15%.
  • the EDAX results show that the weight percentage of oxygen in the composite material is 0.5%.
  • Example 1 Using the same method as in Example 1, the composite material was prepared into an electrode, and the two-electrode experimental button cell 2016 as described in Example 1 was used to study the electrochemical performance of the composite material as the negative electrode active material of a secondary lithium battery.
  • Example 1 was assembled into an experimental battery. The test was performed using the same test method as in Example 1. The experimental data are shown in Table 1.
  • Example 8 According to the preparation method described in Example 1, nano 8 4 81 ) is prepared. 5 ( ⁇ 3 ⁇ 4. 4 alloy / 0 ⁇ 28 composite material. The difference is that: The reducing agent used in step 1 is ultra-fine Zn powder (grain size 20nm), and the amount is 105% of the required stoichiometry. ⁇ The raw material carbon powder used in step 2 was CMS28 with a particle size of 50um.
  • the percentage of nano Sn 0. 4 Sb 0. 56 Zn 0. 04 alloy in the 4 alloy / 0 ⁇ 828 composite material is 35% of the total weight of the composite material, the particle size of the alloy is 100 nm, and the ratio of the free alloy to the total weight of the alloy is It is 5%, and the weight percentage of oxygen in the composite material is 0.001%.
  • Example 1 Using the same method as in Example 1, the composite material was prepared into an electrode, and the two-electrode experimental button cell 2016 as described in Example 1 was used to study the electrochemical performance of the composite material as the negative electrode active material of a secondary lithium battery. Example 1 was assembled into an experimental battery. ⁇ The test was performed using the same test method as in Example 1. The experimental data are shown in Table 1.
  • a nano-Sn / HCS10E composite material is prepared.
  • the difference is that the metal chloride raw material in step 1 does not contain SbCl 3 .
  • the raw material carbon powder used in step 2 is HCS10E, the amount of carbon powder added is 16.5 g, and the total reduction reaction temperature is -10 ° C.
  • nano-Sn / HCS10E composites account for 60% of the total weight of the composite by nano-Sn.
  • the average particle size of Sn deposited on the outer surface of HCS10E was 250 nm, and the percentage of free Sn to the total weight of metal Sn was 15%.
  • the percentage of Sn on the outer surface to the total weight of metal Sn is 50%, and the percentage of Sn on the inner surface to the total weight of metal Sn is 35%. Sizes range from 1 nm to 50 nm.
  • the EDAX results show that the weight percentage of oxygen in the composite material is 0.5%.
  • Example 1 Using the same method as in Example 1, the composite material was prepared into an electrode, and the two-electrode experimental button cell 2016 as described in Example 1 was used to study the electrochemical performance of the composite material as the negative electrode active material of a secondary lithium battery.
  • An experimental battery was assembled as in Example 1. ⁇ The test was performed using the same test method as in Example 1. The experimental data are shown in Table 1.
  • a nano In / HCS10E composite material is prepared.
  • the remaining chloride solution in step 1 is an isopropyl alcohol solution of InCl 3 ;
  • the raw material carbon powder used in step 2 is a spherical pyrolytic hard carbon HCS10E with an average diameter of 100 nm, and the amount of carbon powder added is 34g, co-reduction reaction temperature is -20 o C.
  • nano-In in the nano-In / HCS10E composites accounts for the total The percentage by weight is 30%.
  • the average particle size of In deposited on the outer surface of HCS10E is 10 nm, and the percentage of free In to the total weight of metal In is 5%.
  • the percentage of In on the outer surface to the total weight of metal In is 60%, and the percentage of In on the inner surface to the total weight of metal In is 35%. Sizes range from 1nm to 5nm.
  • EDAX results show that the weight percentage of oxygen in the composite material is 1%.
  • Example 1 Using the same method as in Example 1, the composite material was prepared into an electrode, and the two-electrode experimental button cell 2016 as described in Example 1 was used to study the electrochemical performance of the composite material as the negative electrode active material of a secondary lithium battery.
  • Example 1 was assembled into an experimental battery. The test was performed using the same test method as in Example 1. The experimental data are shown in Table 1.
  • a nano-Zn ⁇ Mg ⁇ / HCSlOE composite material is prepared.
  • the differences are as follows:
  • the metal chloride solution in step 1 is a Z ⁇ 2 solution;
  • the reducing agent used is an ultra-fine Mg powder (99.5% purity, particle size lum).
  • the raw material carbon powder used in step 2 is HCS10E with a particle size of 10um, and the added amount of the carbon powder is 22g.
  • nano-Z ⁇ 95 Mg in nano-Zn ⁇ Mg ⁇ / HCSlOE composites. .. 5 is 30% of the total weight of the composite material.
  • Zn ⁇ . 95 ⁇ & . Deposited on the outer surface The average particle size of 5 is 220 nm, and the proportion of the free alloy to the total alloy weight is 5%.
  • Z 3 ⁇ 495 Mg M5 on the outer surface accounts for 85% of the total weight of the alloy, and Zn on the inner surface.
  • 95 Mg M5 accounts for 10% of the total weight of the alloy, and the size of the alloy in the filled hole ranges from 1nm to 25nm. EDAX results show that the weight percentage of oxygen in the composite material is 0.2%.
  • Example 1 Using the same method as in Example 1, the composite material was prepared into an electrode, and the two-electrode experimental button cell 2016 as described in Example 1 was used to study the electrochemical performance of the composite material as the negative electrode active material of a secondary lithium battery.
  • Example 1 was assembled into an experimental battery. The test was performed using the same test method as in Example 1. The experimental data are shown in Table 1.
  • a nano Sn ⁇ Fe ⁇ Zn ⁇ alloy / CMS28 composite material was prepared.
  • the differences are as follows: the raw material SbCl 3 in step 1 is replaced with FeCl 2 , the concentration of SnCl 2 in the prepared mixed metal chloride solution is 0.6M, and the concentration of FeCl 2 is 0.4M; the reducing agent used is ultrafine Zn Powder (purity is 99.9%, particle size is 20nm), and its amount is 105% of the required stoichiometry.
  • the raw material carbon powder used in step 2 is CMS28 with a particle size of 6um, and the amount of carbon powder added is 56g. According to the results of conventional chemical analysis, the nano-Sn 58 Fe Q.
  • the percentage of nano Sn 0. 58 Fe 0. 4 Zn 0. 02 alloy in the 2 alloy / CMS28 composite material is 35% of the total weight of the composite material, the particle size of the alloy is 160nm, and the percentage of the free alloy in the total weight of the alloy is 5%.
  • the weight percentage of oxygen in the composite material is 3%.
  • Example 1 Using the same method as in Example 1, the composite material was prepared into an electrode, and the two-electrode experimental button cell 2016 as described in Example 1 was used to study the electrochemical performance of the composite material as the negative electrode active material of a secondary lithium battery.
  • Example 1 was assembled into an experimental battery. The test was performed using the same test method as in Example 1. The experimental data are shown in Table 1.
  • nano-Sn was prepared. 78 Ag Q. 2 Zno .. 2 alloy / CMS28 composite. The differences are as follows: The raw material SbCl 3 in step 1 is replaced with AgN0 3. The concentration of SnCl 2 1 ⁇ 2 in the prepared mixed metal salt solution is 0.8M, and the concentration of eight ⁇ 0 3 is 0.2M. The reducing agent used is super Fine Zn powder (99.9% purity, 20nm particle size), the amount of which is 105% of the required stoichiometry. The raw material carbon powder used in step 2 is CMS28 with a particle size of 10um.
  • the percentage of nano Sn 0. 78 Ag 0. 2 Zn 002 alloy in the nano-Sno ⁇ Ag ⁇ Zno ⁇ alloy / CMS28 composite material to the total weight of the composite material is 28%, and the particle size of the alloy is 100 nm The proportion of free alloy to the total alloy weight is 5%. The weight percentage of oxygen in the composite material is 2%.
  • Example 1 Using the same method as in Example 1, the composite material was prepared into an electrode, and the two-electrode experimental button cell 2016 as described in Example 1 was used to study the electrochemical performance of the composite material as the negative electrode active material of a secondary lithium battery.
  • Example 1 was assembled into an experimental battery. The test was performed using the same test method as in Example 1. The experimental data are shown in Table 1.
  • the reducing agent used in step 1 is ultra-fine A1 powder (purity is 99.9%, particle size is lum), and the amount is 90% of the required stoichiometry.
  • the raw material carbon powder used in step 2 is a natural graphite (NG) with a particle size of 15um (origin is Nanshu, China, its specific surface area is 0.5m 2 / g, 'without micropores).
  • nano Sno. 48 Sb. . 5 Based on the results of conventional chemical analysis, nano Sno. 48 Sb. . 5 ⁇ 1.
  • the percentage of nano Sn o . 48 Sb O 5 Al 002 alloy in the 2 alloy / NG composite material is 30% of the total weight of the composite material, the particle size of the alloy is 90nm, and the proportion of the free alloy to the total weight of the alloy is 5%.
  • the weight percentage of oxygen in the composite material is 1%.
  • the composite material was prepared into an electrode, and the two-electrode experimental button cell 2016 as described in Example 1 was used to study the electrochemical performance of the composite material as the negative electrode active material of a secondary lithium battery.
  • Example 1 was assembled into an experimental battery. The test was performed using the same test method as in Example 1. The experimental data are shown in Table 1.
  • nano-Sn was prepared. 5 Sb 5 alloy / PCG composite.
  • the differences are as follows:
  • the reducing agent used in step 1 is ultra-fine Zn powder (purity is 99.9%, particle size is lum), and the amount is 95% of the required stoichiometry.
  • the raw material carbon powder used in step 2 is petroleum coke-coated natural graphite (PCG) with a particle size of 25um (Osaka Gas Company, Japan, specific surface area is 4mVg, excluding micropores); the co-reduction reaction temperature is 200 ° C.
  • PCG petroleum coke-coated natural graphite
  • Nano S 3 ⁇ 4 5 Sb. Nano S 3 ⁇ 45 Sb in 5 alloy / PCG composites.
  • the percentage of the 5 alloy to the total weight of the composite material is 32%
  • the particle size of the alloy is 240nm
  • the proportion of the free alloy to the total weight of the alloy is 5%.
  • the weight percentage of oxygen in the composite material is 2%.
  • Example 2 (2) Using the same method as in Example 1, the composite material was prepared into an electrode, and the two-electrode experimental button cell 2016 as described in Example 1 was used to study the electrochemical performance of the composite material as the negative electrode active material of a secondary lithium battery. An experimental battery was assembled as in Example 1. The test was performed using the same test method as in Example 1. The experimental data are shown in Table 1.
  • nano-Sn was prepared. . 5 Sb. 5 alloy / GPCF28 composite material.
  • the raw material carbon powder used in step 2 is GPCF28 (2800 ° C graphitized pitch-based carbon fiber, Jilin Carbon Factory, with a diameter of 10 ⁇ m, a length of 60-300 ⁇ m, an average of 100 ⁇ m, and a specific surface area of 10 m 2 / g , Without micropores).
  • Nano Sno. 5 Sb. Nano Sn in 5 alloy / GPCF28 composites. 5 Sb.
  • the percentage of the alloy 5 to the total weight of the composite material is 30%, the particle size of the alloy is 60nm, and the proportion of the free alloy to the total weight of the alloy is 5%.
  • the weight percentage of oxygen in the composite material is 1%.
  • Example 1 Using the same method as in Example 1, the composite material was prepared into an electrode, and the two-electrode experimental button cell 2016 as described in Example 1 was used to study the electrochemical performance of the composite material as the negative electrode active material of a secondary lithium battery.
  • Example 1 was assembled into an experimental battery. The test was performed using the same test method as in Example 1. The experimental data are shown in Table 1.
  • Example 17 According to the preparation method described in Example 1, nano 8 3 ⁇ 4 . 77 8 was prepared. . 22 ⁇ 3 ⁇ 4 . 1 alloy / 0 ⁇ 828 composite material. The differences are as follows: The raw material SbCl 3 is replaced by BC1 3 in Step 1. The concentration of SnCl 2 in the prepared chloride solution is 0.8M, and the concentration of BC1 ⁇ is 0.2M. The reducing agent used is ultrafine Zn powder (purity It is 99.9%, the particle size is lum), and the amount is 100% of the required stoichiometry. The raw material carbon powder used in step 2 is CMS28 with a particle size of 6um, and the amount of carbon powder added is 54g.
  • the nano Sn 0. 77 B 0. 22 Zn 001 alloy in the alloy / 0 ⁇ 828 composite material accounts for 35% of the total weight of the composite material, the particle size of the alloy is 120nm, and the ratio of the free alloy to the total weight of the alloy is 2%.
  • the weight percentage of oxygen in the composite material is 2%.
  • Example 1 Using the same method as in Example 1, the composite material was prepared into an electrode, and the two-electrode experimental button cell 2016 as described in Example 1 was used to study the electrochemical performance of the composite material as the negative electrode active material of a secondary lithium battery.
  • Example 1 was assembled into an experimental battery. The test was performed using the same test method as in Example 1. The experimental data are shown in Table 1.
  • nano S 3 ⁇ 4 84 B was prepared. ., Si. .. 5 Zn 0. M alloy / CMS28 composite.
  • the difference is that the raw material SbCl 3 in step 1 is replaced with BCl ⁇ BSiCl 4 , the concentration of SnCl 2 in the prepared chloride solution is 0.85M, the concentration of BC1 3 is 0.1M, and 8 ⁇ : 1 4
  • the concentration is 0.01M;
  • the reducing agent used is ultrafine Zn powder (purity is 99.9%, particle size is lum), and the amount is 100% of the required stoichiometry.
  • the raw material carbon powder used in step 2 is CMS28 with a particle size of 6um, and the amount of carbon powder added is 64g.
  • nano 8 3 ⁇ 4 84 8. . ⁇ . .. 5 211 0 ... 1 alloy / 0 ⁇ 28 composite in the nano 8 84 8. . ⁇ () . () 5 21 1 ⁇ 2 ..
  • the percentage of 1 alloy to the total weight of the composite material is 32%, the particle size of the alloy is 120nm, and the proportion of the free alloy to the total weight of the alloy is 5%.
  • the weight percentage of oxygen in the composite material is 10%.
  • Example 1 Using the same method as in Example 1, the composite material was prepared into an electrode, and the two-electrode experimental button cell 2016 as described in Example 1 was used to study the electrochemical performance of the composite material as the negative electrode active material of a secondary lithium battery.
  • Example 1 was assembled into an experimental battery. The test was performed using the same test method as in Example 1. The experimental data are shown in Table 1.
  • step SbCl 3 was replaced ho CoCl ⁇ BNiCl 2, formulated chloride solution of SnCl 2 in a concentration of 0.8M, CoCl 2 concentration of 0.1M, NiCl 2 at a concentration of 0.1M ;
  • the reducing agent used is Ultrafine Zn powder (purity is 99.9%, particle size is 20nm), and its amount is 100% of the required stoichiometry.
  • the raw material carbon powder used in step 2 is CMS28 with a particle size of 6um.
  • the percentage of the alloy to the total weight of the composite material is 25%, the particles of the alloy The size is 80 nm, and the ratio of the free alloy to the total alloy weight is 5%.
  • the weight percentage of oxygen in the composite material is 2%.
  • Example 1 Using the same method as in Example 1, the composite material was prepared into an electrode, and the two-electrode experimental button cell 2016 as described in Example 1 was used to study the electrochemical performance of the composite material as the negative electrode active material of a secondary lithium battery.
  • Example 1 was assembled into an experimental battery. The test was performed using the same test method as in Example 1. The experimental data are shown in Table 1.
  • nano-Sn ⁇ Sb ⁇ Ti ⁇ alloy / CMS28 composite material was prepared.
  • the difference is that: in step 1 ho increased chloride TiCl 4, the concentration of the chloride solution prepared as 81,102 0.45M, concentration of 31 ⁇ 13 is the concentration of 0.5M, 1 0 4 0.05 M;
  • the reducing agent used is ultra-fine Zn powder (purity is 99.9%, particle size is 20nm), and the amount is 100% of the required stoichiometry.
  • the raw material carbon powder used in step 2 is CMS28 with a particle size of 6um.
  • 5 Nano-Sn in 5 alloy ⁇ 28 composites. 45 Sb. 5 Ti. ..
  • the percentage of the 5 alloy to the total weight of the composite material is 29%, the particle size of the alloy is 80 nm, and the proportion of the free alloy to the total weight of the alloy is 5%.
  • the weight percentage of oxygen in the composite material is 2%.
  • Example 1 Using the same method as in Example 1, the composite material was prepared into an electrode, and the two-electrode experimental button cell 2016 as described in Example 1 was used to study the electrochemical performance of the composite material as the negative electrode active material of a secondary lithium battery.
  • Example 1 was assembled into an experimental battery. The test was performed using the same test method as in Example 1. The experimental data are shown in Table 1.
  • nano-Sn was prepared. 78 V. . 2 Zn M2 alloy / CMS28 composite. The difference is that the raw material SbCl 3 in step 1 is replaced with VC1 4. The concentration of SnCl 2 in the prepared chloride solution is 0.8M and the concentration of 0 4 is 0.2M.
  • the reducing agent used is ultrafine Zn powder ( The purity is 99.9% and the particle size is 20nm), and the amount is 100% of the required stoichiometry.
  • the raw material carbon powder used in step 2 is a particle size of 6um.
  • the nano-Sn ⁇ V ⁇ Zn ⁇ / CMS28 The percentage of Sn 0. 78 V 0 , Zn 0. 02 alloy to the total weight of the composite material is 25%, the particle size of the alloy is 100 nm, and the proportion of free alloy to the total weight of the alloy is 5%.
  • the weight percentage of oxygen in the composite material is 6%.
  • Example 1 Using the same method as in Example 1, the composite material was prepared into an electrode, and the two-electrode experimental button cell 2016 as described in Example 1 was used to study the electrochemical performance of the composite material as the negative electrode active material of a secondary lithium battery.
  • An experimental battery was assembled as in Example 1. The test was performed using the same test method as in Example 1. The experimental data are shown in Table 1.
  • a nano Sno ⁇ Mn ⁇ Zno ⁇ alloy / CMS28 composite material was prepared.
  • the raw material SbCl 3 in step 1 is replaced with MnCl 2
  • the concentration of SnCl S in the prepared chloride solution is 0.8M
  • the concentration of 1 ⁇ 3 ⁇ 4 ⁇ 1 2 is 0.2M
  • the reducing agent used is ultrafine Zn powder (purity is 99.9%, particle size is 20nm), and its amount is 100% of the required stoichiometry.
  • the raw material carbon powder used in step 2 is CMS28 with a particle size of 6um.
  • the results of chemical analysis of a conventional nano S n. 78 M n () . 2 Zn 0 The percentage of nano Sn 0. 78 Mn 0. 2 Zn 0. 02 alloy in the 2 alloy / CMS28 composite material is 25% of the total weight of the composite material, the particle size of the alloy is 150 nm, and the ratio of the free alloy to the total weight of the alloy is 5%. The weight percentage of oxygen in the composite material is 8%.
  • Example 1 Using the same method as in Example 1, the composite material was prepared into an electrode, and the two-electrode experimental button cell 2016 as described in Example 1 was used to study the electrochemical performance of the composite material as the negative electrode active material of a secondary lithium battery.
  • Example 1 was assembled into an experimental battery. The test was performed using the same test method as in Example 1. The experimental data are shown in Table 1.
  • nano-811 was prepared. 5 ( ⁇ .. 49 23 ⁇ 4 .. 1 alloy / 1 ⁇ 810 composite. The difference is that the raw material SbCl 3 in step 1 is replaced by SiCl 4; the reducing agent used is ultra-fine Zn powder (purity 99.9%). %, Particle size is lum), and its amount is 100% of the required stoichiometry.
  • the raw material carbon powder used in step 2 is HCS10 with a particle size of 10um, and the added amount of carbon powder is 46g.
  • Nano Sn 5 Nano-Sn 0. 50 Si 0. 49 Zn 0. 01 alloy in Si 49 Zn Q1 alloy / HCS10 composites accounts for 25% of the total weight of the composite, the particle size of the alloy is 100 nm, and the free alloy accounts for the total weight of the alloy The percentage is 5%. The weight percentage of oxygen in the composite material is 8%.
  • the composite material was prepared into an electrode using the same method as that described in Example 1, and the method described in Example 1 was used.
  • the two-electrode experimental button cell type 2016 was used to study the electrochemical performance of the composite material as the negative electrode active material of a secondary lithium battery. The test was performed using the same test method as in Example 1. The experimental data are shown in Table 1.
  • Nano Sn. 5 Sb Q. 5 alloy / HCS10 composite can also be prepared by hydrothermal reduction method, the steps are as follows-(1) SbCl 3 and SnCl 2 .H 2 0 are mixed at a molar ratio of 1: 1, and then dissolved in ethanol to form 0.1M 180 ml of a mixed metal chloride solution, and then 12 g of spherical pyrolytic hard carbon HCS10 with an average particle size of 10 um was added to the above solution and stirred to obtain a mixed solution. (2) Add the mixed solution of (1) above to a 200ml autoclave, heat it to 200 ° C at 100 ° C / hour, then keep it constant temperature for 12 hours, and then naturally cool to room temperature, then take out the product .
  • step (3) The product of step (2) is filtered and washed with ethanol until no cr ions in the filtrate can be detected with silver nitrate. After the filter residue is dried under vacuum, it is placed in a tube furnace, heated to 250 ° C at a rate of 50 ° C / hour, kept constant for 10 hours, and then naturally cooled to room temperature. During the process of heating, constant temperature, and cooling, H 2 / Ar mixed gas is always introduced, in which H 2 accounts for 8% of the total volume, and the flow rate is 2 ml / min. Finally, nano Sn was obtained. . 5 Sb. . 5 alloy / HCS10 composite samples.
  • the nano Sno. 5 Sb. The weight percentage of nano Sn fl 5 Sb 5 alloy in the 5 alloy / HCS 10 composite material is 35% by weight. Scanning electron microscopy showed that the alloy particles were 30 nm in size and contained no free Sn. 5 Sb. . 5 alloy. EDAX results show that the weight percentage of oxygen in the composite material is 10%. The pore specific surface area of the composite material was reduced by BET to 50 m 2 / g, indicating that a portion of the nano-alloys occupied the internal pores.
  • Example 1 Using the same method as in Example 1, the composite material was prepared into an electrode, and the two-electrode experimental button cell 2016 as described in Example 1 was used to study the electrochemical performance of the composite material as the negative electrode active material of a secondary lithium battery.
  • Example 1 was assembled into an experimental battery. The test was performed using the same test method as in Example 1. The experimental data are shown in Table 1.

Abstract

L'invention concerne un métal nanométrique ou un matériau composite alliage/carbone nanométrique, son procédé de fabrication et ses applications dans un élément secondaire. La fabrication de ce matériau composite s'effectue par un procédé de réduction dans un système solvant organique, les particules de métal nanométrique ou d'alliage nanométrique se déposent sur la surface extérieure des particules de carbone et sur la surface intérieure d'une structure poreuse. La granulométrie moyenne des particules de métal nanométrique ou d'alliage nanométrique oscille entre 1 et 250 nm, la granulométrie des particules de carbone, quant à elle, va de 1 à 50 um et le rapport pondéral entre les particules de métal nanométrique ou d'alliage nanométrique et les particules de carbone varie de 10 à 70 %. Ce matériau composite tient lieu au sein de l'élément secondaire de matériau actif à électrode négative, ce qui contribue à augmenter la capacité réversible, à améliorer le cycle, à renforcer la sécurité et la résistance à la charge-décharge de courant haute intensité.
PCT/CN2001/000918 2000-06-06 2001-06-06 Metal nanometrique ou materiau composite alliage/carbone nanometrique, son procede de fabrication et ses applications dans un element secondaire WO2002027822A1 (fr)

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