WO2017190363A1 - 一种负极活性材料及其制备方法、含所述负极活性材料的负极及二次电池 - Google Patents

一种负极活性材料及其制备方法、含所述负极活性材料的负极及二次电池 Download PDF

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WO2017190363A1
WO2017190363A1 PCT/CN2016/081345 CN2016081345W WO2017190363A1 WO 2017190363 A1 WO2017190363 A1 WO 2017190363A1 CN 2016081345 W CN2016081345 W CN 2016081345W WO 2017190363 A1 WO2017190363 A1 WO 2017190363A1
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active material
negative electrode
electrode active
carbonate
aluminum
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PCT/CN2016/081345
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English (en)
French (fr)
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唐永炳
仝雪峰
张帆
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深圳先进技术研究院
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Priority to CN201680085086.XA priority Critical patent/CN109417157A/zh
Priority to PCT/CN2016/081345 priority patent/WO2017190363A1/zh
Publication of WO2017190363A1 publication Critical patent/WO2017190363A1/zh

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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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention belongs to the field of energy materials, and particularly relates to a negative electrode active material, a preparation method thereof, a negative electrode including the negative electrode active material, and a secondary battery.
  • Secondary batteries have been widely studied in the industry because of their rechargeable and dischargeable, thereby reducing the cost of use and being less polluting. With the advent of secondary batteries, the merger has accelerated the development trend of modern electronic information industry to portability and miniaturization. Secondary batteries have been widely used in mobile phones, notebook computers, digital cameras, MP3 and other portable consumer electronics because of their high open circuit voltage, high energy density, low self-discharge rate, long service life, no memory effect and no pollution. On the product. At present, secondary batteries have achieved great success in terms of production and market size.
  • Representative components constituting the secondary battery include a positive electrode, a negative electrode, an electrolyte, a separator, and the like, and the negative electrode generally includes a negative electrode current collector and a negative electrode active material.
  • the negative active material is critical to the performance requirements of the secondary battery for achieving high capacity and high cycle performance.
  • an object of the present invention is to provide a negative electrode active material, a method for producing the same, a negative electrode including the negative electrode active material, and a secondary battery.
  • the present invention provides an anode active material, the anode active material comprising aluminum particles and a carbon layer coated on the surface of the aluminum particles, wherein the aluminum particles have a particle diameter of 1 to 50000 nm, and the content of the aluminum particles It is 50 to 99% by weight based on the total weight of the negative electrode active material; the carbon layer has a thickness of 1 to 5000 nm.
  • the present invention provides a method for preparing a negative active material, comprising the steps of:
  • the aluminum/carbon precursor obtained in the step (1) is heat-treated at 300 to 650 ° C for 0.1 to 24 hours in an inert or reducing gas to obtain a negative electrode active material, wherein the negative electrode active material includes aluminum particles. And a carbon layer coated on the surface of the aluminum particles, the aluminum particles having a particle diameter of 1 to 50000 nm, the aluminum particles having a content of 50 to 99% by weight based on the total weight of the negative electrode active material; and the thickness of the carbon layer being 1 to 5000 nm.
  • the organic polymer includes, but is not limited to, one of polyacrylonitrile, polyvinylidene fluoride, polyacrylic acid, polyurethane, polyvinyl butyral, polytetrafluoroethylene or polyurethane. kind or several.
  • the organic solvent includes, but is not limited to, dimethylformamide, propylene glycol methyl ether, propylene carbonate, ethylene carbonate, dimethyl carbonate, dipropyl carbonate, and ethylene carbonate.
  • the method further comprises: preheating the aluminum/carbon precursor obtained in the step (1) at 150 to 300 ° C for 0.1 to 24 hours.
  • the method further includes:
  • the etching treatment is performed by using an etchant for 0.1 to 2 hours, and the negative electrode active material is obtained by centrifugation, washing, filtration, and drying.
  • the anode active material according to the first aspect is produced by the method for producing an anode active material according to the second aspect.
  • the present invention provides a negative electrode comprising a negative electrode current collector and a negative electrode active material layer, the negative electrode active material layer comprising the negative electrode active material according to the first aspect of the invention or the second aspect of the invention
  • a negative electrode active material prepared by a method for preparing a negative electrode material is provided.
  • the present invention provides a secondary battery including a battery negative electrode, an electrolyte, a separator, and a battery positive electrode, wherein the battery negative electrode includes a negative electrode current collector and a negative electrode active material layer, and the negative electrode active material layer includes, for example, the first The negative active material of the aspect or the negative active material produced by the method for producing a negative electrode material according to the second aspect.
  • the electrolyte includes, but is not limited to, an electrolyte, a solvent.
  • the electrolyte comprises one of a lithium salt, a sodium salt or a magnesium salt;
  • the solvent comprises one or more of an ester, a sulfone and an ether organic solvent or an ionic liquid.
  • the electrolyte further includes an additive.
  • the additives include, but are not limited to, one or more of organic additives containing esters, sulfones, ethers, nitriles or olefins.
  • the battery positive electrode includes a positive electrode current collector and a positive electrode active material layer.
  • the positive active material includes, but is not limited to, one or more of a graphite-based material, a sulfide, a nitride, an oxide, and a carbide having a layered crystal structure.
  • the negative electrode active material provided by the present invention has a high specific surface area, which is advantageous for diffusion of lithium ions, etc.
  • the carbon layer can serve as a protective layer to protect aluminum particles during charge and discharge of the negative electrode material and maintain the same.
  • the structure is stable, which improves the cycle stability of the new battery.
  • the preparation method of the anode active material in the present invention improves the cycle stability of the aluminum particles; and the complete coating of the carbon layer allows the electrons to conduct well in the aluminum particles, and the electrochemical performance thereof is also good. Improvement, the carbon layer can also suppress Agglomeration of nanoparticles or growth during high temperature processes.
  • the negative electrode active material provided by the present invention and the preparation method comprising the same are simple, economical, and reliable, and are suitable for industrial production, and have great application prospects.
  • FIG. 1 is a schematic view showing the structure of an anode active material provided by an embodiment of the present invention, which includes a carbon layer 11 and aluminum particles 12 coated on the surface of aluminum particles.
  • FIG. 2 is a schematic structural view of a negative electrode active material used in a secondary battery 20 according to an embodiment of the present invention, which includes: a battery negative electrode 21 (a negative electrode current collector 211, a negative electrode active material layer 212), an electrolyte 22, a separator 23, and a battery positive electrode. 24 (positive electrode active material 241, positive electrode current collector 242);
  • an embodiment of the present invention provides an anode active material.
  • the anode active material 10 includes aluminum particles 12 and a carbon layer 11 coated on the surface of the aluminum particles.
  • the content of the aluminum particles is from 1 to 50,000 nm, and the content of the aluminum particles is from 50 to 99% by weight based on the total weight of the negative electrode active material; and the thickness of the carbon layer is from 1 to 5,000 nm.
  • the negative electrode active material has a specific surface area of from 1 to 500 m 2 /g.
  • the anode active material provided by the embodiment of the invention has high specific surface area, and the anode active material can combine or release more ions during the charging and discharging process of the battery, thereby contributing to the improvement of the battery.
  • Capacity; the carbon layer coated on the surface of the aluminum particles can be used as a protective layer to protect the aluminum particles from powdering and falling off during the charging and discharging process of the battery, improve the structural stability of the negative active material, and thereby improve the cycle performance of the battery.
  • an embodiment of the present invention provides a method for preparing an anode active material, comprising the following steps:
  • the aluminum/carbon precursor obtained in the step (1) is heat-treated at 300 to 650 ° C for 0.1 to 24 hours in an inert gas to obtain a negative electrode active material, wherein the negative electrode active material includes aluminum particles and coating In the carbon layer on the surface of the aluminum particles, the aluminum particles have a particle diameter of 1 to 50000 nm, the aluminum particles are 50 to 99% by weight based on the total weight of the negative electrode active material; and the carbon layer has a thickness of 1 to 5000 nm. .
  • the aluminum particle raw material is mixed with the organic solvent in which the organic polymer is dissolved in the step (1), and the mixture is uniformly stirred to make the aluminum foil and the organic polymer uniform. After contact and sufficient contact, after the heat treatment in the step (2), the carbon layer formed on the surface of the aluminum particles is uniformly and tightly bonded together with the aluminum particles.
  • the organic polymer includes, but is not limited to, one of polyacrylonitrile, polyvinylidene fluoride, polyacrylic acid, polyurethane, polyvinyl butyral, polytetrafluoroethylene or polyurethane. kind or several.
  • the organic solvent includes, but is not limited to, dimethylformamide, propylene glycol methyl ether, propylene carbonate, ethylene carbonate, dimethyl carbonate, dipropyl carbonate, ethylene carbonate Ester, vinylene carbonate, ethyl isopropyl carbonate, methylbutyl carbonate, dibutyl carbonate, ethyl butyl carbonate, ethyl methyl carbonate, diethyl carbonate, ⁇ -butyrolactone or N-methyl One or several of pyrrolidone.
  • the temperature is controlled at 40-180 ° C, so that the rate of volatilization of the organic solvent can be effectively controlled, and after the organic solvent is volatilized, an aluminum/carbon precursor can be obtained, thereby avoiding the cause. If the temperature is too high, the organic solvent volatilizes too fast, affecting the contact between the aluminum particles and the organic polymer, thereby affecting the coating effect of the carbon layer in the negative active material; and avoiding the excessive evaporation of the organic solvent caused by the excessive temperature. Slow and time consuming.
  • the inert or reducing gas includes, but is not limited to, one or more of argon gas, helium gas, and hydrogen gas.
  • heat treatment in the inert or reducing gas can effectively prevent the aluminum particles from being oxidized to alumina during the heat treatment.
  • the step (1) and the step (2) further comprise: preheating the aluminum/carbon precursor obtained in the step (1) at 150 to 300 ° C for 0.1 to 24 hours.
  • the aluminum/carbon precursor obtained in the step (1) is preheated at 150 to 300 ° C for 0.1 to 24 hours, which can enhance the bonding force of aluminum and carbon in the aluminum/carbon precursor, and is favorable for heat treatment.
  • the negative active material described above is obtained.
  • the method further comprises:
  • the etching treatment is performed by using an etchant for 0.1 to 2 hours, and the negative electrode active material is obtained by centrifugation, washing, filtration, and drying.
  • the etchant comprises an acid solution or an alkali solution.
  • the concentration of the etchant is 0.01 to 2 mol/L.
  • the etchant is an acid solution, and the acid solution is not limited to one or more of hydrochloric acid, hydrofluoric acid and hydrobromic acid.
  • the etchant is an alkali solution
  • the alkali solution includes, but not limited to, sodium hydroxide, potassium hydroxide and lithium hydroxide.
  • an etching treatment is performed by using an etchant, which can effectively etch the aluminum oxide component on the surface of the aluminum particle, so that between the aluminum particle and the carbon-containing layer in the negative electrode material obtained by the etchant treatment A gap will be left to provide space for the volume effect of the aluminum particles during charging and discharging, which is beneficial to the improvement of the battery capacity and the stability of the structure of the negative active material.
  • the negative electrode active material has a specific surface area of from 1 to 500 m 2 /g.
  • the anode active material according to the first aspect is produced by the method for producing the anode active material according to the second aspect.
  • the present invention provides a negative electrode comprising a negative electrode current collector and a negative electrode active material layer, the negative electrode active material layer comprising the negative electrode active material according to the first aspect or the preparation of the negative electrode material according to the second aspect The negative active material produced by the method.
  • the present invention provides a secondary battery, as shown in FIG. 2, a secondary battery 20 including a battery negative electrode 21, an electrolyte 22, a separator 23, and a battery positive electrode 24 (including a positive electrode active material 241, a positive electrode current collector) 242) and a case for packaging (not shown in FIG. 2), wherein the battery negative electrode 21 includes a negative electrode current collector 211 and a negative electrode active material layer 212, and the negative electrode active material layer includes the negative electrode active body according to the first aspect A material or an anode active material obtained by the method for producing a cathode material according to the second aspect.
  • the battery of the embodiment of the invention uses the anode active material provided by the embodiment of the invention, and the aluminum particle included in the anode active material has a high specific surface area, and the anode active material can be combined or released during the charging and discharging process of the battery. Ions help to increase the capacity of the battery of the embodiment of the invention; the carbon layer coated on the surface of the aluminum particles can serve as a protective layer. The aluminum particles are protected from powdering and falling off during charging and discharging of the battery, and the structural stability of the negative electrode active material is improved, thereby improving the cycle performance of the battery of the embodiment of the present invention.
  • the anode current collector is not particularly limited as long as it is a conductive material, and is capable of conducting and reversibly extracting or embedding a cation.
  • the anode current collector includes, but is not limited to, one of aluminum, magnesium, lithium, vanadium, copper, iron, tin, zinc, nickel, titanium, manganese, or any one of them. A composite or an alloy of any of these.
  • the electrolyte includes an electrolyte and a solvent.
  • the electrolyte is not particularly limited as long as the electrolyte can be dissociated into a cation and an anion.
  • the electrolyte comprises one of a lithium salt, a sodium salt or a magnesium salt.
  • the lithium salt includes, but is not limited to, lithium bistrifluoromethanesulfonimide, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bisfluorosulfonate, lithium perchlorate, and diethylene glycol.
  • lithium bistrifluoromethanesulfonimide lithium hexafluorophosphate
  • lithium tetrafluoroborate lithium bisfluorosulfonate
  • lithium perchlorate lithium perchlorate
  • diethylene glycol diethylene glycol.
  • the sodium salt includes, but is not limited to, sodium chloride, sodium fluoride, sodium sulfate, sodium carbonate, sodium phosphate, sodium nitrate, sodium difluorooxalate, sodium pyrophosphate, dodecane Sodium benzenesulfonate, sodium lauryl sulfate, trisodium citrate, sodium metaborate, sodium borate, sodium molybdate, sodium tungstate, sodium bromide, sodium nitrite, sodium iodate, sodium iodide, silicon Sodium, sodium lignosulfonate, sodium hexafluorophosphate, sodium oxalate, sodium aluminate, sodium methanesulfonate, sodium acetate, sodium dichromate, sodium hexafluoroarsenate, sodium tetrafluoroborate, sodium perchlorate One or more of sodium trifluoromethanesulfonimide.
  • the magnesium salt includes, but is not limited to, magnesium bromide, magnesium chloride, magnesium perchlorate, magnesium format reagent, amino magnesium halide, Mg(BR 2 R' 2 ) 2 (R, R One or more of 'Mc or aryl group', Mg(AX 4-n R n' R' n" ) 2 complex.
  • the concentration of the electrolyte is 0.1 to 10 mol/L.
  • the solvent is not particularly limited as long as the solvent can dissociate the electrolyte into cations and anions, and the cations and anions can freely migrate.
  • the solvent includes, but is not limited to, one or more of an ester, a sulfone, and an ether organic solvent or an ionic liquid.
  • the solvent includes, but is not limited to, one or more of diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, dimethyl sulfone or dimethyl ether.
  • the solvent is ethyl methyl carbonate.
  • the anion in the electrolyte is embedded in the positive electrode active material of the layered crystal structure, and the ethyl carbonate is used as a solvent to prevent the anion in the concentrated electrolyte from being embedded in the positive electrode active material, thereby increasing the battery. capacity.
  • the electrolyte further includes an additive.
  • the additive is also not particularly limited as long as it can promote the formation of a solid electrolyte membrane (SEI) on the surface of the anode active material.
  • SEI solid electrolyte membrane
  • the additive includes, but is not limited to, one or more of an organic additive containing an ester, a sulfone, an ether, a nitrile or an olefin.
  • the additives include, but are not limited to, vinylene carbonate, ethylene sulfite, propylene sulfite, ethylene sulfate, cyclobutyl sulfone, 1,3-dioxolane One or more of an alkane, acetonitrile or long chain olefin.
  • the additive is present in the electrolyte in an amount of from 0.1 to 20% by weight.
  • the additive is vinylene carbonate, and the vinylene carbonate is present in the electrolyte in an amount of 2% by weight.
  • the separator is also not particularly limited, and it is generally used in the art.
  • the separator includes, but is not limited to, an insulating porous polymer film or an inorganic porous film.
  • the separator includes, but is not limited to, a porous polypropylene film, a porous polyethylene film, a porous composite polymer film, a glass fiber paper, or a porous ceramic separator.
  • the membrane is a fiberglass paper.
  • the battery positive electrode includes a positive electrode current collector and a positive electrode active material layer.
  • the cathode current collector includes, but is not limited to, one of aluminum, magnesium, lithium, vanadium, copper, iron, tin, zinc, nickel, titanium, manganese, or any one of them. A composite or an alloy of any of these.
  • the positive electrode active material layer comprises 60 to 90% by weight of the positive electrode active material by weight percentage.
  • the negative active material layer includes 60 to 90% by weight of the negative electrode active material by weight percentage.
  • the positive electrode active material layer comprises, by weight percentage, 1 to 30% by weight of a conductive agent.
  • the negative active material layer comprises, by weight percent, 1 to 30% by weight of a conductive agent, by weight percent.
  • the positive active material layer comprises, by weight, 1 to 10% by weight of a binder.
  • the negative active material layer comprises, by weight percent, 1 to 10% by weight of a binder, by weight percent.
  • the positive active material includes, but is not limited to, one or more of a graphite-based material, a sulfide, a nitride, an oxide, and a carbide having a layered crystal structure.
  • the graphite-based material includes, but is not limited to, natural graphite, artificial graphite or graphite flakes.
  • the sulfide includes, but is not limited to, molybdenum disulfide, tungsten disulfide or vanadium disulfide.
  • the nitride includes, but is not limited to, hexagonal boron nitride or carbon doped hexagonal boron nitride.
  • the oxide includes, but is not limited to, molybdenum trioxide, tungsten trioxide or vanadium pentoxide.
  • the carbide includes, but is not limited to, titanium carbide, tantalum carbide or molybdenum carbide.
  • the positive active material is a graphite-based material having a layered crystal structure.
  • the conductive agent includes, but is not limited to, one or more of conductive acetylene black, conductive carbon spheres, conductive graphite, carbon nanotubes, and graphene.
  • the binder is not limited to one or more of polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, styrene butadiene rubber, and polyolefin.
  • the binder is not limited to one or more of polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, styrene butadiene rubber, and polyolefin.
  • the form of the battery provided by the present invention is not particularly limited, and may be commonly used in the art, such as a button battery, a flat battery, a cylindrical battery, and the like.
  • the aluminum/carbon precursor obtained in the step (1) is preheated at 180 ° C for 24 h;
  • the aluminum/carbon precursor obtained in the step (1) was heat-treated at 400 ° C for 10 h in an argon gas; the etching treatment was carried out for 1 hour using 1 mol/L hydrochloric acid, and the negative electrode was obtained by centrifugation, washing, filtration, and drying. Active material.
  • the first embodiment of the negative electrode active material preparation method is the same as the step of the first embodiment, except that the material in the embodiment 1 is replaced with the material in the table 1.
  • the conditions are replaced by the conditions in Table 2.
  • Preparation of battery positive electrode 0.4 g of natural graphite, 0.05 g of conductive acetylene black, 0.05 g of polyvinylidene fluoride was added to 2 mL of nitromethylpyrrolidone solvent, and fully ground to obtain a uniform slurry; then the slurry was uniformly coated on the surface of the aluminum foil. Dry at 80 ° C for 12 h under vacuum. The electrode sheet obtained by drying was cut into a disk having a diameter of 10 mm, compacted with a hydraulic press (10 MPa, 10 s), and placed in a glove box as a battery positive electrode.
  • Preparation of battery negative electrode using negative electrode active material preparation method Example 1 to obtain negative electrode active material, 0.4 g negative electrode active material, 0.05 g conductive acetylene black, 0.05 g polyvinylidene fluoride was added to 2 mL of nitromethylpyrrolidone solvent, fully ground A uniform slurry was obtained; then the slurry was uniformly applied to the surface of the copper foil, and dried as a battery negative electrode at 80 ° C for 12 h. The electrode sheet obtained by drying was cut into a disk having a diameter of 12 mm, compacted with a hydraulic press (10 MPa, 10 s), and placed in a glove box as a battery negative electrode.
  • a hydraulic press (10 MPa, 10 s
  • Formulation of electrolyte 2.87 g of lithium bistrifluoromethanesulfonimide was added to 5 mL of ethyl methyl carbonate in a glove box. Stir well until the lithium bistrifluoromethanesulfonimide is completely dissolved, and prepare a 2 mol/L lithium bistrifluoromethanesulfonimide/ethyl methyl carbonate solution, continue to add 0.1 wt% of vinylene carbonate, and stir. Uniformly used as an electrolyte.
  • the glass fiber paper was cut into discs having a diameter of 16 mm, dried and placed in a glove box for use as a separator.
  • Battery assembly In the argon-protected glove box, the prepared battery positive electrode, the separator, and the battery negative electrode are sequentially closely stacked, and the electrolyte is dripped to completely infiltrate the separator, and then the stacked portion is packaged into the button battery case. Complete battery assembly.
  • the "0.05 g conductive acetylene black" in the preparation of the battery positive electrode was replaced with "0.05 g carbon nanotube”; "0.05 g conductive acetylene black, 0.4 g negative electrode active material in the battery negative electrode” was prepared.
  • the secondary battery prepared in the above embodiment of the secondary battery preparation method was charged by a constant current of 100 mA/g of the positive electrode active material until its voltage reached 4.8 V, and then discharged at the same current until the voltage reached 3V, measuring its battery capacity and energy density, testing its cycle stability, expressed in cycles, the number of cycles is the number of times the battery is charged and discharged when the battery capacity is attenuated to 85%.
  • Examples 1-6, 8, and 9 using the additive were larger than the number of cycles of Example 7 in which no additive was used, indicating that the addition of the additive can enhance the stability of the structure and function of the negative electrode active material, thereby improving the cycle of the secondary battery. Number of turns;
  • Examples 1, 2, 3, 8, and 9 using vinylene carbonate as an additive have more cycles than Examples 4-6 using other additives, indicating that in the secondary battery of the embodiment of the present invention, the additive is preferably Vinylene carbonate, which has a better effect of improving the stability of the secondary battery;
  • the battery of Example 3 in which the solvent is ethyl methyl carbonate is higher than the battery of Examples 8 and 9 in which the solvent is another substance, and it is shown that the secondary battery of the embodiment of the present invention preferably has a solvent of ethylene carbonate.
  • An ester which can increase the battery capacity of the secondary battery.

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Abstract

一种负极活性材料（10）及其制备方法、含所述负极活性材料（10）的负极（21）及二次电池（20）。负极活性材料（10）包括铝颗粒（12）及包覆在铝颗粒（12）表面的碳层（11），其中，所述铝颗粒（12）的粒径为1～50000nm，所述铝颗粒（12）的含量为所述负极活性材料（10）总重量的50～99wt％，所述碳层（11）的厚度为1～5000nm。该负极活性材料（10）、含所述负极活性材料（10）的负极（21）、含所述负极活性材料（10）的二次电池（20）具有高容量、循环性能优异等优点；制备方法简单、经济、可靠，适合产业化生产，具有应用前景。

Description

一种负极活性材料及其制备方法、含所述负极活性材料的负极及二次电池 技术领域
本发明属于能源材料领域，尤其涉及一种负极活性材料及其制备方法、含所述负极活性材料的负极及二次电池。
背景技术
在能源领域中，二次电池因其可重复充放电，从而降低使用成本，并对环境污染小而被业界广泛研究。二次电池的出现，迎合并加速了现代电子信息产业向便携化、小型化的发展趋势。二次电池因其具有开路电压高、能量密度大、自放电率小、使用寿命长、无记忆效应、无污染等优异性能，已广泛应用于手机，笔记本电脑，数码相机，MP3等便携式消费电子产品上。目前在产量和市场规模方面，二次电池已经取得了很大的成功。
但相对于电子信息产业的更新速度，电池的发展仍然显得十分缓慢，对高能量密度，高功率密度，稳定性好，循环性能优良的电池的需求依然十分迫切。
构成二次电池的代表性部件包含正极、负极、电解质、隔膜等，负极一般包括负极集流体和负极活性材料。其中，负极活性材料对二次电池是否能达到高容量、高循环性能的性能要求非常关键。
因此，有必要提供一种结构稳定的负极活性材料及其制备方法，以及含该负极活性材料的高容量、高循环性能的负极及二次电池。
发明内容
针对现有技术的不足，本发明的目的是提供一种负极活性材料及其制备方法、含所述负极活性材料的负极及二次电池。
第一方面，本发明提供一种负极活性材料，负极活性材料包括铝颗粒及包覆在铝颗粒表面的碳层，其中，所述铝颗粒的粒径为1～50000nm，所述铝颗粒的含量为所述负极活性材料总重量的50～99wt％；所述碳层的厚度为1～5000nm。
第二方面，本发明提供了一种负极活性材料的制备方法，包括如下步骤：
(1)将粒径为1～50000nm的铝颗粒原料与溶解有有机聚合物的有机溶剂混合，在40～180℃条件下搅拌0.1～24h，制得铝/碳前驱体，其中，所述有机聚合物溶液的质量浓度为1～100mg/ml，铝颗粒与有机聚合物的质量比为1～20∶1；
(2)在惰性或还原性气体中，将步骤(1)所得的铝/碳前驱体在300～650℃下热处理0.1～24h，制得负极活性材料，其中，所述负极活性材料包括铝颗粒及包覆在铝颗粒表面的碳层，所述铝颗粒的粒径为1～50000nm，所述铝颗粒的含量为所述负极活性材料总重量的50～99wt％；所述碳层的厚度为1～5000nm。
具体地，所述步骤(1)中，所述有机聚合物包括但不限于聚丙烯腈、聚偏氟乙烯、聚丙烯酸、聚氨酯、聚乙烯醇缩丁醛、聚四氟乙烯或聚氨酯中的一种或几种。
具体地，所述步骤(1)中，所述有机溶剂包括但不限于二甲基甲酰胺、丙二醇甲醚、碳酸丙烯脂、碳酸乙烯脂、碳酸二甲脂、碳酸二丙酯、碳酸乙丙酯、碳酸亚乙烯酯、碳酸乙异丙酯、碳酸甲丁酯、碳酸二丁酯、碳酸乙丁酯、碳酸甲乙酯、碳酸二乙酯、γ-丁内酯或N-甲基吡咯烷酮中的一种及几种。
进一步地，在所述步骤(1)和步骤(2)之间，还包括：将步骤(1)所得的铝/碳前驱体在150～300℃下预热处理0.1～24h。
进一步地，所述步骤(2)之后，还包括：
采用蚀刻剂进行蚀刻处理0.1～2h，经离心、洗涤、过滤、干燥后制得所述负极活性材料。
在本发明一实施例中，如第一方面所述的负极活性材料为采用如第二方面所述的负极活性材料的制备方法制得。
第三方面，本发明提供了一种负极，包括负极集流体和负极活性材料层，所述负极活性材料层包括如本发明第一方面所述的负极活性材料或如本发明第二方面所述的负极材料的制备方法制得的负极活性材料。
第四方面，本发明提供了一种二次电池，包括电池负极、电解液、隔膜、电池正极，其中，所述电池负极包括负极集流体和负极活性材料层，负极活性材料层包括如第一方面所述的负极活性材料或采用如第二方面所述的负极材料的制备方法制得的负极活性材料。
在本发明一实施例中，所述电解液包括但不限于电解质、溶剂。其中，所述电解质包括锂盐、钠盐或镁盐中的一种；所述溶剂包括酯类、砜类和醚类有机溶剂或离子液体中的一种或几种。
进一步地，在本发明一实施例中，所述电解液还包括添加剂。所述添加剂包括但不限于含酯类、砜类、醚类、腈类或烯烃类有机添加剂一种或几种。
在本发明一实施例中，所述电池正极包括正极集流体、正极活性材料层。所述正极活性材料包括但不限于具有层状晶体结构的石墨类材料、硫化物、氮化物、氧化物、碳化物中的一种或多种。
本发明的有益效果在于：
(1)本发明所提供的负极活性材料具有较高的比表面积，有利于锂离子的扩散等；另一方面碳层能够作为保护层，在负极材料充放电过程中，保护铝颗粒，维持其结构稳定，从而改进新型电池的循环稳定性。
(2)本发明中的负极活性材料的制备方法提升了铝颗粒的循环稳定性；同时碳层的完全包覆使得电子能很好的在铝颗粒中传导，其电化学性能也能得到良好的改善，碳层还可以抑 制纳米颗粒的团聚或者在高温过程中的长大。
(3)本发明提供的负极活性材料及包含所述负极活性材料的制备方法简单、经济、可靠，适合产业化生产，具有极大的应用前景。
附图说明
为了更清楚地说明本申请实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1是本发明实施例提供的负极活性材料的结构示意图，其中包括包覆在铝颗粒表面的碳层11及铝颗粒12。
图2是本发明实施例提供的负极活性材料用于二次电池20的结构示意图，其中包括：电池负极21(负极集流体211、负极活性材料层212)、电解液22、隔膜23、电池正极24(正极活性材料241、正极集流体242)；
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例，都属于本发明保护的范围。
第一方面，本发明实施例提供了一种负极活性材料，如图1所示，负极活性材料10，包括铝颗粒12及包覆在铝颗粒表面的碳层11，其中，铝颗粒的粒径为1～50000nm，铝颗粒的含量为所述负极活性材料总重量的50～99wt％；碳层的厚度为1～5000nm。
优选地，所述负极活性材料的比表面积为1～500m2/g。
本发明实施例提供的负极活性材料，其包括的铝颗粒具有较高的比表面积，作为负极活性材料在电池的充电放过程中，可以结合或释放出更多的离子，有助于提高电池的容量；包覆在铝颗粒表面的碳层能够作为保护层，在电池的充放电过程中保护铝颗粒不粉化脱落，提高负极活性材料的结构稳定性，进而提高电池的循环性能。
第二方面，本发明实施例提供了一种负极活性材料的制备方法，包括如下步骤：
(1)将粒径为1～50000nm的铝颗粒原料与溶解有有机聚合物的有机溶剂混合，在40～180℃条件下搅拌0.1～24h，制得铝/碳前驱体，其中，所述有机聚合物溶液的质量浓度为1～100mg/ml，铝颗粒与有机聚合物的质量比为1～20∶1；
(2)在惰性气体中，将步骤(1)所得的铝/碳前驱体在300～650℃下热处理0.1～24h，制得负极活性材料，其中，所述负极活性材料包括铝颗粒及包覆在铝颗粒表面的碳层，所述铝颗粒的粒径为1～50000nm，所述铝颗粒的含量为所述负极活性材料总重量的50～99wt％；所述碳层的厚度为1～5000nm。
可以理解的是，在所述负极材料的制备方法中，步骤(1)中将铝颗粒原料与溶解有有机聚合物的有机溶剂混合，搅拌均匀，可使所述铝箔与所述有机聚合物均匀接触、充分接触，经所述步骤(2)中的热处理后，形成于铝颗粒表面的碳层与铝颗粒均匀、紧密性地结合在一起。
优选地，所述步骤(1)中，所述有机聚合物包括但不限于聚丙烯腈、聚偏氟乙烯、聚丙烯酸、聚氨酯、聚乙烯醇缩丁醛、聚四氟乙烯或聚氨酯中的一种或几种。
优选地，所述步骤(1)中，所述有机溶剂包括但不限于二甲基甲酰胺、丙二醇甲醚、碳酸丙烯脂、碳酸乙烯脂、碳酸二甲脂、碳酸二丙酯、碳酸乙丙酯、碳酸亚乙烯酯、碳酸乙异丙酯、碳酸甲丁酯、碳酸二丁酯、碳酸乙丁酯、碳酸甲乙酯、碳酸二乙酯、γ-丁内酯或N-甲基 吡咯烷酮中的一种及几种。
可以理解的是，所述步骤(1)中，将温度控制在40～180℃，可使得可有效控制所述有机溶剂挥发的速度，有机溶剂挥发后，获得铝/碳前驱体，可避免因温度过高使得有机溶剂挥发速度过快，影响所述铝颗粒与有机聚合物的接触，从而影响负极活性材料中碳层的包覆效果；也可避免温度过低导致的所述有机溶剂挥发太慢，耗时长。
可以理解的是，所述步骤(1)中，铝颗粒与有机聚合物的质量比越高，最终获得的负极活性材料中铝颗粒的含量越高。
可以理解的是，所述步骤(1)中，有机聚合物的质量浓度越大，最终形成的负极活性材料中碳层的厚度越厚。
所述步骤(2)中，所述惰性或还原性气体包括但不限于氩气、氦气、氢气中的一种或几种。
可以理解的是，所述步骤(2)中，在所述惰性或还原性气体中进行热处理，可有效地防止所述铝颗粒在热处理过程中被氧化成氧化铝。
优选地，所述步骤(1)和步骤(2)之间，还包括：将步骤(1)所得的铝/碳前驱体在150～300℃下预热处理0.1～24h。
可以理解的是，所述将步骤(1)所得的铝/碳前驱体在150～300℃下预热处理0.1～24h，能够增强铝/碳前驱体中铝和碳的结合力，有利于热处理获得所述的负极活性材料。
优选地，所述步骤(2)之后，还包括：
采用蚀刻剂进行蚀刻处理0.1～2h，经离心、洗涤、过滤、干燥后制得所述负极活性材料。
优选地，所述步骤(2)中，所述蚀刻剂包括酸溶液或碱溶液。
优选地，所述步骤(2)中，所述蚀刻剂的浓度为0.01～2mol/L。
进一步优选地，所述步骤(2)中，所述蚀刻剂为酸溶液，所述酸溶液但不限于盐酸、氢氟酸和氢溴酸中的一种或几种。
进一步优选地，所述步骤(2)中，所述蚀刻剂为碱溶液，所述碱溶液包括但不限于氢氧化钠、氢氧化钾和氢氧化锂。
可以理解的是，所述蚀刻处理中，采用蚀刻剂进行蚀刻处理，可有效腐蚀所述铝颗粒表面的氧化铝成分，这样经蚀刻剂处理获得的负极材料中的铝颗粒和含碳层之间将会留有一定缝隙，为所述铝颗粒在充放电过程中存在的体积效应提供空间，有利于电池容量的提高和负极活性材料结构的稳定。
优选地，所述步骤(2)中，所述负极活性材料的比表面积为1～500m2/g。
本发明一实施例中，如第一方面所述的负极活性材料为采用如第二方面所述的负极活性材料的制备方法制得。
第三方面，本发明提供了一种负极，包括负极集流体和负极活性材料层，负极活性材料层包括如第一方面所述的负极活性材料或采用如第二方面所述的负极材料的制备方法制得的负极活性材料。
第四方面，本发明提供了一种二次电池，如图2所示，二次电池20，包括电池负极21、电解液22、隔膜23、电池正极24(包括正极活性材料241、正极集流体242)及用于封装的壳体(图2未示出)，其中，所述电池负极21包括负极集流体211和负极活性材料层212，负极活性材料层包括如第一方面所述的负极活性材料或采用如第二方面所述的负极材料的制备方法制得的负极活性材料。
本发明实施例的电池使用本发明实施例提供的负极活性材料，负极活性材料包括的铝颗粒具有较高的比表面积，作为负极活性材料在电池的充电放过程中，可以结合或释放出更多的离子，有助于提高本发明实施例的电池的容量；包覆在铝颗粒表面的碳层能够作为保护层， 在电池的充放电过程中保护铝颗粒不粉化脱落，提高负极活性材料的结构稳定性，进而提高本发明实施例的电池的循环性能。
可以理解的是，所述负极集流体没有特别限制，只要其是导电材料，能够导电以及可逆脱出或嵌入阳离子即可。
在本发明一优选实施例中，所述负极集流体包括但不限于铝、镁、锂、钒、铜、铁、锡、锌、镍、钛、锰中的一种或其中任意一种金属的复合物或其中任意几种的合金。
在本发明一实施例中，所述电解液包括电解质、溶剂。
可以理解的是，所述电解质没有特别限制，只要电解质可以离解成阳离子和阴离子即可。
在本发明一优选实施例中，所述电解质包括锂盐、钠盐或镁盐中的一种。
在本发明一优选实施例中，所述锂盐包括但不限于双三氟甲烷磺酰亚胺锂、六氟磷酸锂、四氟硼酸锂、双氟磺酰亚胺锂、高氯酸锂、双乙二酸硼酸锂和二氟草酸硼酸锂中的一种或几种。
在本发明一优选实施例中，所述钠盐包括但不限于氯化钠、氟化钠、硫酸钠、碳酸钠、磷酸钠、硝酸钠、二氟草酸硼酸钠、焦磷酸钠、十二烷基苯磺酸钠、十二烷基硫酸钠、柠檬酸三钠、偏硼酸钠、硼酸钠、钼酸钠、钨酸钠、溴化钠、亚硝酸钠、碘酸钠、碘化钠、硅酸钠、木质素磺酸钠、六氟磷酸钠、草酸钠、铝酸钠、甲基磺酸钠、醋酸钠、重铬酸钠、六氟砷酸钠、四氟硼酸钠、高氯酸钠、三氟甲烷磺酰亚胺钠中的一种或几种。
在本发明一优选实施例中，所述镁盐包括但不限于溴化镁、氯化镁、高氯酸镁、镁格式试剂、氨基镁卤化物、Mg(BR2R’2)2(R、R’为烷基或芳基)、Mg(AX4-nRn’R’n”)2络合物中的一种或几种。
在本发明一优选实施例中，在所述电解液中，所述电解质的浓度为0.1～10mol/L。
可以理解的是，所述溶剂没有特别限制，只要溶剂可以使电解质离解成阳离子和阴离子，且阳离子和阴离子可以自由迁移即可。
在本发明一优选实施例中，所述溶剂包括但不限于酯类、砜类和醚类有机溶剂或离子液体中的一种或几种。
在本发明一优选实施例中，所述溶剂包括但不限于碳酸二乙酯、碳酸二甲酯、碳酸甲乙酯、二甲基砜或二甲醚中的一种或几种。
在本发明一优选实施例中，所述溶剂为碳酸甲乙酯。电解液中的阴离子嵌入层状晶体结构的正极活性材料中最有一定的限度，采用碳酸甲乙酯作为溶剂，能够保进浓剂电解液中的阴离子嵌入到正极活性材料中，从而增加电池的容量。
在本发明一实施例中，所述电解液还包括添加剂。
可以理解的是，所述添加剂也没有特别限制，只要其能够促进在负极活性材料表面形成固体电解质膜(SEI)即可。通过在负极活性材料表面形成的固体电解质膜(SEI)，可以进一步防止负极活性材料在充放电时因体积变化所造成的破坏，使负极活性材料结构和功能稳定，提高负极材料的使用寿命和性能，以提高二次电池的循环率。
在本发明一优选实施例中，所述添加剂包括但不限于含酯类、砜类、醚类、腈类或烯烃类有机添加剂一种或几种。
在本发明一优选实施例中，所述添加剂包括但不限于碳酸亚乙烯酯、亚硫酸亚乙酯、亚硫酸丙烯酯、硫酸亚乙酯、环丁基砜、1，3-二氧环戊烷、乙腈或长链烯烃中的一种或几种。
在本发明一优选实施例中，在所述电解液中，所述添加剂的含量为0.1～20wt％。
在本发明一优选实施例中，所述添加剂为碳酸亚乙烯酯，所述碳酸亚乙烯酯在所述电解液中的含量为2wt％。
可以理解的是，所述隔膜也没有特别限制，采用本领域现有普通常用的即可。
在本发明一实施例中，所述隔膜包括但不限于绝缘的多孔聚合物薄膜或无机多孔薄膜。
在本发明一优选实施例中，所述隔膜包括但不限于多孔聚丙烯薄膜、多孔聚乙烯薄膜、多孔复合聚合物薄膜、玻璃纤维纸或多孔陶瓷隔膜。
在本发明一优选实施例中，所述隔膜为玻璃纤维纸。
在本发明一实施例中，所述电池正极包括正极集流体、正极活性材料层。
在本发明一优选实施例中，所述正极集流体包括但不限于铝、镁、锂、钒、铜、铁、锡、锌、镍、钛、锰中的一种或其中任意一种金属的复合物或其中任意几种的合金。
在本发明一优选实施例中，所述正极活性材料层，按重量百分比计，包括60～90wt％正极活性材料。所述负极活性材料层，按重量百分比计，包括60～90wt％负极活性材料。
在本发明一优选实施例中，所述正极活性材料层，按重量百分比计，包括1～30wt％导电剂。所述负极活性材料层，按重量百分比计，按重量百分比计，包括1～30wt％导电剂。
在本发明一优选实施例中，所述正极活性材料层，按重量百分比计，包括1～10wt％粘结剂。所述负极活性材料层，按重量百分比计，按重量百分比计，包括1～10wt％粘结剂。
在本发明一优选实施例中，所述正极活性材料包括但不限于具有层状晶体结构的石墨类材料、硫化物、氮化物、氧化物、碳化物中的一种或多种。
在本发明一优选实施例中，所述石墨类材料包括但不限于天然石墨、人造石墨或石墨片。
在本发明一优选实施例中，所述硫化物包括但不限于二硫化钼、二硫化钨或二硫化钒。
在本发明一优选实施例中，所述氮化物包括但不限于六方氮化硼或碳掺杂六方氮化硼。
在本发明一优选实施例中，所述氧化物包括但不限于三氧化钼、三氧化钨或五氧化二钒。
在本发明一优选实施例中，所述碳化物包括但不限于碳化钛、碳化钽或碳化钼。在本 发明一优选实施例中，所述正极活性材料为具有层状晶体结构的石墨类材料。
在本发明一优选实施例中，所述导电剂包括但不限于导电乙炔黑、导电碳球、导电石墨、碳纳米管、石墨烯中的一种或多种。
在本发明一优选实施例中，所述粘结剂但不限于聚偏氟乙烯、聚四氟乙烯、聚乙烯醇、羧甲基纤维素、丁苯橡胶、聚烯烃类中的一种或多种。
可以理解的是，本发明所提供的电池的形态没有特殊限制，本领域常用的即可，例如扣式电池、平板电池、圆柱电池等形态。
负极活性材料制备方法实施例1
将90mg的聚丙烯腈溶于30ml的二甲基甲酰胺中，配置成溶解有有机聚合物的有机溶液；将900mg、平均粒径为10nm的铝粉原料与有机聚合物溶液混合，在40℃条件下搅拌12h，制得铝/碳前驱体；
将步骤(1)所得的铝/碳前驱体在180℃下预热处理24h；
在氩气气体中，将步骤(1)所得的铝/碳前驱体在400℃下热处理10h；采用1mol/L盐酸进行蚀刻处理0.1h，经离心、洗涤、过滤、干燥后制得所述负极活性材料。
负极活性材料制备方法实施例2-9
与负极活性材料制备方法实施例1的方式相比，负极活性材料制备方法实施例2-9步骤与实施例1的步骤相同，只是将实施例1中的物料替换成表1中的物料，处理条件替换成表2中的情形。
表1负极活性材料制备方法实施例1-9中物料
Figure PCTCN2016081345-appb-000001
Figure PCTCN2016081345-appb-000002
表2负极活性材料制备方法实施例2-9中处理条件
Figure PCTCN2016081345-appb-000003
Figure PCTCN2016081345-appb-000004
通过实施例1-9获得的负极活性材料的参数如表3。
Figure PCTCN2016081345-appb-000005
从以上数据可以看出：
有机聚合物的质量浓度越大，最终形成的负极活性材料中碳层的厚度越厚；铝颗粒与有机聚合物的质量比越高，最终获得的负极活性材料中铝颗粒的含量越高。
二次电池制备方法实施例1
制备电池正极：将0.4g天然石墨、0.05g导电乙炔黑、0.05g聚偏氟乙烯加入到2mL氮甲基吡咯烷酮溶剂中，充分研磨获得均匀浆料；然后将浆料均匀涂覆于铝箔表面，80℃真空干燥12h。对干燥所得电极片裁切成直径为10mm的圆片，用油压机压实(10MPa，10s)，置于手套箱中作为电池正极备用。
制备电池负极：使用负极活性材料制备方法实施例1制得负极活性材料，将0.4g负极活性材料、0.05g导电乙炔黑、0.05g聚偏氟乙烯加入到2mL氮甲基吡咯烷酮溶剂中，充分研磨获得均匀浆料；然后将浆料均匀涂覆于铜箔表面，作为电池负极，80℃真空干燥12h。对干燥所得电极片裁切成直径为12mm的圆片，用油压机压实(10MPa，10s)，置于手套箱中作为电池负极备用。
配制电解液：在手套箱中称取2.87g双三氟甲烷磺酰亚胺锂加入到5mL碳酸甲乙酯中， 搅拌均匀至双三氟甲烷磺酰亚胺锂完全溶解，配成2mol/L的双三氟甲烷磺酰亚胺锂/碳酸甲乙酯溶液，继续滴加0.1wt％的碳酸亚乙烯酯，搅拌均匀作为电解液备用。
制备隔膜：将玻璃纤维纸裁切成直径为16mm的圆片，烘干后置于手套箱中作为隔膜备用。
电池组装：在氩气保护的手套箱中，将上述制备好的电池正极、隔膜、电池负极依次紧密堆叠，滴加电解液使隔膜完全浸润，然后将上述堆叠部分封装入扣式电池壳体，完成电池组装。
二次电池制备方法实施例2
与实施例1的方式相比，将制备电池正极中的“0.4g天然石墨、0.05g导电乙炔黑、0.05g聚偏氟乙烯”替换成“0.4g人造石墨、0.05g super P导电碳球、0.05g聚四氟乙烯”；将制备电池负极中的“0.05g导电乙炔黑、0.4g负极活性材料制备方法实施例1制得的负极活性材料、0.05g聚偏氟乙烯、铜箔”替换成“0.05g super P导电碳球、0.4g负极活性材料制备方法实施例2制得的负极活性材料、0.05g聚四氟乙烯、铝箔”；将配制电解液中的“2.87g双三氟甲烷磺酰亚胺锂、0.1wt％的碳酸亚乙烯酯”替换成“3.04g六氟磷酸锂、2wt％的碳酸亚乙烯酯”；将制备隔膜中的“玻璃纤维纸”替换成“多孔聚丙烯隔膜”，其他步骤和实施例1中相同，制造电池。
二次电池制备方法实施例3
与实施例1的方式相比，将制备电池正极中的“0.4g天然石墨、0.05g导电乙炔黑、0.05g聚偏氟乙烯”替换成“0.4g石墨片、0.05g导电石墨、0.05g聚四氟乙烯”；将制备电池负极中的“0.05g导电乙炔黑、0.4g负极活性材料制备方法实施例1制得的负极活性材料、0.05g聚偏氟乙烯、铜箔”替换成“0.05g导电石墨、0.4g负极活性材料制备方法实施例3制得的负极活性材料、0.05g聚四氟乙烯、铁片”；将配制电解液中的“2.87g双三氟甲烷磺酰亚胺锂、0.1wt％的碳酸亚乙烯酯”替换成“1.52g六氟磷酸锂、20wt％的碳酸亚乙烯酯”；将制备隔膜中的“玻璃纤维 纸”替换成“多孔陶瓷隔膜”，其他步骤和实施例1中相同，制造电池。
二次电池制备方法实施例4
与实施例1的方式相比，将制备电池正极中的“0.05g导电乙炔黑”替换成“0.05g碳纳米管”；将制备电池负极中的“0.05g导电乙炔黑、0.4g负极活性材料制备方法实施例1制得的负极活性材料、铜箔”替换成“0.05g碳纳米管、0.4g负极活性材料制备方法实施例4制得的负极活性材料、镍片”；将配制电解液中的“2.87g双三氟甲烷磺酰亚胺锂、5mL碳酸甲乙酯、0.1wt％的碳酸亚乙烯酯”替换成“1.40g高氯酸钠、5mL碳酸甲乙酯/聚碳酸酯(碳酸甲乙酯和聚碳酸酯的体积比为1∶1)、2wt％的环丁基砜”；将制备隔膜中的“玻璃纤维纸”替换成“复合玻璃纤维隔膜”，其他步骤和实施例1中相同，制造电池。
二次电池制备方法实施例5
与实施例1的方式相比，将制备电池正极中的“0.4g天然石墨”替换成“0.4g人造石墨”；正极集流体由“铝箔”替换成“多孔铝”；将制备电池负极中的“0.4g负极活性材料制备方法实施例1制得的负极活性材料、铜箔”替换成“0.4g负极活性材料制备方法实施例5制得的负极活性材料、锌片”；将配制电解液中的“2.87g双三氟甲烷磺酰亚胺锂、5mL碳酸甲乙酯、0.1wt％的碳酸亚乙烯酯”替换成“0.67g乙基溴化镁、5mL四氢呋喃、2wt％的1，3-二氧环戊烷”；其他步骤和实施例1中相同，制造电池。
二次电池制备方法实施例6
与实施例1的方式相比，将制备电池正极中的“0.4g天然石墨、0.05g导电乙炔黑、0.05g聚偏氟乙烯”替换成“0.6g人造石墨、0.3g石墨烯、0.1g聚乙烯醇”；正极集流体由“铝箔”替换成“铝锡合金”；将制备电池负极中的“0.05g导电乙炔黑、0.4g负极活性材料制备方法实施例1制得的负极活性材料、0.05g聚偏氟乙烯、铜箔”替换成“0.3g石墨烯、0.4g负极活性材料制备方法实施例6制得的负极活性材料、0.1g聚乙烯醇、铝箔”；将配制电解液中的“2.87g双三氟 甲烷磺酰亚胺锂、0.1wt％的碳酸亚乙烯酯”替换成“2.56g双乙二酸硼酸锂、1wt％的乙腈和1wt％的碳酸亚乙烯酯”；其他步骤和实施例1中相同，制造电池。
二次电池制备方法实施例7
与实施例1的方式相比，将制备电池正极中的“0.4g天然石墨、0.05g导电乙炔黑、0.05g聚偏氟乙烯”替换成“0.4g二硫化钼、0.05g石墨烯、0.05g聚四氟乙烯”；正极集流体由“铝箔”替换成“锡箔”；将制备电池负极中的“0.05g导电乙炔黑、0.4g负极活性材料制备方法实施例1制得的负极活性材料、0.05g聚偏氟乙烯、铜箔”替换成“0.05g石墨烯、0.4g负极活性材料制备方法实施例7制得的负极活性材料、0.05g聚四氟乙烯、铝箔”；将配制电解液中的“2.87g双三氟甲烷磺酰亚胺锂”替换成“0.14g双三氟甲烷磺酰亚胺锂”，在配制电解液时不继续加入添加剂；其他步骤和实施例1中相同，制造电池。
二次电池制备方法实施例8
与实施例1的方式相比，将制备电池正极中的“0.4g天然石墨、0.05g聚偏氟乙烯”替换成“0.4g三氧化钼、0.05g聚四氟乙烯”；将制备电池负极中的“0.4g负极活性材料制备方法实施例1制得的负极活性材料、0.05g聚偏氟乙烯、铜箔”替换成“0.4g负极活性材料制备方法实施例8制得的负极活性材料、0.05g聚四氟乙烯、铝箔”；将配制电解液中的“5mL碳酸甲乙酯、2.87g双三氟甲烷磺酰亚胺锂、0.1wt％的碳酸亚乙烯酯”替换成“5mL二甲基砜、1.52g六氟磷酸锂、2wt％的碳酸亚乙烯酯”；其他步骤和实施例1中相同，制造电池。
二次电池制备方法实施例9
与实施例1的方式相比，将制备电池正极中的“0.4g天然石墨、0.05g聚偏氟乙烯”替换成“0.4g碳化钛、0.05g羟甲基纤维素”；将制备电池负极中的“0.4g负极活性材料制备方法实施例1制得的负极活性材料、0.05g聚偏氟乙烯、铜箔”替换成“0.4g负极活性材料制备方法实施例9制得的负极活性材料、0.05g羟甲基纤维素、铝箔”；将配制电解液中的“5mL碳酸甲乙 酯、2.87g双三氟甲烷磺酰亚胺锂、0.1wt％的碳酸亚乙烯酯”替换成“5mL二甲基醚、1.52g六氟磷酸锂、2wt％的碳酸亚乙烯酯”；将制备隔膜中的“玻璃纤维纸”替换成“多孔陶瓷隔膜”，其他步骤和实施例1中相同，制造电池。
电池的性能测试
充电-放电试验：将上述二次电池制备方法实施例中制备的二次电池通过100mA/g正极活性材料的恒定电流充电，直至其电压达到4.8V，然后以相同的电流放电，直至其电压达到3V，测量其电池容量及能量密度，测试其循环稳定性，以循环圈数表示，循环圈数是指电池容量衰减至85％时电池所充放电次数。
表4电池的性能测试结果
Figure PCTCN2016081345-appb-000006
从以上测试结果可以看出：
使用了添加剂的实施例1-6、8、9比没有使用添加剂的实施例7的循环圈数多，表明增加添加剂，可以增强负极活性材料结构和功能的稳定性，进而提高二次电池的循环圈数；
使用碳酸亚乙烯酯作为添加剂的实施例1、2、3、8、9比使用其他添加剂的实施例4-6的循环圈数要多，表明本发明实施例的二次电池中，添加剂优选为碳酸亚乙烯酯，其提高二次电池稳定性的效果更好；
碳酸亚乙烯酯浓度不同的实施例1-3，其中碳酸亚乙烯酯为2wt％时循环圈数最多，表明发明实施例的二次电池中，添加剂碳酸亚乙烯酯为2wt％时，其提高二次电池稳定性的效果更好；
电解质浓度相同的情况下，溶剂为碳酸甲乙酯的实施例3比溶剂为其他物质的实施例8、9的电池容量高，表明本发明实施例的二次电池中，溶剂优选为碳酸甲乙酯，其可以提高二次电池的电池容量。
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。

Claims (15)

  1. 一种负极活性材料，其特征在于，所述负极活性材料包括铝颗粒及包覆在铝颗粒表面的碳层，其中，所述铝颗粒的粒径为1～50000nm，所述铝颗粒的含量为所述负极活性材料总重量的50～99wt％；所述碳层的厚度为1～5000nm。
  2. 一种负极活性材料的制备方法，其特征在于，包括如下步骤：
    (1)将粒径为1～50000nm的铝颗粒原料与溶解有有机聚合物的有机溶剂混合，在40～180℃条件下搅拌0.1～24h，制得铝/碳前驱体，其中，所述有机聚合物溶液的质量浓度为1～100mg/ml，铝颗粒与有机聚合物的质量比为1～20∶1；
    (2)在惰性或还原性气体中，将步骤(1)所得的铝/碳前驱体在300～650℃下热处理0.1～24h，制得所述负极活性材料，其中，所述负极活性材料包括铝颗粒及包覆在铝颗粒表面的碳层，所述铝颗粒的粒径为1～50000nm，所述铝颗粒的含量为所述负极活性材料总重量的50～99wt％；所述碳层的厚度为1～5000nm。
  3. 如权利要求2所述负极活性材料的制备方法，其特征在于，所述步骤(1)中，所述有机聚合物包括聚丙烯腈、聚偏氟乙烯、聚丙烯酸、聚氨酯、聚乙烯醇缩丁醛、聚四氟乙烯或聚氨酯中的一种或几种；所述有机溶剂包括二甲基甲酰胺、丙二醇甲醚、碳酸丙烯脂、碳酸乙烯脂、碳酸二甲脂、碳酸二丙酯、碳酸乙丙酯、碳酸亚乙烯酯、碳酸乙异丙酯、碳酸甲丁酯、碳酸二丁酯、碳酸乙丁酯、碳酸甲乙酯、碳酸二乙酯、γ-丁内酯或N-甲基吡咯烷酮中的一种及几种。
  4. 如权利要求2所述负极活性材料的制备方法，其特征在于，所述步骤(1)和步骤(2)之间，还包括：将步骤(1)所得的铝/碳前驱体在150～300℃下预热处理0.1～24h。
  5. 如权利要求2所述负极活性材料的制备方法，其特征在于，所述步骤(2)之后，还包括：
    采用蚀刻剂进行蚀刻处理0.1～2h，经离心、洗涤、过滤、干燥后制得所述负极活性材料。
  6. 一种负极活性材料，其特征在于采用如权利要求2-5中任一所述的负极活性材料的制备方法制得。
  7. 一种负极，其特征在于，包括负极集流体和负极活性材料层，所述负极活性材料层包括如权利要求1所述的负极活性材料或如权利要求2-5所述的负极材料的制备方法制得的负极活性材料。
  8. 一种二次电池，其特征在于，包括电池负极、电解液、隔膜、电池正极，其中，所述电池负极包括负极集流体和负极活性材料层，负极活性材料层包括如权利要求1所述的负极活性材料或采用如权利要求2-5所述的负极活性材料的制备方法制得的负极活性材料。
  9. 如权利要求8所述的二次电池，其特征在于，所述电解液包括电解质、溶剂，其中，所述电解质包括锂盐、钠盐或镁盐中的一种；所述溶剂包括酯类、砜类、醚类有机溶剂或离子液体中的一种或几种。
  10. 如权利要求9所述的二次电池，其特征在于，所述溶剂为碳酸甲乙酯。
  11. 如权利要求9所述的二次电池，其特征在于，在所述电解液中，所述电解质的浓度为0.1～10mol/L。
  12. 如权利要求9所述的二次电池，其特征在于，所述电解液还包括添加剂，所述添加剂包括含酯类、砜类、醚类、腈类或烯烃类有机添加剂一种或几种。
  13. 如权利要求12所述的二次电池，其特征在于，所述电解液中，所述添加剂的含量为0.1～20wt％。
  14. 如权利要求12所述的二次电池，其特征在于，所述添加剂为碳酸亚乙烯酯，所述碳酸亚乙烯酯在所述电解液中的含量为2wt％。
  15. 如权利要求8所述的二次电池，其特征在于，所述电池正极包括正极集流体、正极活 性材料层，其中，所述正极活性材料层包括正极活性材料，所述正极活性材料包括具有层状晶体结构的石墨类材料、硫化物、氮化物、氧化物、碳化物中的一种或几种。
PCT/CN2016/081345 2016-05-06 2016-05-06 一种负极活性材料及其制备方法、含所述负极活性材料的负极及二次电池 WO2017190363A1 (zh)

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