WO2016074479A1 - 一种热解无定型碳材料及其制备方法和用途 - Google Patents

一种热解无定型碳材料及其制备方法和用途 Download PDF

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WO2016074479A1
WO2016074479A1 PCT/CN2015/081841 CN2015081841W WO2016074479A1 WO 2016074479 A1 WO2016074479 A1 WO 2016074479A1 CN 2015081841 W CN2015081841 W CN 2015081841W WO 2016074479 A1 WO2016074479 A1 WO 2016074479A1
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amorphous carbon
carbon material
hours
carbon precursor
precursor
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French (fr)
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胡勇胜
李云明
陈立泉
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中国科学院物理研究所
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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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • 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
    • 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 relates to the technical field of materials, in particular to a pyrolysis amorphous carbon material, a preparation method thereof and use thereof.
  • Lithium-ion batteries are widely used in mobile devices due to their high voltage, high specific energy density, high safety, etc., and have been initially applied in the field of electric vehicles.
  • Sodium-ion batteries are abundant in storage due to their high sodium content and low cost. Energy equipment has broad application prospects.
  • Graphite material is the main anode material of lithium ion battery, but it has the disadvantages of low discharge efficiency, poor cycle performance and high selectivity to electrolyte in the first week.
  • sodium ions cannot be reversibly deintercalated in graphite materials due to thermodynamic reasons, so graphite materials are not suitable for sodium ion batteries.
  • Carbon materials can be classified into soft carbon (evaporable carbon) and hard carbon (hard graphitizable carbon) according to the difficulty of graphitization.
  • soft carbon evaporable carbon
  • hard carbon hard graphitizable carbon
  • petroleum, coal, asphalt, polyvinyl chloride and hydrazine are carbonized and belong to soft carbon, and these precursors such as asphalt are low in cost and high in carbon yield; cellulose, sugar, furan resin, phenolic resin and polydisperse After carbonization, such as vinyl chloride, it is hard carbon.
  • Hard carbon materials have become the most promising anode materials for sodium ion batteries due to their high specific capacity and low sodium storage voltage.
  • the regular spherical hard carbon material has a reversible specific capacity of up to 310 mAh/g, and it is found that with the increase of carbonization temperature, the platform capacity increases below 0.1V, and the hard carbon with 1600 degree cracking has a platform capacity of 220 mAh/g, and the first week efficiency Up to 83% or more, using it as a negative electrode material can significantly improve the voltage and energy density of the whole battery [Journal of Materials Chemistry A, 2014, DOI: 10.1039/C4TA05451B], but the preparation process of this method is complicated and costly, not Suitable for large-scale production applications.
  • hard carbon materials have significant advantages as lithium ion and sodium ion batteries
  • the precursors used to produce hard carbon have low carbon content, high mass loss during high temperature carbonization, low carbon yield, and high hard carbon cost. Restricted its wide range of applications.
  • the invention combines the advantages of both the hard carbon precursor and the soft carbon precursor, and invents an amorphous carbon material with adjustable degree of disorder, simple preparation method and low cost.
  • Embodiments of the present invention provide a pyrolysis amorphous carbon material, a preparation method thereof and use thereof.
  • the pyrolysis amorphous carbon material is simple in preparation, low in raw material cost, and is suitable for mass production.
  • an embodiment of the present invention provides a method for preparing a pyrolytic amorphous carbon material, the method comprising:
  • the hard carbon precursor and the soft carbon precursor are added to the solvent in a mass ratio of 1:(0.1-10), and then mechanically mixed to obtain a slurry; wherein the solvent includes water, ethanol, isopropanol, acetone, dimethyl group. a mixture of one or any of several amides; the hard carbon precursor comprising one or any of glucose, sucrose, lignin, cellulose, starch, phenolic resin, polyacrylonitrile, epoxy resin a mixture; the soft carbon precursor comprises one or a mixture of any one of coal tar pitch, petroleum pitch, mesophase pitch;
  • the heat treatment further includes a temperature rising process
  • the heating rate of the heating process is 0.5-10 ° C / min.
  • the mechanical mixing comprises ball milling, agitation or ultrasonic dispersion, and the combined use of any of the ball milling, agitation or ultrasonic dispersion.
  • the method may further include: introducing a gas containing a hydrocarbon having a flow rate of 0.5-200 mL/min during the heat treatment for surface coating;
  • the hydrocarbon-containing gas includes any one or more of methane, ethane, toluene, ethylene, acetylene, and propyne.
  • the embodiment of the present invention provides a pyrolytic amorphous carbon material prepared by the method according to the above first aspect, wherein the pyrolyzed amorphous carbon material is granular, and the average of the particles a particle size of 1-100 ⁇ m; d 002 value between 0.35-0.44nm, L c value between 0.5-4nm, L a value between 3-5nm; the pyrolytic amorphous carbon raw material prepared comprising Hard carbon precursor and soft carbon precursor;
  • the mass ratio of the hard carbon precursor to the soft carbon precursor is 1: (0.1-10);
  • the hard carbon precursor includes one or a mixture of any one of glucose, sucrose, lignin, cellulose, starch, phenolic resin, polyacrylonitrile, epoxy resin; the soft carbon precursor includes coal tar pitch , one of petroleum pitch, mesophase pitch, or a mixture of any of several.
  • the pyrolytic amorphous carbon material is used for a negative electrode active material of a sodium ion secondary battery or a lithium ion secondary battery.
  • an embodiment of the present invention provides a negative pole piece of a secondary battery, including:
  • an embodiment of the present invention provides a secondary battery of the negative electrode tab according to the above third aspect.
  • the embodiment of the present invention provides the use of the secondary battery according to the fourth aspect, wherein the secondary battery is used for mobile equipment, electric vehicles, and solar power generation, wind power generation, and smart grid peak shaving Large-scale energy storage equipment for distributed power stations, backup power sources, or communication base stations.
  • the amorphous carbon material provided by the embodiment of the invention has simple preparation, low raw material cost and is suitable for mass production.
  • the sodium ion secondary battery or the lithium ion secondary battery using the amorphous carbon material of the present invention as a negative electrode has high working voltage and energy density, stable circulation, and good safety performance, and can be used not only for mobile equipment and electric vehicles.
  • the power supply can also be used for large-scale energy storage equipment for solar power generation, wind power generation, smart grid peak shaving, distributed power stations, backup power sources or communication base stations.
  • Embodiment 1 is a method for preparing a pyrolytic amorphous carbon material according to Embodiment 2 of the present invention
  • Example 2 is an XRD pattern of an amorphous carbon material provided in Example 3 of the present invention.
  • Example 3 is a Raman spectrum of an amorphous carbon material provided in Example 3 of the present invention.
  • Example 4 is an SEM image of an amorphous carbon material provided in Example 3 of the present invention.
  • FIG. 5 is a charging and discharging graph of a lithium ion battery according to Embodiment 3 of the present invention.
  • FIG. 6 is a graph showing charge and discharge curves of a sodium ion battery according to Embodiment 4 of the present invention.
  • Example 7 is an XRD pattern of an amorphous carbon material provided in Example 5 of the present invention.
  • Example 8 is a Raman spectrum of an amorphous carbon material provided in Example 5 of the present invention.
  • FIG. 9 is a graph showing charge and discharge curves of a sodium ion battery according to Embodiment 5 of the present invention.
  • Figure 10 is an XRD pattern of an amorphous carbon material provided in Example 6 of the present invention.
  • Figure 11 is a Raman spectrum of an amorphous carbon material provided in Example 6 of the present invention.
  • Figure 13 is an XRD pattern of an amorphous carbon material provided in Example 7 of the present invention.
  • Figure 14 is a Raman spectrum of an amorphous carbon material provided in Example 7 of the present invention.
  • Figure 16 is an XRD pattern of an amorphous carbon material provided in Example 8 of the present invention.
  • Figure 17 is a Raman spectrum of an amorphous carbon material provided in Example 8 of the present invention.
  • FIG. 19 is a graph showing charge and discharge curves of a sodium ion battery according to Embodiment 9 of the present invention.
  • Example 20 is an XRD pattern of an amorphous carbon material provided in Example 10 of the present invention.
  • Example 21 is a Raman spectrum of an amorphous carbon material provided in Example 10 of the present invention.
  • Example 23 is an XRD pattern of an amorphous carbon material provided in Example 11 of the present invention.
  • Figure 24 is a Raman spectrum of an amorphous carbon material provided in Example 11 of the present invention.
  • Figure 25 is a graph showing charge and discharge curves of a sodium ion battery according to Embodiment 11 of the present invention.
  • Figure 26 is an XRD pattern of the amorphous carbon material provided in Comparative Example 1 of the present invention.
  • Figure 27 is a Raman spectrum of the amorphous carbon material provided in Comparative Example 1 of the present invention.
  • Figure 28 is an XRD pattern of the amorphous carbon material provided in Comparative Example 2 of the present invention.
  • Figure 29 is a Raman spectrum of the amorphous carbon material provided in Comparative Example 2 of the present invention.
  • Figure 30 is a graph showing charge and discharge curves of a sodium ion battery provided in Comparative Example 2 of the present invention.
  • Embodiment 1 of the present invention provides a pyrolytic amorphous carbon material which is in the form of particles, the average particle diameter of the particles is 1-100 ⁇ m; the d 002 value is between 0.35 and 0.44 nm, and the L c value is between 0.5 and 4 nm. , the value of L a is between 3-5 nm;
  • the preparation raw materials include a hard carbon precursor and a soft carbon precursor; the mass ratio of the hard carbon precursor to the soft carbon precursor is 1: (0.1-10).
  • Hard carbon precursors can be selected from glucose, sucrose, lignin, cellulose, starch, and phenolic trees.
  • the pyrolytic amorphous carbon material provided in this embodiment can be used for a negative electrode material of a sodium ion secondary battery or a lithium ion secondary battery.
  • the combination of a hard carbon precursor and a soft carbon precursor is used as a raw material, and the interaction between the selected hard carbon precursor and the soft carbon precursor is utilized to inhibit the graphitization of the asphalt, thereby improving the degree of disorder, and not only improving the amorphous type.
  • the yield of carbon and will increase the overall electrochemical performance of amorphous carbon.
  • the degree of disorder of the amorphous carbon material can be adjusted by adjusting the ratio of the hard carbon precursor to the soft carbon precursor, so that the amorphous carbon material having the best performance can be obtained according to different requirements.
  • This embodiment provides a method for preparing a pyrolytic amorphous carbon material, and the steps thereof are as shown in FIG. 1 and include:
  • Step 101 the hard carbon precursor and the soft carbon precursor are mechanically mixed at a mass ratio of 1: (0.1-10), and then mechanically mixed to obtain a slurry;
  • the solvent may be one of water, ethanol, isopropanol, acetone, dimethylformamide or a mixture of any of the following;
  • the hard carbon precursor may be selected from the group consisting of glucose, sucrose, lignin, cellulose, and starch.
  • the soft carbon precursor may be one or a mixture of any one of coal tar pitch, petroleum pitch, mesophase pitch.
  • Mechanical mixing includes ball milling, agitation or ultrasonic dispersion, and any combination of the above.
  • the time of mechanical mixing can be set according to the precursor selected and the mixing method employed.
  • the hard carbon precursor and the soft carbon precursor in the mixed slurry must be well mixed.
  • Step 102 drying the uniformly mixed slurry in an oven
  • the purpose of drying is to remove the solvent.
  • Step 103 crosslinking and curing in an inert atmosphere at 200 ° C - 600 ° C for 0.5-5 hours;
  • the dried substance is placed in a magnetic boat and placed in a tube furnace, and an inert gas, preferably argon gas, is introduced, and the mixture is crosslinked and solidified at 200 ° C to 600 ° C.
  • an inert gas preferably argon gas
  • Step 104 heat-treating in an inert atmosphere at 1000 ° C - 1600 ° C for 0.5-10 hours to cause a cracking reaction between the hard carbon precursor and the soft carbon precursor;
  • the temperature is raised to 1000 ° C - 1600 ° C at a rate of 0.5-10 ° C / min in a tube furnace, and the holding is continued for 0.5-10 hours.
  • a hydrocarbon-containing gas may be added to the inert gas for surface coating, preferably methane, ethane, toluene, ethylene, acetylene, propyne or the like.
  • the hard carbon precursor and the soft carbon precursor undergo a cracking reaction to form an amorphous carbon material.
  • Step 105 after cooling, the pyrolysis amorphous carbon material is obtained.
  • the cooling can be carried out by natural cooling, and after being cooled to room temperature, it is taken out from the tube furnace, and after pulverization, the desired pyrolysis amorphous carbon material is obtained.
  • the method for preparing the pyrolytic amorphous carbon material provided in the embodiment can be used for preparing the pyrolytic amorphous carbon material described in the above embodiment 1.
  • the method provided in this embodiment is simple, easy to implement, low in cost, and suitable for large-scale manufacturing applications.
  • the preparation uses a mixture of a hard carbon precursor and a soft carbon precursor as a raw material, and utilizes the characteristics of interaction between the selected hard carbon precursor and the soft carbon precursor to inhibit the graphitization of the asphalt, thereby improving the degree of disorder, and not only improving the The yield of carbon is set and the overall electrochemical performance of amorphous carbon is improved.
  • the degree of disorder of the amorphous carbon material can be adjusted by adjusting the ratio of the hard carbon precursor to the soft carbon precursor, so that the amorphous carbon material having the best performance can be obtained according to different requirements, and can be used for a sodium ion secondary battery or A negative electrode active material of a lithium ion secondary battery.
  • the amorphous carbon material L a 4.382 nm can be obtained from Raman spectroscopy.
  • 4 is a scanning electron microscope (SEM) image of the amorphous carbon material prepared in the present embodiment. As can be seen from the figure, the particle size distribution of the amorphous carbon material prepared in the present embodiment is mainly from several micrometers to twenty. A few microns.
  • the amorphous carbon material prepared as described above is used as an active material of a battery negative electrode material for the preparation of a lithium ion battery.
  • the powder of the prepared amorphous carbon material is mixed with the binder polyvinylidene fluoride (PVDF) in a mass ratio of 95:5, and an appropriate amount of N-methylpyrrolidone (NMP) solution is added to be ground in a dry environment at normal temperature.
  • PVDF binder polyvinylidene fluoride
  • NMP N-methylpyrrolidone
  • the assembly of the simulated battery was carried out in a glove box of an Ar atmosphere, using lithium metal as a counter electrode, and dissolving 1 mol of LiPF 6 in 1 L of a mixture of ethylene carbonate and diethyl carbonate in a volume ratio of 1:1 as an electrolyte.
  • CR2032 button battery The charge and discharge test was performed at a C/10 current density using a constant current charge and discharge mode. Under the condition that the discharge cut-off voltage is 0V and the charging cut-off voltage is 3V, the test result is shown in Fig. 5, the reversible specific capacity is 245mAh/g, and the cycle is stable.
  • the preparation method of the amorphous carbon material is the same as that of the above-described Embodiment 3.
  • the prepared amorphous carbon material is used as an active material of a battery negative electrode material for the preparation of a sodium ion battery.
  • the powder of the prepared amorphous carbon material is mixed with the binder PVDF in a mass ratio of 95:5, an appropriate amount of NMP solution is added, and the slurry is ground in a dry environment at normal temperature, and then the slurry is uniformly coated on the set.
  • a pole piece of (8 x 8) mm 2 was cut. The pole pieces were dried under vacuum at 100 ° C for 10 hours and then transferred to a glove box for use.
  • the assembly of the simulated battery was carried out in a glove box of an Ar atmosphere, using sodium metal as a counter electrode, and dissolving 1 mol of NaPF 6 in 1 L of a mixture of ethylene carbonate and diethyl carbonate in a volume ratio of 1:1 as an electrolyte.
  • CR2032 button battery The charge and discharge test was performed at a C/10 current density using a constant current charge and discharge mode. Under the condition that the discharge cut-off voltage is 0V and the charge cut-off voltage is 3V, the test result is shown in Fig. 6. The reversible specific capacity is 230 mAh/g, and the cycle is better.
  • the amorphous carbon material prepared above was used as an active material of a battery negative electrode material for the preparation of a sodium ion battery, and subjected to an electrochemical charge and discharge test.
  • the preparation process and test method are the same as those in Example 4.
  • the test voltage range is 0V ⁇ 3V, the test results are shown in Figure 9, the reversible specific capacity is 150mAh / g, the cycle is stable.
  • the amorphous carbon material prepared above was used as an active material of a battery negative electrode material for the preparation of a sodium ion battery, and subjected to an electrochemical charge and discharge test.
  • the preparation process and test method are the same as those in Example 4.
  • the test voltage range is 0V ⁇ 3V, the test results are shown in Figure 12, the reversible specific capacity is 240mAh / g, the cycle is stable.
  • the amorphous carbon material prepared above was used as an active material of a battery negative electrode material for the preparation of a sodium ion battery, and subjected to an electrochemical charge and discharge test.
  • the preparation process and test method are the same as those in Example 4.
  • the test voltage range is 0V ⁇ 3V, the test results are shown in Figure 15, its reversible specific capacity is 210mAh / g, the cycle is more stable.
  • the amorphous carbon material prepared above was used as an active material of a battery negative electrode material for the preparation of a lithium ion battery, and subjected to an electrochemical charge and discharge test.
  • the preparation process and test method are the same as those in Example 3.
  • the test voltage range is 0V ⁇ 3V, the test results are shown in Figure 18, the reversible specific capacity is 230mAh / g, the cycle is stable.
  • the preparation method of the amorphous carbon material is the same as that of the above-described Embodiment 8.
  • the prepared amorphous carbon material is used as an active material of a battery negative electrode material for the preparation of a sodium ion battery, and subjected to an electrochemical charge and discharge test.
  • the preparation process and test method are the same as those in Example 4.
  • the test voltage range is 0V ⁇ 3V, the test results are shown in Figure 19, and its reversible specific capacity is 170mAh / g, the cycle is more stable.
  • the amorphous carbon material prepared above was used as an active material of a battery negative electrode material for the preparation of a sodium ion battery, and subjected to an electrochemical charge and discharge test.
  • the preparation process and test method are the same as those in Example 4.
  • the test voltage range is 0V ⁇ 3V, the test results are shown in Figure 22, its reversible specific capacity is 250mAh / g, the cycle is stable.
  • the amorphous carbon material prepared above was used as an active material of a battery negative electrode material for the preparation of a sodium ion battery, and subjected to an electrochemical charge and discharge test.
  • the preparation process and test method are the same as those in Example 4.
  • the test voltage range is 0V ⁇ 3V, the test results are shown in Figure 25, the reversible specific capacity is 240mAh / g, the cycle is more stable.
  • the amorphous carbon material prepared above was used as an active material of a battery negative electrode material for the preparation of a sodium ion battery, and subjected to an electrochemical charge and discharge test.
  • the preparation process and test method are the same as those in Example 4.
  • the test voltage range is 0V to 3V, and the results are shown in Table 1 below.
  • the amorphous carbon material prepared above was used as an active material of a battery negative electrode material for the preparation of a sodium ion battery, and subjected to an electrochemical charge and discharge test.
  • the preparation process and test method are the same Example 4.
  • the test voltage range is 0V to 3V, and the results are shown in Table 1 below.
  • the amorphous carbon material prepared above was used as an active material of a battery negative electrode material for the preparation of a sodium ion battery, and subjected to an electrochemical charge and discharge test.
  • the preparation process and test method are the same as those in Example 4.
  • the test voltage range is 0V to 3V, and the results are shown in Table 1 below.
  • the amorphous carbon material prepared above was used as an active material of a battery negative electrode material for the preparation of a sodium ion battery, and subjected to an electrochemical charge and discharge test.
  • the preparation process and test method were the same as in Example 4, the only difference being that 1% of fluorinated ethylene carbonate (FEC) was added to the electrolyte.
  • FEC fluorinated ethylene carbonate
  • the test voltage range is 0V to 3V, and the results are shown in Table 1 below.
  • the amorphous carbon material prepared above was used as an active material of a battery negative electrode material for the preparation of a sodium ion battery, and subjected to an electrochemical charge and discharge test.
  • the preparation process and test method are the same as those in Example 4.
  • the test voltage range is 0V to 3V, and the results are shown in Table 1 below.
  • the amorphous carbon material prepared above was used as an active material of a battery negative electrode material for the preparation of a sodium ion battery, and subjected to an electrochemical charge and discharge test.
  • the preparation process and test method are the same as those in Example 4.
  • the test voltage range is 0V to 3V, and the results are shown in Table 1 below.
  • the amorphous carbon material prepared above was used as an active material of a battery negative electrode material for the preparation of a sodium ion battery, and subjected to an electrochemical charge and discharge test.
  • the preparation process and test method were the same as in Example 4, except that 1% of vinylene carbonate (VC) was added to the electrolyte.
  • VC vinylene carbonate
  • the test voltage range is 0V to 3V, and the results are shown in Table 1 below.
  • the amorphous carbon material prepared above was used as an active material of a battery negative electrode material for the preparation of a sodium ion battery, and subjected to an electrochemical charge and discharge test.
  • the preparation process and test method are the same as those in Example 4.
  • the test voltage range is 0V to 3V, and the results are shown in Table 1 below.
  • the amorphous carbon material prepared above was used as an active material of a battery negative electrode material for the preparation of a sodium ion battery, and subjected to an electrochemical charge and discharge test.
  • the preparation process and test method are the same as those in Example 4.
  • the test voltage range is 0V to 3V, and the results are shown in Table 1 below.
  • the amorphous carbon material prepared above was used as an active material of a battery negative electrode material for the preparation of a sodium ion battery, and subjected to an electrochemical charge and discharge test.
  • the preparation process and test method are the same as in Example 4, except that the water-based binder is water-soluble carboxymethylcellulose-styrene-butadiene rubber (CMC-SBR).
  • CMC-SBR water-soluble carboxymethylcellulose-styrene-butadiene rubber
  • the test voltage range is 0V to 3V, and the results are shown in Table 1 below.
  • the amorphous carbon material prepared above was used as an active material of a battery negative electrode material for the preparation of a sodium ion battery, and subjected to an electrochemical charge and discharge test.
  • the preparation process and test method are the same as those in Example 4.
  • the test voltage range is 0V to 3V, and the results are shown in Table 1 below.
  • the amorphous carbon material prepared above was used as an active material of a battery negative electrode material for the preparation of a sodium ion battery, and subjected to an electrochemical charge and discharge test.
  • the preparation process and test method are the same as those in Example 4.
  • the test voltage range is 0V to 3V, and the results are shown in Table 1 below.
  • the present invention can significantly improve the carbon production rate by preparing the amorphous carbon material by combining the hard carbon precursor and the soft carbon precursor.
  • the amorphous carbon material prepared above was used as an active material of a battery negative electrode material for the preparation of a sodium ion battery, and subjected to an electrochemical charge and discharge test.
  • the preparation process and test method are the same as those in Example 4.
  • the test voltage range is 0V ⁇ 3V, the test results are shown in Figure 30, and the reversible specific capacity is 100mAh / g.
  • the amorphous carbon material prepared by combining the hard carbon precursor and the soft carbon precursor can significantly improve the performance of the battery compared with the amorphous carbon material prepared by using only the soft carbon precursor. .
  • the amorphous carbon material provided in the above embodiments of the present invention is simple in preparation, rich in raw material resources, low in cost, and is a non-polluting green material, and can be used as a sodium ion secondary battery or a lithium ion secondary
  • the negative active material of the battery is used in a secondary battery.
  • the sodium ion secondary battery or the lithium ion secondary battery prepared by using the amorphous carbon material provided by the embodiment of the invention has high working voltage and energy density, stable circulation and good safety performance, and can be applied to mobile equipment power supply, Electric vehicles, as well as large-scale energy storage equipment for solar power, wind power, smart grid peaking, distributed power stations, backup power or communication base stations.

Abstract

一种热解无定形碳材料及其制备方法和用途，该热解无定形碳材料为颗粒状，颗粒的平均直径为1-100μm；d 002值在0.35-0.44nm之间，L c值在0.5-4nm之间，L 8值在3-5nm之间。其制备方法为：将硬碳前驱体与软碳前驱体加入溶剂后充分混合得到浆料；将浆料烘干后再200-600℃条件下的惰性气氛中进行交联、固化0.5-5小时；再在1000℃-1600℃条件下的惰性气氛中高温处理0.5-10小时；冷却后，得到所述热解无定形碳材料。该材料用途广泛，特别适合作为钠离子二次电池或锂离子二次电池的负极材料。

Description

一种热解无定型碳材料及其制备方法和用途 技术领域
本发明涉及材料技术领域，尤其涉及一种热解无定型碳材料及其制备方法和用途。
背景技术
锂离子电池由于其高电压、高比能量密度、高安全性等优点广泛应用于移动设备，并已在电动车领域实现初步应用；而钠离子电池由于钠的含量丰富、成本低廉在大规模储能设备有广泛的应用前景。
石墨材料是目前锂离子电池主要应用的负极材料，但它存在首周放电效率低、循环性能差、对电解液选择性高等缺点。而对于钠离子电池来说，由于热力学原因，钠离子不能在石墨材料中实现可逆的脱嵌，因此石墨材料不适用于钠离子电池。
碳材料按照石墨化的难易程度可以分为软碳(易石墨化碳)和硬碳(难石墨化碳)。其中石油、煤、沥青、聚氯乙烯和蒽等碳化后属于软碳，而且这些前驱物如沥青等成本低廉、产碳率较高；纤维素、糖类、呋喃树脂、酚醛树脂和聚偏二氯乙烯等碳化后属于硬碳。硬碳材料由于其比容量高、储钠电压低等优点成为钠离子电池最有应用前景的负极材料。2000年，Stevens和Dahn最早实现了钠离子在硬碳材料的可逆脱嵌，比容量可达300mAh/g，但其循环性能较差【J.Electrochem.Soc.,2000,147,1271-1273】。Komaba等通过优化电解液显著的提高了硬碳材料的循环稳定性，但其比容量仅有250mAh/g【Adv.Funct.Mater.,2011,21,3859-3867】。最近，胡勇胜等通过水热蔗糖及高温裂解的方法制备了形状 规则的球形硬碳材料，其可逆比容量高达310mAh/g，并且发现随着碳化温度的提高，0.1V以下平台容量增加，经过1600度裂解的硬碳其平台容量达220mAh/g，首周效率达到83％以上，用其做负极材料可以显著的提高全电池的电压和能量密度【Journal of Materials Chemistry A,2014,DOI:10.1039/C4TA05451B】，但是该方法的制备过程复杂、成本较高，不适用于大规模生产应用。
虽然硬碳材料作为锂离子和钠离子电池具有显著的优点，但是生产硬碳所用前驱体中碳含量低，其在高温碳化过程中质量损失大，产碳率低，导致硬碳成本较高，制约了其大范围应用。本发明将结合硬碳前驱物和软碳前驱物两者的优势，发明了一种无序度可调、制备方法简单、成本低廉的无定型碳材料。
发明内容
本发明实施例提供了一种热解无定型碳材料及其制备方法和用途。所述热解无定型碳材料制备简单、原材料成本低廉、适用于大规模生产。
第一方面，本发明实施例提供了一种热解无定型碳材料的制备方法，所述方法包括：
将硬碳前驱体和软碳前驱体按1：(0.1-10)的质量比加入溶剂后进行机械混合，得到浆料；其中，溶剂包括水、乙醇、异丙醇、丙酮、二甲基甲酰胺中的一种或任意几种的混合物；所述硬碳前驱体包括葡萄糖、蔗糖、木质素、纤维素、淀粉、酚醛树脂、聚丙烯腈、环氧树脂中的一种或任意几种的混合物；所述软碳前驱体包括煤焦油沥青、石油沥青、中间相沥青中的一种或任意几种的混合物；
将混合均匀的浆料在烘箱中烘干；
在200℃-600℃条件下的惰性气氛中进行交联、固化0.5-5小时；
再在1000℃-1600℃条件下的惰性气氛中，热处理0.5-10小时，使所 述硬碳前驱体和软碳前驱体发生裂解反应；
冷却后，得到所述热解无定型碳材料。
优选的，所述热处理之前还包括升温过程；
所述升温过程的升温速率为0.5-10℃/min。
优选的，所述机械混合包括球磨、搅拌或超声分散，以及所述球磨、搅拌或超声分散中任意几种的配合使用。
优选的，所述方法还可以包括：在所述热处理过程中通入流量为0.5-200mL/min含碳氢化合物的气体，用于进行表面包覆；
所述含碳氢化合物的气体包括:甲烷、乙烷、甲苯、乙烯、乙炔、丙炔中的任一种或多种。
第二方面，本发明实施例提供了一种如上述第一方面所述的方法制备的热解无定型碳材料，其特征在于，所述的热解无定型碳材料为颗粒状，颗粒的平均粒径为1-100μm；d002值在0.35-0.44nm之间，Lc值在0.5-4nm之间,La值在3-5nm之间；所述热解无定型碳材料的制备原材料包括硬碳前驱体和软碳前驱体；
所述硬碳前驱体和软碳前驱体的质量比为1：(0.1-10)；
所述硬碳前驱体包括葡萄糖、蔗糖、木质素、纤维素、淀粉、酚醛树脂、聚丙烯腈、环氧树脂中的一种或任意几种的混合物；所述软碳前驱体包括煤焦油沥青、石油沥青、中间相沥青中的一种或任意几种的混合物。
优选的，所述热解无定型碳材料用于钠离子二次电池或锂离子二次电池的负极活性材料。
第三方面，本发明实施例提供了一种二次电池的负极极片，包括：
集流体、涂覆于所述集流体之上的粘结剂和如上述第二方面所述的热解无定型碳材料。
第四方面，本发明实施例提供了一种如上述第三方面所述的负极极片的二次电池。
第五方面，本发明实施例提供了一种如上述第四方面所述的二次电池的用途，所述二次电池用于移动设备、电动车，以及太阳能发电、风力发电、智能电网调峰、分布电站、后备电源或通信基站的大规模储能设备。
本发明实施例提供的无定型碳材料制备简单、原材料成本低廉、适用于大规模生产。应用本发明的无定型碳材料作为负极的钠离子二次电池或锂离子二次电池，具有较高的工作电压和能量密度、循环稳定、安全性能好，不仅可以用于移动设备和电动汽车的电源，还可以用于太阳能发电、风力发电、智能电网调峰、分布电站、后备电源或通信基站的大规模储能设备。
附图说明
下面通过附图和实施例，对本发明实施例的技术方案做进一步详细描述。
图1为本发明实施例2提供的热解无定型碳材料的制备方法；
图2为本发明实施例3提供的无定型碳材料的XRD图谱；
图3为本发明实施例3提供的无定型碳材料的Raman光谱；
图4为本发明实施例3提供的无定型碳材料的SEM图；
图5为本发明实施例3提供的一种锂离子电池的充放电曲线图；
图6为本发明实施例4提供的一种钠离子电池的充放电曲线图；
图7为本发明实施例5提供的无定型碳材料的XRD图谱；
图8为本发明实施例5提供的无定型碳材料的Raman光谱；
图9为本发明实施例5提供的一种钠离子电池的充放电曲线图；
图10为本发明实施例6提供的无定型碳材料的XRD图谱；
图11为本发明实施例6提供的无定型碳材料的Raman光谱；
图12为本发明实施例6提供的一种钠离子电池的充放电曲线图；
图13为本发明实施例7提供的无定型碳材料的XRD图谱；
图14为本发明实施例7提供的无定型碳材料的Raman光谱；
图15为本发明实施例7提供的一种钠离子电池的充放电曲线图；
图16为本发明实施例8提供的无定型碳材料的XRD图谱；
图17为本发明实施例8提供的无定型碳材料的Raman光谱；
图18为本发明实施例8提供的一种锂离子电池的充放电曲线图；
图19为本发明实施例9提供的一种钠离子电池的充放电曲线图；
图20为本发明实施例10提供的无定型碳材料的XRD图谱；
图21为本发明实施例10提供的无定型碳材料的Raman光谱；
图22为本发明实施例10提供的一种钠离子电池的充放电曲线图；
图23为本发明实施例11提供的无定型碳材料的XRD图谱；
图24为本发明实施例11提供的无定型碳材料的Raman光谱；
图25为本发明实施例11提供的一种钠离子电池的充放电曲线图；
图26为本发明对比例1提供的无定型碳材料的XRD图谱；
图27为本发明对比例1提供的无定型碳材料的Raman光谱；
图28为本发明对比例2提供的无定型碳材料的XRD图谱；
图29为本发明对比例2提供的无定型碳材料的Raman光谱；
图30为本发明对比例2提供的一种钠离子电池的充放电曲线图。
具体实施方式
下面结合实施例，对本发明进行进一步的详细说明，但并不意于限制本发明的保护范围。
实施例1
本发明实施例1提供了一种热解无定型碳材料，为颗粒状，颗粒的平均粒径为1-100μm；d002值在0.35-0.44nm之间，Lc值在0.5-4nm之间,La值在3-5nm之间；
其制备原材料包括硬碳前驱体和软碳前驱体；硬碳前驱体和软碳前驱体的质量比为1：(0.1-10)。
硬碳前驱体可以选用葡萄糖、蔗糖、木质素、纤维素、淀粉、酚醛树 脂、聚丙烯腈、环氧树脂中的一种或任意几种的混合物；软碳前驱体可以选用煤油沥青、石油沥青、中间相沥青中的一种或任意几种的混合物。
本实施例提供的热解无定型碳材料可以用于钠离子二次电池或锂离子二次电池的负极材料。采用硬碳前驱体与软碳前驱体混合作为原料，利用所选硬碳前驱体与软碳前驱体会发生相互作用的特征，抑制沥青石墨化，从而提高其无序化程度，不仅能够提高无定型碳的产率，而且会提高无定型碳的综合电化学性能。通过调节硬碳前驱体和软碳前驱体的比例可以调节无定型碳材料的无序化程度，从而可以根据不同的需求得到最佳性能的无定型碳材料。
实施例2
本实施例提供了一种热解无定型碳材料的制备方法，其步骤如图1所示，包括：
步骤101，将硬碳前驱体和软碳前驱体按1：(0.1-10)的质量比加溶剂后进行机械混合，得到浆料；
具体的，溶剂可以选用水、乙醇、异丙醇、丙酮、二甲基甲酰胺中的一种或任意几种的混合物；硬碳前驱体可以选用葡萄糖、蔗糖、木质素、纤维素、淀粉、酚醛树脂、聚丙烯腈、环氧树脂中的一种或任意几种的混合物；软碳前驱体可以选用煤焦油沥青、石油沥青、中间相沥青中的一种或任意几种的混合物。
机械混合包括球磨、搅拌或超声分散等方式，以及上述几种方式中任意几种的配合使用。
机械混合的时间可以根据所选用前驱体以及采用的混合方式来设定，混合后的浆料中硬碳前驱体和软碳前驱体必须是充分混合均匀的。
步骤102，将混合均匀的浆料在烘箱中烘干；
具体的，烘干的目的在于去除溶剂。
步骤103，在200℃-600℃条件下的惰性气氛中进行交联、固化0.5-5小时；
具体的，将烘干后的物质装入磁舟中放进管式炉，通入惰性气体，优选为氩气，在200℃-600℃条件下进行交联、固化。
步骤104，在1000℃-1600℃条件下的惰性气氛中，热处理0.5-10小时，使所述硬碳前驱体和软碳前驱体发生裂解反应；
具体的，在固化完成后，在管式炉中，以0.5-10℃/min的速率进行升温至1000℃-1600℃，持续保温0.5-10小时。
可选的，还可以在惰性气体中加入含有碳氢化合物的气体进行表面包覆，优选为甲烷、乙烷、甲苯、乙烯、乙炔、丙炔等。
在此过程中硬碳前驱体和软碳前驱体发生裂解反应，生成无定型碳材料。
步骤105，冷却后，得到所述热解无定型碳材料。
具体的，冷却可以采用自然冷却，降至室温后由管式炉中取出，粉碎后即得到所需的热解无定型碳材料。
本实施例提供的热解无定型碳材料的制备方法，能够用于制备上述实施例1中所述的热解无定型碳材料。本实施例提供的方法简单易行、成本低廉、适用于大规模制造的应用。制备采用硬碳前驱体与软碳前驱体混合作为原料，利用所选硬碳前驱体与软碳前驱体会发生相互作用的特征，抑制沥青石墨化，从而提高其无序化程度，不仅能够提高无定型碳的产率，而且会提高无定型碳的综合电化学性能。通过调节硬碳前驱体和软碳前驱体的比例可以调节无定型碳材料的无序化程度，从而可以根据不同的需求得到最佳性能的无定型碳材料，可以用于钠离子二次电池或锂离子二次电池的负极活性材料。
为更好的理解本发明提供的技术方案，下述以多个具体实例分别说明应用本发明上述实施例提供的热解无定型碳材料的制备方法进行热解无定型碳材料制备的具体过程，以及将其应用于二次电池的方法和电池特性。
实施例3
称取2g木质素，2g石油沥青和适量的水加入到球磨机中，室温下混合球磨5小时，将球磨后得到的浆料烘干后装入磁舟中放进管式炉；通入氩气作为保护气，以1℃/min的速率升至500℃，保温2小时；再以3℃/min的速率升至1300℃，保温2小时；之后自然冷却至室温，取出物料，粉碎后即得到最终的无定型碳材料。经测量，产碳率为60％。其X射线衍射(XRD)图谱参见图2，从XRD图谱可以得到该无定型碳材料的d002＝0.398nm，Lc＝0.834nm。其Raman光谱参见图3，从Raman光谱可以得到该无定型碳材料La＝4.382nm。图4为本实施例制备得到的无定型碳材料的扫描电子显微镜(SEM)图，从图中可以看出，本实施例制备得到的无定型碳材料的颗粒尺寸分布主要从几微米到二十几微米。
将上述制备得到的无定型碳材料作为电池负极材料的活性物质用于锂离子电池的制备。
将制备好的无定型碳材料的粉末与粘结剂聚偏氟乙烯(PVDF)按照95:5的质量比混合，加入适量的N-甲基吡咯烷酮(NMP)溶液，在常温干燥的环境中研磨形成浆料，然后把浆料均匀涂覆于集流体铜箔上，并在红外灯下干燥后，裁成(8×8)mm2的极片。极片在真空条件下，100℃干燥10小时，随即转移到手套箱备用。
模拟电池的装配在Ar气氛的手套箱内进行，以金属锂作为对电极，以1mol的LiPF6溶于1L体积比为1:1的碳酸乙烯酯和碳酸二乙酯溶液作为电解液，装配成CR2032扣式电池。使用恒流充放电模式，在C/10电流密度下进行充放电测试。在放电截至电压为0V，充电截至电压为3V的条件下，测试结果见图5，可逆比容量为245mAh/g,循环稳定。
实施例4
本实施例中，无定型碳材料的制备方法与上述实施例3相同。
将制备得到的无定型碳材料作为电池负极材料的活性物质用于钠离子电池的制备。
将制备好的无定型碳材料的粉末与粘结剂PVDF按照95:5的质量比混合，加入适量的NMP溶液，在常温干燥的环境中研磨形成浆料，然后把浆料均匀涂覆于集流体铜箔上，并在红外灯下干燥后，裁成(8×8)mm2的极片。极片在真空条件下，100℃干燥10小时，随即转移到手套箱备用。
模拟电池的装配在Ar气氛的手套箱内进行，以金属钠作为对电极，以1mol的NaPF6溶于1L体积比为1:1的碳酸乙烯酯和碳酸二乙酯溶液作为电解液，装配成CR2032扣式电池。使用恒流充放电模式，在C/10电流密度下进行充放电测试。在放电截至电压为0V，充电截至电压为3V的条件下，测试结果见图6，可逆比容量为230mAh/g，循环较好。
实施例5
称取2g木质素，2g石油沥青和适量的水加入到球磨机中，室温下混合球磨5小时，将球磨后得到的浆料烘干后装入磁舟中放进管式炉；通入氩气作为保护气，以1℃/min的速率升至500℃，保温2小时，再以3℃/min的速率升至1000℃，保温2小时；之后自然冷却至室温取出物料，粉碎后即得到最终的无定型碳材料。经测量，产碳率为63％。其XRD图谱参见图7，从XRD图谱可以得到该无定型碳材料的d002＝0.391nm，Lc＝0.851nm。其Raman光谱参见图8，从Raman光谱可以得到该无定型碳材料的La＝4.522nm。
将上述制备得到的无定型碳材料作为电池负极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例4。测试电压范围为0V～3V，测试结果见图9，可逆比容量为150mAh/g，循环稳定。
实施例6
称取2g木质素，2g石油沥青和适量的水加入到球磨机中，室温下混合球磨5小时，将球磨后得到的浆料烘干后装入磁舟中放进管式炉；通入氩气作为保护气，以1℃/min的速率升至500℃，保温2小时，再以3℃/min的速率升至1450℃，保温2小时；之后自然冷却至室温取出物料，粉碎后即得到最 终的无定型碳材料。经测量，产碳率为59％。其XRD图谱参见图10，从XRD图谱可以得到该无定型碳材料的d002＝0.383nm，Lc＝0.854nm。其Raman光谱参见图11，从Raman光谱可以得到该无定型碳材料的La＝3.789nm。
将上述制备得到的无定型碳材料作为电池负极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例4。测试电压范围为0V～3V，测试结果见图12,可逆比容量为240mAh/g，循环稳定。
实施例7
称取2g木质素，2g石油沥青和适量的水加入到球磨机中，室温下混合球磨5h，将球磨后得到的浆料烘干后装入磁舟中放进管式炉；通入氩气作为保护气，以1℃/min的速率升至500℃，保温2小时，再以3℃/min的速率升至1600℃，保温2小时；之后自然冷却至室温取出物料，粉碎后即得到最终的无定型碳材料。经测量，产碳率为63％。其XRD图谱参见图13，从XRD图谱可以得到该无定型碳材料的d002＝0.365nm，Lc＝1.067nm。其Raman光谱参见图14，从Raman光谱可以得到该无定型碳材料的La＝3.667nm。
将上述制备得到的无定型碳材料作为电池负极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例4。测试电压范围为0V～3V，测试结果见图15，其可逆比容量210mAh/g，循环较稳定。
实施例8
称取1.2g木质素，2.8g石油沥青和适量的水加入到球磨机中，室温下混合球磨5小时，将球磨后得到的浆料烘干后装入磁舟中放进管式炉；通入氩气作为保护气，以1℃/min的速率升至500℃，保温2小时，再以3℃/min的速率升至1300℃，保温2小时；之后自然冷却至室温取出物料，粉碎后即得到最终的无定型碳材料。经测量，产碳率为64％。其XRD图谱参见图16，从XRD图谱可以得到该无定型碳材料的d002＝0.37nm，Lc＝1.179nm。其Raman 光谱参见图17，从Raman光谱可以得到该无定型碳材料的La＝4.395nm。
将上述制备得到的无定型碳材料作为电池负极材料的活性物质用于锂离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例3。测试电压范围为0V～3V，测试结果见图18，可逆比容量为230mAh/g，循环稳定。
实施例9
本实施例中，无定型碳材料的制备方法与上述实施例8相同。
将制备得到的无定型碳材料作为电池负极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例4。测试电压范围为0V～3V，测试结果见图19,其可逆比容量为170mAh/g，循环较稳定。
实施例10
称取2.8g木质素，1.2g石油沥青和适量的水加入到球磨机中，室温下混合球磨5小时，将球磨后得到的浆料烘干后装入磁舟中放进管式炉；通入氩气作为保护气，以1℃/min的速率升至500℃，保温2小时，再以3℃/min的速率升至1300℃，保温2小时；之后自然冷却至室温取出物料，粉碎后即得到最终的无定型碳材料。经测量，产碳率为54％。其XRD图谱参见图20，从XRD图谱可以得到该无定型碳材料的d002＝0.405nm，Lc＝0.794nm。其Raman光谱参见图21，从Raman光谱可以得到该无定型碳材料的La＝4.318nm。
将上述制备得到的无定型碳材料作为电池负极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例4。测试电压范围为0V～3V，测试结果见图22,其可逆比容量250mAh/g，循环稳定。
实施例11
称取2.8g木质素，1.2g石油沥青和适量的水加入到球磨机中，室温下混合球磨5小时，将球磨后得到的浆料烘干后装入磁舟中放进管式炉；通入氩 气作为保护气，以1℃/min的速率升至500℃，保温2小时，再以3℃/min的速率升至1600℃，保温2小时；之后自然冷却至室温取出物料，粉碎后即得到最终的无定型碳材料。经测量，产碳率为53％。其XRD图谱参见图23，从XRD图谱可以得到该无定型碳材料的d002＝0.383nm，Lc＝0.865nm。其Raman光谱参见图24，从Raman光谱可以得到该无定型碳材料的La＝3.833nm。
将上述制备得到的无定型碳材料作为电池负极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例4。测试电压范围为0V～3V，测试结果见图25，可逆比容量为240mAh/g，循环较稳定。
实施例12
称取0.8g木质素，3.2g石油沥青和适量的水加入到球磨机中，室温下混合球磨5小时，将球磨后得到的浆料烘干后装入磁舟中放进管式炉；通入带有甲苯的氩气作为保护气，以1℃/min的速率升至500℃，保温2小时，再以3℃/min的速率升至1300℃，保温2小时；之后自然冷却至室温取出物料，粉碎后即得到最终的无定型碳材料。
将上述制备得到的无定型碳材料作为电池负极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例4。测试电压范围为0V～3V，结果见下表1。
实施例13
称取0.8g木质素，3.2g石油沥青和适量的水加入到球磨机中，室温下混合球磨5小时，将球磨后得到的浆料烘干后装入磁舟中放进管式炉；通入氩气作为保护气，以1℃/min的速率升至500℃，保温2小时，再以3℃/min的速率升至1450℃，保温2小时；之后自然冷却至室温取出物料，粉碎后即得到最终的无定型碳材料。
将上述制备得到的无定型碳材料作为电池负极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实 施例4。测试电压范围为0V～3V，结果见下表1。
实施例14
称取0.8g木质素，3.2g石油沥青和适量的水加入到球磨机中，室温下混合球磨5小时，将球磨后得到的浆料烘干后装入磁舟中放进管式炉；通入氩气作为保护气，以1℃/min的速率升至500℃，保温2小时，再以3℃/min的速率升至1600℃，保温2小时；之后自然冷却至室温取出物料，粉碎后即得到最终的无定型碳材料。
将上述制备得到的无定型碳材料作为电池负极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例4。测试电压范围为0V～3V，结果见下表1。
实施例15
称取1.6g木质素，2.4g石油沥青和适量的水加入到球磨机中，室温下混合球磨5小时，将球磨后得到的浆料烘干后装入磁舟中放进管式炉；通入氩气作为保护气，以1℃/min的速率升至500℃，保温2小时，再以3℃/min的速率升至1300℃，保温2小时；之后自然冷却至室温取出物料，粉碎后即得到最终的无定型碳材料。
将上述制备得到的无定型碳材料作为电池负极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例4，唯一的区别是在电解液中加入1％的氟化碳酸乙烯酯(FEC)。测试电压范围为0V～3V，结果见下表1。
实施例16
称取1.6g木质素，2.4g石油沥青和适量的水加入到球磨机中，室温下混合球磨5小时，将球磨后得到的浆料烘干后装入磁舟中放进管式炉；通入氩气作为保护气，以1℃/min的速率升至500℃，保温2小时，再以3℃/min的速率升至1450℃，保温2小时；之后自然冷却至室温取出物料，粉碎后即得到最终的无定型碳材料。
将上述制备得到的无定型碳材料作为电池负极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例4。测试电压范围为0V～3V，结果见下表1。
实施例17
称取1.6g木质素，2.4g石油沥青和适量的水加入到球磨机中，室温下混合球磨5小时，将球磨后得到的浆料烘干后装入磁舟中放进管式炉；通入氩气作为保护气，以1℃/min的速率升至500℃，保温2小时，再以3℃/min的速率升至1600℃，保温2小时；之后自然冷却至室温取出物料，粉碎后即得到最终的无定型碳材料。
将上述制备得到的无定型碳材料作为电池负极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例4。测试电压范围为0V～3V，结果见下表1。
实施例18
称取2.4g木质素，1.6g石油沥青和适量的水加入到球磨机中，室温下混合球磨5小时，将球磨后得到的浆料烘干后装入磁舟中放进管式炉；通入氩气作为保护气，以1℃/min的速率升至500℃，保温2小时，再以3℃/min的速率升至1300℃，保温2小时；之后自然冷却至室温取出物料，粉碎后即得到最终的无定型碳材料。
将上述制备得到的无定型碳材料作为电池负极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例4,唯一的区别是在电解液中加入1％的碳酸亚乙烯酯(VC)。测试电压范围为0V～3V，结果见下表1。
实施例19
称取2.4g木质素，1.6g石油沥青和适量的水加入到球磨机中，室温下混合球磨5小时，将球磨后得到的浆料烘干后装入磁舟中放进管式炉；通入氩气作为保护气，以1℃/min的速率升至500℃，保温2小时，再以3℃/min的 速率升至1450℃，保温2小时；之后自然冷却至室温取出物料，粉碎后即得到最终的无定型碳材料。
将上述制备得到的无定型碳材料作为电池负极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例4。测试电压范围为0V～3V，结果见下表1。
实施例20
称取2.4g木质素，1.6g石油沥青和适量的水加入到球磨机中，室温下混合球磨5小时，将球磨后得到的浆料烘干后装入磁舟中放进管式炉；通入氩气作为保护气，以1℃/min的速率升至500℃，保温2小时，再以3℃/min的速率升至1600℃，保温2小时；之后自然冷却至室温取出物料，粉碎后即得到最终的无定型碳材料。
将上述制备得到的无定型碳材料作为电池负极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例4。测试电压范围为0V～3V，结果见下表1。
实施例21
称取3.2g木质素，0.8g石油沥青和适量的水加入到球磨机中，室温下混合球磨5小时，将球磨后得到的浆料烘干后装入磁舟中放进管式炉；通入氩气作为保护气，以1℃/min的速率升至500℃，保温2小时，再以3℃/min的速率升至1300℃，保温2小时；之后自然冷却至室温取出物料，粉碎后即得到最终的无定型碳材料。
将上述制备得到的无定型碳材料作为电池负极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例4，唯一的区别在于水系粘结剂用的是水溶性羧甲基纤维素-丁苯橡胶(CMC-SBR)。测试电压范围为0V～3V，结果见下表1。
实施例22
称取3.2g木质素，0.8g石油沥青和适量的水加入到球磨机中，室温下混 合球磨5小时，将球磨后得到的浆料烘干后装入磁舟中放进管式炉；通入氩气作为保护气，以1℃/min的速率升至500℃，保温2小时，再以3℃/min的速率升至1450℃，保温2小时；之后自然冷却至室温取出物料，粉碎后即得到最终的无定型碳材料。
将上述制备得到的无定型碳材料作为电池负极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例4。测试电压范围为0V～3V，结果见下表1。
实施例23
称取3.2g木质素，0.8g石油沥青和适量的水加入到球磨机中，室温下混合球磨5小时，将球磨后得到的浆料烘干后装入磁舟中放进管式炉；通入氩气作为保护气，以1℃/min的速率升至500℃，保温2小时，再以3℃/min的速率升至1600℃，保温2小时；之后自然冷却至室温取出物料，粉碎后即得到最终的无定型碳材料。
将上述制备得到的无定型碳材料作为电池负极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例4。测试电压范围为0V～3V，结果见下表1。
对比例1
称取4g木质素放进管式炉，并通入氩气作为保护气，以1℃/min的速率升至500℃，保温2小时，再以3℃/min的速率升至1300℃，保温2小时；之后自然冷却至室温取出物料，粉碎后即得到最终的无定型碳材料。经测量，产碳率为40％。其XRD图谱和Raman光谱参见图26和图27。
由此可见，相对于仅采用硬碳前驱体制备得到的无定型碳材料来说，本发明通过将硬碳前驱体与软碳前驱体复合制备无定型碳材料，能够显著的提高产碳率。
对比例2
称取4g石油沥青放进管式炉，并通入氩气作为保护气，以1℃/min的速 率升至500℃，保温2小时，再以3℃/min的速率升至1300℃，保温2小时；之后自然冷却至室温取出物料，粉碎后即得到最终的无定型碳材料。经测量，产碳率为65％。其XRD图谱和Raman光谱参见图28和图29。
将上述制备得到的无定型碳材料作为电池负极材料的活性物质用于钠离子电池的制备，并进行电化学充放电测试。其制备过程和测试方法同实施例4。测试电压范围为0V～3V，测试结果见图30，可逆比容量为100mAh/g。
由此可见，相对于仅采用软碳前驱体制备得到的无定型碳材料来说，利用本发明将硬碳前驱体与软碳前驱体复合制备的无定型碳材料，能够显著的提高电池的性能。
Figure PCTCN2015081841-appb-000001
表1
本发明上述实施例中提供的无定型碳材料制备简单、原材料资源丰富、成本低廉，是无污染的绿色材料，可以作为钠离子二次电池或锂离子二次 电池的负极活性材料应用于二次电池中。采用本发明实施例提供的无定型碳材料制备获得的钠离子二次电池或锂离子二次电池，具有较高的工作电压和能量密度、循环稳定、安全性能好，可以应用于移动设备电源、电动汽车，以及太阳能发电、风力发电、智能电网调峰、分布电站、后备电源或通信基站的大规模储能设备。
以上所述的具体实施方式，对本发明的目的、技术方案和有益效果进行了进一步详细说明，所应理解的是，以上所述仅为本发明的具体实施方式而已，并不用于限定本发明的保护范围，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (9)

  1. 一种热解无定型碳材料的制备方法，其特征在于，所述方法包括：
    将硬碳前驱体和软碳前驱体按1：(0.1-10)的质量比加入溶剂后进行机械混合，得到浆料；其中，溶剂包括水、乙醇、异丙醇、丙酮、二甲基甲酰胺中的一种或任意几种的混合物；所述硬碳前驱体包括葡萄糖、蔗糖、木质素、纤维素、淀粉、酚醛树脂、聚丙烯腈、环氧树脂中的一种或任意几种的混合物；所述软碳前驱体包括煤焦油沥青、石油沥青、中间相沥青中的一种或任意几种的混合物；
    将混合均匀的浆料在烘箱中烘干；
    在200℃-600℃条件下的惰性气氛中进行交联、固化0.5-5小时；
    再在1000℃-1600℃条件下的惰性气氛中，热处理0.5-10小时，使所述硬碳前驱体和软碳前驱体发生裂解反应；
    冷却后，得到所述热解无定型碳材料。
  2. 根据权利要求1所述的制备方法，其特征在于，所述热处理之前还包括升温过程；
    所述升温过程的升温速率为0.5-10℃/min。
  3. 根据权利要求1所述的制备方法，其特征在于，所述机械混合包括球磨、搅拌或超声分散，以及所述球磨、搅拌或超声分散中任意几种的配合使用。
  4. 根据权利要求1所述的制备方法，其特征在于，所述方法还包括：在所述热处理过程中通入流量为0.5-200mL/min含碳氢化合物的气体，用于进行表面包覆；
    所述含碳氢化合物的气体包括:甲烷、乙烷、甲苯、乙烯、乙炔、丙炔中的任一种或多种。
  5. 一种如上述权利要求1所述的方法制备的热解无定型碳材料，其特征在于，所述的热解无定型碳材料为颗粒状，颗粒的平均粒径为1-100μm； d002值在0.35-0.44nm之间，Lc值在0.5-4nm之间,La值在3-5nm之间；所述热解无定型碳材料的制备原材料包括硬碳前驱体和软碳前驱体；
    所述硬碳前驱体和软碳前驱体的质量比为1：(0.1-10)；
    所述硬碳前驱体包括葡萄糖、蔗糖、木质素、纤维素、淀粉、酚醛树脂、聚丙烯腈、环氧树脂中的一种或任意几种的混合物；所述软碳前驱体包括煤焦油沥青、石油沥青、中间相沥青中的一种或任意几种的混合物。
  6. 根据权利要求5所述的热解无定型碳材料，其特征在于，所述热解无定型碳材料用于钠离子二次电池或锂离子二次电池的负极活性材料。
  7. 一种二次电池的负极极片，其特征在于，所述负极极片包括：
    集流体、涂覆于所述集流体之上的粘结剂和如上述权利要求5-6所述的热解无定型碳材料。
  8. 一种包括上述权利要求7所述的负极极片的二次电池。
  9. 一种如上述权利要求8所述的二次电池的用途，其特征在于，所述二次电池用于移动设备、电动车，以及太阳能发电、风力发电、智能电网调峰、分布电站、后备电源或通信基站的大规模储能设备。
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