WO2024087740A1 - 一种基于红磷的新型磷碳负极材料及制备方法 - Google Patents

一种基于红磷的新型磷碳负极材料及制备方法 Download PDF

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WO2024087740A1
WO2024087740A1 PCT/CN2023/107270 CN2023107270W WO2024087740A1 WO 2024087740 A1 WO2024087740 A1 WO 2024087740A1 CN 2023107270 W CN2023107270 W CN 2023107270W WO 2024087740 A1 WO2024087740 A1 WO 2024087740A1
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phosphorus
carbon
carbon nanotube
red phosphorus
negative electrode
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French (fr)
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郑磊
龚晓飞
沈维云
马会娟
习本军
罗宝瑞
池汝安
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湖北三峡实验室
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    • H—ELECTRICITY
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    • 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
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    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
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    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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    • 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
    • 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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • 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
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    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention specifically relates to a method for preparing a phosphorus-carbon composite negative electrode based on red phosphorus-doped carbon nanotube technology.
  • the preparation of a phosphorus-carbon composite negative electrode with high reversible specific capacity and good rate performance is achieved by embedding a low-melting point transition metal compound inside a carbon tube ball and then compounding red phosphorus, which is conducive to further realizing a new commercial lithium-ion battery system with high energy density, high rate performance and low cost. It belongs to the lithium-ion battery negative electrode direction in the field of lithium-ion new energy material technology.
  • lithium-ion batteries are expected to have a larger application market in the fields of consumption, power and energy storage, but more opportunities also mean more challenges.
  • conventional commercial negative electrode materials are mainly based on carbon-based negative electrodes (such as the most conventional and widely used graphite negative electrode).
  • the layered structure of lithium insertion and lithium extraction has good cycle performance, but it also has disadvantages such as low theoretical specific capacity (372mA ⁇ h ⁇ g -1 ) and poor high-rate charge and discharge performance.
  • phosphorus-based negative electrodes have higher theoretical specific capacity (such as Li 3 P, 2596mA ⁇ h ⁇ g -1 ) and excellent rate performance, and the cost is relatively low. It is one of the research directions that is expected to further achieve high energy density and high-rate performance in the future.
  • phosphorus-based materials have poor conductivity and large volume expansion during the cycle (volume expansion rate is as high as 300%). The material cycle performance needs to be further optimized and improved, which greatly limits the application of phosphorus-based negative electrode materials in lithium-ion batteries.
  • the phosphorus-carbon composite negative electrode is expected to combine the advantages of both, and achieve higher energy density and better rate performance by means of the synergistic effect of phosphorus-based and multidimensional carbon materials.
  • carbon nanotubes can form a three-dimensional skeleton structure, which can effectively solve the problems of volume expansion of phosphorus-based negative electrodes.
  • a method for preparing a red phosphorus/carbon nanotube composite material for the negative electrode of a lithium ion battery is disclosed.
  • the method uses a low-temperature liquid phase method to make red phosphorus uniformly adsorbed on the wall of carbon nanotubes by means of the difference in surface electronegativity between red phosphorus and carbon nanotubes in a solvent, and obtains a uniform red phosphorus/carbon nanotube composite material.
  • the preparation method is simple and environmentally friendly, and the obtained material significantly improves the specific capacity and cyclic charge and discharge stability of lithium ion batteries.
  • a MXene/red phosphorus composite negative electrode material with high capacity and high cycle performance was obtained by mixing and calcining large-spacing MXene with red phosphorus at high temperature.
  • the composite material is based on the high theoretical specific capacity of red phosphorus and makes full use of the advantages of large-spacing MXene such as high electronic conductivity, large specific surface area, strong mechanical properties, surface modifiability and unique layered structure, as an ideal carbon carrier to improve the conductivity and structural stability of red phosphorus.
  • CN112420999 discloses a phosphorus-carbon composite material with a core-shell coating structure, including a phosphorus-based material core and a carbon-based material coating layer, which can not only alleviate the volume expansion during the charge and discharge process, but also inhibit the charge and discharge cycle process of lithium batteries.
  • a tin phosphide@carbon composite negative electrode active precursor material includes a carbon skeleton and tin phosphide nanoparticles embedded on its outer surface and distributed in a dotted manner.
  • the material described in CN109309 has tin phosphide nanodots evenly dispersed on the outer surface of the carbon skeleton. Based on the innovative morphology and structural characteristics, combined with the rich specific surface area and good conductivity of the carbon skeleton, the local current density is effectively reduced, and more uniform lithium deposition and dissolution during the cycle are achieved.
  • the purpose of this patent is to protect a method for preparing a high-performance composite phosphorus-carbon negative electrode by using carbon nanotube balls doped with red phosphorus and internal low-melting-point transition metal compounds through low-temperature liquid phase immersion.
  • Pure phosphorus-based negative electrode materials have poor conductivity (the conductivity of red phosphorus is only 10-14 S ⁇ cm -1 ), slow redox kinetics during lithium insertion/extraction, severe internal polarization of the battery, and severe lithium ion loss caused by thickening of the SEI film.
  • the huge volume expansion during the charge and discharge cycle (volume expansion rate of up to 300%) can easily cause pulverization of the active material, seriously affecting the coulombic efficiency and rate cycling performance of the material.
  • the theoretical specific capacity of pure carbon-based negative electrode materials is relatively low (372mA ⁇ h ⁇ g -1 ), and during high-current charge and discharge, the lithium ion diffusion rate and diffusion channel are limited, and the lithium extraction/insertion rate is slow. At the same time, during the insertion process, compounds LixC6 will be formed between graphite carbon layers, increasing the interlayer spacing of the carbon layers, which can easily cause the carbon layers to fall off, reducing the capacity, cycle performance and service life of the carbon-based negative electrode materials.
  • phosphorus-carbon composite negative electrode materials connect the carbon carrier and the phosphorus active component with a stable chemical bond.
  • the carbon material has high conductivity, large specific surface area and flexible surface, which can easily form a conductive network, promote the uniform dispersion of the active component, and absorb the mechanical stress generated by the volume change process, preventing the phosphorus active component from breaking and pulverizing, and improving the rate performance and cycle stability.
  • phosphorus-carbon negative electrodes generally have problems such as unstable interface and poor wettability to metallic lithium.
  • High-temperature pyrolysis process With phosphorus material as the substrate, amorphous carbon produced by high-temperature pyrolysis of organic matter in an inert atmosphere is used as the carbon source to coat the phosphorus material, thereby obtaining a phosphorus-carbon composite material with a core-shell coating structure.
  • phosphorus as the core in the composite material prepared by the high-temperature pyrolysis process has poor dispersion, and the carbon layer produced by the pyrolysis of organic matter is prone to uneven distribution, and the agglomeration phenomenon between particles is serious when the pyrolysis temperature is slightly higher.
  • Carbon thermal reduction process At a certain temperature, inorganic carbon is used as a reducing agent to reduce phosphides to prepare phosphorus-carbon composite materials. Its disadvantages are that the reduction process is difficult to control, the phosphorus-carbon ratio requires high precision, and impurities are easily generated, making product quality control difficult, and the particle size is inconsistent and the dispersion is poor.
  • the performance of the phosphorus-carbon composite negative electrode is improved by the method of low-temperature liquid phase immersion: First, the generation of white phosphorus byproducts can be effectively reduced by controlling the temperature and atmosphere, effectively reducing the manufacturing cost and improving the safety of the preparation process; second, by forming similar solid solutions such as lithium tin inside the carbon tube ball during the first charge and discharge, the wettability of the phosphorus-carbon composite ball to metallic lithium during the cycle is improved.
  • SnS2 and the like can be precisely controlled to form a nanosheet structure with highly exposed active sites, which can easily form uniformly distributed alloy sites when in contact with molten metallic lithium at high temperatures.
  • the third aspect is that there is a potential difference of about 0.3V between the series of lithium-tin alloys formed and metallic lithium, which can be used as a driving force for lithium diffusion.
  • metallic lithium due to the low deposition overpotential of metallic lithium on tin, it is helpful for metallic lithium to penetrate into the interior of the phosphorus-carbon composite microspheres, so that the first charge specific capacity of the phosphorus-carbon negative electrode is increased by 30% or more.
  • lithium-tin alloy has a relatively high chemical potential, so compared with pure metallic lithium anode or phosphorus-carbon anode, it is less likely to have side reactions with liquid electrolyte, thereby ensuring less electrolyte consumption and longer cycle life.
  • the present invention provides a red phosphorus-based carbon nanotube-doped phosphorus-carbon composite negative electrode material, comprising red phosphorus and composite carbon nanotube balls.
  • the mass ratio of the red phosphorus to the composite carbon nanotube sphere is 1:1-3:1.
  • the mass concentration of the composite carbon nanotube balls in the solution is 10%-20%.
  • the small-size red phosphorus of the present invention is uniformly compounded on the carbon nanotube microspheres with a three-dimensional porous skeleton, which prevents the large-scale agglomeration of red phosphorus particles, improves the conductivity of the red phosphorus material, and effectively solves the volume expansion problem during the charging and discharging process.
  • the red phosphorus can be in a powder state of 60-100 mesh or in a microsphere particle state of 10-20 mesh.
  • the solvent in the thermal reaction process includes at least one of deionized water, anhydrous ethanol, anhydrous methanol, and anhydrous ether.
  • the composite carbon nanotube ball is doped and embedded with a low melting point transition metal compound ( ⁇ 200° C.); the mass concentration of the low melting point transition metal compound is 0.2-3%.
  • the low-melting-point transition metal compound intermediates embedded inside the carbon nanotubes help lithium to be evenly infiltrated into the internal channels of the carbon tube balls, significantly improving the specific capacity and rate performance of the phosphorus-carbon composite negative electrode material (the first charge specific capacity is increased by 30% or more), while avoiding the deposition of metallic lithium on the electrode surface and reacting with the electrolyte, thereby improving the cycle performance of the material.
  • the low melting point transition metal compound is obtained by reacting a metal source of tin, titanium, cadmium, iron, cobalt, chromium, manganese, germanium, or nickel with a non-metal source, and the molar ratio of the non-metal source to the metal source is 1:1-3:1.
  • the metal salts include fluorides, chlorides, nitrates, sulfates and carbonates of tin, titanium, cadmium, iron, cobalt, chromium, manganese and nickel;
  • the non-metallic source includes any one or more of sulfides, selenides, tellurides and phosphides;
  • the sulfides include at least one of sublimated sulfur, thioacetamide and thiourea,
  • the selenides include at least one of elemental selenium powder and sodium selenite,
  • the tellurides include at least one of elemental tellurium powder and sodium tellurite, and
  • the phosphides include at least one of sodium hypophosphite, phosphoric acid, ammonium dihydrogen phosphate and diammonium hydrogen phosphate.
  • Further examples include Fe 2 S 3 , GeS 2 , SnS 2 , Co 9 S 8 , NiSe, SnTe 2 or TiP, but are not limited thereto.
  • the precursor of the three-dimensional carbon tube material can be any one of carbon nanofibers, carbon nanotubes, mesoporous carbon, porous carbon, and commonly used conductive agents such as carbon black and Super P.
  • the carbon nanotube spheres may also be materials with different particle sizes and skeleton structures obtained by surface modification through any one or more of amination, carboxylation, hydroxylation, phosphination, or graphitization.
  • the surface-modified three-dimensional porous skeleton of carbon nanotubes can enhance the composite strength with low-melting-point transition metal compounds and red phosphorus, avoid the consumption of lithium ions by the SEI film, reduce the occurrence of side reactions, and improve the reversible charge and discharge performance and cycle stability of the phosphorus-carbon composite negative electrode material.
  • the phosphorus-carbon composite negative electrode prepared based on red phosphorus carbon nanotube ball doping technology has good morphological and structural stability due to the strong interaction between the components. It can still maintain the basic morphological structure after multiple charge and discharge cycles at a high current density, avoiding structural collapse and causing lithium precipitation problems.
  • the second aspect of the present invention is a method for preparing a phosphorus-carbon composite negative electrode material doped with red phosphorus carbon nanotubes, which is based on a liquid phase method to prepare a low melting point transition metal compound intermediate, has a simple preparation process, is easy to operate, and the prepared intermediate material has a uniform morphology and a small particle size, which is conducive to the subsequent doping in the carbon tube ball.
  • the method specifically comprises the following steps:
  • red phosphorus dispersion After ball milling, red phosphorus is subjected to hydrothermal treatment, and the dried solid matter is dispersed in a solvent to obtain a uniform red phosphorus dispersion;
  • the introduction of the liquid phase and the molten phase in the process of the present invention is conducive to better achieving uniform compounding of the phosphorus-carbon material, improving the bonding strength between the components, enhancing the structural stability of the material, and improving the cycle performance of the phosphorus-carbon composite negative electrode material.
  • the metal source in step (1) comprises any one of fluorides, chlorides, nitrates, sulfates or carbonates of tin, titanium, cadmium, iron, cobalt, chromium, manganese, germanium or nickel.
  • the non-metallic source includes one of a sulfide, a selenide, a telluride or a phosphide; preferably, the sulfide includes at least one of sublimated sulfur, thioacetamide and thiourea, the selenide includes at least one of elemental selenium powder and sodium selenite, the telluride includes at least one of elemental tellurium powder and sodium tellurite, and the phosphide includes at least one of sodium hypophosphite, phosphoric acid, ammonium dihydrogen phosphate and diammonium hydrogen phosphate.
  • the sulfide includes at least one of sublimated sulfur, thioacetamide and thiourea
  • the selenide includes at least one of elemental selenium powder and sodium selenite
  • the telluride includes at least one of elemental tellurium powder and sodium tellurite
  • the phosphide includes at least one of sodium hypophosphite, phospho
  • it includes Fe 2 S 3 , GeS 2 , SnS 2 , Co 9 S 8 , NiSe, SnTe 2 or TiP, but is not limited thereto.
  • the molar ratio of the non-metal source to the metal source is 1:1-3:1.
  • the solvent includes at least one of deionized water, anhydrous ethanol, anhydrous methanol or anhydrous ether.
  • the mass concentration of the low melting point transition metal compound intermediate is 0.2-3%.
  • the solvent/hydrothermal reaction temperature is 50-100° C.
  • the reaction time is 5-50 mins
  • magnetic stirring is used during the solvent/hydrothermal reaction at a rotation speed of 300-2000 rpm.
  • the carbon nanotube spheres may also be materials with different particle sizes and skeleton structures obtained by surface modification through any one or more of amination, carboxylation, hydroxylation, phosphination, or graphitization.
  • the mass ratio of the carbon nanotube spheres to the low-melting-point transition metal compound intermediate is 1:1-3:1.
  • the solvent/hydrothermal reaction temperature is 40-90°C
  • the reaction time is 20-80 minutes
  • solid-liquid separation is carried out by suction filtration and washing, and the obtained filter cake is placed in a vacuum drying oven at 50-60°C and dried overnight.
  • red phosphorus and stainless steel balls are loaded into a stainless steel ball tank at a mass ratio of 1:10-1:50, and ball milled at a speed of 300-500 rpm for 1-5 hours under a nitrogen atmosphere.
  • the hydrothermal reaction temperature is 150-200° C. and the reaction time is 10-20 hours.
  • the mass concentration of the red phosphorus dispersion in step (4) is 10%-20%; the mass concentration of the composite carbon nanotube ball powder material in the solution is 10%-20%; and the mass ratio of red phosphorus to the composite carbon nanotube ball powder material is 1:1-3:1.
  • the solvent/hydrothermal reaction temperature is 150-500° C., and the reaction time is 20-60 minutes.
  • the third aspect of the present invention is to use the prepared red phosphorus-based carbon nanotube-doped phosphorus-carbon composite negative electrode material as a negative electrode for a lithium-ion battery.
  • the present invention uses a battery assembled from the phosphorus-carbon composite negative electrode material under the doping system.
  • the composite negative electrode material of the present invention is used in a high-capacity and high-rate lithium-ion battery system.
  • PVDF binder
  • AB acetylene black
  • NMP N-methylpyrrolidone
  • Solve the volume expansion problem Use the three-dimensional skeleton structure of carbon nanotubes to effectively inhibit the volume expansion problem of phosphorus-based materials during the cycle; Improve the wettability of phosphorus-carbon composite negative electrode: The process of transition metal compound intermediates, composite carbon nanotube balls, and red phosphorus doping all involve liquid or molten phases, which is conducive to the uniform compounding of materials. Good wettability maintains the granularity and electrode morphology of the composite negative electrode. Even after a high charge and discharge depth and a long number of cycles, the electrode structure remains basically unchanged, avoiding the deposition of metallic lithium on the outer wall of the carbon skeleton, resulting in inactivated lithium agglomeration or dead lithium in the electrode;
  • the overpotential of Li + deposition on tin is lower than that on carbon materials. Its lithium affinity helps to evenly immerse the molten metal lithium into the internal channels of the carbon tube balls during the stirring process, obtaining fuller and denser phosphorus-carbon composite microsphere particles, which increases the first charge specific capacity of the pretreated composite material by 30% or more;
  • the dense filling of metallic lithium inside the composite material avoids the side reaction between metallic lithium and electrolyte, effectively improving the utilization rate of electrolyte and active lithium.
  • the half-cell assembled by phosphorus-carbon composite material still maintains a low overpotential at a high current density of 2.5mA ⁇ cm -2 , and the capacity retention rate still reaches 85% after 150 cycles, achieving a double breakthrough in the cycle life and capacity retention rate of phosphorus-carbon composite materials.
  • FIG1 is a schematic diagram of the preparation of a phosphorus-carbon composite negative electrode material.
  • Figure 2 is an optical image of the carbon tube ball/red phosphorus/phosphorus-carbon composite material.
  • Figure 3 is the SEM images of CNT and P-CNT@ SnS2 materials prepared in Example 1, wherein A is the SEM image of CNT material and B is the SEM image of P-CNT@ SnS2 material.
  • FIG4 is an XRD graph of the carbon tube ball/red phosphorus/phosphorus-carbon composite material prepared in Example 1 before and after being doped with SnS 2 .
  • FIG. 5 is a histogram of the deposition potential of the carbon tube ball/doped SnS 2 phosphorus-carbon composite material prepared in Example 1.
  • FIG. 6 is the first discharge curve of the red phosphorus/carbon tube and SnS 2 @red phosphorus/carbon tube materials prepared in Example 1.
  • FIG. 6 is the first discharge curve of the red phosphorus/carbon tube and SnS 2 @red phosphorus/carbon tube materials prepared in Example 1.
  • FIG. 7 is a cycle performance diagram and a potential-time curve of the CNT and SnS 2 @CNT materials prepared in Example 1 (attached figure).
  • FIG8 is a DFT simulation of the binding energy of Li + and different substrates in Example 1: (a) Li + and Sn substrate; (b) Li + and C substrate.
  • FIG. 9 is the SEM images of CNT and P-CNT@Ni 3 S 4 materials prepared in Example 2, wherein A is the SEM image of CNT material, and B is the SEM image of P-CNT@Ni 3 S 4 material.
  • FIG10 is the SEM images of the CNT and P-CNT@CoSe 2 materials prepared in Example 3, wherein A is the SEM image of the CNT material, and B is the SEM image of the P-CNT@CoSe 2 material.
  • FIG11 is an SEM image of CNT and P-CNT@GeS 2 materials prepared in Example 4, wherein A is an SEM image of CNT material, and B is an SEM image of P-CNT@GeS 2 material.
  • FIG12 is the SEM images of the CNT and P-CNT@TiP materials prepared in Example 5, wherein A is the SEM image of the CNT material, and B is the SEM image of the P-CNT@TiP material.
  • Phosphorus-based negative electrode It has a high theoretical specific capacity and good rate performance, with a theoretical lithium storage capacity of 2596mA ⁇ h ⁇ g -1 ( Li3P ) and a high safe reaction electrode potential (0.8V vs Li/Li + ), but has poor conductivity, a large volume change during lithium insertion and extraction, and a volume expansion rate of 300%, resulting in the need to improve the material's cycle stability, which greatly limits its application in lithium-ion batteries.
  • Carbon-based negative electrode Typical commercial electrodes such as graphite, with low cost, simple and mature preparation process, strong conductivity, low operating voltage, good reversible charge and discharge performance, and strong safety, but it has disadvantages such as low specific capacity (372mA ⁇ h ⁇ g -1 ), low coulombic efficiency and poor high-rate charge and discharge performance.
  • Phosphorus-carbon composite negative electrode It is a new composite material with carbon as the dispersed matrix and phosphorus as the active material. It combines the composite advantages of phosphorus negative electrode and carbon negative electrode: it has good electrical conductivity, improves the conductivity of the negative electrode, and alleviates the volume expansion of the electrode during the cycle. However, the internal structure of the composite negative electrode has large voids and poor internal wettability to metallic lithium, which to a certain extent increases the contact area between active lithium and the electrolyte, thereby inducing side reactions and reducing the initial coulombic efficiency.
  • Energy density refers to the amount of energy stored in a certain unit of space or mass.
  • the energy density of a battery refers to the amount of electrical energy released per unit volume or unit mass of the battery.
  • Rate performance refers to storing or releasing a certain amount of energy into or out of the battery at a certain speed.
  • the premise of this storage and release process is controllable and safe, and will not significantly affect the battery life and other performance indicators.
  • the diameter of the carbon nanotubes is preferably 2-50 nm, more preferably 5-40 nm, more preferably 10-30 nm, and most preferably 15-25 nm.
  • the length of the carbon nanotube is preferably 0.1-500 ⁇ m, more preferably 1-400 ⁇ m, more preferably 10-300 ⁇ m, more preferably 50-200 ⁇ m, and most preferably 100-150 ⁇ m.
  • the present invention has no particular limitation on the source of the carbon nanotube, and carbon nanotubes well known to those skilled in the art can be used, which can be purchased from the market.
  • the carbon nanotubes are preferably carboxylated carbon nanotubes, aminated carbon nanotubes, hydroxylated carbon nanotubes, phosphorylated carbon nanotubes, and graphitized carbon nanotubes.
  • the present invention has no particular restrictions on the source of the modified carbon nanotubes, and the modified carbon nanotubes well known to those skilled in the art can be used, such as commercially available carbon nanotubes with carboxyl groups (purchased by Jiangsu Xianfeng Nanomaterial Technology Co., Ltd.).
  • Carbon nanotubes can also be surface oxidized to obtain carboxylated carbon nanotubes.
  • the oxidant for the surface oxidation preferably includes sulfuric acid and nitric acid, more preferably a mixed solution of sulfuric acid and nitric acid.
  • the purpose of this patent is to protect a method for preparing a high-performance composite phosphorus-carbon negative electrode by using carbon nanotube balls doped with red phosphorus and internal low-melting-point transition metal compounds through low-temperature liquid phase immersion.
  • the preparation method of the composite phosphorus-carbon negative electrode material comprises the following steps:
  • red phosphorus dispersion After ball milling, red phosphorus is subjected to hydrothermal treatment, and the dried solid matter is dispersed in a solvent to obtain a uniform red phosphorus dispersion;
  • the metal source in step (1) includes any one of fluorides, chlorides, nitrates, sulfates and carbonates of tin, titanium, cadmium, iron, cobalt, chromium, manganese and nickel.
  • the non-metallic source includes one of sulfide, selenide, telluride and phosphide; preferably, the sulfide includes at least one of sublimated sulfur, thioacetamide and thiourea, the selenide includes at least one of elemental selenium powder and sodium selenite, the telluride includes at least one of elemental tellurium powder and sodium tellurite, and the phosphide includes at least one of sodium hypophosphite, phosphoric acid, ammonium dihydrogen phosphate and diammonium hydrogen phosphate.
  • the molar ratio of the non-metal source to the metal source is 1:1-3:1.
  • the solvent includes at least one of deionized water, anhydrous ethanol, anhydrous methanol and anhydrous ether.
  • the mass concentration of the low melting point transition metal compound intermediate is 0.2-3%.
  • the solvent/hydrothermal reaction temperature is 50-100° C.
  • the reaction time is 5-50 mins
  • the solvent/hydrothermal reaction is performed with magnetic stirring at a rotation speed of 300-2000 rpm.
  • the precursor of the carbon nanotube ball is any one of carbon nanofiber, carbon nanotube, mesoporous carbon, porous carbon, common conductive agent carbon black and Super P;
  • the carbon nanotube spheres may also be materials with different particle sizes and skeleton structures obtained by surface modification through any one or more of amination, carboxylation, hydroxylation, phosphination, and graphitization.
  • the mass ratio of the carbon nanotube ball to the low melting point transition metal compound intermediate is 1:1-3:1.
  • the solvent/hydrothermal reaction temperature is 40-90°C
  • the reaction time is 20-80 minutes
  • solid-liquid separation is carried out by suction filtration and washing.
  • the filter cake is placed in a vacuum drying oven at 50-60°C and dried overnight.
  • the red phosphorus precursor of step (3) is in the form of a 60-100 mesh powder, or in the form of a 10-20 mesh microsphere particle;
  • red phosphorus and stainless steel balls are loaded into a stainless steel ball tank at a mass ratio of 1:10-1:50, and ball milled at a speed of 300-500rpm for 1-5h in a nitrogen atmosphere.
  • the hydrothermal reaction temperature is 150-200°C and the reaction time is 10-20h.
  • the mass concentration of the red phosphorus dispersion in step (4) is 10%-20%; the mass concentration of the composite carbon nanotube ball powder material in the solution is 10%-20%; the mass ratio of red phosphorus to the composite carbon nanotube ball powder material is 1:1-3:1.
  • step (4) the solvent/hydrothermal reaction temperature is 150-500° C., and the reaction time is 20-60 minutes.
  • the present invention uses the prepared red phosphorus-based carbon nanotube-doped phosphorus-carbon composite negative electrode material as a lithium ion Application of battery negative electrode.
  • PVDF binder
  • AB acetylene black
  • SnS2 nanosheet intermediate solution Dissolve tin tetrachloride and thioacetamide in a molar ratio of 1:1 in a high-purity ethanol solution, stir at 300 rpm to mix thoroughly, and react at 60°C for 30 mins to obtain a 2 wt.% SnS2 intermediate solution for standby use;
  • red phosphorus was dispersed in deionized water for ball milling.
  • the red phosphorus and stainless steel balls were loaded into a stainless steel ball tank at a mass ratio of 1:30.
  • the mixture was ball milled at a speed of 300 rpm for 1 h under a nitrogen atmosphere and then transferred to a reactor.
  • the mixture was hydrothermally treated at 200°C for 12 h.
  • the product was placed in a vacuum drying oven at 50°C for overnight drying.
  • the dried red phosphorus was dispersed in a mixed solvent of ethanol/deionized water at a mass fraction of 2%, and ultrasonically dispersed for 80 mins to obtain a uniform red phosphorus dispersion.
  • PVDF binder
  • AB acetylene black
  • Figure 1 is a schematic diagram of the preparation of a phosphorus-carbon composite negative electrode material.
  • a carbon tube ball (or a modified carbon tube ball, which is a material with different particle sizes and skeleton structures obtained by surface modification of the modified carbon tube ball by any one or more of amination, carboxylation, hydroxylation, phosphorylation, and graphitization) is placed in a transition metal nano-doping solution to obtain a transition metal nanosheet-doped carbon tube ball, which is then placed in a small-particle red phosphorus dispersion treated with ball milling and reacted in a constant temperature water bath to obtain a phosphorus-carbon composite negative electrode material.
  • Figure 2 is an optical image of the carbon tube ball/red phosphorus/phosphorus-carbon composite material. It can be seen that the carbon tube ball/red phosphorus/phosphorus-carbon composite material is uniformly dispersed in the solvent, and no agglomeration precipitation phenomenon is observed.
  • FIG. 1 shows the SEM images of CNT and P-CNT@SnS 2 materials.
  • CNT presents a spherical structure assembled by nanotubes, and on P-CNT@SnS 2 , it can be observed that carbon nanotube microspheres and small-size red phosphorus are evenly mixed and co-coated.
  • FIG. 4 shows the XRD patterns of carbon tube/red phosphorus/phosphorus-carbon composite material before and after doping with SnS 2.
  • the carbon tube/red phosphorus carbon tube composite material before and after doping showed a typical broad carbon peak at 26.5°.
  • the doped material showed two characteristic peaks at 28.5° and 51.1° belonging to SnS 2 , indicating that SnS 2 was successfully doped into the carbon tube.
  • FIG. 1 is the SEM image and potential bar graph of carbon nanotube/doped SnS 2 phosphorus-carbon composite material.
  • the doping amount increases from 0% to 10%, the uneven surface formed by the carbon nanotube gradually becomes smooth.
  • the doping amount increases to 15%, the surface becomes rough again.
  • the size of the carbon nanotube becomes larger. This may be due to the change in the internal structure of the carbon nanotube caused by the excessive doping amount.
  • the potential of the SnS 2 intermediate doped electrode material has decreased to varying degrees, and when the doping amount is 10%, the potential is the lowest (65mV), indicating that there is a potential difference of about 0.3V between the lithium-tin alloy and the metallic lithium, so that the carbon nanotube doped SnS 2 has excellent lithium affinity, which is conducive to the uniform immersion of molten metal lithium into the internal channel of the carbon nanotube during the stirring process, and obtains fuller and denser phosphorus-carbon composite microsphere particles, which have better specific capacity and rate performance, and at the same time avoids the side reaction between the metallic lithium and the electrolyte, effectively improving the utilization rate of the electrolyte and active lithium.
  • Figure 6 shows the first discharge curves of red phosphorus/carbon tube and SnS 2 @ red phosphorus/carbon tube materials.
  • the first discharge capacity of the phosphorus-carbon negative electrode material after doping is 3020 mA ⁇ h ⁇ g -1 , which is significantly improved compared with the discharge capacity before doping (2355 mA ⁇ h ⁇ g -1 ).
  • Figure 7 shows the cycle performance diagram and potential-time curve of CNT and SnS 2 @CNT materials (attached picture).
  • the coulombic efficiency of SnS 2 @CNT is still basically maintained at 99.6% after 200 cycles, while the coulombic efficiency of CNT shows obvious fluctuations after 100 cycles, indicating that SnS 2 @CNT material has better cycle stability; and the potential-time diagram also shows that compared with CNT (-150 mV), SnS 2 @CNT has a relatively high potential (-71 mV), and is less likely to have side reactions with liquid electrolytes, which can ensure less Reduced electrolyte consumption and longer cycle life.
  • Figure 8 is a DFT simulation of the binding energy of Li + with different substrates. It can be seen that Li + has a lower binding energy (-1.12 eV) with the doped SnS 2 three-dimensional conductive carbon substrate, indicating that it has better lithium affinity.
  • Ni 3 S 4 nanosheet intermediate solution nickel nitrate hexahydrate and thiourea in a molar ratio of 1:2 were dissolved in anhydrous methanol solution, and stirred at a speed of 500 rpm to mix thoroughly. After reacting at 80°C for 20 minutes, a 1wt.% Ni 3 S 4 intermediate solution was obtained for standby use. With the introduction of Ni 3 S 4 nanosheet intermediates, the generation of by-product white phosphorus can be effectively reduced, and the safety of the preparation process can be improved;
  • Ni 3 S 4 @CNT composite material Place carbon nanotubes (CNT diameter is 15-25nm, tube length is 100-150 ⁇ m) in a concentrated H 2 SO 4 and concentrated HNO 3 solution with a volume ratio of 3:1, reflux at 80 degrees for 12 hours, wash the product to neutrality and then dry it, remove impurities on the surface of carbon nanotubes with carboxyl and hydroxyl groups, which are easier to disperse in the solvent and are also conducive to the composite with Ni 3 S 4 intermediates and red phosphorus particles.
  • Red phosphorus was dispersed in deionized water and ball-milled. Red phosphorus and stainless steel balls were loaded into a stainless steel ball tank at a mass ratio of 1:20. After ball-milling at 300 rpm for 2 h under a nitrogen atmosphere, the mixture was transferred to a reactor. After hydrothermal treatment at 150 °C for 20 h, the mixture was placed in a vacuum drying oven at 50 °C for overnight drying. The dried red phosphorus was dispersed in anhydrous methanol and ultrasonically dispersed for 60 mins to obtain a uniform 1 wt.% red phosphorus dispersion.
  • PVDF binder
  • AB acetylene black
  • FIG. 9 shows the SEM images of CNT and P-CNT@Ni 3 S 4 materials.
  • the carbon nanotube microspheres are fully mixed with red phosphorus, which increases the conductivity of the red phosphorus material and inhibits the volume expansion during the charge and discharge process.
  • CoSe2 nanosheet intermediate solution Cobalt chloride and selenium powder in a molar ratio of 1:2 were dissolved in anhydrous ethanol solution, and stirred at 400 rpm to mix well. After reacting at 60°C for 50 mins, a 0.5 wt.% CoSe2 intermediate solution was obtained for standby use;
  • the carbon tubes modified with phosphorus-containing groups are immersed in the above-mentioned CoSe 2 intermediate solution at a mass fraction of 0.5%, and continuously heated to 50°C at a speed of 400rpm for 80mins. After the sample is cooled to room temperature, it is washed and filtered several times to collect the obtained sample. Finally, the obtained sample is placed in a vacuum oven at 50°C and dried overnight to obtain CoSe 2 @CNT composite carbon tube powder material;
  • red phosphorus was dispersed in deionized water and ball-milled.
  • the red phosphorus and stainless steel balls were loaded into a stainless steel ball tank at a mass ratio of 1:40.
  • the mixture was ball-milled at 400 rpm for 4 h under a nitrogen atmosphere and then transferred to a reactor. After hydrothermal treatment at 170 °C for 16 h, the mixture was placed in a 50 °C vacuum drying oven and dried overnight.
  • the dried red phosphorus was dispersed in anhydrous ethanol and ultrasonically dispersed for 80 mins to obtain a uniform 0.5 wt.% red phosphorus dispersion.
  • the phosphorus-carbon composite negative electrode material prepared in the above process is mixed with a binder (PVDF) and acetylene black (AB) in a mass ratio of 8:1:1, mixed in NMP solvent and coated on a copper foil.
  • PVDF binder
  • AB acetylene black
  • Figure 10 shows the SEM images of CNT and P-CNT@CoSe 2 materials. After the phosphorus-carbon composite material is formed, carbon tubes are attached to the surface of the red phosphorus material, and small-sized red phosphorus is attached to the inside of the carbon tubes.
  • red phosphorus dispersion ball-mill the red phosphorus in deionized water, load the red phosphorus and stainless steel balls into a stainless steel ball tank at a mass ratio of 1:30, ball-mill at 350 rpm for 5 h under a nitrogen atmosphere, transfer to a reactor, hydrothermally treat at 180 °C for 10 h, place in a 50 °C vacuum drying oven for overnight drying, disperse the dried red phosphorus in anhydrous ether at a mass fraction of 1%, and ultrasonically disperse for 40 mins to obtain a uniform red phosphorus dispersion;
  • PVDF binder
  • AB acetylene black
  • Figure 11 shows the SEM images of CNT and P-CNT@GeS 2 materials.
  • TiP nanosheet intermediate solution titanium sulfate and sodium hypophosphite in a molar ratio of 1:1 were dissolved in anhydrous ether solution, stirred at 1500 rpm to mix well, and reacted at 70°C for 20 mins to obtain a 2 wt.% TiP intermediate solution for standby use;
  • TiP@CNT composite materials Place carbon nanotubes (CNT diameter is 15-25nm, tube length is 100-150 ⁇ m) in a tubular furnace and bake at 800°C for 2h under an inert atmosphere to enhance the graphitization strength of the carbon tube balls. Then, soak the baked carbon tube balls in a TiP intermediate solution at a mass fraction of 2%, and continue to heat to 70°C at a speed of 1500rpm. React for 50mins. After the sample is cooled to room temperature, wash and filter the obtained sample several times. Finally, place the obtained sample in a vacuum oven at 50°C and dry overnight to obtain a TiP@CNT composite carbon tube ball powder material;
  • red phosphorus was dispersed in deionized water and ball-milled.
  • the red phosphorus and stainless steel balls were loaded into a stainless steel ball tank at a mass ratio of 1:30.
  • the mixture was ball-milled at 400 rpm for 2 h under a nitrogen atmosphere and then transferred to a reactor. After hydrothermal treatment at 180 °C for 15 h, the mixture was placed in a vacuum drying oven at 50 °C for overnight drying.
  • the dried red phosphorus was dispersed in anhydrous ether at a mass fraction of 2%, and ultrasonically dispersed for 40 mins to obtain a uniform red phosphorus dispersion.
  • PVDF binder
  • AB acetylene black
  • Figure 12 is the SEM images of CNT and P-CNT@TiP materials.
  • Example 2 The implementation steps are the same as those in Example 1, except that the non-metallic source is sodium tellurite, 2 wt.% SnTe 2 is obtained in step 6.1, and the other steps are the same as those in Example 1, to obtain a doped and modified phosphorus-carbon composite negative electrode material (P-CNT@SnTe 2 ).
  • the non-metallic source is sodium tellurite
  • 2 wt.% SnTe 2 is obtained in step 6.1
  • the other steps are the same as those in Example 1, to obtain a doped and modified phosphorus-carbon composite negative electrode material (P-CNT@SnTe 2 ).
  • Example 2 The implementation steps are the same as those in Example 1, except that the non-metal source is sodium selenite and the metal source is nickel nitrate hexahydrate. 2 wt.% NiSe is obtained in step 6.1, and the other steps are the same as those in Example 1 to obtain a doped and modified phosphorus-carbon composite negative electrode material (P-CNT@NiSe).
  • the non-metal source is sodium selenite and the metal source is nickel nitrate hexahydrate.
  • 2 wt.% NiSe is obtained in step 6.1, and the other steps are the same as those in Example 1 to obtain a doped and modified phosphorus-carbon composite negative electrode material (P-CNT@NiSe).
  • the implementation steps are the same as those in Example 1, and the carbon nanotubes (CNT) are subjected to surface modification by amino treatment to obtain an amino-modified carbon nanotube/red phosphorus/phosphorus-carbon composite material NH 3 -P-CNT@SnS 2 .
  • Example 2 The implementation steps are the same as those in Example 1, and the carbon nanotube spheres are surface-modified by carboxylation to obtain graphitized modified carbon nanotube spheres/red phosphorus/phosphorus-carbon composite material COOH-P-CNT@SnS 2 .
  • Example 2 The implementation steps are the same as those in Example 1, and the carbon nanotube sphere is subjected to phosphorus-based surface modification to obtain a phosphorus-based modified carbon nanotube sphere/red phosphorus/phosphorus-carbon composite material PP-CNT@SnS 2 .
  • the cycle stability of the materials prepared in each embodiment and comparative example was determined by testing the capacity retention rate after 150 cycles. Due to the lower deposition overpotential of Li + on titanium, lithium is more easily immersed in the carbon tube ball, forming a denser and fuller phosphorus-carbon composite microsphere, thereby improving the utilization rate of lithium during the first charge and discharge process, thereby improving the specific capacity and cycle performance of the phosphorus-carbon composite electrode, as shown in Table 1:
  • Example 11 refers to the phosphorus-carbon negative electrode in Example 1 that is not modified with SnS2 .
  • Example 12 refers to the phosphorus-carbon negative electrode of SnS2 in Example 8 without SnS2 modification.

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Abstract

本发明提供一种基于红磷的新型磷碳负极材料及制备方法，包括红磷和复合碳纳米管球。红磷和复合碳纳米管球在溶剂混合后经热反应得到的产物，复合碳纳米管球在溶液中的质量浓度为10％-20％。磷碳复合材料所组装的半电池在2.5mA·cm-2的高电流密度下仍然保持着较低的过电位，在150次的循环圈数后容量保持率仍达到85％，实现了磷碳复合材料循环寿命和容量保持率的双突破。

Description

一种基于红磷的新型磷碳负极材料及制备方法 技术领域
本发明具体涉及一种基于红磷的碳纳米管掺杂技术制备磷碳复合负极的方法。通过低熔点过渡金属化合物镶嵌于碳管球内部后复合红磷的手段实现一种较高可逆比容量及良好倍率性能的磷碳复合负极的制备，有利于进一步实现高能量密度、高倍率性能以及低成本的新型商用锂离子电池体系。属于锂电新能源材料技术领域的锂离子电池负极方向。
背景技术
在目前全球范围内“碳达峰”、“碳中和”的双碳背景下，锂离子电池有望在消费、动力和储能领域有着更大的应用市场，但更多的机遇也意味着更多的挑战。随着锂离子电池在新能源汽车、移动设备等领域的蓬勃发展，人们也对锂离子电池体系的能量密度及高倍率性能提出了更高的要求。目前常规的商用负极材料主要以碳基负极为主(如最常规、应用最广泛的石墨负极)，层状结构的嵌锂脱锂有着良好循环性能，但同时也存在理论比容量低(372mA·h·g-1)、高倍率充放电性能不佳等缺点。相反，在众多负极材料体系中，磷基负极具有较高的理论比容量(如Li3P，2596mA·h·g-1)及优异的倍率性能，且成本相对较低，是未来有望进一步实现高能量密度、高倍率性能的研究方向之一。但磷基材料的导电性较差，循环过程中体积膨胀大(体积膨胀率高达300％)，材料循环性能有待进一步优化提升，这很大程度上限制了磷基负极材料在锂离子电池中的应用。
为了解决这一问题，磷碳复合负极有望结合两者优势，借助磷基与多维碳材料的协同效应实现更高的能量密度及更好的倍率性能。在众多碳基材料中，碳纳米管可以形成三维骨架结构，可以有效解决磷基负极体积膨胀等问题。在CN109309199的工作中，公开了一种锂离子电池负极红磷/碳纳米管复合材料制备方法。所述方法通过低温液相法，借助红磷和碳纳米管在溶剂中的表面电负性差异，使红磷均匀吸附于碳纳米管管壁，获得均匀的红磷/碳纳米管复合材料。制备方法简单、环境友好，所得材料显著地提高了锂离子电池的比容量以及循环充放电稳定性。在CN111769271的工作中，通过将大间距MXene与红磷高温混合焙烧，得到具备高容量和高循环性能的MXene/红磷复合负极材料，该复合材料基于红磷的高理论比容量，充分利用大间距MXene电子传导率高、比表面积大、机械性能强、表面可修饰以及独特层状结构等优点，作为理想的碳载体改善红磷导电性和结构稳定性。CN112420999则公开了一种具有核壳包覆结构的磷碳复合材料，包括磷基材料核心体和碳基材料包覆层，不仅可以缓解充放电过程中的体积膨胀，而且可以抑制锂电池充放电循环过程 中磷化锂的溶出以及电极界面/电解液之间的副反应，从而具备良好的充放电比容量和循环性能。在CN114122386的工作中，一种磷化锡@碳复合负极活性前驱材料，包括碳单质骨架，以及镶嵌在其外表面且呈点状分布的磷化锡纳米粒子。在CN109309所述的材料，在碳单质骨架外表面均匀弥散分布磷化锡纳米点，基于所述的创新形貌和结构特性，结合碳单质骨架丰富的比表面积、良好的导电性，有效地降低了局部电流密度，实现了循环过程中更均匀的锂沉积和溶解。
发明内容
本专利的目的在于保护一种利用红磷与内部低熔点过渡金属化合物镶嵌掺杂的碳纳米管球通过低温液相浸泡的手段制备高性能复合磷碳负极的方法。
单纯磷基负极材料的导电性较差(红磷的电导率仅为10-14S·cm-1)，在嵌/脱锂过程中氧化还原动力学缓慢，电池内部极化严重，SEI膜增厚导致锂离子损耗严重，同时在充放电循环过程中巨大的体积膨胀(体积膨胀率高达300％)易引起活性材料粉化，严重影响了材料的库伦效率和倍率循环性能。
单纯碳基负极材料理论比容量偏低(372mA·h·g-1)，且在大电流充放电过程中，锂离子扩散速率和扩散通道受限，脱/嵌锂速率缓慢，同时嵌入过程中会在石墨碳层间形成化合物LixC6，增大碳层层间距，容易引起碳层脱落，降低碳基负极材料的容量、循环性能与使用寿命。
现有磷碳复合负极材料以稳定的化学键连接碳载体和磷活性组分，碳材料高导电性、大比表面积和柔性表面易形成导电网络，促进活性组分均匀分散的同时吸收体积变化过程产生的机械应力，防止磷活性组分破碎粉化，提高倍率性能和循环稳定性。但现阶段磷碳负极普遍存在界面不稳定、对金属锂浸润性较差等问题。
气化冷凝工艺：利用红磷高于450℃时的升华特性，使得红磷蒸气通过毛细作用力和压差均匀沉积在碳纳米管的管壁上，冷却后吸附沉积到碳纳米管内表面。其缺点在于磷通过气化冷凝工艺在导电碳框架上的沉积量有限，而磷负载量是影响电池容量性能的重要因素。此外，在降温的过程中易形成的白磷副产物，易燃，有一定的危险性，而白磷的去除则需要用到二硫化碳等有毒试剂，安全隐患较大。
高温热解工艺：以磷材料为基底，采用有机物在惰性气氛下高温热解产生的无定形碳为碳源包覆磷材料，获得具有核壳包覆结构的磷碳复合材料。然而，高温热解工艺制备的复合材料中磷作为核心体，分散性较差，同时有机物热解产生的碳层容易出现分布不均的状况，并且热解温度稍高时颗粒间团聚现象严重。
碳热还原工艺：在一定温度下，利用无机碳作为还原剂还原磷化物制备磷碳复合材料。其缺点在于还原过程控制难度高，对磷碳比例要求精度高，同时易产生杂质，产品品控难度大，颗粒尺寸大小不一致，分散性差。
基于上述相关技术手段，借助碳管球内部SnS2等类似中间产物的引入，通过低温液相浸泡的方法，改善磷碳复合负极的性能：第一方面可以通过控制温度和气氛有效降低白磷副产物的生成，有效降低制造成本并且提高制备工艺的安全性；第二方面通过首次充放电在碳管球内部形成锂锡等类似固溶体，改善磷碳复合球在循环中对金属锂的浸润性。同时SnS2等类似物可以被精确调控成具有高度暴露活性位点的纳米片结构，高温下接触熔融金属锂易形成分布均匀的合金位点。第三方面形成的锂锡等系列合金与金属锂之间存在0.3V左右的电位差，以此可作为锂扩散的驱动力。同时由于金属锂在锡上较低的沉积过电位，有助于金属锂浸入磷碳复合微球内部，使磷碳负极首次充电比容量提升30％及以上。第四方面锂锡合金具有相对较高的化学势，因此与纯的金属锂负极或磷碳负极相比，其与液体电解质发生副反应性的可能性更小，从而保证更少的电解液消耗和更长的循环寿命。
针对上述技术问题，本发明提供一种基于红磷的碳纳米管掺杂的磷碳复合负极材料，包括红磷和复合碳纳米管球。
更进一步的，所述的红磷与复合碳纳米管球的质量比为1:1-3:1。
更进一步的，红磷和复合碳纳米管球在溶剂混合后经热反应得到的产物，复合碳纳米管球在溶液中的质量浓度为10％-20％。
本发明所述的小粒径红磷均匀复合于具有三维多孔骨架的碳纳米管微球上，防止了红磷颗粒的大量团聚，提升了红磷材料的导电性，有效解决充放电过程中的体积膨胀问题。红磷可以是60-100目的粉末状态，也可以是10-20目的微球颗粒状态。
更进一步的，热反应过程中所述的溶剂包括去离子水、无水乙醇、无水甲醇、无水乙醚中的至少一种。
更进一步的，所述的复合碳纳米管球内部掺杂镶嵌低熔点过渡金属化合物(≤200℃)；低熔点过渡金属化合物的质量浓度为0.2-3％。
碳纳米管内部镶嵌的低熔点过渡金属化合物中间体有助于锂均匀地浸入碳管球内部通道中，显著提高磷碳复合负极材料的比容量和倍率性能(首次充电比容量提升30％及以上)，同时避免了金属锂在电极表面沉积与电解液发生反应，提高了材料的循环性能。
更进一步的，所述的低熔点过渡金属化合物包括锡、钛、镉、铁、钴、铬、锰、锗、或镍的金属源与非金属源进行反应所得，所述非金属源和所述金属源摩尔比为1:1-3:1。
更进一步的，所述的金属盐包括锡、钛、镉、铁、钴、铬、锰和镍的氟化物、氯化物、硝酸盐、硫酸盐和碳酸盐；所述的非金属源包括硫化物、硒化物、碲化物、磷化物中的任意一种或多种；所述硫化物包括升华硫、硫代乙酰胺和硫脲中的至少一种，所述硒化物包括单质硒粉和亚硒酸钠中的至少一种，所述碲化物包括单质碲粉和亚碲酸钠中的至少一种，所述磷化物包括次磷酸钠、磷酸、磷酸二氢铵和磷酸氢二铵中的至少一种。
更进一步的包括Fe2S3、GeS2、SnS2、Co9S8、NiSe、SnTe2或TiP等，但并不限于此。
更进一步的，所述的三维碳管球材料的前驱体可以是碳纳米纤维、碳纳米管、介孔碳、多孔碳以及常用导电剂炭黑和Super P中的任意一种。
所述碳纳米管球还可以是经过氨基化、羧基化、羟基化、磷基化、或石墨化中的任意一种或多种进行表面修饰得到的粒径及骨架结构不同的材料。
经过表面修饰后的碳纳米管三维多孔骨架可以增强与低熔点过渡金属化合物和红磷的复合强度，避免SEI膜对锂离子的消耗，减少副反应的发生，提高磷碳复合负极材料的可逆充放电性能和循环稳定性。
基于红磷的碳纳米管球掺杂技术制备的磷碳复合负极由于各组元之间的强作用力具备着良好的形貌结构稳定性，在较高电流密度下经历多次充放电循环仍能维持基本形貌结构，避免结构坍塌导致锂析出问题。
本发明的第二方面是基于红磷的碳纳米管掺杂的磷碳复合负极材料的制备方法，基于液相法制备低熔点过渡金属化合物中间体，制备工艺简单，易于操作，制得的中间体材料形貌均一，尺寸粒径较小，有利于后续碳管球中的掺杂，具体包括以下步骤：
(1)低熔点过渡金属化合物中间体溶液的制备：将金属源和非金属源溶于溶剂中，溶剂/水热反应后得到低熔点过渡金属化合物中间体溶液；
(2)复合碳纳米管球的制备：将碳纳米管球分散于所述的低熔点过渡金属化合物中间体溶液中，溶剂/水热反应后实行固液分离，滤饼烘干后得到复合碳纳米管球粉体材料；将低熔点过渡金属化合物中间体引入碳管球中，一方面可以更好实现磷碳材料的复合，另一方面与金属锂合金化将其导入碳管球内部通道中，防止在碳管球外表面沉积与电解液反应，同时提高材料比容量和倍率性能。
(3)红磷分散液的制备：红磷球磨后进行水热处理，烘干后的固体物质分散于溶剂中得到均匀的红磷分散液；
(4)复合磷碳负极材料的制备：将所述的复合碳纳米管球粉体材料超声分散于溶剂中，加 入所述的红磷分散液，超声处理后进行溶剂/水热反应，离心洗涤后收集固体物质冷冻干燥，得到复合磷碳负极材料。
本发明的工艺过程中液相以及熔融相的引入有利于更好实现磷碳材料的均一复合，提高各组元间的键合强度，增强材料的结构稳定性，提升磷碳复合负极材料的循环性能。
优选的，步骤(1)中所述金属源包括锡、钛、镉、铁、钴、铬、锰、锗、或镍的氟化物、氯化物、硝酸盐、硫酸盐或碳酸盐中的任意一种。
优选的，所述非金属源包括硫化物、硒化物、碲化物或磷化物中的一种；优选地，所述硫化物包括升华硫、硫代乙酰胺和硫脲中的至少一种，所述硒化物包括单质硒粉和亚硒酸钠中的至少一种，所述碲化物包括单质碲粉和亚碲酸钠中的至少一种，所述磷化物包括次磷酸钠、磷酸、磷酸二氢铵和磷酸氢二铵中的至少一种。
优选的，包括Fe2S3、GeS2、SnS2、Co9S8、NiSe、SnTe2或TiP等，但并不限于此。
优选的，所述非金属源和所述金属源摩尔比为1:1-3:1。
优选的，所述溶剂包括去离子水、无水乙醇、无水甲醇或无水乙醚中的至少一种。
优选的，所述低熔点过渡金属化合物中间体质量浓度为0.2-3％。
优选的，所述低熔点过渡金属化合物中间体溶液的制备过程中，溶剂/水热反应温度为50-100℃，反应时间为5-50mins，所述溶剂/水热反应时采用磁力搅拌，转速为300-2000rpm。
所述碳纳米管球还可以是经过氨基化、羧基化、羟基化、磷基化、或石墨化中的任意一种或多种进行表面修饰得到的粒径及骨架结构不同的材料。
优选的，所述碳纳米管球和所述低熔点过渡金属化合物中间体的质量比为1:1-3:1。
优选的，步骤(2)所述复合碳纳米管球的制备过程中，溶剂/水热反应温度为40-90℃，反应时间为20-80mins，并采取抽滤洗涤的方式进行固液分离，得到的滤饼置于50-60℃的真空干燥箱中过夜烘干。
优选的，步骤(3)的红磷球磨过程中，红磷与不锈钢球以1:10-1:50的质量比装入不锈钢球罐中，在氮气气氛下以300-500rpm的转速球磨1-5h，水热处理过程中水热反应温度为150-200℃，反应时间为10-20h。
球磨过程不同组元之间形成牢固且稳定的化学键对实现磷碳复合材料高倍率和循环性能至关重要。然而，通过机械球磨实现磷碳复合的工艺中，并不能很好的保证材料的均一一致性，颗粒团聚现象严重，组元间难以通过化学键的方式建立连接，并且球磨会导致碳纳米管三维骨架的损伤，不利于抑制循环中体积膨胀效应。而本发明借助液相以及熔融等形 态，能在不损伤材料三维骨架的基础上，有效实现材料的均一复合。
优选的，步骤(4)中红磷分散液的质量浓度为10％-20％；复合碳纳米管球粉体材料在溶液中的质量浓度为10％-20％；红磷与复合碳纳米管球粉体材的质量比为1:1-3:1。
优选的，步骤(4)中溶剂/水热反应温度为150-500℃，反应时间为20-60mins。
本发明的第三方面是将所述制备得到的基于红磷的碳纳米管掺杂的磷碳复合负极材料作为锂离子电池负极的应用。
本发明利用该掺杂体系下的磷碳复合负极材料所组装成的电池。
本发明的复合负极材料在高容量、高倍率锂离子电池体系内的应用。
高容量、高倍率锂离子电池的组装步骤如下，将上述制备的磷碳复合负极材料与粘结剂(PVDF)和乙炔黑(AB)按质量比为8:1:1混合，在N-甲基吡咯烷酮(NMP)溶剂中混浆均匀，涂覆在铜箔上，80℃真空干燥后冲片作为工作电极，以金属锂片为对电极，以1.0M LiTFSI in DOL:DME(V:V＝1:1)+1.0wt.％LiNO3为实验电解液体系进行扣式电池(半电池)组装并进行充放电循环测试。
采用本发明的技术方案具有如下有益效果：
提高安全性：借助低熔点过渡金属化合物中间体的引入，可以有效降低副产物白磷的生成，有效降低制造成本并且提高制备工艺的安全性；
解决体积膨胀：利用碳纳米管的三维骨架结构有效抑制磷基材料循环过程中体积膨胀问题；改善磷碳复合负极的浸润性：工艺过程过渡金属化合物中间体、复合碳纳米管球、红磷掺杂均涉及到液相或熔融相，有利于材料的均匀复合。良好的浸润性保持了复合负极的颗粒感和电极形貌，即使经历较高的充放电深度和较长的循环圈数，电极结构基本保持不变，避免了金属锂沉积在碳骨架外壁导致电极出现失活锂结块或死锂产生；
降低成本：工艺简单可行，成本较低，安全性较高，有大规模应用前景；
提高比容量：Li+在锡上沉积过电位低于碳材料，其亲锂性在搅拌过程中有助于将熔融金属锂均匀地浸入碳管球内部通道中，获得更加饱满致密的磷碳复合微球颗粒，使预处理复合材料首次充电比容量提升30％及以上；
提高电化学稳定性方面：复合材料内部金属锂的致密填充，避免了金属锂与电解液发生副反应，有效提高了电解液和活性锂的利用率。磷碳复合材料所组装的半电池在2.5mA·cm-2的高电流密度下仍然保持着较低的过电位，在150次的循环圈数后容量保持率仍达到85％，实现了磷碳复合材料循环寿命和容量保持率的双突破。
附图说明
图1为磷碳复合负极材料的制备示意图。
图2为碳管球/红磷/磷碳复合材料光学图。
图3为实施例1所制备的CNT和P-CNT@SnS2材料SEM图，其中A为CNT材料SEM图，B为P-CNT@SnS2材料SEM图。
图4为实施例1所制备的碳管球/红磷/磷碳复合材料掺杂SnS2前后XRD图。
图5为实施例1所制备的碳管球/掺杂SnS2磷碳复合材料沉积电位柱状图。
图6为实施例1所制备的红磷/碳管和SnS2@红磷/碳管材料首次放电曲线。
图7为实施例1所制备的CNT和SnS2@CNT材料的循环性能图与电位-时间曲线(附图)。
图8为实施例1中DFT模拟Li+与不同基底的结合能图：(a)Li+与Sn基底；(b)Li+与C基底。
图9为实施例2所制备的CNT和P-CNT@Ni3S4材料SEM图，其中A为CNT材料SEM图，B为P-CNT@Ni3S4材料SEM图。
图10为实施例3所制备的CNT和P-CNT@CoSe2材料SEM图，其中A为CNT材料SEM图，B为P-CNT@CoSe2材料SEM图。
图11为实施例4所制备的CNT和P-CNT@GeS2材料SEM图，其中A为CNT材料SEM图，B为P-CNT@GeS2材料SEM图。
图12为实施例5所制备的CNT和P-CNT@TiP材料SEM图，其中A为CNT材料SEM图，B为P-CNT@TiP材料SEM图。
具体实施方式
术语解释
磷基负极：具有较高的理论比容量以及较好的倍率性能，理论储锂比容量2596mA·h·g-1(Li3P)，且有较高的安全反应电极电位(0.8V vs Li/Li+)，但导电性较差，脱嵌锂过程体积变化较大，体积膨胀率达到300％，导致材料循环稳定性有待提升，很大程度上限制了其在锂离子电池中的应用。
碳基负极：如石墨等典型商用电极，成本低廉，制备工艺简单成熟，导电性强，工作电压低，拥有良好的可逆充放电性能，安全性强，但存在比容量偏低(372mA·h·g-1)、库伦效率低和高倍率充放电性能不佳等缺点。
磷碳复合负极：是以碳为分散基体，磷为活性物质的新型复合材料，结合磷负极与碳负极的复合优点：具备良好的电导性、提高负极的电导率、缓解循环过程中电极的体积膨 胀问题从而提升循环稳定性。但复合负极内部结构的空隙较大、内部对金属锂的浸润性较差，在一定程度上增大了活性锂与电解液接触面积从而引发副反应，降低了首次库伦效率。
能量密度：指在单位一定的空间或质量物质中储存能量的大小。电池的能量密度即指电池平均单位体积或单位质量下所释放出的电能。
倍率性能：指以一定的速度，将一定的能量存储到电池里面或者释放出来。这个存储和释放的过程的前提是可控且安全的，不会显著影响电池的寿命和其他性能指标。一般我们称1.0C放电的锂电池为标准电池，2.0C-10C放电的为较小倍率电池，超过10C的为高倍率电池。
在本发明中，所述碳纳米管的直径优选为2-50nm，更优选为5-40nm，更优选为10-30nm，最优选为15-25nm。
在本发明中，所述碳纳米管的长度优选为0.1-500μm，更优选为1-400μm，更优选为10-300μm，更优选为50-200μm，最优选为100-150μm。本发明对所述碳纳米管的来源没有特殊的限制，采用本领域技术人员熟知的碳纳米管即可，可由市场购买获得。
在本发明中，所述碳纳米管优选为羧基化的碳纳米管、氨基化的碳纳米管、羟基化的碳纳米管、磷基化的碳纳米管、石墨化的碳纳米管。本发明对所述修饰的碳纳米管的来源没有特殊的限制，采用本领域技术人员熟知的修饰的碳纳米管即可，如可采用自带羧基的碳纳米管市售商品(江苏先丰纳米材料科技有限公司购买)。也可将碳纳米管进行表面氧化得到羧基化的碳纳米管。如在本发明中，所述表面氧化的氧化剂优选包括硫酸和硝酸，更优选为硫酸和硝酸的混合液。
本专利的目的在于保护一种利用红磷与内部低熔点过渡金属化合物镶嵌掺杂的碳纳米管球通过低温液相浸泡的手段制备高性能复合磷碳负极的方法。
复合磷碳负极材料的制备方法，包括以下步骤：
(1)低熔点过渡金属化合物中间体溶液的制备：将金属源和非金属源按一定比例溶于溶剂中，溶剂/水热反应后得到低熔点过渡金属化合物中间体溶液；
(2)复合碳纳米管球的制备：将碳纳米管球分散于所述的低熔点过渡金属化合物中间体溶液中，溶剂/水热反应后实行固液分离，滤饼烘干后得到复合碳纳米管球粉体材料；
(3)红磷分散液的制备：红磷球磨后进行水热处理，烘干后的固体物质分散于溶剂中得到均匀的红磷分散液；
(4)复合磷碳负极材料的制备：将所述的复合碳纳米管球粉体材料超声分散于溶剂中，加入所述的红磷分散液，超声处理后进行溶剂/水热反应，离心洗涤后收集固体物质冷冻干 燥，得到复合磷碳负极材料。
步骤(1)中所述金属源包括锡、钛、镉、铁、钴、铬、锰和镍的氟化物、氯化物、硝酸盐、硫酸盐和碳酸盐中的任意一种。
所述非金属源包括硫化物、硒化物、碲化物和磷化物中的一种；优选地，所述硫化物包括升华硫、硫代乙酰胺和硫脲中的至少一种，所述硒化物包括单质硒粉和亚硒酸钠中的至少一种，所述碲化物包括单质碲粉和亚碲酸钠中的至少一种，所述磷化物包括次磷酸钠、磷酸、磷酸二氢铵和磷酸氢二铵中的至少一种。
所述非金属源和所述金属源摩尔比为1:1-3:1。
所述溶剂包括去离子水、无水乙醇、无水甲醇和无水乙醚中的至少一种。
所述低熔点过渡金属化合物中间体质量浓度为0.2-3％。
所述低熔点过渡金属化合物中间体溶液的制备过程中，溶剂/水热反应温度为50-100℃，反应时间为5-50mins，所述溶剂/水热反应时采用磁力搅拌，转速为300-2000rpm。
所述的碳纳米管球的前驱体为碳纳米纤维、碳纳米管、介孔碳、多孔碳以及常用导电剂炭黑和Super P中的任意一种；
所述碳纳米管球还可以是经过氨基化、羧基化、羟基化、磷基化、石墨化中的任意一种或多种进行表面修饰得到的粒径及骨架结构不同的材料。
所述碳纳米管球和所述低熔点过渡金属化合物中间体的质量比为1:1-3:1。
步骤(2)所述复合碳纳米管球的制备过程中，溶剂/水热反应温度为40-90℃，反应时间为20-80mins，并采取抽滤洗涤的方式进行固液分离，得到的滤饼置于50-60℃的真空干燥箱中过夜烘干。
步骤(3)的红磷的前驱体红磷为60-100目的粉末状态，或为10-20目的微球颗粒状态；
所述红磷球磨过程中，红磷与不锈钢球以1:10-1:50的质量比装入不锈钢球罐中，在氮气气氛下以300-500rpm的转速球磨1-5h，水热处理过程中水热反应温度为150-200℃，反应时间为10-20h。
步骤(4)中红磷分散液的质量浓度为10％-20％；复合碳纳米管球粉体材料在溶液中的质量浓度为10％-20％；红磷与复合碳纳米管球粉体材的质量比为1:1-3:1。
步骤(4)中溶剂/水热反应温度为150-500℃，反应时间为20-60mins。
本发明将所述制备得到的基于红磷的碳纳米管掺杂的磷碳复合负极材料作为锂离子 电池负极的应用。
高容量、高倍率锂离子电池的组装步骤如下，将上述制备的磷碳复合负极材料与粘结剂(PVDF)和乙炔黑(AB)按质量比为8:1:1混合，在NMP溶剂中混浆均匀，涂覆在铜箔上，80℃真空干燥后冲片作为工作电极，以金属锂片为对电极，以1.0M LiTFSI in DOL:DME(V:V＝1:1)+1.0wt.％LiNO3为实验电解液体系进行扣式电池(半电池)组装并进行充放电循环测试。
实施例1
1.1 SnS2纳米片中间体溶液的制备：取摩尔比为1:1的四氯化锡和硫代乙酰胺溶于高纯度乙醇溶液中，并以300rpm的转速搅拌充分混合均匀，在60℃下反应30mins后得到2wt.％SnS2中间体溶液待用；
1.2 SnS2@CNT复合材料的制备：以2％的质量分数将碳纳米管(CNT管径为15-25nm，管长为100-150μm)浸泡在上述SnS2中间体溶液中，并在300rpm转速下持续加热至60℃，反应40mins，待样品冷却至室温后，利用高纯度乙醇多次洗涤抽滤收集所得样品。最后，将获得的样品放置于50℃的真空烘箱中干燥过夜，得到SnS2@CNT复合碳管球粉体材料；
1.3制备碳纳米管球分散液：称取上述SnS2@CNT复合碳管球粉体以质量分数2％分散在乙醇/去离子水的混合溶剂中，超声分散50mins，得到均匀的复合碳纳米管球分散液；
1.4红磷分散液的制备：将红磷分散于去离子水中进行球磨，红磷与不锈钢球以1:30的质量比装入不锈钢球罐中，在氮气气氛下以300rpm的转速球磨1h后转入反应釜中，于200℃下水热处理12h，产物置于50℃真空干燥箱中过夜烘干，将烘干的红磷以2％的质量分数分散在乙醇/去离子水的混合溶剂中，超声分散80mins，得到均匀的红磷分散液；
1.5分散液混合反应并提纯：将上述红磷分散液按红磷/碳纳米管质量比2:1加入到复合碳纳米管分散液球中超声分散50mins，将所获得的混合液装入反应釜中进行水热反应，反应温度为200℃，反应时间为60mins，待冷却至室温后将上层清液移除，将下层沉积的固相物质离心洗涤数次，得到复合磷碳负极材料；
1.6复合磷碳负极材料的冷冻干燥：将上述所获得的复合磷碳负极材料放入-80℃冷冻干燥机冻干，得到掺杂修饰的磷碳复合负极材料(P-CNT@SnS2)；
1.7高容量、高倍率锂离子电池的组装：将上述过程中制备的磷碳复合负极材料与粘结剂(PVDF)和乙炔黑(AB)按质量比为8:1:1混合，在NMP溶剂中混浆均匀，涂覆在铜箔上，80℃真空干燥后冲片作为工作电极，以金属锂片为对电极，以1.0M LiTFSI in DOL:DME(V:V＝1:1)+1.0wt.％LiNO3为实验电解液体系进行扣式电池(半电池)组装并进 行充放电循环测试；
1.8图1为磷碳复合负极材料的制备示意图。将碳管球(或者改性碳管球，所述的是改性碳管球经过氨基化、羧基化、羟基化、磷基化、石墨化中的任意一种或多种进行表面修饰得到的粒径及骨架结构不同的材料)置于过渡金属纳米掺杂液中得到过渡金属纳米片掺杂的碳管球，再放入经球磨处理后的小粒径红磷分散液中恒温水浴反应得到磷碳复合负极材料。
1.9图2为碳管球/红磷/磷碳复合材料光学图。可以看到碳管球/红磷/磷碳复合材料均匀分散于溶剂中，并未观察到团聚沉淀现象。
1.10图3为CNT和P-CNT@SnS2材料SEM图。CNT呈现出纳米管组装而成的球状结构，P-CNT@SnS2上可以观察到碳纳米管微球与小粒径红磷均匀混合，实现共同包覆。
1.11图4为碳管球/红磷/磷碳复合材料掺杂SnS2前后XRD图。其中碳管球/掺杂前后红磷碳管复合材料均在26.5°出现了典型的碳宽峰，同时对比掺杂前后红磷碳管复合材料的XRD图，掺杂后材料在28.5°和51.1°出现了两个归属于SnS2的特征峰，表明SnS2成功掺入碳管球内部。
1.12图5为碳管球/掺杂SnS2磷碳复合材料的SEM图和电位柱状图。当掺杂量由0％增加至10％时，材料由碳管球形成的凹凸不平的表面逐渐变得平滑，当掺杂量增加至15％时，表面再次变得粗糙同时可以观察到碳管球尺寸变大，这可能是由于过高的掺杂量导致碳管球内部结构发生变化所致。从电位柱状图可以看出，SnS2中间体掺杂电极材料电位均有不同程度的下降，而当掺杂量为10％时，电位最低(65mV)，说明锂锡合金与金属锂之间存在0.3V左右的电位差，使得掺杂SnS2的碳纳米管球具备优良的亲锂性，有利于在搅拌过程中将熔融金属锂均匀地浸入碳管球内部通道中，获得更加饱满致密的磷碳复合微球颗粒，具有更佳的比容量和倍率性能，同时避免了金属锂与电解液发生副反应，有效提高了电解液和活性锂的利用率。
1.13图6为红磷/碳管和SnS2@红磷/碳管材料首次放电曲线。掺杂后磷碳负极材料首次放电比容量3020mA·h·g-1，相比于掺杂前放电比容量(2355mA·h·g-1)显著提升。
1.14图7为CNT和SnS2@CNT材料的循环性能图与电位-时间曲线(附图)。在3mA cm-2的高电流密度下，经历200次循环圈数后SnS2@CNT库伦效率仍基本维持在99.6％，而CNT在100次循环圈数后库伦效率出现了明显的波动，表明SnS2@CNT材料具备着更优异的循环稳定性；而电位-时间图中也表明，与CNT(-150mV)相比，SnS2@CNT具有相对较高的电位(-71mV)，与液体电解质发生副反应性的可能性更小，能够保证更少 的电解液消耗和更长的循环寿命。
1.15图8为DFT模拟Li+与不同基底的结合能图，可以看出，Li+与掺杂SnS2三维导电碳基底具备着更低的结合能(-1.12eV)，表明其具备着更佳的亲锂性。
实施例2
2.1 Ni3S4纳米片中间体溶液的制备：取摩尔比为1:2的六水合硝酸镍和硫脲溶于无水甲醇溶液中，并以500rpm的转速搅拌充分混合均匀，在80℃下反应20mins后得到1wt.％Ni3S4中间体溶液待用，借助Ni3S4纳米片中间体的引入，可以有效降低副产物白磷的生成，提高制备工艺的安全性；
2.2 Ni3S4@CNT复合材料的制备：将碳纳米管(CNT管径为15-25nm，管长为100-150μm)置于体积比为3:1的浓H2SO4和浓HNO3溶液中,在80度下回流12个小时，产物洗涤至中性后干燥，去除碳纳米管表面杂质并带有羧基、羟基基团，更易分散于溶剂中同时有利于与Ni3S4中间体和红磷颗粒的复合。取改性后的碳管球以1％质量分数浸泡在Ni3S4中间体溶液中，并在500rpm转速下持续加热至80℃，反应40mins，待样品冷却至室温后，多次洗涤抽滤收集所得样品。最后，将获得的样品放置于50℃的真空烘箱中干燥过夜，得到Ni3S4@CNT复合碳管球粉体材料；
2.3制备碳纳米管球分散液：取上述Ni3S4@CNT复合碳管球粉体以1％的质量分数分散在无水甲醇中，超声分散30mins，得到均匀的复合碳纳米管球分散液；
2.4红磷分散液的制备：将红磷分散在去离子水中进行球磨，红磷与不锈钢球以1:20的质量比装入不锈钢球罐中，在氮气气氛下以300rpm的转速球磨2h后转入反应釜中，在150℃下水热处理20h后，置于50℃真空干燥箱中过夜烘干，将烘干的红磷分散在无水甲醇中，超声分散60mins，得到均匀的1wt.％红磷分散液；
2.5分散液混合反应并提纯：将上述红磷分散液按红磷/碳纳米管质量比3:1加入到复合碳纳米管分散液球中超声分散30mins，将所获得的混合液装入反应釜中进行水热反应，反应温度为150℃，反应时间为50mins，待冷却至室温后将上层清液移除，将下层沉积的固相物质离心洗涤数次，得到掺杂修饰的磷碳复合负极材料(P-CNT@Ni3S4)；
2.6复合磷碳负极材料的冷冻干燥：将上述所获得的复合磷碳负极材料放入-80℃冷冻干燥机冻干，得到红磷/碳纳米管复合材料；
2.7高容量、高倍率锂离子电池的组装：将上述过程中制备的磷碳复合负极材料与粘结剂(PVDF)和乙炔黑(AB)按质量比为8:1:1混合，在NMP溶剂中混浆均匀，涂覆在铜箔上，80℃真空干燥后冲片作为工作电极，以金属锂片为对电极，以1.0M LiTFSI in  DOL:DME(V:V＝1:1)+1.0wt.％LiNO3为实验电解液体系进行扣式电池(半电池)组装并进行充放电循环测试；
2.8图9为CNT和P-CNT@Ni3S4材料SEM图。在P-CNT@Ni3S4材料的SEM图可以观察到碳纳米管微球与红磷充分混合，增大红磷材料的导电性，同时抑制充放电过程中的体积膨胀。
实施例3
3.1 CoSe2纳米片中间体溶液的制备：取摩尔比为1:2的氯化钴和硒粉溶于无水乙醇溶液中，并以400rpm的转速搅拌以充分混合均匀，在60℃下反应50mins后得到0.5wt.％CoSe2中间体溶液待用；
3.2 CoSe2@CNT复合材料的制备：将碳纳米管(CNT管径为15-25nm，管长为100-150μm)分散于含有甲基磷酸的甲醇溶剂中，磁力搅拌60mins使其混合均匀，随后置于110℃的油浴锅中继续搅拌，直至甲醇完全挥发，通过高温还原氧化使含磷基团修饰到碳管球表面，具备的化学吸附和催化作用有利于提高材料的电化学性能。以0.5％的质量分数将含磷基团修饰的碳管球浸泡在上述CoSe2中间体溶液中，并在400rpm转速下持续加热至50℃，反应80mins，待样品冷却至室温后，多次洗涤抽滤收集所得样品。最后，将获得的样品放置于50℃的真空烘箱中干燥过夜，得到CoSe2@CNT复合碳管球粉体材料；
3.3制备碳纳米管球分散液：将上述CoSe2@CNT复合碳管球粉体分散在无水乙醇中，超声分散40mins，得到均匀的0.5wt.％复合碳纳米管球分散液；
3.4红磷分散液的制备：将红磷分散在去离子水中球磨，红磷与不锈钢球以1:40的质量比装入不锈钢球罐中，在氮气气氛下以400rpm的转速球磨4h后转入反应釜中，在170℃下水热处理16h后，置于50℃真空干燥箱中过夜烘干，将烘干的红磷分散在无水乙醇中，超声分散80mins，得到均匀的0.5wt.％红磷分散液；
3.5分散液混合反应并提纯：将上述红磷分散液按红磷/碳纳米管质量比3:1加入到复合碳纳米管分散液球中超声分散40mins，将所获得的混合液装入反应釜中进行水热反应，反应温度为180℃，反应时间为40mins，待冷却至室温后将上层清液移除，将下层沉积的固相物质离心洗涤数次，得到掺杂修饰的磷碳复合负极材料(P-CNT@CoSe2)；
3.6复合磷碳负极材料的冷冻干燥：将上述所获得的复合磷碳负极材料放入-80℃冷冻干燥机冻干，得到红磷/碳纳米管复合材料；
3.7高容量、高倍率锂离子电池的组装：将上述过程中制备的磷碳复合负极材料与粘结剂(PVDF)和乙炔黑(AB)按质量比为8:1:1混合，在NMP溶剂中混浆均匀，涂覆在铜箔 上，80℃真空干燥后冲片作为工作电极，以金属锂片为对电极，以1.0M LiTFSI in DOL:DME(V:V＝1:1)+1.0wt.％LiNO3为实验电解液体系进行扣式电池(半电池)组装并进行充放电循环测试。
3.8图10为CNT和P-CNT@CoSe2材料SEM图。形成磷碳复合材料后有碳管球附着于红磷材料表面，同时存在小粒径红磷附着于碳管球内部。
实施例4
4.1 GeS2纳米片中间体溶液的制备：取摩尔比为1:3的氟化锗和硫代乙酰胺溶于无水乙醚溶液中，并以1000rpm的转速搅拌以充分混合均匀，在100℃下反应40mins后得到1wt.％GeS2溶液待用；
4.2 GeS2@CNT复合材料的制备：将碳纳米管(CNT管径为15-25nm，管长为100-150μm)置于管式炉中，于惰性气氛下600℃焙烧4h，增强碳管球的石墨化强度，利用碳纳米管的三维骨架结构有效抑制磷基材料在充放电循环过程中体积膨胀问题，随后将焙烧后的碳管球按1％的质量分数浸泡在GeS2中间体溶液中，并在1000rpm转速下持续加热至90℃，反应60mins，待样品冷却至室温后，多次洗涤抽滤收集所得样品。最后，将获得的样品置于50℃的真空烘箱中干燥过夜，得到GeS2@CNT复合碳管球粉体材料；
4.3制备碳纳米管球分散液：将上述GeS2@CNT复合碳管球粉体分散在无水乙醚中，超声分散80mins，得到均匀的1wt.％复合碳纳米管球分散液；
4.4红磷分散液的制备：将红磷在去离子水中球磨，红磷与不锈钢球以1:30的质量比装入不锈钢球罐中，在氮气气氛下以350rpm的转速球磨5h后转入反应釜中，在180℃下水热处理10h后，置于50℃真空干燥箱中过夜烘干，将烘干的红磷以1％的质量分数分散在无水乙醚中，超声分散40mins，得到均匀的红磷分散液；
4.5分散液混合反应并提纯：将上述红磷分散液按红磷/碳纳米管质量比2:1加入到复合碳纳米管分散液球中，继续超声分散45mins，将所获得的混合液装入反应釜中进行水热反应，反应温度为300℃，反应时间为30mins，待冷却至室温后将上层清液移除，将下层沉积的固相物质离心洗涤数次，得到复合磷碳负极材料；
4.6复合磷碳负极材料的冷冻干燥：将上述所获得的复合磷碳负极材料放入-80℃冷冻干燥机冻干，得到掺杂修饰的磷碳复合负极材料(P-CNT@GeS2)；
4.7高容量、高倍率锂离子电池的组装：将上述过程中制备的磷碳复合负极材料与粘结剂(PVDF)和乙炔黑(AB)按质量比为8:1:1混合，在NMP溶剂中混浆均匀，涂覆在铜箔上，80℃真空干燥后冲片作为工作电极，以金属锂片为对电极，以1.0M LiTFSI in  DOL:DME(V:V＝1:1)+1.0wt.％LiNO3为实验电解液体系进行扣式电池(半电池)组装并进行充放电循环测试；
4.8图11为CNT和P-CNT@GeS2材料SEM图。
实施例5
5.1 TiP纳米片中间体溶液的制备：取摩尔比为1:1的硫酸钛和次磷酸钠溶于无水乙醚溶液中，以1500rpm的转速搅拌以充分混合均匀，在70℃下反应20mins后得到2wt.％的TiP中间体溶液待用；
5.2 TiP@CNT复合材料的制备：将碳纳米管(CNT管径为15-25nm，管长为100-150μm)置于管式炉中，于惰性气氛下800℃焙烧2h，增强碳管球的石墨化强度，随后将焙烧后的碳管球按2％的质量分数浸泡在TiP中间体溶液中，以1500rpm的转速持续加热至70℃，反应50mins，待样品冷却至室温后，多次洗涤抽滤收集所得样品。最后，将获得的样品放置于50℃的真空烘箱中干燥过夜，得到TiP@CNT复合碳管球粉体材料；
5.3制备碳纳米管球分散液：将上述TiP@CNT复合碳管球粉体以2％的质量分数分散在无水乙醚中，超声分散90mins，得到均匀复合碳纳米管球分散液；
5.4红磷分散液的制备：将红磷分散在去离子水中球磨，红磷与不锈钢球以1:30的质量比装入不锈钢球罐中，在氮气气氛下以400rpm的转速球磨2h后转入反应釜中，在180℃下水热处理15h后，置于50℃真空干燥箱中过夜烘干，将烘干的红磷按质量分数2％分散在无水乙醚中，超声分散40mins，得到均匀的红磷分散液；
5.5分散液混合反应并提纯：将上述红磷分散液按红磷/碳纳米管质量比1:1加入到复合碳纳米管分散液球中，继续超声分散30mins，将所获得的混合液装入反应釜中进行水热反应，反应温度为150℃，反应时间为40mins，待冷却至室温后将上层清液移除，将下层沉积的固相物质离心洗涤数次，得到掺杂修饰的磷碳复合负极材料(P-CNT@TiP)；
5.6复合磷碳负极材料的冷冻干燥：将上述所获得的复合磷碳负极材料放入-80℃冷冻干燥机冻干，得到红磷/碳纳米管复合材料；
5.7高容量、高倍率锂离子电池的组装：将上述过程中制备的磷碳复合负极材料与粘结剂(PVDF)和乙炔黑(AB)按质量比为8:1:1混合，在NMP溶剂中混浆均匀，涂覆在铜箔上，80℃真空干燥后冲片作为工作电极，以金属锂片为对电极，以1.0M LiTFSI in DOL:DME(V:V＝1:1)+1.0wt.％LiNO3为实验电解液体系进行扣式电池(半电池)组装并进行充放电循环测试；
5.8图12为CNT和P-CNT@TiP材料SEM图。
实施例6
实施步骤同实施例1，仅非金属源为亚碲酸钠，步骤6.1中得到2wt.％SnTe2，其他步骤同实施例1，得到掺杂修饰的磷碳复合负极材料(P-CNT@SnTe2)。
实施例7
实施步骤同实施例1，仅非金属源为亚硒酸钠，金属源为六水合硝酸镍，步骤6.1中得到2wt.％NiSe，其他步骤同实施例1，得到掺杂修饰的磷碳复合负极材料(P-CNT@NiSe)。
实施例8
实施步骤同实施例1，对碳纳米管(CNT)进行了氨基化表面修饰，得到氨基化改性碳管球/红磷/磷碳复合材料NH3-P-CNT@SnS2。
实施例9
实施步骤同实施例1，对碳纳米管球进行了羧基化表面修饰，得到石墨化改性碳管球/红磷/磷碳复合材料COOH-P-CNT@SnS2。
实施例10
实施步骤同实施例1，对碳纳米管球进行了磷基化表面修饰，得到磷基化改性碳管球/红磷/磷碳复合材料P-P-CNT@SnS2。
通过测试150次循环圈数后的容量保持率来确定各实施例和对比例所制备材料的循环稳定性，由于Li+在钛上较低的沉积过电位，使锂更易浸入碳管球内部，形成更为致密饱满的磷碳复合微球，提高首次充放电过程中对锂的利用率，进而提升磷碳复合电极的比容量和循环性能，具体如表1所示：
表1各实施例和对比例所制备材料的循环稳定性

实施例11是指实施例1中未经SnS2修饰的磷碳负极。
实施例12是指实施例8中未经SnS2修饰的SnS2的磷碳负极。
应当理解的是，上述实施例仅为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围。凡根据本发明精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围之内。

Claims (22)

  1. 基于红磷的碳纳米管掺杂的磷碳复合负极材料，其特征在于，包括红磷和复合碳纳米管球。
  2. 根据权利要求1所述的基于红磷的碳纳米管掺杂的磷碳复合负极材料，其特征在于，红磷与复合碳纳米管球的质量比为1:1-3:1。
  3. 根据权利要求2所述的基于红磷的碳纳米管掺杂的磷碳复合负极材料，其特征在于，红磷和复合碳纳米管球在溶剂混合后经热反应得到的产物，复合碳纳米管球在溶液中的质量浓度为10％-20％。
  4. 根据权利要求3所述的基于红磷的碳纳米管掺杂的磷碳复合负极材料，其特征在于，热反应过程中所述的溶剂包括去离子水、无水乙醇、无水甲醇、无水乙醚中的至少一种。
  5. 根据权利要求4所述的基于红磷的碳纳米管掺杂的磷碳复合负极材料，其特征在于，所述的复合碳纳米管球内部掺杂镶嵌低熔点过渡金属化合物(≤200℃)；低熔点过渡金属化合物的质量浓度为0.2-3％。
  6. 根据权利要求5所述的基于红磷的碳纳米管掺杂的磷碳复合负极材料，其特征在于，所述的低熔点过渡金属化合物包括锡、钛、镉、铁、钴、铬、锰、锗、或镍的金属源与非金属源进行反应所得，所述非金属源和所述金属源摩尔比为1:1-3:1。
  7. 根据权利要求6所述的基于红磷的碳纳米管掺杂的磷碳复合负极材料，其特征在于，所述的金属盐包括锡、钛、镉、铁、钴、铬、锰、锗、或镍的氟化物、氯化物、硝酸盐、硫酸盐或碳酸盐；所述的非金属源包括硫化物、硒化物、碲化物、或磷化物中的任意一种或多种；
    所述硫化物包括升华硫、硫代乙酰胺、或硫脲中的至少一种；
    所述硒化物包括单质硒粉、或亚硒酸钠中的至少一种；
    所述碲化物包括单质碲粉、或亚碲酸钠中的至少一种；
    所述磷化物包括次磷酸钠、磷酸、磷酸二氢铵或磷酸氢二铵中的至少一种。
  8. 根据权利要求5所述的基于红磷的碳纳米管掺杂的磷碳复合负极材料，其特征在于，所述碳纳米管球还可以是经过氨基化、羧基化、羟基化、磷基化、或石墨化中的任意一种或多种进行表面修饰得到的粒径及骨架结构不同的材料。
  9. 基于红磷的碳纳米管掺杂的磷碳复合负极材料的制备方法，其特征在于，包括以下步骤：
    (1)低熔点过渡金属化合物中间体溶液的制备：将金属源和非金属源溶于溶剂中，溶剂/水热反应后得到低熔点过渡金属化合物中间体溶液；
    (2)复合碳纳米管球的制备：将碳纳米管球分散于所述的低熔点过渡金属化合物中间体溶液中，溶剂/水热反应后实行固液分离，滤饼烘干后得到复合碳纳米管球粉体材料；
    (3)红磷分散液的制备：红磷球磨后进行水热处理，烘干后的固体物质分散于溶剂中得到均匀的红磷分散液；
    (4)复合磷碳负极材料的制备：将所述的复合碳纳米管球粉体材料超声分散于溶剂中，加入所述的红磷分散液，超声处理后进行溶剂/水热反应，离心洗涤后收集固体物质冷冻干燥，得到复合磷碳负极材料。
  10. 根据权利要求9所述的基于红磷的碳纳米管掺杂的磷碳复合负极材料的制备方法，其特征在于，步骤(1)中所述金属源包括锡、钛、镉、铁、钴、铬、锰、锗、或镍的氟化物、氯化物、硝酸盐、硫酸盐和碳酸盐中的任意一种。
  11. 根据权利要求10所述的基于红磷的碳纳米管掺杂的磷碳复合负极材料的制备方法，其特征在于，所述非金属源包括硫化物、硒化物、碲化物和磷化物中的一种；
    优选地，所述硫化物包括升华硫、硫代乙酰胺或硫脲中的至少一种；
    所述硒化物包括单质硒粉或亚硒酸钠中的至少一种；
    所述碲化物包括单质碲粉或亚碲酸钠中的至少一种；
    所述磷化物包括次磷酸钠、磷酸、磷酸二氢铵或磷酸氢二铵中的至少一种。
  12. 根据权利要求11所述的基于红磷的碳纳米管掺杂的磷碳复合负极材料的制备方法，其特征在于，所述非金属源和所述金属源摩尔比为1:1-3:1。
  13. 根据权利要求12所述的基于红磷的碳纳米管掺杂的磷碳复合负极材料的制备方法，其特征在于，所述溶剂包括去离子水、无水乙醇、无水甲醇或无水乙醚中的至少一种。
  14. 根据权利要求13所述的基于红磷的碳纳米管掺杂的磷碳复合负极材料的制备方法，其特征在于，所述低熔点过渡金属化合物中间体质量浓度为0.2-3％。
  15. 根据权利要求14所述的基于红磷的碳纳米管掺杂的磷碳复合负极材料的制备方法，其特征在于，所述低熔点过渡金属化合物中间体溶液的制备过程中，溶剂/水热反应温度为50-100℃，反应时间为5-50mins，所述溶剂/水热反应时采用磁力搅拌，转速为300-2000rpm。
  16. 根据权利要求15所述的基于红磷的碳纳米管掺杂的磷碳复合负极材料的制备方法，其特征在于，所述的碳纳米管球的前驱体为碳纳米纤维、碳纳米管、介孔碳、多孔碳、常用导电剂炭黑和Super P中的任意一种；
    所述碳纳米管球还可以是经过氨基化、羧基化、羟基化、磷基化、或石墨化中的任意一种或 多种进行表面修饰得到的粒径及骨架结构不同的材料。
  17. 根据权利要求16所述的基于红磷的碳纳米管掺杂的磷碳复合负极材料的制备方法，其特征在于，所述碳纳米管球和所述低熔点过渡金属化合物中间体的质量比为1:1-3:1。
  18. 根据权利要求9所述的基于红磷的碳纳米管掺杂的磷碳复合负极材料的制备方法，其特征在于，步骤(2)所述复合碳纳米管球的制备过程中，溶剂/水热反应温度为40-90℃，反应时间为20-80mins，并采取抽滤洗涤的方式进行固液分离，得到的滤饼置于50-60℃的真空干燥箱中过夜烘干。
  19. 根据权利要求18所述的基于红磷的碳纳米管掺杂的磷碳复合负极材料的制备方法，其特征在于，步骤(3)的红磷的前驱体红磷为60-100目的粉末状态，或为10-20目的微球颗粒状态；
    红磷球磨过程中，红磷与不锈钢球以1:10-1:50的质量比装入不锈钢球罐中，在氮气气氛下以300-500rpm的转速球磨1-5h，水热处理过程中水热反应温度为150-200℃，反应时间为10-20h。
  20. 根据权利要求19所述的基于红磷的碳纳米管掺杂的磷碳复合负极材料的制备方法，其特征在于，步骤(4)中红磷分散液的质量浓度为10％-20％；复合碳纳米管球粉体材料在溶液中的质量浓度为10％-20％；红磷与复合碳纳米管球粉体材料的质量比为1:1-3:1。
  21. 根据权利要求20所述的基于红磷的碳纳米管掺杂的磷碳复合负极材料的制备方法，其特征在于，步骤(4)中溶剂/水热反应温度为150-500℃，反应时间为20-60mins。
  22. 一种锂离子电池负极材料，其特征在于，采用权利要求21所述制备得到的基于红磷的碳纳米管掺杂的磷碳复合负极材料。
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