WO2016008455A2 - 一种多元复合负极材料、其制备方法及包含其的锂离子电池 - Google Patents

一种多元复合负极材料、其制备方法及包含其的锂离子电池 Download PDF

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WO2016008455A2
WO2016008455A2 PCT/CN2015/087266 CN2015087266W WO2016008455A2 WO 2016008455 A2 WO2016008455 A2 WO 2016008455A2 CN 2015087266 W CN2015087266 W CN 2015087266W WO 2016008455 A2 WO2016008455 A2 WO 2016008455A2
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precursor
graphite
combination
nano
organic
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French (fr)
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WO2016008455A3 (zh
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岳敏
何鹏
李胜
任建国
黄友元
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深圳市贝特瑞新能源材料股份有限公司
惠州市贝特瑞新材料科技有限公司
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Priority to JP2017502234A priority Critical patent/JP6563477B2/ja
Priority to US15/326,829 priority patent/US10522834B2/en
Publication of WO2016008455A2 publication Critical patent/WO2016008455A2/zh
Publication of WO2016008455A3 publication Critical patent/WO2016008455A3/zh

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Definitions

  • the present invention relates to the field of lithium ion battery anode materials, and in particular, to a multicomponent composite anode material and a preparation method thereof, and a lithium ion battery comprising the same.
  • Lithium-ion batteries have been widely used in portable electronic products and electric vehicles because of their high operating voltage, long cycle life, no memory effect, low self-discharge, and environmental friendliness.
  • commercial lithium-ion batteries mainly use graphite-based anode materials, but its theoretical specific capacity is only 372 mAh / g, which can not meet the demand for high energy density of lithium-ion batteries in the future.
  • researches at home and abroad have reported that metal elements, metal oxides and metal alloy compounds capable of forming alloys with lithium, such as Si, Sn, Ge, Pb, SiO, SnO, SbSn, Mg2Si, etc., have a high specific capacity.
  • the battery capacity of these materials is attenuated during use, which limits their practical application.
  • the metal bulk, alloy and metal oxide anode material deintercalation lithium volume expansion shrinkage caused by material damage and pulverization, which is the main reason for the rapid decay of material capacity. Therefore, suppressing the volume expansion of the material and improving the structural stability of the material are of great significance for improving the cycle stability of the alloy and the metal oxide negative electrode material.
  • the volume expansion of materials is improved mainly by nanocrystallization, alloying, and multi-component compounding (combination with active or inactive materials).
  • CN 103199223A discloses a Cu-Cr-Si ternary anode material and a preparation method thereof.
  • the invention combines copper powder, chromium powder and silicon powder to prepare an alloy ingot by mixing and calcining, and then pulverizing to obtain Cu having a size below micrometer.
  • -Cr-Si ternary alloy powder the obtained material has high capacity and good cycle performance, but the continuous phase formed by silicon and chromium in the ternary material prepared by the method is still large, and copper, chromium and silicon are not used. Evenly dispersed.
  • CN 103560249A discloses a multi-component composite anode material and preparation method thereof Method, which adds silicon powder, carbon nanotubes, expanded graphite to a polyvinyl alcohol or polyethylene glycol aqueous system, and then is stirred and calcined to obtain nano silicon powder, carbon nanotubes, expanded graphite and no A multi-component composite material composed of shaped carbon, the composite material has good conductivity and high capacity, but in the preparation process of the method, it is difficult to sufficiently disperse the nano-silica powder, thereby causing the first charge and discharge efficiency of the material to be low.
  • one of the objects of the present invention is to provide a multi-component composite anode material which has good electrical conductivity, high capacity, high first coulombic efficiency, and excellent cycle performance.
  • a multi-component composite anode material is a multi-shell core-shell structure, the inner core is composed of graphite and a nano-active material coated on the surface of the graphite; the outer layer of the core is in turn: the first shell layer is electrically conductive The carbon material, the second shell layer is a nano active material, and the third shell layer is a conductive carbon material coating layer.
  • the anode material contains 1 to 40% by weight of the nano-active material, 30 to 80% by weight of graphite, and 10 to 50% by weight of the conductive carbon material.
  • the multicomponent composite negative electrode material has a median diameter of 5.0 to 45.0 ⁇ m, preferably 8.0 to 35.0 ⁇ m, and more preferably 10.0 to 25.0 ⁇ m.
  • the multicomponent composite negative electrode material has a specific surface area of 1.0 to 20.0 m 2 /g, preferably 1.5 to 8.0 m 2 /g.
  • the multicomponent composite negative electrode material has a powder compaction density of 1.0 to 2.0 g/cm 3 , preferably 1.1 to 1.7 g/cm 3 .
  • the graphite is natural crystalline graphite, natural cryptocrystalline graphite, natural crystalline vein graphite, One or a combination of at least two of artificial graphite or conductive graphite.
  • the shape of the graphite is one or a combination of at least two of a sheet shape, a spherical-like block shape, or a spherical shape.
  • the graphite has a median diameter of 5.0 to 30.0 ⁇ m, preferably 8.0 to 25.0 ⁇ m, and more preferably 10.0 to 20.0 ⁇ m.
  • the nano-active material is a material that is electrochemically active to lithium, and is preferably a combination of one or at least two of an active metal element, an active metal element, a metal oxide, and a metal alloy compound, more preferably Silicon elemental, tin elemental, bismuth simple, bismuth simple, aluminum elemental, magnesium elemental, zinc elemental, singular, cadmium, titanium oxide, silicon oxide, tin oxide, cobalt oxide, iron oxide, copper oxide A combination of one or at least two of manganese oxide, nickel oxide, tin antimony alloy, indium antimony alloy, silver antimony alloy, aluminum antimony alloy, silver tin alloy, and silicon magnesium compound.
  • the nanoactive material has a median diameter of from 30.0 to 300.0 nm, preferably from 25.0 to 250.0 nm, and more preferably from 20.0 to 200.0 nm.
  • the conductive carbon material is one or a combination of at least two of carbon nanotubes, graphene, conductive graphite, carbon fibers, nano-graphite, conductive carbon black or organic pyrolysis carbon.
  • a second object of the present invention is to provide a method for preparing the multi-component composite anode material of the present invention, comprising the following steps:
  • the third precursor is coated and modified to obtain a multicomponent composite anode material.
  • step (5) pulverizes the composite material obtained in step (4), After sieving and demagnetization, a multicomponent composite negative electrode material having a median diameter of 5.0 to 45.0 ⁇ m was obtained.
  • the coating in the steps (1) and (3) is carried out by using one or a combination of at least two of a vapor phase coating method, a liquid phase coating method or a solid phase coating method.
  • the vapor phase coating method comprises the steps of: placing the graphite of the step (1) or the second precursor of the step (2) in a rotary kiln, passing a protective gas, and raising the temperature to The nano active material vapor is introduced at 600 to 1500 ° C, and the temperature is maintained for 0.5 to 10.0 hours, and then cooled to room temperature to obtain a first precursor of the step (1) or a third precursor of the step (3).
  • the nano active material vapor is obtained by sublimation of a nano active material or cracking of an organic gas.
  • the rotary furnace speed is from 0.1 to 5.0 r/min.
  • the heating rate is 1.0 to 20.0 ° C / min.
  • the nano active material has a flow rate of 0.1 to 1.0 L/min.
  • the liquid phase coating method comprises the steps of: dispersing the nano active material, the dispersing agent, and the graphite of the step (1) or the second precursor of the step (2) in an organic solvent, and drying.
  • the first precursor of step (1) or the third precursor of step (3) is obtained.
  • the dispersing agent is sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate, triethylhexylphosphoric acid, sodium lauryl sulfate, methylpentanol, cellulose derivative, polyacrylamide, ancient Glue, fatty acid polyethylene glycol ester, cetyltrimethylammonium bromide, polyethylene glycol p-octyl phenyl ether, polyacrylic acid, polyvinylpyrrolidone, polyoxyethylene sorbitan monooleate And a combination of one or at least two of p-ethylbenzoic acid and polyetherimide.
  • the organic solvent is one or a combination of at least two of an alcohol, a ketone and an ether.
  • the step of the solid phase coating method is: the nano active material and the graphite of the step (1) or the second precursor of the step (2) are fused in a fusion machine to obtain a step.
  • the fusion machine has a rotational speed of 500 to 3000 r/min and a tool gap width of 0.01 to 0.5 cm.
  • the fusion time is not less than 0.5 h.
  • the surface composite modification in the step (2) is mechanical physical modification, gas phase chemical modification or liquid phase chemical modification.
  • the mechanical physical modification step is: the conductive carbon material and the first precursor of the step (1) are fused in a fusion machine, and then placed in the reactor, and the protective property is introduced.
  • the gas is heated to 600 to 1200 ° C, kept for 0.5 to 10.0 h, and then cooled to room temperature to obtain the second precursor described in the step (2).
  • the speed of the fusion machine is 500 to 3000 r/min.
  • the fusion machine has a gap width of 0.01 to 0.5 cm.
  • the fusion time is at least 0.5 h.
  • the gas phase chemical modification step is: placing the first precursor in the step (1) in a rotary kiln, introducing a protective gas, heating up to 600 to 1200 ° C, and introducing organic
  • the carbon source gas is kept at a temperature of 0.5 to 10.0 h, and then cooled to room temperature to obtain a second precursor according to the step (2).
  • the organic carbon source gas is one or a combination of at least two of a hydrocarbon and/or one to three ring aromatic hydrocarbon derivatives; preferably methane, ethylene, acetylene, benzene, toluene, and two One or a combination of at least two of toluene, styrene, and phenol.
  • the rotary furnace has a rotational speed of 0.1 to 5.0 r/min.
  • the flow rate of the organic carbon source gas is 0.1 to 2.0 L/min.
  • the liquid phase chemical modification step is: dispersing the first precursor and the organic substance in the step (1) in an organic solvent system, drying, and then placing in the reactor, and protecting the solution. Gas, heat up to 600 ⁇ 1200 ° C, keep warm for 0.5 ⁇ 10.0h, then cool to room temperature, get the step The second precursor of the step (2).
  • the organic solvent is one or a combination of at least two of an ether, an alcohol and a ketone.
  • the organic substance is a combination of one or at least two of a polymer, a saccharide, an organic acid, a pitch, and a polymer material, and is preferably an epoxy resin, a phenol resin, a furfural resin, a urea resin, or a polyvinyl alcohol.
  • the temperature rise rate of the reactor in the mechanical physical modification, the gas phase chemically modified rotary kiln, and the liquid phase chemically modified reactor is 0.5 to 20.0 ° C / min.
  • the reactor is a vacuum furnace, a box furnace, a rotary kiln, a roller kiln, a pusher kiln or a tube furnace.
  • the coating modification in the step (4) is carried out by gas phase coating modification, liquid phase coating modification or solid phase coating modification.
  • the gas phase coating modification step is: placing the third precursor in the step (3) in a rotary kiln, introducing a protective gas, and heating the temperature to 600 to 1200 ° C, and introducing The organic carbon source gas is kept at a temperature of 0.5 to 10.0 h, and then cooled to room temperature to obtain the multicomponent composite negative electrode material of the step (4).
  • the organic carbon source gas is one or a combination of at least two of a hydrocarbon and/or one to three ring aromatic hydrocarbon derivatives; preferably methane, ethylene, acetylene, benzene, toluene, and two One or a combination of at least two of toluene, styrene, and phenol.
  • the rotary furnace has a rotational speed of 0.1 to 5.0 r/min.
  • the flow rate of the organic carbon source gas is 0.1 to 2.0 L/min.
  • the liquid phase coating modification step is: dispersing the third precursor of the step (3) and the organic substance in an organic solvent system, drying, and then placing in the reactor, and introducing Guarantee
  • the protective gas is heated to 600 to 1200 ° C, kept for 0.5 to 10.0 h, and then cooled to room temperature to obtain the multicomponent composite negative electrode material of the step (4).
  • the organic solvent is one or a combination of at least two of an ether, an alcohol and a ketone.
  • the step of solid phase coating modification is: mixing the third precursor of the step (3) and the organic matter in a VC mixer, and then placing it in the reactor for protection.
  • the gas is heated to 600 to 1200 ° C, kept for 0.5 to 10.0 h, and then cooled to room temperature to obtain a step (4) multicomponent composite anode material.
  • the speed of the VC mixer is 500 to 3000 r/min.
  • the mixing time is not less than 0.5 h.
  • the vapor phase coating modified rotary kiln, the liquid phase coating modified reactor, and the solid phase coating modified reactor have a heating rate of 0.5 to 20.0 ° C / min.
  • the reactor is a vacuum furnace, a box furnace, a rotary kiln, a roller kiln, a pusher kiln or a tube furnace.
  • the organic substance is a combination of one or at least two of a polymer, a saccharide, an organic acid, a pitch, and a polymer material, and is preferably an epoxy resin, a phenol resin, a furfural resin, a urea resin, or a polyvinyl alcohol.
  • the organic carbon source is in the form of a powder having a median diameter of 0.1 to 25.0 ⁇ m, particularly preferably 0.5 to 8.0 ⁇ m.
  • the protective gas is one or a combination of at least two of nitrogen, helium, neon, argon, helium and neon.
  • a third object of the present invention is to provide a lithium ion battery, wherein the negative electrode tab is a multi-component composite anode material, a conductive agent and a binder according to the present invention in a solvent percentage of 91 to 94:1 to 3:3 to 6 in a solvent. Mixed, It is coated on a copper foil current collector and dried under vacuum.
  • the positive electrode active material used in the positive electrode tab of the lithium ion battery is a ternary material, a lithium rich material, lithium cobaltate, lithium nickelate, lithium spinel manganate, lithium layer lithium manganate or lithium iron phosphate.
  • a ternary material a lithium rich material, lithium cobaltate, lithium nickelate, lithium spinel manganate, lithium layer lithium manganate or lithium iron phosphate.
  • the conductive agent is graphite powder and/or nano conductive liquid.
  • the nano-conductive liquid is composed of 0.5-20% by weight of a nano-carbon material and a dispersion solvent.
  • the nanocarbon material is one or a combination of at least two of graphene, carbon nanotubes, nanocarbon fibers, fullerenes, carbon black, and acetylene black.
  • the number of graphite sheets of the graphene is between 1 and 100.
  • the carbon nanotubes and the nanocarbon fibers have a diameter of 0.2 to 500 nm.
  • the fullerene, carbon black and acetylene black have a particle diameter of from 1 to 200 nm.
  • the binder is one or a combination of at least two of a polyimide resin, an acrylic resin, polyvinylidene fluoride, polyvinyl alcohol, sodium carboxymethyl cellulose or styrene-butadiene rubber.
  • the lithium ion battery is of a conventional aluminum shell, steel shell, or soft pack lithium ion battery.
  • the multi-component composite anode material of the invention has successfully prepared a core-shell multi-component composite anode material having a multi-shell structure by a combination of coating treatment technology, surface composite modification and coating modification technology.
  • the invention applies the nano active material to the surface of the graphite to form an inner core, and composites conductive carbon on the surface of the inner core to form a first shell layer, and then applies the nano active material to the surface of the first shell layer to form a second shell layer, and finally
  • the two-shell layer is uniformly coated to obtain a high-performance multi-component composite anode material;
  • the nano-active material is uniformly coated on the surface of the graphite particles as a buffer matrix, and is secondarily coated on the surface of the conductive carbon layer as a buffer layer and a conductive layer , thereby achieving high load and high dispersion of the nano active material, thereby greatly improving material specific capacity, cycle performance (400 cycles capacity retention rate of more than 90%) and The first efficiency (>90%), in addition
  • Embodiment 1 is an electron micrograph of a composite negative electrode material according to Embodiment 1 of the present invention.
  • Embodiment 2 is an XRD diagram of a composite anode material in Embodiment 1 of the present invention.
  • Example 4 is a cycle performance curve of a composite negative electrode material according to Example 1 of the present invention.
  • the spherical natural graphite having a particle diameter of 5-20 ⁇ m, Si having a particle diameter of 30-250 nm and polyoxyethylene sorbitan monooleate are dispersed in propanol at a mass ratio of 80:5:0.5, and dried by rotary evaporation to obtain First precursor; the first precursor and graphene are placed in a fusion machine at a mass ratio of 85:5, the rotation speed is 3000.0r/min, the tool gap width is 0.01cm, the fusion is 0.5h, and then placed in a box furnace In the middle, argon gas is introduced, the temperature is raised to 600.0 ° C at a heating rate of 0.5 ° C / min, the temperature is kept for 10.0 h, and naturally cooled to room temperature to obtain a second precursor; the second precursor, Si and fatty acid having a particle diameter of 30-250 nm
  • the polyethylene glycol ester is dispersed into ethanol at a mass ratio of 90:5:0.2, and spray-dried
  • the speed is adjusted to 3000.0r/min, mixed for 0.5h, then placed in a box furnace, argon gas is introduced, the temperature is raised to 1050.0 °C at a heating rate of 10.0 °C / min, the temperature is kept for 10.0h, and naturally cooled to room temperature. , crushing, sieving and demagnetization, to obtain a new high-capacity multi-component composite anode material with a particle size of 5.0-45.0 ⁇ m
  • FIG. 1 is an electron micrograph of a composite anode material in the present embodiment
  • FIG. 2 is an XRD pattern of the composite anode material in the present embodiment
  • FIG. 3 is a first charge and discharge curve of the composite anode material in the present embodiment
  • Cycle performance curve of composite anode material
  • Fig. 1 the surface of the obtained material is densely coated. It can be seen from Fig. 2 that there are diffraction peaks of graphite and silicon in the material. It can be seen in Fig. 3 and Fig. 4 that the material has a higher first time. Charge and discharge efficiency and excellent cycle performance.
  • the spherical artificial graphite with the particle size of 10.0-30.0 ⁇ m is placed in a rotary kiln, the rotation speed is adjusted to 0.1r/min, argon gas is introduced, the temperature is raised to 800 °C at a heating rate of 1.0 °C/min, and then silane gas is introduced to control
  • the flow rate of the silane gas is 0.5 L/min, the temperature is kept for 5.0 h, and the mixture is naturally cooled to room temperature to obtain a first precursor.
  • the first precursor and the polyvinyl alcohol are dispersed in methanol at a mass ratio of 80:20, spray dried, and then placed.
  • the tube furnace nitrogen gas is introduced, the temperature is raised to 900.0 ° C at a heating rate of 0.5 ° C / min, the temperature is kept for 0.5 h, and naturally cooled to room temperature to obtain a second precursor; the second precursor is placed in a rotary kiln to adjust the rotation speed.
  • nitrogen gas was introduced, and the temperature was raised to 800 °C at a heating rate of 10.0 ° C / min.
  • silane gas was introduced to control the flow rate of silane gas to 1.0 L/min, and the temperature was kept for 0.5 h, and naturally cooled to room temperature to obtain a third.
  • Precursor the third precursor and phenolic resin were dispersed in ethanol at a mass ratio of 85:25, spray dried, then placed in a box, nitrogen gas was introduced, and the temperature was raised to 900.0 ° C at a heating rate of 10.0 ° C / min, and the temperature was maintained at 10.0 ° h, naturally cooled to room temperature, crushed, sieved and Demagnetization, a new high-capacity multi-component composite anode material having a particle diameter of 5.0 to 45.0 ⁇ m was obtained.
  • SiO 0.4 with a particle size of 50-300 nm and spherical natural graphite with a particle size of 10-25 ⁇ m were placed in a fusion machine at a mass ratio of 10:30, the rotation speed was 2000.0 r/min, the tool gap width was 0.5 cm, and the fusion was 0.5 h.
  • the first precursor is obtained; the first precursor is placed in a rotary kiln, the rotation speed is adjusted to 3.0 r/min, nitrogen gas is introduced, the temperature is raised to 700 ° C at a heating rate of 5.0 ° C / min, and acetylene gas is introduced, and the flow rate is 1.0L/min, kept for 2.0h, naturally cooled to room temperature, to obtain a second precursor; SiO 0.4 with a particle size of 50-300nm and a second precursor were placed in a fusion machine at a mass ratio of 10:80, and adjusted The speed is 3000.0r/min, the tool gap width is 0.5cm, and the fusion is 1.0h to obtain the third precursor.
  • the third precursor and the pitch powder with the particle size of 5-10.0 ⁇ m are placed in the VC high-efficiency mixer at a mass ratio of 80:30.
  • By sieving and demagnetizing a novel high-capacity multi-component composite anode material having a particle diameter of 5-45 ⁇ m is obtained.
  • the SnO with a particle size of 50-200 nm and the natural graphite with a particle size of 20.0-30.0 ⁇ m were placed in a fusion machine at a mass ratio of 20:40, the rotation speed was 2000.0 r/min, the tool gap width was 0.5 cm, and the fusion 2.0 h, the first precursor is obtained; the first precursor and the carbon nanotubes are placed in a fusion machine at a mass ratio of 80:10, the rotation speed is 2000.0 r/min, the tool gap width is 0.03 cm, the fusion is 1.0 h, and then In a box furnace, nitrogen gas is introduced, and the temperature is raised to 700.0 ° C at a heating rate of 10.0 ° C / min, and the temperature is kept for 2.0 h, and naturally cooled to room temperature to obtain a second precursor; the second precursor has a particle diameter of 50-200 nm.
  • SnO and polyacrylamide are dispersed in ethanol at a mass ratio of 20:60:0.1, and spray-dried to obtain a third precursor; the third precursor and the polyvinyl chloride powder having a particle diameter of 2.0 to 10.0 ⁇ m are placed at a mass ratio of 80:20.
  • the speed is adjusted to 1000.0r/min, mixed for 1h, then placed in a roller kiln, nitrogen is introduced, and the temperature is raised to 800.0 °C at a heating rate of 3.0 °C/min, and the temperature is kept for 4.0 hours.
  • pulverization, sieving and demagnetization a new high-capacity multi-component composite anode with a particle size of 18-45 ⁇ m is obtained.
  • Material is adjusted to 1000.0r/min, mixed for 1h, then placed in a roller kiln, nitrogen is introduced, and the temperature is raised to 800.0 °C at a heating rate of 3.0 °C/min, and the temperature is kept for 4.0 hours
  • a tin antimony alloy having a particle diameter of 100-300 nm and a spherical natural graphite having a particle diameter of 10.0-20.0 ⁇ m were placed in a fusion machine at a mass ratio of 5:60, and the rotation speed was 3000.0 r/min, and the tool gap width was 0.05.
  • first precursor fused for 0.5 h, to obtain a first precursor;
  • first precursor and epoxy resin were dispersed in ethanol at a mass of 65:15, spray dried, and then placed in a tube furnace, and nitrogen gas was introduced at 0.5 ° C /
  • the heating rate of min is raised to 800.0 ° C, the temperature is kept for 0.5 h, and naturally cooled to room temperature to obtain a second precursor; the second precursor, the tin antimony alloy with a particle diameter of 100-300 nm and the polyetherimide are mass ratio 80.
  • a third precursor 10:0.2 dispersed in ethanol, spray-dried to obtain a third precursor; the third precursor and the epoxy resin powder having a particle size of 5-10 ⁇ m were placed in a VC high-efficiency mixer at a mass ratio of 80:20 to adjust the rotation speed. It is 800.0r/min, mixed for 1h, then placed in a box furnace, helium gas is introduced, heated to 1200.0 °C at a heating rate of 5.0 °C / min, 8.0 h, chilled to room temperature, pulverized, sieved and demagnetized. A novel high-capacity multi-component composite anode material having a particle diameter of 5.0 to 45.0 ⁇ m is obtained.
  • the tin antimony alloy having a particle diameter of 80-150 nm and the spherical natural graphite having a particle diameter of 5.0-15.0 ⁇ m were placed in a fusion machine at a mass ratio of 50:6, the rotation speed was adjusted to 500.0 r/min, and the tool gap width was 0.2 cm.
  • the first precursor was obtained; the first precursor and epoxy resin were dispersed in ethanol at a mass of 50:30, spray dried, and then placed in a tube furnace, and nitrogen gas was introduced to raise the temperature at 20 ° C / min.
  • the temperature is raised to 1200.0 ° C, kept for 5 h, and naturally cooled to room temperature to obtain a second precursor; the second precursor, the tin antimony alloy having a particle diameter of 100-300 nm and the polyetherimide are 40:20 by mass ratio: 1 Disperse into ethanol, spray-dry to obtain a third precursor; place the third precursor and epoxy resin powder with a particle size of 5-10 ⁇ m in a VC high-efficiency mixer at a mass ratio of 50:30, and adjust the rotation speed to 1500.0r.
  • a multi-component composite anode material was prepared in substantially the same manner as in Example 1, except that: A third precursor was prepared, and silicon powder used for preparing the third precursor was added to the first precursor; a battery was fabricated in the same manner as in Example 1.
  • the specific surface area of the material was tested using a Tristar 3000 fully automatic surface area and porosity analyzer from Mike Instruments.
  • the particle size range of the material and the average particle size of the raw material particles were measured using a Malvern laser particle size tester MS 2000.
  • the structure of the material was tested using an X-ray diffractometer X'Pert Pro, PANalytical.
  • the surface morphology, particle size, and the like of the sample were observed using a Hitachi S4800 scanning electron microscope.
  • the diaphragm and the outer casing are assembled with a 18650 cylindrical single cell using a conventional production process.
  • the charge and discharge test of the cylindrical battery is carried out on the LAND battery test system of Wuhan Jinnuo Electronics Co., Ltd. under normal temperature conditions, 0.2C constant current charge and discharge, and the charge and discharge voltage is limited to 2.75 ⁇ 4.2V.
  • the present invention illustrates the detailed process equipment and process flow of the present invention by the above embodiments, but the present invention is not limited to the above detailed process equipment and process flow, that is, does not mean that the present invention must rely on the above detailed process equipment and The process can only be implemented. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitution of the various materials of the products of the present invention, addition of auxiliary components, selection of specific means, and the like, are all within the scope of the present invention.

Abstract

一种多元复合负极材料及其制备方法，以及使用该负极材料的锂离子电池。所述锂离子电池用多元复合负极材料为多壳层核-壳结构，内核为石墨与涂覆在石墨表面的纳米活性物质构成，所述内核的外层依次为：第一壳层为导电碳材料，第二壳层为纳米活性物质，第三壳层为导电碳材料包覆层。本发明多元复合负极材料采用涂覆处理技术、表面复合改性与包覆改性技术相结合的方式成功制备了具有多壳层结构的核-壳多元复合负极材料，实现了纳米活性物质的高负载与高分散，从而大大提升材料比容量、循环性能与首次效率。此外本发明多元复合负极材料压实密度高、加工性能良好；该负极材料制备工艺简单，原料成本低廉，环境友好无污染。

Description

一种多元复合负极材料、其制备方法及包含其的锂离子电池 技术领域
本发明涉及锂离子电池负极材料领域，具体地，本发明涉及一种多元复合负极材料及其制备方法，以及包含其的锂离子电池。
背景技术
锂离子电池因具有工作电压高、循环使用寿命长、无记忆效应、自放电小、环境友好等优点，已被广泛应用于便携式电子产品和电动汽车中。目前，商业化的锂离子电池主要采用石墨类负极材料，但它的理论比容量仅为372mAh/g，无法满足未来锂离子电池对高能量密度的需求。国内外研究报道，能够与锂形成合金的金属元素、金属氧化物与金属合金化合物，如Si、Sn、Ge、Pb、SiO、SnO、SbSn、Mg2Si等，具有较高的比容量。然而，这些材料在使用过程中电池容量衰减较快，使其实际应用受到一定的限制。
分析认为金属单质、合金与金属氧化物负极材料脱嵌锂体积膨胀收缩较大造成材料破坏和粉碎，是导致材料容量衰减较快的主要原因。因此，抑制材料的体积膨胀，提高材料的结构稳定对于提高合金与金属氧化物负极材料循环稳定性意义重大。目前主要通过纳米化、合金化以及与多元复合(与活性或者非活性材料的复合)来改善材料的体积膨胀。
如CN 103199223A公开了一种Cu-Cr-Si三元负极材料及其制备方法，该发明将铜粉、铬粉、硅粉混合煅烧处理制备合金铸块，然后粉碎，获得具有微米级以下尺寸Cu-Cr-Si三元合金粉体，所得材料具有较高的容量，循环性能良好，但该方法制备的三元材料中硅与铬形成的连续相尺寸仍然较大，未将铜、铬与硅均匀的分散。CN 103560249A公开了一种多元复合负极材料及制备方 法，其将硅粉、碳纳米管、膨胀石墨添加到聚乙烯醇或聚乙二醇水体系中，然后搅干并进行烧成，制得由纳米硅粉、碳纳米管、膨胀石墨和无定形碳组成的多元复合材料，该复合材料导电性好，容量高，但该方法制备过程中，难于将纳米硅粉充分的分散，从而导致该材料的首次充放电效率较低。
因此，研发一种高导电性、高容量、高首次充放电效率与循环稳定性好的多元复合负极材料是锂离子电池领域的技术难题。
发明内容
针对现有技术的不足，本发明的目的之一在于提供一种多元复合负极材料，所述负极材料的导电性好、容量高、首次库伦效率高、循环性能优异。
为达上述目的，本发明采用如下技术方案：
一种多元复合负极材料，所述负极材料为多壳层核-壳结构，内核由石墨与涂覆在石墨表面的纳米活性物质构成；所述内核的外层依次为：第一壳层为导电碳材料，第二壳层为纳米活性物质，第三壳层为导电碳材料包覆层。
对于本发明的多元复合负极材料，所述负极材料含纳米活性物质1～40wt％，石墨30～80wt％，导电碳材料10-50wt％。
优选地，所述多元复合负极材料的中值粒径为5.0～45.0μm，优选为8.0～35.0μm，进一步优选为10.0～25.0μm。
优选地，所述多元复合负极材料的比表面积为1.0～20.0m2/g，优选为1.5～8.0m2/g。
优选地，所述多元复合负极材料的粉体压实密度为1.0～2.0g/cm3，优选为1.1～1.7g/cm3。
优选地，所述石墨为天然晶质石墨、天然隐晶质石墨、天然结晶脉状石墨、 人造石墨或导电石墨的1种或至少2种的组合。
优选地，所述石墨的形状为片状、类球形块状或球形的1种或至少2种的组合。
优选地，所述石墨的中值粒径为5.0～30.0μm，优选为8.0～25.0μm，进一步优选为10.0～20.0μm。
优选地，所述纳米活性物质为对锂具有电化学活性的材料，优选为活性金属单质、活性类金属单质、金属氧化物、金属合金化合物中的1种或至少2种的组合，更优选为硅单质、锡单质、锑单质、锗单质、铝单质、镁单质、锌单质、稼单质、镉单质、钛氧化物、硅氧化物、锡氧化物、钴氧化物、铁氧化物、铜氧化物、锰氧化物、镍氧化物、锡锑合金、铟锑合金、银锑合金、铝锑合金、银锡合金和硅镁化合物中的1种或至少2种的组合。
优选地，所述纳米活性物质的中值粒径为30.0～300.0nm，优选为25.0～250.0nm，进一步优选为20.0～200.0nm。
优选地，所述导电碳材料为碳纳米管、石墨烯、导电石墨、碳纤维、纳米石墨、导电碳黑或有机物裂解碳中的1种或至少2种的组合。
本发明的目的之二在于提供一种本发明所述多元复合负极材料的制备方法，包括以下步骤：
(1)在石墨表面涂覆纳米活性物质，得到第一前驱体；
(2)将所述第一前驱体使用导电碳材料进行表面复合改性，得到第二前驱体；
(3)在第二前驱体表面涂覆纳米活性物质，得到第三前驱体；
(4)将所述第三前驱体进行包覆改性，得到多元复合负极材料。
优选地，步骤(4)后进行：步骤(5)将步骤(4)得到的复合材料粉碎、 筛分并除磁，得到中值粒径为5.0～45.0μm的多元复合负极材料。
优选地，步骤(1)与(3)中所述涂覆采用气相涂覆法、液相涂覆法或固相涂覆法中的1种或至少2种的组合。
对于本发明的制备方法，所述气相涂覆法的步骤为：将所述步骤(1)的石墨或步骤(2)的第二前驱体置于回转炉中，通入保护性气体，升温至600～1500℃通入纳米活性物质蒸汽，保温0.5～10.0h后冷却至室温，得到步骤(1)第一前驱体或步骤(3)第三前驱体。
优选地，所述纳米活性物质蒸汽为纳米活性物质升华或有机气体裂解而得。
优选地，所述回转炉速度为0.1～5.0r/min。
优选地，所述升温速率为1.0～20.0℃/min。
优选地，所述纳米活性物质流量为0.1～1.0L/min。
对于本发明的制备方法，所述液相涂覆法的步骤为：将纳米活性物质、分散剂和步骤(1)的石墨或步骤(2)的第二前驱体分散在有机溶剂中，干燥，得到步骤(1)第一前驱体或步骤(3)第三前驱体。
优选地，所述分散剂为三聚磷酸钠、六偏磷酸钠、焦磷酸钠、三乙基己基磷酸、十二烷基硫酸钠、甲基戊醇、纤维素衍生物、聚丙烯酰胺、古尔胶、脂肪酸聚乙二醇酯、十六烷基三甲基溴化铵、聚乙二醇对异辛基苯基醚、聚丙烯酸、聚乙烯吡咯烷酮、聚氧乙烯脱水山梨醇单油酸酯、对乙基苯甲酸和聚醚酰亚胺中的1种或至少2种的组合。
优选地，所述有机溶剂为醇、酮和醚中的1种或至少2种的组合。
对于本发明的制备方法，所述固相涂覆法的步骤为：将纳米活性物质和所述步骤(1)的石墨或步骤(2)的第二前驱体置于融合机中融合，得到步骤(1)第一前驱体或步骤(3)第三前驱体。
优选地，所述融合机转速为500～3000r/min，刀具间隙宽度为0.01～0.5cm。
优选地，所述融合时间不少于0.5h。
对于本发明的制备方法，步骤(2)所述表面复合改性采用机械物理改性、气相化学改性或液相化学改性。
对于本发明的制备方法，所述机械物理改性的步骤为：将导电碳材料和步骤(1)所述第一前驱体置于融合机中融合，然后置于反应器中，通入保护性气体，升温至600～1200℃，保温0.5～10.0h后冷却至室温，得到步骤(2)所述第二前驱体。
优选地，所述融合机的转速为500～3000r/min。
优选地，所述融合机刀具间隙宽度为0.01～0.5cm。
优选地，所述融合时间至少为0.5h。
对于本发明的制备方法，所述气相化学改性的步骤为：将步骤(1)所述第一前驱体置于回转炉中，通入保护性气体，升温至600～1200℃，通入有机碳源气体，保温0.5～10.0h后冷却至室温，得到步骤(2)所述第二前驱体。
优选地，所述有机碳源气体为烃类和/或1～3个环的芳香烃类衍生物中的1种或至少2种的组合；优选为甲烷、乙烯、乙炔、苯、甲苯、二甲苯、苯乙烯和苯酚中的1种或至少2种的组合。
优选地，所述回转炉的回转速度为0.1～5.0r/min。
优选地，所述有机碳源气体的流量为0.1～2.0L/min。
对于本发明的制备方法，所述液相化学改性的步骤为：将步骤(1)所述第一前驱体和有机物分散在有机溶剂体系中，干燥，然后置于反应器中，通入保护性气体，升温至600～1200℃，保温0.5～10.0h后冷却至室温，得到步 骤(2)所述第二前驱体。
优选地，所述有机溶剂为醚、醇和酮中的1种或至少2种的组合。
优选地，所述有机物为聚合物、糖类、有机酸、沥青和高分子材料中的1种或至少2种的组合，优选为环氧树脂、酚醛树脂、糠醛树脂、脲醛树脂、聚乙烯醇、聚氯乙烯、聚乙二醇、聚环氧乙烷、聚偏氟乙烯、丙烯酸树脂和聚丙烯腈中的1种或至少2种的组合。
对于本发明的制备方法，所述机械物理改性中的反应器、气相化学改性的回转炉、液相化学改性的反应器的升温速率为0.5～20.0℃/min。
优选地，所述反应器为真空炉、箱式炉、回转炉、辊道窑、推板窑或管式炉。
对于本发明的制备方法，步骤(4)所述包覆改性采用气相包覆改性、液相包覆改性或固相包覆改性。
对于本发明的制备方法，所述气相包覆改性的步骤为：将步骤(3)所述第三前驱体置于回转炉中，通入保护性气体，升温至600～1200℃，通入有机碳源气体，保温0.5～10.0h后冷却至室温，得到步骤(4)所述多元复合负极材料。
优选地，所述有机碳源气体为烃类和/或1～3个环的芳香烃类衍生物中的1种或至少2种的组合；优选为甲烷、乙烯、乙炔、苯、甲苯、二甲苯、苯乙烯和苯酚中的1种或至少2种的组合。
优选地，所述回转炉的回转速度为0.1～5.0r/min。
优选地，所述通入有机碳源气体的流量为0.1～2.0L/min。
对于本发明的制备方法，所述液相包覆改性的步骤为：将所述步骤(3)第三前驱体和有机物分散在有机溶剂体系中，干燥，然后置于反应器中，通入保 护性气体，升温至600～1200℃，保温0.5～10.0h后冷却至室温，得到步骤(4)所述多元复合负极材料。
优选地，所述有机溶剂为醚、醇和酮中的1种或至少2种的组合。
对于本发明的制备方法，所述固相包覆改性的步骤为：将所述步骤(3)第三前驱体和有机物置于VC混合机中混合，然后置于反应器中，通入保护性气体，升温至600～1200℃，保温0.5～10.0h后冷却至室温，得到步骤(4)多元复合负极材料。
优选地，所述VC混合机的转速为500～3000r/min。
优选地，所述的混合时间不低于0.5h。
对于本发明的制备方法，所述气相包覆改性的回转炉、液相包覆改性的反应器、固相包覆改性的反应器升温速率为0.5～20.0℃/min。
优选地，所述反应器为真空炉、箱式炉、回转炉、辊道窑、推板窑或管式炉。
优选地，所述有机物为聚合物、糖类、有机酸、沥青和高分子材料中的1种或至少2种的组合，优选为环氧树脂、酚醛树脂、糠醛树脂、脲醛树脂、聚乙烯醇、聚氯乙烯、聚乙二醇、聚环氧乙烷、聚偏氟乙烯、丙烯酸树脂和聚丙烯腈中的1种或至少2种的组合。
优选地，所述有机碳源为粉末状，中值粒径为0.1～25.0μm，特别优选为0.5～8.0μm。
对于本发明的制备方法，所述保护性气体为氮气、氦气、氖气、氩气、氪气和氙气中的1种或至少2种的组合。
本发明的目的之三在于提供一种锂离子电池，其负极极片为本发明所述多元复合负极材料、导电剂和粘结剂按质量百分比91～94∶1～3∶3～6在溶剂中混合、 涂覆于铜箔集流体上，真空氛围下烘干制得。
优选地，所述锂离子电池的正极极片采用的正极活性材料为三元材料、富锂材料、钴酸锂、镍酸锂、尖晶石锰酸锂、层装锰酸锂或磷酸铁锂1种或至少2种的组合。
优选地，所述导电剂为石墨粉和/或纳米导电液。
优选地，所述纳米导电液由0.5-20wt％的纳米碳材料与分散溶剂组成。
优选地，所述纳米碳材料为石墨烯、碳纳米管、纳米碳纤维、富勒烯、炭黑和乙炔黑中的1种或至少2种的组合。
优选地，所述石墨烯的石墨片层数在1-100之间。
优选地，所述碳纳米管和纳米碳纤维的直径在0.2-500nm。
优选地，所述富勒烯、炭黑和乙炔黑的粒径为1-200nm。
优选地，所述粘结剂为聚酰亚胺树脂、丙烯酸树脂、聚偏二氟乙烯、聚乙烯醇、羧甲基纤维素钠或丁苯橡胶的1种或至少2种的组合。
优选地，所述锂离子电池种类为常规铝壳、钢壳、或软包锂离子电池。
与现有技术相比，本发明多元复合负极材料采用涂覆处理技术、表面复合改性与包覆改性技术相结合的方式成功制备了具有多壳层结构的核-壳多元复合负极材料。本发明将纳米活性物质涂覆于石墨表面形成内核，并且在内核表面复合导电碳形成第一壳层，随后再将纳米活性物质涂覆于第一壳层表面形成第二壳层，最后对第二壳层进行均相包覆，得到高性能的多元复合负极材料；纳米活性物质均匀涂覆于作为缓冲基体的石墨颗粒表面，并且二次涂覆于作为缓冲层与导电层的导电碳层表面，从而实现了纳米活性物质的高负载与高分散，从而大大提升材料比容量、循环性能(400次循环容量保持率在90％以上)与 首次效率(＞90％)，此外本发明多元复合负极材料压实密度高、加工性能良好；该负极材料制备工艺简单，原料成本低廉，环境友好无污染。
附图说明
图1为本发明实施例1中复合负极材料的电镜图片；
图2为本发明实施例1中复合负极材料的XRD图；
图3为本发明实施例1中复合负极材料的首次充放电曲线；
图4为本发明实施例1的复合负极材料循环性能曲线。
具体实施方式
为便于理解本发明，本发明列举实施例如下。本领域技术人员应该明了，所述实施例仅仅用于帮助理解本发明，不应视为对本发明的具体限制。
实施例1
将粒径为5-20μm类球形天然石墨、粒径为30-250nm的Si与聚氧乙烯脱水山梨醇单油酸酯按质量比80∶5∶0.5分散到丙醇中，旋转蒸发干燥，得到第一前驱体；将第一前驱体和石墨烯按质量比85∶5置于融合机中，调节转速为3000.0r/min，刀具间隙宽度为0.01cm，融合0.5h，然后置于箱式炉中，通入氩气，以0.5℃/min升温速率升温至600.0℃，保温10.0h，自然冷却至室温，得到第二前驱体；将第二前驱体、粒径为30-250nm的Si与脂肪酸聚乙二醇酯按质量比90∶5∶0.2分散到乙醇中，喷雾干燥，得到第三前驱体；第三前驱体和粒径为0.1-6.0μm沥青粉末按质量比95∶20置于VC高效混合机中，调节转速为3000.0r/min，混合0.5h，然后置于箱式炉中，通入氩气，以10.0℃/min升温速率升温至1050.0℃，保温10.0h，自然冷却至室温，粉碎、筛分并除磁，得到粒径为5.0-45.0μm新型高容量多元复合负极材料。
图1为本实施例中复合负极材料的电镜图片；图2为本实施例中复合负极材料的XRD图；图3为本实施例中复合负极材料的首次充放电曲线；图4为本实施例的复合负极材料循环性能曲线。
从图1中可以看出，制得的材料表面包覆较致密，从图2中可以看出材料中具有石墨及硅的衍射峰，图3和图4中可以看出材料具有较高的首次充放电效率并且具有优异的循环性能。
实施例2
将粒径为10.0-30.0μm球形人造石墨置于回转炉中，调节回转速度为0.1r/min，通入氩气，以1.0℃/min升温速率升温至800℃，然后通入硅烷气体，控制硅烷气体流量为0.5L/min，保温5.0h，自然冷却至室温，得到第一前驱体；将第一前驱体和聚乙烯醇按质量比80∶20分散在甲醇中，喷雾干燥，然后置于管式炉中，通入氮气，以0.5℃/min升温速率升温至900.0℃，保温0.5h，自然冷却至室温，得到第二前驱体；将第二前驱体置于回转炉中，调节回转速度为0.5r/min，通入氮气，以10.0℃/min升温速率升温至800℃，然后通入硅烷气体，控制硅烷气体流量为1.0L/min，保温0.5h，自然冷却至室温，得到第三前驱体；将第三前驱体和酚醛树脂按质量比85∶25分散在乙醇中，喷雾干燥，然后置于箱式中，通入氮气，以10.0℃/min升温速率升温至900.0℃，保温10.0h，自然冷却至室温，粉碎、筛分并除磁，得到粒径为5.0-45.0μm新型高容量多元复合负极材料。
实施例3
将粒径为50-300nm的SiO0.4和粒径为10-25μm球形天然石墨按质量比10∶30置于融合机中，调节转速为2000.0r/min，刀具间隙宽度为0.5cm，融合0.5h，得到第一前驱体；将第一前驱体置于回转炉中，调节回转速度为 3.0r/min，通入氮气，以5.0℃/min升温速率升温至700℃，通入乙炔气体，流量为1.0L/min，保温2.0h，自然冷却至室温，得到第二前驱体；将粒径为50-300nm的SiO0.4和第二前驱体按质量比10∶80驱体置于融合机中，调节转速为3000.0r/min，刀具间隙宽度为0.5cm，融合1.0h，得到第三前驱体；第三前驱体和粒径为5-10.0μm沥青粉末按质量比80∶30置于VC高效混合机中，调节转速为1000.0r/min，混合1.0h，然后置于箱式炉中，通入氦气，以5.0℃/min升温速率升温至1200.0℃，保温0.5h，自然冷却至室温，粉碎、筛分并除磁，得到粒径为5-45μm新型高容量多元复合负极材料。
实施例4
将粒径为50-200nm的SnO和粒径为20.0-30.0μm片状天然石墨按质量比20∶40置于融合机中，调节转速为2000.0r/min，刀具间隙宽度为0.5cm，融合2.0h，得到第一前驱体；将第一前驱体和碳纳米管按质量比80∶10置于融合机中，调节转速为2000.0r/min，刀具间隙宽度为0.03cm，融合1.0h，然后置于箱式炉中，通入氮气，以10.0℃/min升温速率升温至700.0℃，保温2.0h，自然冷却至室温，得到第二前驱体；将第二前驱体、粒径为50-200nm的SnO与聚丙烯酰胺按质量比20∶60∶0.1分散到乙醇中，喷雾干燥，得到第三前驱体；第三前驱体和粒径为2.0-10.0μm聚氯乙烯粉末按质量比80∶20置于VC高效混合机中，调节转速为1000.0r/min，混合1h，然后置于辊道窑炉中，通入氮气，以3.0℃/min升温速率升温至800.0℃，保温4.0h，自然冷却至室温，粉碎、筛分并除磁，得到粒径为18-45μm新型高容量多元复合负极材料。
实施例5
将粒径为100-300nm的锡化锑合金和粒径为10.0-20.0μm球形天然石墨按质量比5∶60置于融合机中，调节转速为3000.0r/min，刀具间隙宽度为0.05 cm，融合0.5h，得到第一前驱体；将第一前驱体和环氧树脂按质量65∶15分散在乙醇中，喷雾干燥，然后置于管式炉中，通入氮气，以0.5℃/min升温速率升温至800.0℃，保温0.5h，自然冷却至室温，得到第二前驱体；将第二前驱体、粒径为100-300nm的锡化锑合金与聚醚酰亚胺按质量比80∶10∶0.2分散到乙醇中，喷雾干燥，得到第三前驱体；将第三前驱体和粒径为5-10μm环氧树脂粉末按质量比80∶20置于VC高效混合机中，调节转速为800.0r/min，混合1h，然后置于箱式炉中，通入氦气，以5.0℃/min升温速率升温至1200.0℃，保温8.0h，自然冷却至室温，粉碎、筛分并除磁，得到粒径为5.0-45.0μm新型高容量多元复合负极材料。
实施例6
将粒径为80-150nm的锡化锑合金和粒径为5.0-15.0μm球形天然石墨按质量比50∶6置于融合机中，调节转速为500.0r/min，刀具间隙宽度为0.2cm，融合4.5h，得到第一前驱体；将第一前驱体和环氧树脂按质量50∶30分散在乙醇中，喷雾干燥，然后置于管式炉中，通入氮气，以20℃/min升温速率升温至1200.0℃，保温5h，自然冷却至室温，得到第二前驱体；将第二前驱体、粒径为100-300nm的锡化锑合金与聚醚酰亚胺按质量比40∶20∶1分散到乙醇中，喷雾干燥，得到第三前驱体；将第三前驱体和粒径为5-10μm环氧树脂粉末按质量比50∶30置于VC高效混合机中，调节转速为1500.0r/min，混合3h，然后置于箱式炉中，通入氦气，以20℃/min升温速率升温至600.0℃，保温2.0h，自然冷却至室温，粉碎、筛分并除磁，得到粒径为5.0-45.0μm新型高容量多元复合负极材料。
对比例1
按照与实施例1基本相同的方法制备多元复合负极材料，区别在于：不制 备第三前驱体，将制备第三前驱体所用的硅粉添加到第一前驱体中；按与实施例1相同的方法制作电池。
采用以下方法对实施例1～5和对比例1的负极材料进行测试：
本发明所述的粉体压实密度采用CARVER粉体压实机测试，其中，粉体压实密度＝测试样品的质量/测试样品的体积；极片压实密度＝(负极片质量-铜箔质量)/(极片面积×极片压实后的厚度)。
采用美国麦克仪器公司的Tristar3000全自动比表面积和孔隙度分析仪测试材料的比表面积。
采用马尔文激光粒度测试仪MS 2000测试材料粒径范围以及原料颗粒的平均粒径。
采用X射线衍射仪X′Pert Pro，PANalytical测试材料的结构。
采用日立公司S4800扫描电子显微镜观察样品的表面形貌、颗粒大小等。
采用以下方法测试电化学循环性能：将负极材料、导电剂和粘结剂按质量百分比94∶1∶5将他们溶解在溶剂中混合，控制固含量在50％，涂覆于铜箔集流体上，真空烘干、制得负极极片；然后将传统成熟工艺制备的三元正极极片、1mol/L的LiPF6/EC+DMC+EMC(v/v＝1∶1∶1)电解液、Celgard2400隔膜、外壳采用常规生产工艺装配18650圆柱单体电池。圆柱电池的充放电测试在武汉金诺电子有限公司LAND电池测试系统上，在常温条件，0.2C恒流充放电，充放电电压限制在2.75～4.2V。
实施例1-5及对比例1所制备的负极材料的电化学测试结果如表1所示。
表1
Figure PCTCN2015087266-appb-000001
Figure PCTCN2015087266-appb-000002
由以上表格中数据可以看出，根据实施例1所述方法制备的负极材料首次可逆容量、首次库伦效率、循环容量保持率等方面电化学性能均优于对比例1所述方法制备的负极材料。
申请人声明，本发明通过上述实施例来说明本发明的详细工艺设备和工艺流程，但本发明并不局限于上述详细工艺设备和工艺流程，即不意味着本发明必须依赖上述详细工艺设备和工艺流程才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。

Claims (9)

  1. 一种多元复合负极材料，其特征在于，所述负极材料为多壳层核-壳结构，内核由石墨与涂覆在石墨表面的纳米活性物质构成；所述内核的外层依次为：第一壳层为导电碳材料，第二壳层为纳米活性物质，第三壳层为导电碳材料包覆层。
  2. 根据权利要求1所述的多元复合负极材料，其特征在于，所述负极材料含纳米活性物质1～40wt％，石墨30～80wt％，导电碳材料10-50wt％；
    优选地，所述多元复合负极材料的中值粒径为5.0～45.0μm，优选为8.0～35.0μm，进一步优选为10.0～25.0μm；
    优选地，所述多元复合负极材料的比表面积为1.0～20.0m2/g，优选为1.5～8.0m2/g；
    优选地，所述多元复合负极材料的粉体压实密度为1.0～2.0g/cm3，优选为1.1～1.7g/cm3；
    优选地，所述石墨为天然晶质石墨、天然隐晶质石墨、天然结晶脉状石墨、人造石墨或导电石墨的1种或至少2种的组合；
    优选地，所述石墨的形状为片状、类球形块状或球形的1种或至少2种的组合；
    优选地，所述石墨的中值粒径为5.0～30.0μm，优选为8.0～25.0μm，进一步优选为10.0～20.0μm；
    优选地，所述纳米活性物质为对锂具有电化学活性的材料，优选为活性金属单质、活性类金属单质、金属氧化物、金属合金化合物中的1种或至少2种的组合，更优选为硅单质、锡单质、锑单质、锗单质、铝单质、镁单质、锌单质、稼单质、镉单质、钛氧化物、硅氧化物、锡氧化物、钴氧化物、铁氧化物、 铜氧化物、锰氧化物、镍氧化物、锡锑合金、铟锑合金、银锑合金、铝锑合金、银锡合金和硅镁化合物中的1种或至少2种的组合；
    优选地，所述纳米活性物质的中值粒径为30.0～300.0nm，优选为25.0～250.0nm，进一步优选为20.0～200.0nm；
    优选地，所述导电碳材料为碳纳米管、石墨烯、导电石墨、碳纤维、纳米石墨、导电碳黑或有机物裂解碳中的1种或至少2种的组合。
  3. 一种权利要求1或2所述多元复合负极材料的制备方法，包括以下步骤：
    (1)在石墨表面涂覆纳米活性物质，得到第一前驱体；
    (2)将所述第一前驱体使用导电碳材料进行表面复合改性，得到第二前驱体；
    (3)在第二前驱体表面涂覆纳米活性物质，得到第三前驱体；
    (4)将所述第三前驱体进行包覆改性，得到多元复合负极材料。
  4. 根据权利要求3所述的制备方法，其特征在于，步骤(4)后进行：步骤(5)将步骤(4)得到的复合材料粉碎、筛分并除磁，得到中值粒径为5.0～45.0μm的多元复合负极材料。
  5. 根据权利要求3或4所述的制备方法，其特征在于，步骤(1)与(3)中所述涂覆采用气相涂覆法、液相涂覆法或固相涂覆法中的1种或至少2种的组合；
    优选地，所述气相涂覆法的步骤为：将所述步骤(1)的石墨或步骤(2)的第二前驱体置于回转炉中，通入保护性气体，升温至600～1500℃通入纳米活性物质蒸汽，保温0.5～10.0h后冷却至室温，得到步骤(1)第一前驱体或步骤(3)第三前驱体；
    优选地，所述保护性气体为氮气、氦气、氖气、氩气、氪气或氙气中的1种 或至少2种的组合；
    优选地，所述纳米活性物质蒸汽为纳米活性物质升华或有机气体裂解而得；
    优选地，所述回转炉速度为0.1～5.0r/min；
    优选地，所述升温速率为1.0～20.0℃/min；
    优选地，所述纳米活性物质流量为0.1～1.0L/min；
    优选地，所述液相涂覆法的步骤为：将纳米活性物质、分散剂和步骤(1)的石墨或步骤(2)的第二前驱体分散在有机溶剂中，干燥，得到步骤(1)第一前驱体或步骤(3)第三前驱体；
    优选地，所述分散剂为三聚磷酸钠、六偏磷酸钠、焦磷酸钠、三乙基己基磷酸、十二烷基硫酸钠、甲基戊醇、纤维素衍生物、聚丙烯酰胺、古尔胶、脂肪酸聚乙二醇酯、十六烷基三甲基溴化铵、聚乙二醇对异辛基苯基醚、聚丙烯酸、聚乙烯吡咯烷酮、聚氧乙烯脱水山梨醇单油酸酯、对乙基苯甲酸和聚醚酰亚胺中的1种或至少2种的组合；
    优选地，所述有机溶剂为醇、酮和醚中的1种或至少2种的组合；
    优选地，所述固相涂覆法的步骤为：将纳米活性物质和所述步骤(1)的石墨或步骤(2)的第二前驱体置于融合机中融合，得到步骤(1)第一前驱体或步骤(3)第三前驱体；
    优选地，所述融合机转速为500～3000r/min，刀具间隙宽度为0.01～0.5cm；
    优选地，所述融合时间不少于0.5h。
  6. 根据权利要求3或4所述的制备方法，其特征在于，步骤(2)所述表面复合改性采用机械物理改性、气相化学改性或液相化学改性；
    优选地，所述机械物理改性的步骤为：将导电碳材料和步骤(1)所述第一 前驱体置于融合机中融合，然后置于反应器中，通入保护性气体，升温至600～1200℃，保温0.5～10.0h后冷却至室温，得到步骤(2)所述第二前驱体；
    优选地，所述融合机的转速为500～3000r/min；
    优选地，所述融合机刀具间隙宽度为0.01～0.5cm；
    优选地，所述融合时间至少为0.5h；
    优选地，所述气相化学改性的步骤为：将步骤(1)所述第一前驱体置于回转炉中，通入保护性气体，升温至600～1200℃，通入有机碳源气体，保温0.5～10.0h后冷却至室温，得到步骤(2)所述第二前驱体；
    优选地，所述有机碳源气体为烃类和/或1～3个环的芳香烃类衍生物中的1种或至少2种的组合；优选为甲烷、乙烯、乙炔、苯、甲苯、二甲苯、苯乙烯和苯酚中的1种或至少2种的组合；
    优选地，所述回转炉的回转速度为0.1～5.0r/min；
    优选地，所述有机碳源气体的流量为0.1～2.0L/min；
    优选地，所述液相化学改性的步骤为：将步骤(1)所述第一前驱体和有机物分散在有机溶剂体系中，干燥，然后置于反应器中，通入保护性气体，升温至600～1200℃，保温0.5～10.0h后冷却至室温，得到步骤(2)所述第二前驱体；
    优选地，所述有机溶剂为醚、醇和酮中的1种或至少2种的组合；
    优选地，所述有机物为聚合物、糖类、有机酸、沥青和高分子材料中的1种或至少2种的组合，优选为环氧树脂、酚醛树脂、糠醛树脂、脲醛树脂、聚乙烯醇、聚氯乙烯、聚乙二醇、聚环氧乙烷、聚偏氟乙烯、丙烯酸树脂和聚丙烯腈中的1种或至少2种的组合；
    优选地，所述保护性气体为氮气、氦气、氖气、氩气、和氙气中的1种或 至少2种的组合；
    优选地，所述机械物理改性中的反应器、气相化学改性的回转炉、液相化学改性的反应器的升温速率为0.5～20.0℃/min；
    优选地，所述反应器为真空炉、箱式炉、回转炉、辊道窑、推板窑或管式炉。
  7. 根据权利要求3或4所述的制备方法，其特征在于，步骤(4)所述包覆改性采用气相包覆改性、液相包覆改性或固相包覆改性；
    优选地，所述气相包覆改性的步骤为：将步骤(3)所述第三前驱体置于回转炉中，通入保护性气体，升温至600～1200℃，通入有机碳源气体，保温0.5～10.0h后冷却至室温，得到步骤(4)所述多元复合负极材料；
    优选地，所述有机碳源气体为烃类和/或1～3个环的芳香烃类衍生物中的1种或至少2种的组合；优选为甲烷、乙烯、乙炔、苯、甲苯、二甲苯、苯乙烯和苯酚中的1种或至少2种的组合；
    优选地，所述回转炉的回转速度为0.1～5.0r/min；
    优选地，所述通入有机碳源气体的流量为0.1～2.0L/min；
    优选地，所述液相包覆改性的步骤为：将所述步骤(3)第三前驱体和有机物分散在有机溶剂体系中，干燥，然后置于反应器中，通入保护性气体，升温至600～1200℃，保温0.5～10.0h后冷却至室温，得到步骤(4)所述多元复合负极材料；
    优选地，所述有机溶剂为醚、醇和酮中的1种或至少2种的组合；
    优选地，所述固相包覆改性的步骤为：将所述步骤(3)第三前驱体和有机物置于VC混合机中混合，然后置于反应器中，通入保护性气体，升温至600～1200℃，保温0.5～10.0h后冷却至室温，得到步骤(4)多元复合负极材料；
    优选地，所述VC混合机的转速为500～3000r/min；
    优选地，所述的混合时间不低于0.5h；
    优选地，所述气相包覆改性的回转炉、液相包覆改性的反应器、固相包覆改性的反应器升温速率为0.5～20.0℃/min；
    优选地，所述反应器为真空炉、箱式炉、回转炉、辊道窑、推板窑或管式炉；
    优选地，所述有机物为聚合物、糖类、有机酸、沥青和高分子材料中的1种或至少2种的组合，优选为环氧树脂、酚醛树脂、糠醛树脂、脲醛树脂、聚乙烯醇、聚氯乙烯、聚乙二醇、聚环氧乙烷、聚偏氟乙烯、丙烯酸树脂和聚丙烯腈中的1种或至少2种的组合；
    优选地，所述有机碳源为粉末状，中值粒径为0.1～25.0μm，特别优选为0.5～8.0μm；
    优选地，所述保护性气体为氮气、氦气、氖气、氩气、和氙气中的1种或至少2种的组合。
  8. 一种锂离子电池，其特征在于其负极极片为权利要求1或2所述多元复合负极材料、导电剂和粘结剂按质量百分比91～94∶1～3∶3～6在溶剂中混合、涂覆于铜箔集流体上，真空氛围下烘干制得。
  9. 根据权利要求8所述的锂离子电池，其特征在于，所述锂离子电池的正极极片采用的正极活性材料为三元材料、富锂材料、钴酸锂、镍酸锂、尖晶石锰酸锂、层装锰酸锂或磷酸铁锂1种或至少2种的组合；
    优选地，所述导电剂为石墨粉和/或纳米导电液；
    优选地，所述纳米导电液由0.5-20wt％的纳米碳材料与分散溶剂组成；
    优选地，所述纳米碳材料为石墨烯、碳纳米管、纳米碳纤维、富勒烯、炭 黑和乙炔黑中的1种或至少2种的组合；
    优选地，所述石墨烯的石墨片层数在1-100之间；
    优选地，所述碳纳米管和纳米碳纤维的直径在0.2-500nm；
    优选地，所述富勒烯、炭黑和乙炔黑的粒径为1-200nm；
    优选地，所述粘结剂为聚酰亚胺树脂、丙烯酸树脂、聚偏二氟乙烯、聚乙烯醇、羧甲基纤维素钠或丁苯橡胶的1种或至少2种的组合；
    优选地，所述锂离子电池种类为常规铝壳、钢壳、或软包锂离子电池。
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