WO2024259580A1 - 一种复合补锂材料、其制备方法和应用 - Google Patents

一种复合补锂材料、其制备方法和应用 Download PDF

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Publication number
WO2024259580A1
WO2024259580A1 PCT/CN2023/101345 CN2023101345W WO2024259580A1 WO 2024259580 A1 WO2024259580 A1 WO 2024259580A1 CN 2023101345 W CN2023101345 W CN 2023101345W WO 2024259580 A1 WO2024259580 A1 WO 2024259580A1
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Prior art keywords
lithium supplement
composite lithium
lithium
positive electrode
dimensional carbon
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PCT/CN2023/101345
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English (en)
French (fr)
Inventor
赵舒琰
李长东
阮丁山
刘伟健
缪建麟
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Application filed by Hunan Brunp Recycling Technology Co Ltd, Guangdong Brunp Recycling Technology Co Ltd filed Critical Hunan Brunp Recycling Technology Co Ltd
Priority to CN202380009487.7A priority Critical patent/CN117099227A/zh
Priority to PCT/CN2023/101345 priority patent/WO2024259580A1/zh
Publication of WO2024259580A1 publication Critical patent/WO2024259580A1/zh
Anticipated expiration legal-status Critical
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    • 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 disclosure belongs to the technical field of lithium-ion battery materials, and in particular, relates to a composite lithium supplement material, a preparation method and application thereof.
  • Lithium-ion batteries have high energy density and long cycle life, and are widely used in portable electronic products and electric vehicles. During the first week of charging of lithium-ion batteries, SEI will form on the surface of the negative electrode, which will consume the active lithium in the positive electrode and cause irreversible capacity loss.
  • Positive electrode lithium replenishment technology is to compensate for the irreversible capacity loss of lithium-ion batteries by replenishing lithium, so that the capacity of the positive electrode can be restored. Its process is simple, perfectly compatible with existing battery processes, effectively improves the energy density of the whole battery, and can accurately control the capacity of pre-lithiation lithium ions, which is very conducive to large-scale commercial applications.
  • organic pre-lithiation reagents Li 2 C x O y (such as: Li 2 C 2 O 4 , Li 2 C 4 O 4 , Li 2 C 3 O 5 , Li 2 C 4 O 6 ), also known as sacrificial lithium salts, not only produce gases after delithiation, which are easy to remove from the battery system without any residue, but also Li 2 C x O y has a high specific capacity (>300mAh g -1 ), a simple synthesis process, a reasonable price, and can exist stably in the air.
  • organic pre-lithiation reagents are insulators with poor conductivity and high decomposition voltage (>4.7V), which cannot be applied to current positive electrode materials.
  • the purpose of the present disclosure includes providing a composite lithium supplement material, a preparation method and application thereof, aiming to provide an organic pre-lithiation agent with good conductivity and low decomposition voltage to improve the electrochemical performance of the battery.
  • the solution provided by the present disclosure includes a composite lithium supplement material, including: a carbon nano-skeleton having a three-dimensional conductive network and an organic lithium supplement agent dispersed on the carbon nano-skeleton.
  • the carbon nanoskeleton includes a one-dimensional carbon nanomaterial and a two-dimensional carbon nanomaterial.
  • the mass ratio of the carbon nanoframework to the organic lithium supplement agent is (3-30):100.
  • the mass ratio of the carbon nanoframework to the organic lithium supplement agent is (5-15):100.
  • the mass ratio of the one-dimensional carbon nanomaterial to the two-dimensional carbon nanomaterial is (0.1-10):1.
  • the mass ratio of the one-dimensional carbon nanomaterial to the two-dimensional carbon nanomaterial is (0.3-3.0):1.
  • the one-dimensional carbon nanomaterial is selected from at least one of carbon nanotubes and carbon nanofibers.
  • the two-dimensional carbon nanomaterial is selected from at least one of graphene, graphene oxide and redox graphene.
  • the carbon nanoframework is formed by mixing a one-dimensional carbon nanomaterial and a two-dimensional carbon nanomaterial, followed by ultrasonic dispersion and spray drying.
  • the organic lithium supplement is selected from at least one of Li 2 C 2 O 4 , Li 2 C 4 O 4 , Li 2 C 3 O 5 and Li 2 C 4 O 6 .
  • the particle size of the composite lithium supplementing material is 1 ⁇ m-30 ⁇ m.
  • the particle size of the composite lithium supplementing material is 2 ⁇ m-10 ⁇ m.
  • the diameter of the one-dimensional carbon nanomaterial is 0.01 ⁇ m-8 ⁇ m, and the particle size of the two-dimensional carbon nanomaterial is 5 ⁇ m-50 ⁇ m.
  • the solution provided by the present disclosure includes a method for preparing a composite lithium supplement material, comprising: loading an organic lithium supplement agent on a carbon nano-skeleton having a three-dimensional conductive network.
  • one-dimensional carbon nanomaterials, two-dimensional carbon nanomaterials and an organic lithium supplement are mixed in a solvent system, subjected to ultrasonic treatment to obtain a dispersed system, and the dispersed system is spray-dried to obtain powder particles.
  • the mass ratio of the one-dimensional carbon nanomaterial, the two-dimensional carbon nanomaterial and the organic lithium supplement agent is (1.5-15):(1.5-15):100.
  • the mass ratio of the one-dimensional carbon nanomaterial, the two-dimensional carbon nanomaterial and the organic lithium supplement agent is (4-7.5):(4-7.5):100.
  • the total solid content of the one-dimensional carbon nanomaterial, the two-dimensional carbon nanomaterial and the organic lithium supplement agent is 0.2%-10%.
  • the total solid content of the one-dimensional carbon nanomaterial, the two-dimensional carbon nanomaterial and the organic lithium supplement agent is 1%-8%.
  • the feed inlet temperature is controlled to be 170°C-240°C
  • the discharge port temperature is controlled to be 90°C-120°C.
  • the feed inlet temperature is controlled to be 200°C-220°C
  • the discharge port temperature is controlled to be 100°C-120°C.
  • the feed rate is controlled to be 10 mL/min-60 mL/min.
  • the feed rate is controlled to be 30 mL/min-50 mL/min.
  • the method further includes calcining the powder particles.
  • the calcination temperature is controlled to be 200° C.-350° C., and the calcination time is 3 h-8 h.
  • the heating rate is controlled to be 3° C./min-5° C./min.
  • calcination is performed under an inert atmosphere.
  • the inert atmosphere is selected from at least one of argon and nitrogen.
  • the solution provided in the present disclosure includes a positive electrode plate slurry, including a positive electrode active material and a lithium supplement additive, wherein the lithium supplement additive is a composite lithium supplement material in any of the above embodiments or a composite lithium supplement material prepared by the preparation method in any of the above embodiments.
  • the mass ratio of the positive electrode active material to the composite lithium supplement material is 100:(1-10).
  • the positive electrode active material is selected from at least one of lithium nickel manganese oxide (LiNi 0.5 Mn 1.5 O 4 ), lithium cobalt oxide (LiCoO 2 ), lithium manganese oxide (LiMn 2 O 4 ), lithium iron phosphate (LiFePO 4 ), lithium nickel cobalt manganese oxide (Li(Ni,Co,Mn)O 2 ) and lithium nickel cobalt aluminum oxide (Li(Ni,Co,Al)O 2 ).
  • the solution provided by the present disclosure includes a positive electrode sheet, including a positive electrode current collector and a positive electrode active coating coated on the positive electrode current collector, wherein the positive electrode active coating is formed by the positive electrode sheet slurry in any of the above embodiments.
  • the solution provided by the present disclosure includes a lithium-ion battery, including the positive electrode plate in the above embodiment.
  • the three-dimensional conductive network structure is used to make the organic lithium supplement agent more evenly dispersed, thereby improving the utilization rate of the active sites of the organic lithium supplement agent participating in the electrochemical reaction.
  • the addition of the carbon nano skeleton can also improve the conductivity of the composite lithium supplement material, thereby reducing the decomposition voltage platform, so that lithium can be removed within the battery voltage range, thereby achieving a lithium supplement effect.
  • the composite lithium supplement material provided in the present disclosure does not have mass residue after lithium is removed from the battery, which can improve energy density and cycle storage performance.
  • FIG1 is a process flow chart of a method for preparing a composite lithium supplement material provided by the present disclosure
  • FIG2 is an electron microscope image of the composite lithium supplement material prepared in Example 1;
  • FIG3 is an XRD comparison diagram of the composite lithium supplement material of Example 1 before and after sintering.
  • any values of the ranges disclosed in this disclosure are not limited to the precise ranges or values, and these ranges or values should be understood to include values close to these ranges or values.
  • the endpoint values of each range, the endpoint values of each range and the individual point values, and the individual point values can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.
  • the embodiment of the present disclosure provides a composite lithium supplement material, including a carbon nano-skeleton and an organic lithium supplement agent dispersed on the carbon nano-skeleton, wherein the carbon nano-skeleton has a three-dimensional conductive network structure.
  • the carbon nanoskeleton includes a one-dimensional carbon nanomaterial and a two-dimensional carbon nanomaterial, and a three-dimensional conductive network is formed by the one-dimensional carbon nanomaterial and the two-dimensional carbon nanomaterial.
  • dispersing the organic lithium supplement in a three-dimensional conductive network can improve the utilization rate of the active sites of the organic lithium supplement participating in the electrochemical reaction; the carbon nano skeleton prepared by the one-dimensional carbon nanomaterial and the two-dimensional carbon nanomaterial can improve the conductivity of the composite lithium supplement material, thereby reducing the decomposition voltage platform, so that lithium can be removed within the battery voltage range, thereby achieving a lithium supplement effect.
  • the composite lithium supplement material does not have mass residue after lithium is removed from the battery, which can improve energy density and cycle storage performance, and has broad application prospects.
  • the mass ratio of the carbon nanoframework to the organic lithium supplement is (3-30): 100, preferably (5-15): 100.
  • the mass ratio of the one-dimensional carbon nanomaterial to the two-dimensional carbon nanomaterial in the carbon nanoframework is (0.1-10): 1, preferably (0.3-3.0): 1.
  • the mass ratio of the carbon nanoframe to the organic lithium supplement can be 3:100, 5:100, 8:100, 10:100, 15:100, 20:100, 25:100, 30:100, etc.
  • the mass ratio of the one-dimensional carbon nanomaterial to the two-dimensional carbon nanomaterial can be 0.1:1, 0.3:1, 0.5:1, 1.0:1, 2.0:1, 3.0:1, 4.0:1, 5.0:1, 6.0:1, 7.0:1, 8.0:1, 9.0:1, 10.0:1, etc.
  • the one-dimensional carbon nanomaterial is selected from at least one of carbon nanotubes and carbon nanofibers, and may be any one or two of the above, and the carbon nanotube may be a single-walled carbon nanotube, a multi-walled carbon nanotube, etc.
  • the two-dimensional carbon nanomaterial is selected from at least one of graphene, graphene oxide, and redox graphene, and may be any one, two, or three of the above.
  • the organic lithium supplement agent is selected from at least one of Li 2 C 2 O 4 , Li 2 C 4 O 4 , Li 2 C 3 O 5 and Li 2 C 4 O 6 , and may be any one or more of the above.
  • the carbon nano skeleton is formed by mixing a one-dimensional carbon nano material and a two-dimensional carbon nano material, and then sequentially subjected to ultrasonic dispersion and spray drying, and a uniformly mixed three-dimensional conductive network structure is obtained after ultrasonic dispersion and spray drying.
  • the particle size of the prepared composite lithium supplement material is 1 ⁇ m-30 ⁇ m, preferably 2 ⁇ m-10 ⁇ m.
  • the distribution uniformity of the organic lithium supplement agent is higher at a smaller particle size, which is conducive to further improving the utilization rate of the active sites of the organic lithium supplement agent particles participating in the electrochemical reaction.
  • the particle size of the composite lithium supplement material can be 1 ⁇ m, 2 ⁇ m, 5 ⁇ m, 8 ⁇ m, 10 ⁇ m, 15 ⁇ m, 20 ⁇ m, 25 ⁇ m, 30 ⁇ m, etc.
  • the diameter of the one-dimensional carbon nanomaterial is 0.01 ⁇ m-8 ⁇ m
  • the particle size of the two-dimensional carbon nanomaterial is 5 ⁇ m-50 ⁇ m
  • the average particle size of the organic lithium supplement is 2 ⁇ m-20 ⁇ m. It is preferable to control the particle size within the above range to further improve the utilization rate of the active sites of the organic lithium supplement particles participating in the electrochemical reaction.
  • the composite lithium supplement material provided by the embodiment of the present disclosure uses one-dimensional carbon nanomaterials and two-dimensional carbon nanomaterials to form a multifunctional conductive agent with a three-dimensional conductive network, which can simultaneously have the multifunctional characteristics of catalyzing the decomposition of organic lithium supplement agents and improving electrical conductivity.
  • the catalytic effect of the three-dimensional conductive network is better than that of traditional metal oxides, and the price is cheap, which is conducive to reducing costs.
  • using carbon materials as catalysts completely avoids the quality residue caused by the addition of metal catalysts and some other subsequent problems.
  • the present disclosure also provides a method for preparing a composite lithium supplement material, comprising: loading an organic lithium supplement agent on a carbon nanoframe having a three-dimensional conductive network.
  • the specific loading method is not limited, and the loading can be performed by spray drying. As shown in FIG1 , the method specifically comprises the following steps:
  • One-dimensional carbon nanomaterials, two-dimensional carbon nanomaterials and an organic lithium supplement are mixed in a solvent system, and a dispersed system is obtained after ultrasonic treatment, and the raw materials are mixed uniformly through ultrasonic treatment.
  • the mass ratio of the one-dimensional carbon nanomaterial, the two-dimensional carbon nanomaterial and the organic lithium supplement agent is (1.5-15):(1.5-15):100, preferably (4-7.5):(4-7.5):100.
  • the prepared composite lithium supplement material has good conductivity and can also achieve a good lithium supplement effect.
  • the mass ratio of the one-dimensional carbon nanomaterial, the two-dimensional carbon nanomaterial and the organic lithium supplement agent can be 1.5:1.5:100, 2.5:2.5:100, 4.0:4.0:100, 5.5:5.5:100, 7.5:7.5:100, 9.0:10.0:100, 12.0:13.0:100, 15.0:15.0:100, etc.
  • the amount of the one-dimensional carbon nanomaterial and the two-dimensional carbon nanomaterial can be the same or slightly different, within the above ratio range.
  • the raw material selection of the one-dimensional carbon nanomaterial, the two-dimensional carbon nanomaterial and the organic lithium supplement agent refers to the above description of the composite lithium supplement material.
  • the total solid content of the one-dimensional carbon nanomaterial, the two-dimensional carbon nanomaterial and the organic lithium supplement is 0.2%-10%, preferably 1%-8%.
  • the solid content of the dispersed system is controlled to ensure that the raw materials are mixed evenly, and the solvent can be quickly removed by spray drying.
  • the specific type of the solvent is not limited, and it can be water.
  • the total solid content of the one-dimensional carbon nanomaterial, the two-dimensional carbon nanomaterial and the organic lithium supplement agent can be 0.2%, 0.5%, 1.0%, 3.0%, 5.0%, 8.0%, 10.0%, etc.
  • the dispersed system (suspension) is spray-dried to obtain powder particles.
  • a three-dimensional conductive network can be formed, and the organic lithium supplement agent can be evenly dispersed to form a composite lithium supplement material.
  • the feed inlet temperature is controlled to be 170°C-240°C
  • the discharge port temperature is controlled to be 90°C-120°C
  • the feed rate is 10mL/min-60mL/min
  • the feed inlet temperature is controlled to be 200°C-220°C
  • the discharge port temperature is controlled to be 100°C-120°C
  • the feed rate is 30mL/min-50mL/min.
  • the spray drying method is to spray the prepared slurry into dispersed, fine droplets, and then use hot gas to remove the water in the droplets to form fine particles with controllable moisture and easy to form.
  • the spray-dried powder is spherical.
  • the organic lithium supplement and carbon material particles in the spray slurry are relatively fine.
  • the particles aggregate and the droplets form a spherical shape under the action of surface tension. After the water evaporates, the spherical shape is retained.
  • the spherical particles formed are of different sizes.
  • spray drying is carried out in a spray drying granulation device, and the specific process includes: using a peristaltic pump to transport the prepared suspension to a spray dryer for spray drying, the peristaltic pump transports the suspension to the nozzle and sprays it out together with compressed air and dries it (feeding and drying are carried out simultaneously), and the drying time is controlled to be about 1s.
  • the compressed air pressure of the spray dryer is 0.1-0.8MPa, and the particle size of the powder can be adjusted by controlling the pressure of the compressed air.
  • the nozzle size of the nozzle is integrated into 0.5-2mm, for example, it can be 0.5mm, 0.8mm, 1.0mm, 1.2mm, 1.5mm, 1.8mm or 2.0mm, etc.
  • the feed port temperature can be controlled to be 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, etc.
  • the discharge port temperature can be 90°C, 100°C, 110°C, 120°C, etc.
  • the feed rate can be 10mL/min, 20mL/min, 30mL/min, 40mL/min, 50mL/min, 60mL/min, etc.
  • the powder particles are calcined, and the solid phase sintering between the initial particles is heat treated, which greatly improves the crystallinity and structural stability of the composite lithium supplement material.
  • the present invention uses a method combining spray drying and solid phase method to prepare the obtained particles, which have narrow size distribution, good fluidity, and controllable morphology and composition.
  • the spherical particles reduce the diffusion resistance of Li + , shorten the diffusion path of Li + , and are conducive to improving the capacity of the battery.
  • the calcination temperature is controlled to be 200°C-350°C
  • the calcination time is 3h-8h
  • the heating rate is controlled to be 3°C/min-5°C/min.
  • the low-temperature calcination method is adopted, and under the calcination temperature condition, the organic lithium supplement agent will not decompose (thermogravimetric analysis of lithium oxalate Li2C2O4 shows that the decomposition temperature is about 450°C), and the thermal decomposition temperature of lithium squarate Li2C4O4 is higher than 300°C.
  • the calcination temperature can be 200°C, 250°C, 300°C, 350°C, etc.
  • the calcination time can be 3h, 4h, 5h, 6h, 7h, 8h, etc.
  • the heating rate can be 3°C/min, 4°C/min, 5°C/min, etc.
  • calcination is performed under an inert atmosphere to avoid uncontrolled oxidation.
  • the type of the inert atmosphere is not limited, and it may be argon, nitrogen, etc., and may be a single type of gas or a mixed gas.
  • the disclosed embodiment also provides a positive electrode plate slurry, comprising a positive electrode active material and a lithium supplement additive, wherein the lithium supplement additive is the above-mentioned composite lithium supplement material.
  • the mass ratio of the positive electrode active material to the composite lithium supplement material is 100:(1-10), and the amount of the composite lithium supplement material is preferably controlled within the above range to achieve a more ideal lithium supplement effect.
  • the positive electrode active material is selected from at least one of lithium nickel manganese oxide (LiNi 0.5 Mn 1.5 O 4 ), lithium cobalt oxide (LiCoO 2 ), lithium manganese oxide (LiMn 2 O 4 ), lithium iron phosphate (LiFePO 4 ), lithium nickel cobalt manganese oxide (Li(Ni,Co,Mn)O 2 ) and lithium nickel cobalt aluminum oxide (Li(Ni,Co,Al)O 2 ), and may be any one or more of the above.
  • a binder may be PVDF, etc.
  • the conductive agent may be carbon black, etc.
  • the embodiment of the present disclosure also provides a positive electrode plate, including a positive electrode current collector and a positive electrode active coating coated on the positive electrode current collector, wherein the positive electrode active coating is formed by the positive electrode plate slurry.
  • the type of the positive electrode current collector is not limited, and it can be a positive electrode current collector commonly used in lithium-ion batteries, such as aluminum foil.
  • the present disclosure also provides a lithium-ion battery, including the above-mentioned positive electrode plate, and may also include a negative electrode plate, an electrolyte, a separator, etc.
  • a composite lithium supplement material into the positive electrode plate, a multifunctional conductive agent with a three-dimensional conductive network is formed using one-dimensional carbon nanomaterials and two-dimensional carbon nanomaterials, which can simultaneously have the multifunctional properties of catalyzing the decomposition of an organic lithium supplement agent and improving electrical conductivity.
  • the decomposition voltage of the prepared composite lithium supplement material is lower than the decomposition voltage of a single conductive carbon composite lithium supplement agent, and the decomposition potential can be below 4.4V.
  • This embodiment provides a method for preparing a composite lithium supplement material, which adopts a spray drying method to prepare a carbon composite lithium oxalate material, comprising the following steps:
  • the carbon nanotube is a hydroxylated carbon nanotube with a length of 0.5-2 ⁇ m; the graphene is graphene oxide with a particle size between 10-30 ⁇ m.
  • the dispersed system was spray dried to obtain powder particles.
  • the corresponding drying feed inlet temperature was 220° C.
  • the discharge port temperature was 110° C.
  • the feed rate was 50 mL/min
  • the drying time was 1 s to obtain powder particles.
  • the powder particles were calcined at low temperature, and the temperature was raised to 300°C at a heating rate of 4°C/min and kept warm for 5 hours to finally prepare a composite lithium supplement material.
  • the electron microscope image of the composite lithium supplement material prepared in this embodiment is shown in Figure 2, and it can be seen that the composite lithium supplement material has a spherical morphology and a three-dimensional conductive network structure.
  • the XRD comparison diagram of the composite lithium supplement material before and after calcination is shown in Figure 3, and it can be seen that the peak intensity of the material before and after calcination is significantly enhanced, and the crystal structure is well developed, indicating that the material has a high degree of crystallization and high crystallinity, which is conducive to ion diffusion and improves electrochemical performance.
  • This embodiment provides a method for preparing a composite lithium supplement material, which adopts a spray drying method to prepare a carbon composite lithium oxalate material, comprising the following steps:
  • the dispersed system was spray dried to obtain powder particles.
  • the corresponding drying feed port temperature was 180° C.
  • the discharge port temperature was 90° C.
  • the feed rate was 50 mL/min to obtain powder particles.
  • the powder particles were calcined at low temperature, the temperature was raised to 300°C at a heating rate of 4°C/min, and the temperature was kept for 5 hours to finally prepare a composite lithium supplement material.
  • This embodiment provides a method for preparing a composite lithium supplement material, which adopts a spray drying method to prepare a carbon composite lithium oxalate material, comprising the following steps:
  • the dispersed system was spray dried to obtain powder particles.
  • the corresponding drying feed port temperature was 220° C.
  • the discharge port temperature was 110° C.
  • the feed rate was 50 mL/min to obtain powder particles.
  • the powder particles were calcined at low temperature, and the temperature was raised to 300°C at a heating rate of 4°C/min and kept warm for 5 hours to finally prepare a composite lithium supplement material.
  • This embodiment provides a method for preparing a composite lithium supplement material, which adopts a spray drying method to prepare a carbon composite lithium oxalate material, comprising the following steps:
  • the dispersed system was spray dried to obtain powder particles.
  • the corresponding drying feed port temperature was 220° C.
  • the discharge port temperature was 110° C.
  • the feed rate was 50 mL/min to obtain powder particles.
  • the powder particles were calcined at low temperature, and the temperature was raised to 300°C at a heating rate of 4°C/min and kept warm for 5 hours to finally prepare a composite lithium supplement material.
  • This embodiment provides a method for preparing a composite lithium supplement material, which adopts a spray drying method to prepare a carbon composite lithium oxalate material, comprising the following steps:
  • the powder particles were calcined at low temperature, and the temperature was raised to 350°C at a heating rate of 4°C/min and kept warm for 5 hours to finally prepare a composite lithium supplement material.
  • This embodiment provides a method for preparing a composite lithium supplement material, which adopts a spray drying method to prepare a carbon composite lithium squarate material, comprising the following steps:
  • the dispersed system was spray dried to obtain powder particles.
  • the corresponding drying feed port temperature was 220° C.
  • the discharge port temperature was 110° C.
  • the feed rate was 50 mL/min to obtain powder particles.
  • the powder particles were calcined at low temperature, and the temperature was raised to 250°C at a heating rate of 4°C/min and kept warm for 5 hours to finally prepare a composite lithium supplement material.
  • This comparative example provides a method for preparing a composite lithium supplement material, which adopts a spray drying method to prepare a carbon composite lithium oxalate material, comprising the following steps:
  • the powder particles were calcined at low temperature, and the temperature was raised to 300°C at a heating rate of 4°C/min and kept warm for 5 hours to finally prepare a composite lithium supplement material.
  • This comparative example provides a method for preparing a composite lithium supplement material, which adopts a spray drying method to prepare a carbon composite lithium oxalate material, comprising the following steps:
  • the dispersed system was spray dried to obtain powder particles.
  • the corresponding drying feed inlet temperature was 220°C and the discharge outlet temperature was The temperature was 110° C. and the feed rate was 50 mL/min to obtain powder particles.
  • the powder particles were calcined at low temperature, and the temperature was raised to 300°C at a heating rate of 4°C/min and kept warm for 5 hours to finally prepare a composite lithium supplement material.
  • This comparative example provides a method for preparing a composite lithium supplement material, which adopts a spray drying method to prepare a carbon composite lithium oxalate material, comprising the following steps:
  • the dispersed system was spray dried to obtain powder particles.
  • the corresponding drying feed port temperature was 180° C.
  • the discharge port temperature was 80° C.
  • the feed rate was 50 mL/min to obtain powder particles.
  • the powder particles were calcined at low temperature, and the temperature was raised to 300°C at a heating rate of 4°C/min and kept warm for 5 hours to finally prepare a composite lithium supplement material.
  • This comparative example provides a method for preparing a composite lithium supplement material, which adopts a spray drying method to prepare a carbon composite lithium oxalate material, comprising the following steps:
  • the dispersed system was spray dried to obtain powder particles.
  • the corresponding drying feed port temperature was 240° C.
  • the discharge port temperature was 120° C.
  • the feed rate was 50 mL/min to obtain powder particles.
  • This comparative example provides a method for preparing a composite lithium supplement material, which adopts a spray drying method to prepare a carbon composite lithium oxalate material, comprising the following steps:
  • the dispersed system was spray dried to obtain powder particles.
  • the corresponding drying feed port temperature was 220° C.
  • the discharge port temperature was 110° C.
  • the feed rate was 50 mL/min to obtain powder particles.
  • Example 11 does not have a sintering process. During the spray drying process, the three-dimensional skeleton and the organic lithium supplement agent are instantly combined and formed simultaneously.
  • This embodiment provides a method for preparing a composite lithium supplement material, which adopts a spray drying method to prepare a carbon composite lithium oxalate material, comprising the following steps:
  • the carbon nanotube is a hydroxylated carbon nanotube with a length of 0.5-2 ⁇ m; the graphene is graphene oxide with a particle size between 10-30 ⁇ m.
  • This embodiment provides a method for preparing a composite lithium supplement material, which adopts a spray drying method to prepare a carbon composite lithium oxalate material, comprising the following steps:
  • the carbon nanotube is a hydroxylated carbon nanotube with a length of 0.5-2 ⁇ m; the graphene is graphene oxide with a particle size between 10-30 ⁇ m.
  • This embodiment provides a method for preparing a composite lithium supplement material, which adopts a spray drying method to prepare a carbon composite lithium oxalate material, comprising the following steps:
  • the carbon nanotube is a hydroxylated carbon nanotube with a length of 0.5-2 ⁇ m; the graphene is graphene oxide with a particle size between 10-30 ⁇ m.
  • This embodiment provides a method for preparing a composite lithium supplement material, which adopts a spray drying method to prepare a carbon composite lithium oxalate material, comprising the following steps:
  • the carbon nanotube is a hydroxylated carbon nanotube with a length of 0.5-2 ⁇ m; the graphene is graphene oxide with a particle size between 10-30 ⁇ m.
  • This comparative example provides a method for preparing a composite lithium supplement material, which adopts a spray drying method to prepare a carbon composite lithium oxalate material, comprising the following steps:
  • the dispersed system was spray dried to obtain powder particles.
  • the corresponding drying feed port temperature was 220° C.
  • the discharge port temperature was 100° C.
  • the feed rate was 50 mL/min to obtain powder particles.
  • the powder particles were calcined at low temperature, and the temperature was raised to 300°C at a heating rate of 4°C/min and kept warm for 5 hours to finally prepare a composite lithium supplement material.
  • This comparative example provides a method for preparing a composite lithium supplement material, which adopts a spray drying method to prepare a carbon composite lithium oxalate material, comprising the following steps:
  • the dispersed system was spray dried to obtain powder particles.
  • the corresponding drying feed port temperature was 220° C.
  • the discharge port temperature was 110° C.
  • the feed rate was 50 mL/min to obtain powder particles.
  • the powder particles were calcined at low temperature, and the temperature was raised to 300°C at a heating rate of 4°C/min and kept warm for 5 hours to finally prepare a composite lithium supplement material.
  • This comparative example provides a method for preparing a composite lithium supplement material, which adopts a spray drying method to prepare a carbon composite lithium oxalate material, comprising the following steps:
  • the dispersed system was spray dried to obtain powder particles.
  • the corresponding drying feed port temperature was 200° C.
  • the discharge port temperature was 100° C.
  • the feed rate was 50 mL/min to obtain powder particles.
  • the powder particles were calcined at low temperature, and the temperature was raised to 300°C at a heating rate of 4°C/min and kept warm for 5 hours to finally prepare a composite lithium supplement material.
  • the test method includes the steps of slurry stirring, coating, drying, tableting, assembly, and cabinet testing. Specifically, the composite lithium supplement material, conductive agent SP, and binder PVDF are mixed in a mass ratio of 90:5:5, and NMP is added to stir the system in a stirrer until the system is uniform to obtain a uniform slurry. The slurry is evenly coated on the positive electrode current collector aluminum foil. The surface was placed in a vacuum oven at 120°C for drying, and then pressed to obtain a positive electrode sheet. Finally, the positive electrode sheet, the isolation film (2500), metal lithium, and the electrolyte (1 mol/L lithium hexafluorophosphate solution) were assembled into a button battery.
  • Performance test conditions The specific capacity is tested at a charging voltage of 4.5V and a charging rate of 0.1C.
  • Comparing Examples 1-4 and Comparative Examples 1-3 since Comparative Example 1 did not use carbon source 1 and carbon source 2 at the same time, Comparative Example 2 did not use carbon source 1, and Comparative Example 3 did not use carbon source 2, the sample after spray drying failed to form a three-dimensional conductive network, the contact sites between the lithium replenishing material and the carbon material were few, and the utilization rate of the active sites was low, resulting in poor conductivity of the composite lithium replenishing material, a high lithium desorption voltage platform, and lithium cannot be desorbed within the operating voltage range, and the lithium replenishment effect cannot be achieved.
  • Example 1 has the lowest decomposition voltage platform, mainly because the ratio of the organic lithium supplement agent and the conductive agent is appropriate, the sintering temperature is appropriate, the crystallinity is improved, and the lithium supplement effect is the best.
  • Example 7 after reducing the ratio of carbon source 1 and carbon source 2, the voltage platform increased and the battery capacity decreased, indicating that the ratio of carbon source 1 to carbon source 2 was too small, and the conductive network formed could not be completely composited with the lithium supplement material, resulting in low activity of some lithium supplement materials and low performance of the composite lithium supplement material.
  • Example 8 increasing the ratio of carbon source 1 to carbon source 2 can improve conductivity to a certain extent and reduce the voltage platform, but because the carbon source itself does not participate in the discharge reaction, the excessive amount of carbon source with no active substance will inevitably promote side reactions, affect the material strength, and weaken the lithium supplement effect, so the amount added should be appropriate.
  • Example 9 and Example 10 the spray drying temperature was changed to 180°C and 240°C, the voltage platform increased, and the performance decreased. Since the temperature was too low, the evaporation of water during the spraying process slowed down, the amount of solvent increased, and the already dried or semi-dried product dissolved, resulting in a decrease in yield. If the temperature was too high, the melting point of the material or the denaturation temperature of the active substance would be reached, affecting the dry strength of the powder particles and resulting in reduced performance of the composite lithium supplement material.
  • Example 11 the low-temperature sintering step is not adopted.
  • the powder particles obtained after spray drying are directly used for the buckle test.
  • the voltage platform increases and the performance decreases. Since the low-temperature sintering process is not added, the material crystallinity is low, and the composite effect of the carbon material and the organic lithium replenisher is poor, resulting in poor lithium replenishment effect.
  • Examples 12-15 changed the amount of carbon nanotubes and graphene used.
  • Examples 13 and 14 had low voltage platforms and better overall performance.
  • the material prepared in Example 15 had limitations when used as a positive electrode material due to its high voltage platform.
  • the present invention disperses an organic lithium supplement agent on a carbon nano skeleton with a three-dimensional conductive network structure, so that the organic lithium supplement agent is more evenly dispersed, and the utilization rate of the organic lithium supplement agent participating in the electrochemical reaction active site is improved.
  • the carbon nano skeleton can also improve the conductivity of the composite lithium supplement material, thereby reducing the decomposition voltage platform, so that lithium can be removed within the battery voltage range, thereby achieving a lithium supplement effect.
  • the preparation method provided by the present invention mainly includes ultrasonic dispersion, spray drying and calcination. The process is simple and easy, the feasibility is strong, and it can be mass-produced continuously, and has very good industrial application prospects.

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Abstract

本公开属于锂离子电池材料技术领域，具体涉及一种复合补锂材料、其制备方法和应用。将有机补锂剂分散在具有的三维导电网络结构的碳纳米骨架上，利用该三维导电网络结构使有机补锂剂得到更均匀地分散，提高有机补锂剂参与电化学反应活性位点的利用率，同时碳纳米骨架还可以提高复合补锂材料的导电性，从而降低分解电压平台。

Description

一种复合补锂材料、其制备方法和应用 技术领域
本公开属于锂离子电池材料技术领域，具体而言，涉及一种复合补锂材料、其制备方法和应用。
背景技术
锂离子电池具有较高的能量密度和较长的循环寿命，在便携式电子产品和电动汽车等领域都得到非常广泛的应用。在锂离子电池的首周充电过程，会在负极表面形成SEI，这会消耗正极中的活性锂，导致不可逆容量损失。
正极补锂技术是通过补锂的方法补偿锂离子电池的不可逆容量损失，使正极的容量得到恢复，其工艺简单，与现有电池工艺完美兼容，有效提升全电池能密度，还能精准控制预锂化锂离子的容量，非常有利于大规模的商业应用。其中，有机预锂化试剂Li2CxOy(如：Li2C2O4、Li2C4O4、Li2C3O5、Li2C4O6)，也被称为牺牲式锂盐，不仅脱锂后产物为气体，易从电池体系中移除，无任何残留，而且Li2CxOy比容量都较高(＞300mAh g-1)，合成工艺简单，价格适宜，能在空气中稳定存在。然而，有机预锂化试剂为绝缘体，导电性差，分解电压较高(＞4.7V)，无法应用于目前的正极材料中。
因此，亟需开发一种导电性好且分解电压低的有机预锂化试剂。
鉴于此，特提出本公开。
发明内容
本公开的目的包括提供一种复合补锂材料、其制备方法和应用，旨在提供一种导电性好且分解电压低的有机预锂化试剂，以提高电池的电化学性能。
为了实现本公开的上述目的，可采用以下技术方案：
第一方面，本公开的提供的方案包括一种复合补锂材料，包括：具有三维导电网络的碳纳米骨架和分散于碳纳米骨架上的有机补锂剂。
在本公开的一些实施方式中，碳纳米骨架包括一维碳纳米材料和二维碳纳米材料。
在本公开的一些实施方式中，碳纳米骨架和有机补锂剂的质量比为(3-30):100。
在本公开的一些实施方式中，碳纳米骨架和有机补锂剂的质量比为(5-15):100。
在本公开的一些实施方式中，在碳纳米骨架中，一维碳纳米材料和二维碳纳米材料的质量比为(0.1-10):1。
在本公开的一些实施方式中，在碳纳米骨架中，一维碳纳米材料和二维碳纳米材料的质量比为(0.3-3.0):1。
在本公开的一些实施方式中，一维碳纳米材料选自碳纳米管和碳纳米纤维中的至少一种。
在本公开的一些实施方式中，二维碳纳米材料选自石墨烯、氧化石墨烯和氧化还原石墨烯中的至少一种。
在本公开的一些实施方式中，碳纳米骨架是由一维碳纳米材料和二维碳纳米材料混合后再依次经过超声分散和喷雾干燥形成。
在本公开的一些实施方式中，有机补锂剂选自Li2C2O4、Li2C4O4、Li2C3O5和Li2C4O6中的至少一种。
在本公开的一些实施方式中，复合补锂材料的粒径为1μm-30μm。
在本公开的一些实施方式中，复合补锂材料的粒径为2μm-10μm。
在本公开的一些实施方式中，一维碳纳米材料的直径为0.01μm-8μm，二维碳纳米材料的粒径为5μm-50μm。
在本公开的一些实施方式中，有机补锂剂的粒径为2μm-20μm。
第二方面，本公开的提供的方案包括一种复合补锂材料的制备方法，包括：将有机补锂剂负载于具有三维导电网络的碳纳米骨架上。
在本公开的一些实施方式中，将一维碳纳米材料、二维碳纳米材料和有机补锂剂在溶剂体系中混合，经超声处理后得到分散体系，对分散体系进行喷雾干燥得到粉末颗粒。
在本公开的一些实施方式中，一维碳纳米材料、二维碳纳米材料和有机补锂剂的质量比为(1.5-15):(1.5-15):100。
在本公开的一些实施方式中，一维碳纳米材料、二维碳纳米材料和有机补锂剂的质量比为(4-7.5):(4-7.5):100。
在本公开的一些实施方式中，在分散体系中，一维碳纳米材料、二维碳纳米材料和有机补锂剂的总固含量为0.2％-10％。
在本公开的一些实施方式中，在分散体系中，一维碳纳米材料、二维碳纳米材料和有机补锂剂的总固含量为1％-8％。
在本公开的一些实施方式中，在喷雾干燥的过程中，控制进料口温度为170℃-240℃，出料口温度为90℃-120℃。
在本公开的一些实施方式中，在喷雾干燥的过程中，控制进料口温度为200℃-220℃，出料口温度为100℃-120℃。
在本公开的一些实施方式中，在喷雾干燥的过程中，控制进料速率为10mL/min-60mL/min。
在本公开的一些实施方式中，在喷雾干燥的过程中，控制进料速率为30mL/min-50mL/min。
在本公开的一些实施方式中，还包括：将粉末颗粒进行煅烧。
在本公开的一些实施方式中，将粉末颗粒进行煅烧的过程中，控制煅烧温度为200℃-350℃，煅烧时间为3h-8h。
在本公开的一些实施方式中，在煅烧的过程中，控制升温速率为3℃/min-5℃/min。
在本公开的一些实施方式中，在惰性气氛下进行煅烧。
在本公开的一些实施方式中，惰性气氛选自氩气和氮气中的至少一种。
第三方面，本公开的提供的方案包括一种正极极片浆料，包括正极活性材料和补锂添加剂，补锂添加剂为上述任一实施方式中的复合补锂材料或上述任一实施方式中的制备方法制备得到的复合补锂材料。
在本公开的一些实施方式中，正极活性材料和复合补锂材料的质量比为100:(1-10)。
在本公开的一些实施方式中，正极活性材料选自镍锰酸锂(LiNi0.5Mn1.5O4)、钴酸锂(LiCoO2)、锰酸锂(LiMn2O4)、磷酸铁锂(LiFePO4)、镍钴锰酸锂(Li(Ni,Co,Mn)O2)和镍钴铝酸锂(Li(Ni,Co,Al)O2)中的至少一种。
第四方面，本公开的提供的方案包括一种正极极片，包括正极集流体和涂覆于正极集流体上的正极活性涂层，正极活性涂层是由上述任一实施方式中的正极极片浆料形成。
第五方面，本公开的提供的方案包括一种锂离子电池，包括上述实施方式中的正极极片。
通过将有机补锂剂分散在具有的三维导电网络结构的碳纳米骨架上，利用三维导电网络结构使有机补锂剂得到更均匀地分散，提高有机补锂剂参与电化学反应活性位点的利用率，同时碳纳米骨架加入还可以提高复合补锂材料的导电性，从而降低分解电压平台，使得在电池使用电压范围内可以实现脱锂，从而起到补锂效果。同时，本公开中所提供的复合补锂材料在电池中脱锂后不存在质量残留，可以提升能量密度和循环存储性能。
附图说明
为了更清楚地说明本公开实施例的技术方案，下面将对实施例中所需要使用的附 图作简单地介绍，应当理解，以下附图仅示出了本公开的某些实施例，因此不应被看作是对范围的限定，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他相关的附图。
图1为本公开提供复合补锂材料的制备方法的工艺流程图；
图2为实施例1制备得到的复合补锂材料的电镜图；
图3为实施例1的复合补锂材料烧结前后的XRD对比图。
具体实施方式
下面将结合实施例对本公开的实施方案进行详细描述，但是本领域技术人员将会理解，下列实施例仅用于说明本公开，而不应视为限制本公开的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
在本公开中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
本公开实施例提供一种复合补锂材料，包括碳纳米骨架和分散于碳纳米骨架上的有机补锂剂，该碳纳米骨架具有三维导电网络的结构。
在一些实施例中，碳纳米骨架包括一维碳纳米材料和二维碳纳米材料，由一维碳纳米材料和二维碳纳米材料构成三维导电网络。
需要说明的是，将有机补锂剂分散在三维导电网络中，能够提高有机补锂剂参与电化学反应活性位点的利用率；由一维碳纳米材料和二维碳纳米材料制备形成的碳纳米骨架可以提高复合补锂材料的导电性，从而降低分解电压平台，使得在电池使用电压范围内可以实现脱锂，从而起到补锂效果。此外，该复合补锂材料在电池中脱锂后不存在质量残留，可以提升能量密度和循环存储性能，具有广阔的应用前景。
在一些实施例中，碳纳米骨架和有机补锂剂的质量比为(3-30):100，优选为(5-15):100。在碳纳米骨架中一维碳纳米材料和二维碳纳米材料的质量比为(0.1-10):1，优选为(0.3-3.0):1。通过控制一维碳纳米材料、二维碳纳米材料、有机补锂剂的质量比，有利于进一步提高导电性同时降低分解电压，提高电池的电化学性能。
具体地，碳纳米骨架和有机补锂剂的质量比可以为3:100、5:100、8:100、10:100、15:100、20:100、25:100、30:100等，一维碳纳米材料和二维碳纳米材料的质量比可以为0.1:1、0.3:1、0.5:1、1.0:1、2.0:1、3.0:1、4.0:1、5.0:1、6.0:1、7.0:1、8.0:1、9.0:1、 10.0:1等。
在一些实施例中，一维碳纳米材料选自碳纳米管和碳纳米纤维中的至少一种，可以为以上任意一种或两种，碳纳米管可以为单壁碳纳米管、多壁碳纳米管等。二维碳纳米材料选自石墨烯、氧化石墨烯和氧化还原石墨烯中的至少一种，可以为以上任意一种、两种或三种。
在一些实施例中，有机补锂剂选自Li2C2O4、Li2C4O4、Li2C3O5和Li2C4O6中的至少一种，可以为以上任意一种或多种。
在一些实施例中，碳纳米骨架是由一维碳纳米材料和二维碳纳米材料混合后再依次经过超声分散和喷雾干燥形成，通过超声分散和喷雾干燥后得到混合均匀的三维导电网络结构。制备得到的复合补锂材料的粒径为1μm-30μm，优选为2μm-10μm，在较小的粒径下有机补锂剂的分布均匀性更高，有利于进一步提高有机补锂剂颗粒参与电化学反应活性位点的利用率。具体地，复合补锂材料的粒径可以为1μm、2μm、5μm、8μm、10μm、15μm、20μm、25μm、30μm等。
进一步地，一维碳纳米材料的直径为0.01μm-8μm，二维碳纳米材料的粒径为5μm-50μm，有机补锂剂的平均粒径为2μm-20μm。将粒径控制在上述范围内为宜，以进一步提高有机补锂剂颗粒参与电化学反应活性位点的利用率。
需要补充的是，本公开实施例提供的复合补锂材料，利用一维碳纳米材料和二维碳纳米材料形成具有三维导电网络的多功能导电剂，能够同时具有催化有机补锂剂分解和提高电导率的多功能特性，三维导电网络的催化效果优于传统的金属氧化物，且价格便宜，有利于降低成本。此外，以碳材料作为催化剂完全避免了金属催化加入导致的质量残留以及后续一些其他问题。
本公开实施例还提供一种复合补锂材料的制备方法，包括：将有机补锂剂负载于具有三维导电网络的碳纳米骨架上，具体的负载方式不限，可以采用喷雾干燥的方式进行负载，如图1所示，具体包括如下步骤：
S1、超声分散
将一维碳纳米材料、二维碳纳米材料和有机补锂剂在溶剂体系中混合，经超声处理后得到分散体系，通过超声处理使各原料之间混合均匀。
在一些实施例中，一维碳纳米材料、二维碳纳米材料和有机补锂剂的质量比为(1.5-15):(1.5-15):100，优选为(4-7.5):(4-7.5):100，通过控制一维碳纳米材料、二维碳纳米材料和有机补锂剂的质量比，以使制备得到的复合补锂材料具有良好导电性的同时还能够起到很好的补锂效果。
具体地，一维碳纳米材料、二维碳纳米材料和有机补锂剂的质量比可以为 1.5:1.5:100、2.5:2.5:100、4.0:4.0:100、5.5:5.5:100、7.5:7.5:100、9.0:10.0:100、12.0:13.0:100、15.0:15.0:100等，一维碳纳米材料、二维碳纳米材料的用量可以相同也可以略有差别，在上述比例范围内即可。一维碳纳米材料、二维碳纳米材料和有机补锂剂的具有原料选择参照上述关于复合补锂材料的说明内容。
在一些实施例中，在分散体系中，一维碳纳米材料、二维碳纳米材料和有机补锂剂的总固含量为0.2％-10％，优选为1％-8％。通过控制分散体系的固含量保证原料混合均匀，并可以通过喷雾干燥的方式快速去除溶剂。溶剂的具体种类不限，可以为水。
具体地，在分散体系中，一维碳纳米材料、二维碳纳米材料和有机补锂剂的总固含量可以为0.2％、0.5％、1.0％、3.0％、5.0％、8.0％、10.0％等。
S2、喷雾干燥
对分散体系(悬浮液)进行喷雾干燥得到粉末颗粒，在喷雾干燥的过程中能够形成三维导电网络，并均匀分散有机补锂剂形成复合补锂材料。
在一些实施例中，在喷雾干燥的过程中，控制进料口温度为170℃-240℃，出料口温度为90℃-120℃，进料速率为10mL/min-60mL/min；优选地，在喷雾干燥的过程中，控制进料口温度为200℃-220℃，出料口温度为100℃-120℃，进料速率为30mL/min-50mL/min。通过控制喷雾干燥的温度和进料速率，在干燥后得到均一的粉末。
需要说明的是，喷雾干燥方法是将配制的料浆喷洒为分散的、细小的液滴，再用热气体将液滴中水分排除，制成水分可控、易于成型的细颗粒。喷雾干燥粉料呈球形，喷雾料浆中的有机补锂剂和碳材料颗粒较细小，颗粒间聚集和雾滴在表面张力作用下形成球状，水分蒸发掉后，球形被保留下来。同时，由于喷雾形成的雾滴大小不一，水分蒸发速率不同，所以形成的球形颗粒大小不同。
具体地，喷雾干燥是在喷雾干燥造粒设备中进行，具体过程包括：将配制的悬浮液利用蠕动泵输送至喷雾干燥器中进行喷雾干燥，蠕动泵将悬浮液输送至喷嘴处和压缩空气一起喷出并干燥(进料和干燥同时进行)，干燥时间控制约为1s。其中喷雾干燥器的压缩空气压力为0.1～0.8MPa，，可通过控制压缩空气的压力调整粉体的粒径尺寸大小。喷头的喷嘴尺寸一体化为0.5～2mm，例如可以是0.5mm、0.8mm、1.0mm、1.2mm、1.5mm、1.8mm或2.0mm等。
具体地，在喷雾干燥的过程中，控制进料口温度可以为170℃、180℃、190℃、200℃、210℃、220℃、230℃、240℃等，出料口温度可以为90℃、100℃、110℃、120℃等，进料速率可以为10mL/min、20mL/min、30mL/min、40mL/min、50mL/min、60mL/min等。
S3、煅烧
将粉末颗粒进行煅烧，通过热处理初始颗粒间的固相烧结，极大地提高了复合补锂材料的结晶度和结构稳定性。本公开利用喷雾干燥-固相法相结合的方法进行制备，得到的颗粒具有窄的尺寸分布、良好的流动性，而且还具有形貌和成分可控等优点；球形颗粒减小了Li+的扩散阻力，缩短了Li+的扩散路径，有利于提高电池的容量。
在一些实施例中，将粉末颗粒进行煅烧的过程中，控制煅烧温度为200℃-350℃，煅烧时间为3h-8h，控制升温速率为3℃/min-5℃/min。采用低温煅烧的方式，在该煅烧温度条件下使有机补锂剂不会分解(草酸锂Li2C2O4热重分析显示分解温度为450℃左右)，方酸锂Li2C4O4热解温度高于300℃。
具体地，煅烧温度可以为200℃、250℃、300℃、350℃等，煅烧时间可以为3h、4h、5h、6h、7h、8h等，升温速率可以为3℃/min、4℃/min、5℃/min等。
在一些实施例中，在惰性气氛下进行煅烧，以避免不可控的氧化，惰性气氛的种类不限，可以为氩气、氮气等，可以为单一种类的气体也可以为混合气体。
本公开实施例还提供一种正极极片浆料，包括正极活性材料和补锂添加剂，补锂添加剂为上述复合补锂材料。
在一些实施例中，正极活性材料和复合补锂材料的质量比为100:(1-10)，复合补锂材料的用量控制在上述范围内为宜，以起到更理想的补锂效果。
在一些实施例中，正极活性材料选自镍锰酸锂(LiNi0.5Mn1.5O4)、钴酸锂(LiCoO2)、锰酸锂(LiMn2O4)、磷酸铁锂(LiFePO4)、镍钴锰酸锂(Li(Ni,Co,Mn)O2)和镍钴铝酸锂(Li(Ni,Co,Al)O2)中的至少一种，可以为以上任意一种或几种。
在一些实施例中，还可以包括制备正极极片浆料的其他常规组分，如粘结剂、导电剂等，具体种类不限。粘结剂可以为PVDF等，导电剂可以为炭黑等。
本公开实施例还提供一种正极极片，包括正极集流体和涂覆于正极集流体上的正极活性涂层，正极活性涂层是由上述正极极片浆料形成。
需要说明的是，正极集流体的种类不限，可以为锂离子电池常用的正极集流体，如铝箔等。
本公开实施例还提供的一种锂离子电池，包括上述正极极片，还可以包括负极极片、电解液、隔膜等。通过在正极极片中引入复合补锂材料，利用一维碳纳米材料和二维碳纳米材料形成具有三维导电网络的多功能导电剂，能够同时具有催化有机补锂剂分解和提高电导率的多功能特性，所制备的复合补锂材料分解电压低于单一的导电碳复合补锂剂的分解电压，分解电位可以为4.4V以下。
以下结合实施例对本公开的特征和性能作进一步的详细描述。
实施例1
本实施例提供了一种复合补锂材料的制备方法，采用喷雾干燥的方式制备碳复合草酸锂材料，包括以下步骤：
(1)超声分散
按质量比草酸锂：碳纳米管：石墨烯＝100:5:5称取上述原料，将其溶解并分散与去离子水中，浆料固含量为5％。其中碳纳米管为羟基化碳纳米管，长度为0.5-2μm；石墨烯为氧化石墨烯，粒径在10-30μm之间。
(2)喷雾干燥
对分散体系进行喷雾干燥得到粉末颗粒，相应干燥的进料口温度220℃，出料口温度为110℃，进料速率为50mL/min，干燥时间为1s，得到粉末颗粒。
(3)煅烧
将粉末颗粒进行低温煅烧，控制以4℃/min的升温速率升温至300℃，保温5h，最终制备出复合补锂材料。
本实施例制备得到的复合补锂材料的电镜图如图2所示，可以看出复合补锂材料形貌为球形，具有三维导电网络结构。复合补锂材料煅烧前后的XRD对比图如图3所示，可以看出，煅烧前后材料的峰强明显增强，晶体结构发育良好，说明该材料晶体化程度高，结晶度高，有利于离子扩散，提升电化学性能。
实施例2
本实施例提供了一种复合补锂材料的制备方法，采用喷雾干燥的方式制备碳复合草酸锂材料，包括以下步骤：
(1)超声分散
具体步骤同实施例1的步骤(1)。
(2)喷雾干燥
对分散体系进行喷雾干燥得到粉末颗粒，相应干燥的进料口温度为180℃，出料口温度为90℃，进料速率为50mL/min，得到粉末颗粒。
(3)煅烧
将粉末颗粒进行低温煅烧，控制以4℃/min的升温速率升温至300℃，保温5h，最终制备出复合补锂材料。
实施例3
本实施例提供了一种复合补锂材料的制备方法，采用喷雾干燥的方式制备碳复合草酸锂材料，包括以下步骤：
(1)超声分散
按质量比草酸锂：碳纳米管：石墨烯＝100:5:2.5称取原料，将其溶解并分散与去离子水中，浆料固含量为5％，将所得浆料超声分散30min得到分散体系。
(2)喷雾干燥
对分散体系进行喷雾干燥得到粉末颗粒，相应干燥的进料口温度为220℃，出料口温度为110℃，进料速率为50mL/min，得到粉末颗粒。
(3)煅烧
将粉末颗粒进行低温煅烧，控制以4℃/min的升温速率升温至300℃，保温5h，最终制备出复合补锂材料。
实施例4
本实施例提供了一种复合补锂材料的制备方法，采用喷雾干燥的方式制备碳复合草酸锂材料，包括以下步骤：
(1)超声分散
按质量比草酸锂：碳纤维：石墨烯＝100:2.5:5称取原料，将其溶解并分散与去离子水中，浆料固含量为5％，将所得浆料超声分散30min得到分散体系。
(2)喷雾干燥
对分散体系进行喷雾干燥得到粉末颗粒，相应干燥的进料口温度为220℃，出料口温度为110℃，进料速率为50mL/min，得到粉末颗粒。
(3)煅烧
将粉末颗粒进行低温煅烧，控制以4℃/min的升温速率升温至300℃，保温5h，最终制备出复合补锂材料。
实施例5
本实施例提供了一种复合补锂材料的制备方法，采用喷雾干燥的方式制备碳复合草酸锂材料，包括以下步骤：
(1)超声分散
按质量比草酸锂：碳纤维：石墨烯＝100:2.5:5称取原料，将其溶解并分散与去离子水中，浆料固含量为5％，将所得浆料超声分散30min得到分散体系。
(2)喷雾干燥
对分散体系进行喷雾干燥得到粉末颗粒，相应干燥的进料口温度为220℃，出料口温度为110℃，进料速率为50mL/min，得到粉末颗粒。
(3)煅烧
将粉末颗粒进行低温煅烧，控制以4℃/min的升温速率升温至350℃，保温5h，最终制备出复合补锂材料。
实施例6
本实施例提供了一种复合补锂材料的制备方法，采用喷雾干燥的方式制备碳复合方酸锂材料，包括以下步骤：
(1)超声分散
按质量比方酸锂(Li2C4O4)：碳纤维：石墨烯＝100:5:5称取原料，将其溶解并分散与去离子水中，浆料固含量为5％，将所得浆料超声分散30min得到分散体系。
(2)喷雾干燥
对分散体系进行喷雾干燥得到粉末颗粒，相应干燥的进料口温度为220℃，出料口温度为110℃，进料速率为50mL/min，得到粉末颗粒。
(3)煅烧
将粉末颗粒进行低温煅烧，控制以4℃/min的升温速率升温至250℃，保温5h，最终制备出复合补锂材料。
实施例7
本对比例提供了一种复合补锂材料的制备方法，采用喷雾干燥的方式制备碳复合草酸锂材料，包括以下步骤：
(1)超声分散
按质量比草酸锂：碳纳米管：石墨烯＝100:2.5:2.5称取原料，将其溶解并分散与去离子水中，浆料固含量为5％，将所得浆料超声分散30min得到分散体系。
(2)喷雾干燥
对分散体系进行喷雾干燥得到粉末颗粒，相应干燥的进料口温度为220℃，出料口温度为110℃，进料速率为50mL/min，得到粉末颗粒。
(3)煅烧
将粉末颗粒进行低温煅烧，控制以4℃/min的升温速率升温至300℃，保温5h，最终制备出复合补锂材料。
实施例8
本对比例提供了一种复合补锂材料的制备方法，采用喷雾干燥的方式制备碳复合草酸锂材料，包括以下步骤：
(1)超声分散
按质量比草酸锂：碳纳米管：石墨烯＝100:10:10称取原料，将其溶解并分散与去离子水中，浆料固含量为5％，将所得浆料超声分散30min得到分散体系。
(2)喷雾干燥
对分散体系进行喷雾干燥得到粉末颗粒，相应干燥的进料口温度为220℃，出料口 温度为110℃，进料速率为50mL/min，得到粉末颗粒。
(3)煅烧
将粉末颗粒进行低温煅烧，控制以4℃/min的升温速率升温至300℃，保温5h，最终制备出复合补锂材料。
实施例9
本对比例提供了一种复合补锂材料的制备方法，采用喷雾干燥的方式制备碳复合草酸锂材料，包括以下步骤：
(1)超声分散
按质量比草酸锂：碳纳米管：石墨烯＝100:5:5称取原料，将其溶解并分散与去离子水中，浆料固含量为5％，将所得浆料超声分散30min得到分散体系。
(2)喷雾干燥
对分散体系进行喷雾干燥得到粉末颗粒，相应干燥的进料口温度为180℃，出料口温度为80℃，进料速率为50mL/min，得到粉末颗粒。
(3)煅烧
将粉末颗粒进行低温煅烧，控制以4℃/min的升温速率升温至300℃，保温5h，最终制备出复合补锂材料。
实施例10
本对比例提供了一种复合补锂材料的制备方法，采用喷雾干燥的方式制备碳复合草酸锂材料，包括以下步骤：
(1)超声分散
按质量比草酸锂：碳纳米管：石墨烯＝100:5:5称取原料，将其溶解并分散与去离子水中，浆料固含量为5％，将所得浆料超声分散30min得到分散体系。
(2)喷雾干燥
对分散体系进行喷雾干燥得到粉末颗粒，相应干燥的进料口温度为240℃，出料口温度为120℃，进料速率为50mL/min，得到粉末颗粒。
(3)煅烧
将粉末颗粒进行低温煅烧，控制以4℃/min的升温速率升温至300℃，保温5h，最终制备出复合补锂材料。
实施例11
本对比例提供了一种复合补锂材料的制备方法，采用喷雾干燥的方式制备碳复合草酸锂材料，包括以下步骤：
(1)超声分散
按质量比草酸锂：碳纳米管：石墨烯＝100:5:5称取原料，将其溶解并分散与去离子水中，浆料固含量为5％，将所得浆料超声分散30min得到分散体系。
(2)喷雾干燥
对分散体系进行喷雾干燥得到粉末颗粒，相应干燥的进料口温度为220℃，出料口温度为110℃，进料速率为50mL/min，得到粉末颗粒。
注：实施例11无烧结工艺，在喷雾干燥过程中，三维骨架和有机补锂剂同时瞬时组合形成。
实施例12
本实施例提供了一种复合补锂材料的制备方法，采用喷雾干燥的方式制备碳复合草酸锂材料，包括以下步骤：
(1)超声分散
按质量比草酸锂：碳纳米管：石墨烯＝100:1.5:1.5称取上述原料，将其溶解并分散与去离子水中，浆料固含量为5％。其中碳纳米管为羟基化碳纳米管，长度为0.5-2μm；石墨烯为氧化石墨烯，粒径在10-30μm之间。
(2)喷雾干燥
具体步骤同实施例1的步骤(2)。
(3)煅烧
具体步骤同实施例1的步骤(3)。
实施例13
本实施例提供了一种复合补锂材料的制备方法，采用喷雾干燥的方式制备碳复合草酸锂材料，包括以下步骤：
(1)超声分散
按质量比草酸锂：碳纳米管：石墨烯＝100:4:4称取上述原料，将其溶解并分散与去离子水中，浆料固含量为5％。其中碳纳米管为羟基化碳纳米管，长度为0.5-2μm；石墨烯为氧化石墨烯，粒径在10-30μm之间。
(2)喷雾干燥
具体步骤同实施例1的步骤(2)。
(3)煅烧
具体步骤同实施例1的步骤(3)。
实施例14
本实施例提供了一种复合补锂材料的制备方法，采用喷雾干燥的方式制备碳复合草酸锂材料，包括以下步骤：
(1)超声分散
按质量比草酸锂：碳纳米管：石墨烯＝100:7.5:7.5称取上述原料，将其溶解并分散与去离子水中，浆料固含量为5％。其中碳纳米管为羟基化碳纳米管，长度为0.5-2μm；石墨烯为氧化石墨烯，粒径在10-30μm之间。
(2)喷雾干燥
具体步骤同实施例1的步骤(2)。
(3)煅烧
具体步骤同实施例1的步骤(3)。
实施例15
本实施例提供了一种复合补锂材料的制备方法，采用喷雾干燥的方式制备碳复合草酸锂材料，包括以下步骤：
(1)超声分散
按质量比草酸锂：碳纳米管：石墨烯＝100:15:15称取上述原料，将其溶解并分散与去离子水中，浆料固含量为5％。其中碳纳米管为羟基化碳纳米管，长度为0.5-2μm；石墨烯为氧化石墨烯，粒径在10-30μm之间。
(2)喷雾干燥
具体步骤同实施例1的步骤(2)。
(3)煅烧
具体步骤同实施例1的步骤(3)。
对比例1
本对比例提供了一种复合补锂材料的制备方法，采用喷雾干燥的方式制备碳复合草酸锂材料，包括以下步骤：
(1)超声分散
按质量比草酸锂：碳纳米管：石墨烯＝100:0:0称取原料，将其溶解并分散与去离子水中，浆料固含量为5％，将所得浆料超声分散30min得到分散体系。
(2)喷雾干燥
对分散体系进行喷雾干燥得到粉末颗粒，相应干燥的进料口温度为220℃，出料口温度为100℃，进料速率为50mL/min，得到粉末颗粒。
(3)煅烧
将粉末颗粒进行低温煅烧，控制以4℃/min的升温速率升温至300℃，保温5h，最终制备出复合补锂材料。
对比例2
本对比例提供了一种复合补锂材料的制备方法，采用喷雾干燥的方式制备碳复合草酸锂材料，包括以下步骤：
(1)超声分散
按质量比草酸锂：碳纳米管：石墨烯＝100:0:5称取原料，将其溶解并分散与去离子水中，浆料固含量为5％，将所得浆料超声分散30min得到分散体系。
(2)喷雾干燥
对分散体系进行喷雾干燥得到粉末颗粒，相应干燥的进料口温度为220℃，出料口温度为110℃，进料速率为50mL/min，得到粉末颗粒。
(3)煅烧
将粉末颗粒进行低温煅烧，控制以4℃/min的升温速率升温至300℃，保温5h，最终制备出复合补锂材料。
对比例3
本对比例提供了一种复合补锂材料的制备方法，采用喷雾干燥的方式制备碳复合草酸锂材料，包括以下步骤：
(1)超声分散
按质量比草酸锂：碳纳米管：石墨烯＝100:5:0称取原料，将其溶解并分散与去离子水中，浆料固含量为5％，将所得浆料超声分散30min得到分散体系。
(2)喷雾干燥
对分散体系进行喷雾干燥得到粉末颗粒，相应干燥的进料口温度为200℃，出料口温度为100℃，进料速率为50mL/min，得到粉末颗粒。
(3)煅烧
将粉末颗粒进行低温煅烧，控制以4℃/min的升温速率升温至300℃，保温5h，最终制备出复合补锂材料。
试验例1
实施例1-5和对比例1-6合成的复合补锂材料分别制成扣式电池，并进行性能测试，结果如表1所示。
测试方法包括搅浆，涂布，干燥，压片，组装，上柜测试等步骤，具体如下：将复合补锂材料、导电剂SP、粘结剂PVDF按质量比90:5:5进行混合，加入NMP在搅拌机作用下搅拌至体系均匀，获得均一浆料。将该浆料均匀涂覆在正极集流体铝箔的 表面上，放入真空烘箱120℃干燥，后续经过压片得到正极极片。最后将正极极片、隔离膜(2500)、金属锂、电解液(为1mol/L的六氟磷酸锂溶液)组装成扣式电池。
性能测试条件：在充电电压4.5V，充电倍率0.1C的条件下测试比容量。
表1复合补锂材料电化学性能


注：表1中碳源1表示一维碳纳米材料，碳源2表示二维碳纳米材料。
由表1可知，实施例中制备得到的复合补锂材料性能明显优于对比例1-3。
对比实施例1-4和对比例1-3，由于对比例1未同时使用碳源1和碳源2，对比例2未使用碳源1，对比例3未使用碳源2，导致喷雾干燥后的样品未能形成三维导电网络，补锂材料和碳材料接触位点少，活性位点利用率低，使得复合补锂材料导电性差，脱锂电压平台高，在使用电压范围内无法脱锂，未能起到补锂效果。
对比实施例1-6，可以看出通过控制有机补锂剂和导电剂(即碳源1和碳源2)的配比、喷雾干燥制备过程、低温烧结过程的参数，可以降低复合补锂材料分解电压平台在4.4V以下，和正极材料混合能达到理想的补锂效果。其中实施例1分解电压平台最低，主要是由于有机补锂剂和导电剂的配比合适，适当的烧结温度，提高结晶度，补锂效果最佳。
实施例7中减少碳源1和碳源2的比例后，出现电压平台升高，电池容量降低的现象，说明碳源1和碳源2用量比过小，所形成的的导电网络无法完全和补锂材料复合，导致部分补锂材料活性较低，复合补锂材料的性能低。实施例8中提高碳源1和碳源2用量比，可一定程度上提高导电性，电压平台降低，但由于碳源本身不参加放电反应，无活性物质的碳源用量比过多会不可避免促进副反应，影响材料强度，削弱补锂效果，故添加量要适当。
实施例9和对实施例10中改变喷雾干燥温度为180℃和240℃，电压平台升高，性能降低，由于温度过低导致喷雾过程中水分挥发变慢，溶剂增多，导致已经干燥或半干的产品溶解，产率降低；温度过高，会达到物料的融化点或活性物质的变性温度，影响粉末颗粒的干燥强度，导致复合补锂材料性能降低。
实施例11不采用低温烧结步骤，将喷雾干燥后得到的粉末颗粒直接用于扣电测试，电压平台升高，性能下降，由于未增加低温烧结工艺，材料结晶度低，碳材料和有机补锂剂复合效果差，导致补锂效果差。
实施例12-15改变了碳纳米管和石墨烯用量，实施例13和实施例14电压平台低，综合性能更好，实施例15制备的材料由于电压平台高应用于正极材料时会有局限性。
以上详细描述了本公开的优选实施方式，但是，本公开并不限于此。在本公开的技术构思范围内，可以对本公开的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本公开所公开的内 容，均属于本公开的保护范围。
工业实用性
本公开将有机补锂剂分散在具有的三维导电网络结构的碳纳米骨架上，使有机补锂剂得到更均匀地分散，提高有机补锂剂参与电化学反应活性位点的利用率，同时碳纳米骨架还可以提高复合补锂材料的导电性，从而降低分解电压平台，使得在电池使用电压范围内可以实现脱锂，从而起到补锂效果。本公开所提供的制备方法主要步骤是超声分散、喷雾干燥和煅烧，工艺简便易行，可实施性强，且可规模化连续生产，具有非常好的工业应用前景。

Claims (33)

  1. 一种复合补锂材料，其特征在于，包括：具有三维导电网络的碳纳米骨架和分散于所述碳纳米骨架上的有机补锂剂。
  2. 根据权利要求1所述的复合补锂材料，其特征在于，所述碳纳米骨架中包括一维碳纳米材料和二维碳纳米材料。
  3. 根据权利要求1或2所述的复合补锂材料，其特征在于，所述碳纳米骨架和所述有机补锂剂的质量比为(3-30):100。
  4. 根据权利要求3所述的复合补锂材料，其特征在于，所述碳纳米骨架和所述有机补锂剂的质量比为(5-15):100。
  5. 根据权利要求2-4中任一项所述的复合补锂材料，其特征在于，在所述碳纳米骨架中，所述一维碳纳米材料和所述二维碳纳米材料的质量比为(0.1-10):1。
  6. 根据权利要求5所述的复合补锂材料，其特征在于，在所述碳纳米骨架中，所述一维碳纳米材料和所述二维碳纳米材料的质量比为(0.3-3.0):1。
  7. 根据权利要求2-6中任一项所述的复合补锂材料，其特征在于，所述一维碳纳米材料选自碳纳米管和碳纳米纤维中的至少一种。
  8. 根据权利要求2-7中任一项所述的复合补锂材料，其特征在于，所述二维碳纳米材料选自石墨烯、氧化石墨烯和氧化还原石墨烯中的至少一种。
  9. 根据权利要求1-8中任一项所述的复合补锂材料，其特征在于，所述有机补锂剂选自Li2C2O4、Li2C4O4、Li2C3O5和Li2C4O6中的至少一种。
  10. 根据权利要求2-9中任一项所述的复合补锂材料，其特征在于，所述复合补锂材料的粒径为1μm-30μm。
  11. 根据权利要求10所述的复合补锂材料，其特征在于，所述复合补锂材料的粒径为2μm-10μm。
  12. 根据权利要求10或11所述的复合补锂材料，其特征在于，所述一维碳纳米材料的直径为0.01μm-8μm，所述二维碳纳米材料的粒径为5μm-50μm。
  13. 根据权利要求10-12中任一项所述的复合补锂材料，其特征在于，所述有机补锂剂的粒径为2μm-20μm。
  14. 一种权利要求1-13中任一项所述复合补锂材料的制备方法，其特征在于，包括：将所述有机补锂剂负载于具有三维导电网络的所述碳纳米骨架上。
  15. 根据权利要求14所述的制备方法，其特征在于，将所述一维碳纳米材料、所述二维碳纳米材料和所述有机补锂剂在溶剂体系中混合，经超声处理后得到分散体系，对所述分散体系进行喷雾干燥得到粉末颗粒。
  16. 根据权利要求15所述的制备方法，其特征在于，所述一维碳纳米材料、所述二维碳纳米材料和所述有机补锂剂的质量比为(1.5-15):(1.5-15):100。
  17. 根据权利要求16所述的制备方法，其特征在于，所述一维碳纳米材料、所述二维碳纳米材料和所述有机补锂剂的质量比为(4-7.5):(4-7.5):100。
  18. 根据权利要求15-17中任一项所述的制备方法，其特征在于，在所述分散体系中，所述一维碳纳米材料、所述二维碳纳米材料和所述有机补锂剂的总固含量为0.2％-10％。
  19. 根据权利要求18所述的制备方法，其特征在于，在所述分散体系中，所述一维碳纳米材料、所述二维碳纳米材料和所述有机补锂剂的总固含量为1％-8％。
  20. 根据权利要求15-19中任一项所述的制备方法，其特征在于，在所述喷雾干燥的过程中，控制进料口温度为170℃-240℃，出料口温度为90℃-120℃。
  21. 根据权利要求20所述的制备方法，其特征在于，在所述喷雾干燥的过程中，控制进料口温度为200℃-220℃，出料口温度为100℃-120℃。
  22. 根据权利要求15-21中任一项所述的制备方法，其特征在于，在所述喷雾干燥的过程中，控制进料速率为10mL/min-60mL/min。
  23. 根据权利要求22所述的制备方法，其特征在于，在所述喷雾干燥的过程中，控制进料速率为30mL/min-50mL/min。
  24. 根据权利要求15-23中任一项所述的制备方法，其特征在于，还包括：将所述粉末颗粒进行煅烧。
  25. 根据权利要求24所述的制备方法，其特征在于，将所述粉末颗粒进行煅烧的过程中，控制煅烧温度为200℃-350℃，煅烧时间为3h-8h。
  26. 根据权利要求25所述的制备方法，其特征在于，在煅烧的过程中，控制升温速率为3℃/min-5℃/min。
  27. 根据权利要求24-26中任一项所述的制备方法，其特征在于，在惰性气氛下进行煅烧。
  28. 根据权利要求27所述的制备方法，其特征在于，所述惰性气氛选自氩气和氮气中的至少一种。
  29. 一种正极极片浆料，其特征在于，包括正极活性材料和补锂添加剂，所述补锂添加剂为权利要求1-13中任一项所述复合补锂材料或权利要求14-28中任一项所述制备方法制备得到的复合补锂材料。
  30. 根据权利要求29所述的正极极片浆料，其特征在于，所述正极活性材料和所述复合补锂材料的质量比为100:(1-10)。
  31. 根据权利要求29或30所述的正极极片浆料，其特征在于，所述正极活性材料选自镍锰酸锂(LiNi0.5Mn1.5O4)、钴酸锂(LiCoO2)、锰酸锂(LiMn2O4)、磷酸铁锂(LiFePO4)、镍钴锰酸锂(Li(Ni,Co,Mn)O2)和镍钴铝酸锂(Li(Ni,Co,Al)O2)中的至少一种。
  32. 一种正极极片，其特征在于，包括正极集流体和涂覆于所述正极集流体上的正极活性涂层，所述正极活性涂层是由权利要求29-31中任一项所述正极极片浆料形成。
  33. 一种锂离子电池，其特征在于，包括权利要求32中所述正极极片。
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