WO2020125282A1 - 具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料及其制备方法。 - Google Patents

具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料及其制备方法。 Download PDF

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WO2020125282A1
WO2020125282A1 PCT/CN2019/118250 CN2019118250W WO2020125282A1 WO 2020125282 A1 WO2020125282 A1 WO 2020125282A1 CN 2019118250 W CN2019118250 W CN 2019118250W WO 2020125282 A1 WO2020125282 A1 WO 2020125282A1
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carbon
lithium ion
ion conductor
fiber structure
carbon fiber
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PCT/CN2019/118250
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English (en)
French (fr)
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何婉芳
王卫涛
杨颉
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浙江伏打科技有限公司
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Priority to JP2021504472A priority Critical patent/JP7070876B2/ja
Priority to EP19898077.3A priority patent/EP3832760A1/en
Priority to KR1020237043638A priority patent/KR20240001267A/ko
Priority to KR1020217002478A priority patent/KR20210022744A/ko
Priority to US17/265,696 priority patent/US20210384507A1/en
Publication of WO2020125282A1 publication Critical patent/WO2020125282A1/zh

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    • H—ELECTRICITY
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
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    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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    • D01F1/00—General methods for the manufacture of artificial filaments or the like
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    • D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
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    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
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    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
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    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
    • D01F9/225—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles from stabilised polyacrylonitriles
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    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H—ELECTRICITY
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2101/00—Inorganic fibres
    • D10B2101/10—Inorganic fibres based on non-oxides other than metals
    • D10B2101/12—Carbon; Pitch
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    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
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    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention relates to a method for preparing a carbon-bound lithium ion conductor-carbon composite negative electrode material with a carbon fiber structure, and uses the material as a negative electrode material for a lithium ion battery.
  • the carbon material and the metal ion compound lithium ion conductor can be combined together to prepare a new negative electrode material for a lithium ion battery with high capacity, excellent rate performance, and long life, it will promote the performance of the lithium ion battery.
  • the present invention provides a carbon-bonded "lithium ion conductor-carbon" composite negative electrode material with a carbon fiber structure and a preparation method thereof.
  • a high-strength carbon network structure with a carbon fiber structure synthesized on site is used to convert lithium ions
  • the conductor and the carbon anode material are bound together to prepare a lithium battery anode material with high power density.
  • the invention provides a method for preparing a carbon-bound lithium ion conductor-carbon composite anode material with a carbon fiber structure, which includes the following steps:
  • the solid particles M are subjected to high-temperature carbonization treatment in an inert atmosphere to obtain a carbon-bonded lithium ion conductor-carbon composite negative electrode material having a carbon fiber structure.
  • the carbon material in step S1 is selected from at least one of graphite, soft carbon, and hard carbon.
  • the lithium ion conductor described in step S1 is a metal ion compound.
  • the metal ions contained in the lithium ion conductor described in step S1 are Mn, Fe, Co, Ni, Cu, Au, Ag, Zn, Cd, Cr, Cd, Hg, Ge, Pb, Ru, Rh, Pd, Os, Ir, Pt and other metals other than the corresponding ions of the metal.
  • the metal nitride in the lithium ion conductor described in step S1 may be selected from Li 3 N, Li 3 N-LiCl, Li 9 N 2 Cl, Li 3 AlN 2 , LiSi 2 N 3 , Li 0.85 Ca 0.075 Si 2 At least one of N.
  • the weight ratio of the lithium ion conductor to the carbon material in step S1 is selected from 1:2 to 1:100, preferably from 1:7 to 1:9.
  • the organic polymer material described in step S1 is selected from organic polymer materials that can be converted into carbon fibers after high-temperature carbonization.
  • the organic polymer material described in step S1 is at least one selected from polyacrylonitrile, phenolic resin, and asphalt.
  • the weight of the organic polymer material in step S1 accounts for 1% to 30% of the total weight of other materials excluding solvent, preferably 1.5% to 10%.
  • the organic solvent described in step S1 is a liquid organic substance capable of dissolving the target polymer material
  • the organic solvent capable of dissolving polyacrylonitrile is selected from dimethylformamide (DMF), N,N-dimethyl At least one of acetamide (DMAc) and dimethyl sulfoxide (DMSO), but not limited to these solvents
  • the organic solvent that can dissolve the phenolic resin is selected from at least one of methanol, ethanol, and propanol, but It is not limited to these solvents
  • the organic solvent capable of dissolving asphalt is at least one selected from liquid hydrocarbon solvents such as gasoline and diesel.
  • the carbonization temperature in step S3 is selected from 400-1500°C.
  • the carbonization treatment time in step S3 is selected from 1-50h.
  • the method of the present invention prepares a carbon-bonded lithium ion conductor-carbon composite anode material with a carbon fiber structure that has a high-strength three-dimensional carbon fiber network structure.
  • the carbon anode active material and the crystal of the lithium ion conductor material are bound in the same particle by the carbon fiber network , It has the following advantages:
  • this material has better lithium ion conductivity
  • the carbon fiber-bound lithium ion conductor-carbon composite negative electrode material particles prepared by the method of the present invention are formed by binding small particles of lithium ion conductor and small particles of carbon anode active material through carbon fibers, and the small crystals and small carbon particles inside the particles The gap between them ensures that the electrolyte solution can fully enter the infiltration, shortens the diffusion distance of lithium ions in the small carbon particles, and improves the high-power charge and discharge current density of the material;
  • Carbon fiber has two characteristics of high tensile strength and fiber flexibility. After binding the lithium ion conductor and the small carbon particles, the volume change of the material during charging and discharging is buffered or delayed to a certain extent. Powdering and agglomeration can also effectively prevent the bound small carbon particles from being stripped into multilayer graphite under long-term cyclic charge and discharge conditions, thereby improving the cycling stability of the electrode.
  • Bundling the lithium ion conductor-carbon particles together in a three-dimensional carbon fiber network is more conducive to lithium ion and charge transfer at the interface between the lithium ion conductor and the electrolyte, which in turn improves the rate performance of the material.
  • the production process of this material is short and the cost is low.
  • the polymer material is carbonized into a three-dimensional carbon fiber network with a carbon fiber structure, and the lithium ion conductor and the small carbon particles are bound in the same particle.
  • One-step completion of material production is short and the cost is low.
  • FIG. 1 is a magnification cycle diagram of the pure mesophase carbon microsphere material of Example 1 as a negative electrode material. In the voltage range of 0.01V-2.00V, the test is conducted at current densities of 100, 200, 300, 400, 500, and 600 mA/g.
  • Example 2 is a magnification cycle diagram of a carbon-bound ZrO 2 /MgO-carbon composite negative electrode material prepared by the phenolic resin prepared in Example 2 in a carbon fiber structure. In the voltage range of 0.01V-2.00V, the test is conducted at current densities of 100, 200, 300, 400, 500, and 600 mA/g.
  • FIG. 3 is an SEM photograph of a carbon-bound ZrO 2 /MgO-carbon composite negative electrode material prepared by the phenolic resin prepared in Example 2 in a carbon fiber structure. In the voltage range of 0.01V-2.00V, the test is conducted at current densities of 100, 200, 300, 400, 500, and 600 mA/g.
  • Example 4 is a magnification cycle diagram of a carbon-bound ZrO 2 /CaO-carbon composite negative electrode material prepared from the polyacrylonitrile prepared in Example 3 and having a carbon fiber structure. In the voltage range of 0.01V-2.00V, the test is conducted at current densities of 100, 200, 300, 400, 500, and 600 mA/g.
  • FIG. 5 is a magnification cycle diagram of carbon-bound TiO 2 /MgO/CaO-carbon composite negative electrode materials prepared from polyacrylonitrile prepared in Example 4 with a carbon fiber structure. In the voltage range of 0.01V-2.00V, the test is conducted at current densities of 100, 200, 300, 400, 500, and 600 mA/g.
  • Example 6 is a magnification cycle diagram of a carbon-bound TiO 2 /Li 2 O-carbon composite negative electrode material prepared by a phenolic resin prepared in Example 5 with a carbon fiber structure. In the voltage range of 0.01V-2.00V, the test is conducted at current densities of 100, 200, 300, 400, 500, and 600 mA/g.
  • Example 7 is a magnification cycle diagram of a carbon-bound ZrO 2 /Y 2 O 3 -carbon composite negative electrode material prepared by the phenolic resin prepared in Example 6 in a carbon fiber structure. In the voltage range of 0.01V-2.00V, the test is conducted at current densities of 100, 200, 300, 400, 500, and 600 mA/g.
  • Example 8 is a magnification cycle diagram of a carbon-bound TiO 2 /La 2 O 3 -carbon composite negative electrode material prepared from a phenolic resin prepared in Example 7 and having a carbon fiber structure. In the voltage range of 0.01V-2.00V, the test is conducted at current densities of 100, 200, 300, 400, 500, and 600 mA/g.
  • FIG. 9 is a magnification cycle diagram of a carbon-bound Li 3 PO 4 -carbon composite negative electrode material prepared by a phenolic resin prepared in Example 8 and having a carbon fiber structure. In the voltage range of 0.01V-2.00V, the test is conducted at current densities of 100, 200, 300, 400, 500, and 600 mA/g.
  • this example uses pure mesophase carbon microsphere materials to prepare half-cells for testing.
  • This embodiment is a method for preparing a carbon-bonded ZrO 2 /MgO-carbon composite negative electrode material using a phenolic resin for a carbon fiber structure, and making it into a button battery for measurement.
  • Battery production process Weigh the above composite negative electrode material, conductive carbon black, PVDF according to the mass ratio of 94:3:3, add NMP to make the solid content 24%, stir on a vacuum mixer for 20 minutes, then apply it on the surface of copper foil and apply The thickness is 120 ⁇ m, dried in a 90°C blast drying oven for 30min. After drying, the slices are rolled, and then placed in a vacuum drying oven at 90°C for 12h. Half-cells are made in the glove box. Weigh small discs in the positive electrode case, put the separator, 60 ⁇ L electrolyte, metal lithium film, gasket, shrapnel and negative electrode case in turn, and then encapsulate the button battery on the hydraulic press. .
  • Battery test process cycle the above button batteries at a constant current charge and discharge at 33mA/g for 1 turn, and then at 100mA/g, 200mA/g, 300mA/g, 400mA/g, 500mA/g, 600mA/g, The current densities of 700mA/g, 800mA/g, 900mA/g, and 1000mA/g were circulated for 10 turns each, and finally the current density was circulated for 10 turns with a current density of 100mA/g, and the results as shown in FIG. 2 of the specification were obtained.
  • the battery material can still maintain a larger capacity than the pure mesophase carbon material at a large current density (Example 1), and has good stability. It can be seen from the SEM image of the negative electrode material in FIG. 3 of the specification that the lithium ion conductor metal oxide small crystals (ZrO 2 /MgO) and small carbon particles are uniformly dispersed, the particle size is small, and the carbon fibers that play a role in binding are evenly distributed. The gaps between them ensure that the electrolyte solution can fully enter the infiltration, shorten the diffusion distance of lithium ions in the carbon crystal, and ensure the stability of the entire particle.
  • the lithium ion conductor metal oxide small crystals (ZrO 2 /MgO) and small carbon particles are uniformly dispersed, the particle size is small, and the carbon fibers that play a role in binding are evenly distributed. The gaps between them ensure that the electrolyte solution can fully enter the infiltration, shorten the diffusion distance of lithium ions in the carbon crystal, and ensure the stability of the entire
  • This embodiment is a method for preparing a carbon-bound ZrO 2 /CaO-carbon composite negative electrode material using polyacrylonitrile to prepare a carbon fiber structure, and making it into a button battery for measurement.
  • the battery manufacturing and battery testing process is the same as that in the second embodiment.
  • the material has excellent high current density performance and can exhibit high capacity under high current density.
  • This embodiment is a method for preparing a carbon-bonded TiO 2 /MgO/CaO-carbon composite negative electrode material using polyacrylonitrile to prepare a carbon fiber structure, and making it into a button battery for measurement.
  • the battery manufacturing and battery testing process is the same as that in the second embodiment.
  • the material has excellent high current density performance and can exhibit high capacity under high current density.
  • This embodiment is a method for preparing a carbon-bonded TiO 2 /Li 2 O-carbon composite negative electrode material using a phenolic resin for a carbon fiber structure, and making it into a button battery for measurement.
  • Molar ratio 2:1 weighs 2.0498g of LiOH ⁇ H 2 O and 1.9509g of TiO 2 respectively , then weighs 6.040g of flake graphite (HC-7), 30.99g of 5wt.% phenolic
  • HC-7 flake graphite
  • the ethanol solution of the resin and 40.0 ml of ethanol were weighed in a ball milling tank, and after milling at 180 r/min for 6 hours, the material was discharged to obtain a mixed slurry.
  • the battery manufacturing and battery testing process is the same as in the second embodiment.
  • the material has excellent high current density performance and can exhibit high capacity under large current density.
  • This embodiment is a method for preparing a carbon-bound ZrO 2 /Y 2 O 3 -carbon composite negative electrode material using a phenolic resin to prepare a carbon fiber structure, and making it into a button battery for measurement.
  • the battery manufacturing and battery testing process in this embodiment is the same as that in embodiment 2, and the results are shown in FIG. 7.
  • the material has excellent high current density performance and can exhibit high capacity at high current density.
  • This embodiment is a method for preparing a carbon-bonded TiO 2 /La 2 O 3 -carbon composite negative electrode material using phenolic resin to prepare a carbon fiber structure, and making it into a button battery for measurement.
  • the battery manufacturing and battery testing process is the same as in the second embodiment.
  • the material has excellent high current density performance and can exhibit high capacity under high current density. .
  • This embodiment is a method for preparing a carbon-bonded Li 3 PO 4 -carbon composite negative electrode material using a phenolic resin for a carbon fiber structure, and making it into a button battery for measurement.
  • the battery manufacturing and battery testing process is the same as that in the second embodiment.
  • the material has excellent high current density performance and can exhibit high capacity at high current density.
  • the voltage range is 0.01V-2.00V
  • the test is carried out under the current density of 100, 200, 300, 400, 500, 600mA/g rate cycle diagram, the test results are For example, as shown in Table 1.

Abstract

本发明涉及一种具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料及其制备方法，本方法制备的材料颗粒内部是由锂离子导体小晶体和碳负极活性材料小微粒经过碳纤维绑定形成，提高了材料的充放电电流密度。碳纤维有很高的抗拉强度和纤维柔软性，在一定程度上缓冲了材料在充放电过程中发生的体积变化、粉化和团聚，还有效防止被绑定的碳小微粒在长期循环充放电条件下剥离成多层石墨，从而提高了电极的循环稳定性，提高材料的倍率性能，并具有较大的容量。本材料的生产工艺流程短，成本低，对制成的混合颗粒进行高温处理时，高分子材料被碳化成具有碳纤维结构的三维碳纤维网，把锂离子导体和碳小微粒捆绑在同一颗粒中，实现材料生产的一步完成。

Description

具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料的合成 技术领域
本发明涉及一种具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料的制备方法，并把该材料用作锂离子电池的负极材料。
背景技术
随着锂离子电池技术在电动车行业、航空产业、电子设备等方面的运用日益增多，人们对锂离子电池的性能提出了更高的要求，而电极材料是提高锂离子电池性能的关键性因素。在负极材料方面，目前商业化的锂离子电池负极材料大多都是石墨，石墨的理论嵌锂容量为372mAh/g，其结晶完整并具有高取向性，在锂离子嵌入和脱出的过程中，会产生10％左右的体积膨胀和收缩，其层状结构在循环过程中易被破坏。另外在循环过程中难免会有电解质溶剂共嵌于石墨层间，会产生气体和体积膨胀，致使石墨片层剥落，造成活性物质不可逆损失以及固体电解质界面膜(SEI膜)的不断被破坏和重生，消耗锂离子，从而导致电池循环寿命缩短。金属离子化合物有很好的导锂离子的性能，但是具有导电性较差的缺点，而且伴随着锂离子的嵌入和脱出存在较大的体积变化，因此其电化学性能、循环稳定性、倍率性并不理想。
因此如果能将碳材料和金属离子化合物锂离子导体复合在一起制备出新型容量高、倍率性能优异、寿命长的锂离子电池的负极材料，将对提高锂离子电池的性能产生促进作用。
发明内容
为解决上述问题，本发明提供了一种具有碳纤维结构的碳绑定的“锂离子导体-碳”复合负极材料及其制备方法，采用现场合成的具有碳纤维结构的高强度碳网结构将锂离子导体和碳负极材料绑定在一起制备出具有高功率密度的锂电池负极材料。
本发明提供了一种具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料的制备方法，其包括以下步骤：
S1：将碳材料、锂离子导体、有机高分子材料和有机溶剂(可以溶解有机高分子材料)混合搅拌均匀后得到混合浆料A；
S2：将混合浆料A造粒干燥得到固体颗粒M；
S3：将固体颗粒M在惰性氛围中，经过高温碳化处理，得到具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料。
作为优选，步骤S1中所述碳材料选自石墨、软碳、硬碳中的至少一种。
作为优选，步骤S1中所述的锂离子导体是金属离子化合物。
作为优选，步骤S1中所述的锂离子导体中所含的金属离子是除Mn、Fe、Co、Ni、Cu、Au、Ag、Zn、Cd、Cr、Cd、Hg、Ge、Pb、Ru、Rh、Pd、Os、Ir、Pt等金属以外的其余金属的相应离子。
作为优选，步骤S1中所述的锂离子导体是选自导锂离子的金属氧化物、金属复合氧化物、金属硫化物、金属氮化物、金属氟化物、金属碳化物、金属硒化物、金属蹄(Te)化物、金属磷酸盐、Li 2CO 3、Li 2TiO 3、Li 4Ti 5O 12、Li 2ZrO 3、LiVO 3、Li 3VO 4、LiNbO 3、Li 3NbO 4、Li 3Ln 3M 2O 12(M＝Te、W；Ln＝Y、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm,Yb,Lu)中的至少一种。
作为优选，步骤S1中所述的锂离子导体中金属氮化物可以选自Li 3N、Li 3N-LiCl、Li 9N 2Cl、Li 3AlN 2、LiSi 2N 3、Li 0.85Ca 0.075Si 2N中的至少一种。
作为优选，步骤S1中所述的锂离子导体中金属磷酸盐选自Li 3PO 4、LiMPO 4(M是Mg 2+、Ca 2+、Sr 2+、Ba 2+中的致少一种)、LiM 2(PO 4) 3(M＝Ge、Ti、Hf)和Li 1+xM xTi 2-x(PO 4) 3(M＝Al、Sc、Y、La)中的至少一种。
作为优选，步骤S1中所述锂离子导体与所述碳材料重量比选自1:2～1:100，优选自1：7～1:9。
作为优选，步骤S1中所述的有机高分子材料选自有机高分子材料中那些在经过高温碳化后可以转化为碳纤维的有机高分子材料。
作为优选，步骤S1中所述的有机高分子材料选自聚丙烯腈、酚醛树脂、沥青中的至少一种。
作为优选，步骤S1中所述的有机高分子材料的重量占不包括溶剂在内的其它物料总重量的百分比为1％～30％,优选为1.5％～10％。
作为优选，步骤S1中所述的有机溶剂是能溶解目标高分子材料的液体有机物，具体如：能溶解聚丙烯腈的有机溶剂选自二甲基甲酰胺(DMF)、N，N-二甲基乙酰胺(DMAc)、二甲基亚砜(DMSO)中的至少一种，但是不限于这几种溶剂，能溶解酚醛树脂的有机溶剂选自甲醇、乙醇、丙醇中至少一种，但是不限于这几种溶剂，以及能溶解沥青的有机溶剂选自液体烃类溶剂如汽油、柴油种的至少一种。
作为优选，步骤S3中所述碳化处理温度选自400-1500℃。
作为优选，步骤S3中所述碳化处理时间选自1-50h。
本发明的有益效果：
本发明方法制备具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料具有高强度的三维碳纤维网状结构，碳负极活性材料与锂离子导体材料的晶体被碳纤维网绑定在同一颗粒中，它有如下优点：
(1)本材料与相同颗粒尺寸的纯石墨碳负极材料相比较，具有更好的导锂离子性能；
(2)本发明方法制备的碳纤维绑定的锂离子导体-碳复合负极材料颗粒内部是由锂离子导体小晶体和碳负极活性材料小微粒经过碳纤维绑定形成，颗粒内部小晶体和碳小微粒之间的缝隙保证了电解质溶液可以充分地进入浸润，缩短了锂离子在碳小微粒中的扩散距离，提高了材料的高功率充放电电流密度；
(3)由于绑定锂离子导体小晶体和碳小微粒的是碳纤维，而碳纤维本身是导电的，所以材料也具有良好的导电性；
(4)可以容忍电池在充放电时材料的体积变化，颗粒内部锂离子导体小晶体和碳小微粒之间的缝隙可以缓冲体积变化；
(5)碳纤维有很高的抗拉强度和纤维柔软性两大特性，将锂离子导体和碳小微粒绑定后，在一定程度上缓冲或延缓了材料在充放电过程中发生的体积变化、粉化和团聚，还可以有效防止被绑定的碳小微粒在长期循环充放电条件下被剥离成多层石墨，从而提高了电极的循环稳定性。
(6)将锂离子导体-碳小微粒捆绑在一起包裹在三维碳纤维网内，更有利于锂离子导体和电解质界面的锂离子和电荷传输，继而提高材料的倍率性能。
(7)由于有些锂离子导体在碳负极材料和碳纤维网提供良好的导电性的条件下，也能提供较大的容量，所以有些复合材料的容量会比单独的碳负极材料容量更大。
本材料的生产工艺流程短，成本低，对制成的混合颗粒进行高温处理时，高分子材料被碳化成具有碳纤维结构的三维碳纤维网，把锂离子导体和碳小微粒捆绑在同一颗粒中，实现材料生产的一步完成。
附图说明
图1为实施例1纯中间相碳微球材料作为负极材料的倍率循环图。在电压范围为0.01V-2.00V，测试在电流密度分别为100、200、300、400、500、600mA/g下进行。
图2为实施例2制备的酚醛树脂制备碳纤维结构的碳绑定ZrO 2/MgO-碳复合负极材料的倍率循环图。在电压范围为0.01V-2.00V，测试在电流密度分别为100、200、300、400、500、600mA/g下进行。
图3为实施例2制备的酚醛树脂制备碳纤维结构的碳绑定ZrO 2/MgO-碳复合负极材料的SEM照片。在电压范围为0.01V-2.00V，测试在电流密度分别为100、200、300、400、500、600mA/g下进行。
图4为实施例3制备的聚丙烯腈制备碳纤维结构的碳绑定ZrO 2/CaO-碳复合负极材料的倍率循环图。在电压范围为0.01V-2.00V，测试在电流密度分别为100、200、300、400、500、600mA/g下进行。
图5为实施例4制备的聚丙烯腈制备碳纤维结构的碳绑定TiO 2/MgO/CaO-碳复合负极材料的倍率循环图。在电压范围为0.01V-2.00V，测试在电流密度分别为100、200、300、400、500、600mA/g下进行。
图6为实施例5制备的酚醛树脂制备碳纤维结构的碳绑定TiO 2/Li 2O-碳复合负极材料的倍率循环图。在电压范围为0.01V-2.00V，测试在电流密度分别为100、200、300、400、500、600mA/g下进行。
图7为实施例6制备的酚醛树脂制备碳纤维结构的碳绑定ZrO 2/Y 2O 3-碳复合负极材料的倍率循环图。在电压范围为0.01V-2.00V，测试在电流密度分别为100、200、300、400、500、600mA/g下进行。
图8为实施例7制备的酚醛树脂制备碳纤维结构的碳绑定TiO 2/La 2O 3-碳复合负极材料的倍率循环图。在电压范围为0.01V-2.00V，测试在电流密度分别为100、200、300、400、500、600mA/g下进行。
图9为实施例8制备的酚醛树脂制备碳纤维结构的碳绑定Li 3PO 4-碳复合负极材料的倍率循环图。在电压范围为0.01V-2.00V，测试在电流密度分别为100、200、300、400、500、600mA/g下进行。
具体实施方式
以下结合具体实施例及附图说明，对本发明的技术方案具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料的制备方法进行进一步详细的说明。
实施例1
作为对比,本实施例用纯中间相碳微球材料制备半电池进行测试。
电池制作过程：称取0.8000g的中间相碳微球(N 7)，加入0.1003g的导电炭黑和3.3333g的含3.0％PVDF的NMP溶液，使N 7比导电炭黑比PVDF的质量比为8:1:1，球磨30min得浆料，把浆料涂在铜箔上，涂成厚度为90μm的极片，在120℃下在氮气氛的烘箱中烘3h，将极片在手套箱中制成半电池，先称取小圆片放在正极壳内，依次放入隔膜、60μL电解液、金属锂片、垫片、弹片和负极壳，在液压机上液压封装成纽扣电池。
电池测试过程：将上述纽扣电池，在电压范围为0.01V-2.00V，测试在电流密度分别为100、200、300、400、500、600mA/g下进行，测定在不同电流密度下的克容量数据，得到说明书附图一的结果。
从说明书附图一中可以分析出，该实施例一中制备纯中间相碳微球材料测定结果表明在电流密度升高时，材料的克容量大幅度下降，在300mA/g时容量为150mAh/g；在400mA/g时容量为90mAh/g。
实施例2
本实施例是一种用酚醛树脂制备碳纤维结构的碳绑定ZrO 2/MgO-碳复合负极材料的制备方法,并将其制作成纽扣电池进行测定。
材料制作过程：
(一)称取1324.00g无水乙醇，加入25.91g的ZrO 2、16.94g的MgO和385.65g的中间相碳微球(平均粒度20μm)，使金属氧化物/碳质量比为1:9，再加入64.27g的含20wt％的酚醛树脂的乙醇溶液，酚醛树脂占ZrO 2、MgO、碳含量总量的3％，球磨混合后，出料得到混合浆料。
(二)在100℃下喷雾干燥，得到固体粉末。
(三)取上述固体粉末5.0012g在管式炉中,在N 2下,在800℃烧制5h，得到酚醛树脂制备碳纤维结构的碳绑定ZrO 2/MgO-碳复合负极材料。
电池制作过程：按质量比为94:3:3称取上述复合负极材料、导电炭黑、PVDF，加NMP使得固含量为24％，在真空搅拌机上搅拌20min后涂在铜箔表面，涂布厚度为120μm，在90℃鼓风干燥箱干燥30min，烘干后辊压切片，再放入真空干燥箱90℃烘12h。在手套箱中制成半电池，先称取小圆片放在正极壳内，依次放入隔膜、60μL电解液、金属锂片、垫片、弹片和负极壳，在液压机上液压封装成纽扣电池。
电池测试过程：将上述纽扣电池，以恒流充放电在33mA/g下循环1圈，再分别以100mA/g、200mA/g、300mA/g、400mA/g、500mA/g、600mA/g、700mA/g、800mA/g、900mA/g、1000mA/g的电流密度各循环10圈，最后再以100mA/g的电流密度循环10圈，得到如说明书附图2的结果。
从说明书附图2可知，在大电流密度下，该电池材料仍然可以保持比纯中间相碳材料大的容量(例一),并且具有很好的稳定性。从说明书附图3该负极材料的SEM图像可知，锂离子导体金属氧化物小晶体(ZrO 2/MgO)和碳小微粒分散均匀，颗粒度小，起捆绑作用的碳纤维分布均匀，颗粒内部以及颗粒之间存在的间隙保证了电解质溶液可以充分进入浸润，缩短了锂离子在碳晶体中的扩散距离，保证了整个颗粒的稳定性。
实施例3
本实施例是一种用聚丙烯腈制备碳纤维结构的碳绑定ZrO 2/CaO-碳复合负极材料的制备方法,并将其制作成纽扣电池进行测定。
材料制作过程：
(一)称取100.00g的水，加入21.54g的ZrO 2和20.01g的CaCO 3，使Zr:Ca的摩尔比为1:2，加入12.52g的聚乙烯醇(PEG)，使PEG占ZrO 2和CaCO 3总量的30％，在球磨机250r/min球磨10h，出料，加入120.0mL水冲洗，在120℃下喷雾干燥，得到白色的粉末。取白色粉末25.00g放在空气氛的管式炉中1000℃烧制7h，烧制后的样品粉碎过80目筛。
(二)称取6.96g上述烧制后的样品，加入10.0mL NMP和27.84g的碳(N7)，使无机物/碳质量比为2:8，再加入34.8g的5wt.％的聚丙烯腈NMP溶液，聚丙烯腈占无机物、碳含量总量的5％，最后加入20.0mL的NMP，球磨后得到混合浆体。
(三)将混合浆体，在喷雾干燥器上150℃干燥，得到固体粉末。
(四)将固体粉末放入管式炉中，在N 2氛围下1000℃烧制5h，得到用酚醛树脂制备碳纤维结构的碳绑定ZrO 2/CaO-碳复合负极材料。
本实施例中电池制作和电池测试过程与实施例二相同，结果如图4所示，材料具有优良的高电流密度性能，能在大电流密度下发挥出高容量。
实施例4
本实施例是一种用聚丙烯腈制备碳纤维结构的碳绑定TiO 2/MgO/CaO-碳复合负极材料的制备方法,并将其制作成纽扣电池进行测定。
材料制作过程：
(一)称取100.00g的水，加入15.92g的TiO 2、10.47g的MgO、5.642g的CaO、9.61g的PEG，使PEG占TiO 2、MgO、CaO总量的30％，球磨后，在120℃下喷雾干燥，得到白色的粉末。将25.07g的白色粉末放在空气氛的管式炉下1350℃烧制7h，烧制后的样品粉碎过80目筛。
(二)称取6.78g烧制后的上述样品，加入10.0mL NMP，球磨后加入12.59g的碳(N7)，使无机物/碳质量比为3.5:6.5，再加入30.99g的5wt.％的聚丙烯腈NMP溶液，聚丙烯腈占无机物、碳含量总量的5％，最后加入30.0mL的NMP，球磨得到混合浆料。
(三)将混合浆料，喷雾干燥得到固体粉末。
(四)将上述固体粉末放入管式炉中，在N 2氛围下900℃烧制5h，得到用聚丙烯腈制备碳纤维结构的碳绑定TiO 2/MgO/CaO-碳复合负极材料。
本实施例中电池制作和电池测试过程与实施例二相同，结果如图5所示，材料具有优良的高电流密度性能，能在大电流密度下发挥出高容量。
实施例5
本实施例是一种用酚醛树脂制备碳纤维结构的碳绑定TiO 2/Li 2O-碳复合负极材料的制备方法,并将其制作成纽扣电池进行测定。
材料制作过程：
(一)按摩尔比2:1分别称量2.0498g的LiOH·H 2O和1.9509g的TiO 2，然后称量6.0040g的片状石墨(HC-7)、30.99g的5wt.％的酚醛树脂的乙醇溶液和量取40.0ml的乙醇于球磨罐中，在180r/min下球磨6h后，出料，得到混合浆料。
(二)将混合浆料，喷雾干燥，得到固体粉末。
(三)将上述固体粉末放入高温管式炉中，在氩气气氛下，在850℃下保温4h，得用酚醛树脂制备碳纤维结构的碳绑定TiO 2/Li 2O-碳复合负极材料。
本实施例中电池制作和电池测试过程与实施例二相同，结果如图6所示，材料具有优良的高电流密度性能，能在大电流密度下发挥出高容量。
实施例6
本实施例是一种用酚醛树脂制备碳纤维结构的碳绑定ZrO 2/Y 2O 3-碳复合负极材料的制备方法,并将其制作成纽扣电池进行测定。
材料制作过程：
(一)称取1310.90g的无水乙醇、42.8559g的ZrO 2、1.2856g的Y 2O 3搅拌5min，在砂磨机上以2500r/min转速砂磨15min，再加入397.22g的碳(FSN)、66.25g的20wt.％的酚醛树脂无水乙醇溶液，在2500r/min下砂磨10min，出料，得到混合浆料。
(二)将混合浆料在100℃下喷雾干燥，得到固体粉末。
(三)将上述固体粉末放入高温管式炉中，在N 2气氛下下800℃烧制5h，得到用酚醛树脂制备碳纤维结构的碳绑定的ZrO 2/Y 2O 3-碳复合负极材料。
本实施例中电池制作和电池测试过程与实施例二相同，结果如图7所示，材料具有优良的高电流密度性能，能在大电流密度下发挥出高容量。
实施例7
本实施例是一种用酚醛树脂制备碳纤维结构的碳绑定TiO 2/La 2O 3-碳复合负极材料的制备方法,并将其制作成纽扣电池进行测定。
材料制作过程：
(一)称取1335.06g的无水乙醇、42.8556g的TiO 2、2.1436g的La 2O 3，搅拌5min，在砂磨机上在2500r/min下砂磨15min，再加入404.96g的碳(FSN)和67.56g的20wt.％的酚醛树脂无水乙醇溶液，球磨得混合浆料。
(二)将混合浆料，在喷雾干燥器上100℃干燥，得到黑色粉末。
(三)取上述6.8952g的黑色粉末放入高温管式炉中，在N 2气氛下800℃烧制5h，得到用酚醛树脂制备碳纤维结构的碳绑定TiO 2/La 2O 3-碳复合负极材料。
本实施例中电池制作和电池测试过程与实施例二相同，结果如图8所示，材料具有优良的高电流密度性能，能在大电流密度下发挥出高容量。。
实施例8
本实施例是一种用酚醛树脂制备碳纤维结构的碳绑定Li 3PO 4-碳复合负极材料的制备方法,并将其制作成纽扣电池进行测定。
材料制作过程：
(一)称取900.05g的无水乙醇，加入30.06g的磷酸锂，搅拌5min，搅拌后在2500r/min下砂磨15min，加入270.05g的碳(FSN)，使磷酸锂/碳质量比为1:9，再加入45.06g的20wt.％的酚醛树脂，酚醛树脂占磷酸锂、碳含量总量的3％，2500r/min砂磨10min，出料，得到混合浆料。
(二)将混合浆料，在100℃喷雾干燥器干燥，得到固体粉末。
(三)取上述固体粉末8.6043g放入高温管式炉中，在N 2气氛下800℃烧制5h，得到用酚醛树脂制备碳纤维结构的碳绑定Li 3PO 4-碳复合负极材料。
本实施例中电池制作和电池测试过程与实施例二相同，结果如图9所示，材料具有优良的高电流密度性能，能在大电流密度下发挥出高容量。
根据实施例1-8获得的负极材料，在电压范围为0.01V-2.00V，测试在电流密度分别为100、200、300、400、500、600mA/g下进行的倍率循环图，检测结果对比如表1所示。
表1
Figure PCTCN2019118250-appb-000001
根据表1及说明书附图1-9所示数据，可以看出按照本发明方法制备的各种具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料在大电流密度下仍然保持了比纯碳材料高得多的容量，在高电流密度时，能保持高的克容量，并且具有很好的稳定性。与现有技术相比具有显著的进步。
上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和应用本发明。本领域技术人员根据本说明书公开的内容可以很容易地想到，可以根据实际需要对各实施例进行适当调整和重新组合，而不会脱离本申请的精神。本申请的保护范围以本申请的权利要求书为准。

Claims (17)

  1. 一种具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料的制备方法，其特征在于：
    该方法包括以下步骤：
    S1：将碳材料、锂离子导体、有机高分子材料和有机溶剂混合搅拌均匀后得到混合浆料A；
    S2：将混合浆料A造粒并且干燥得到固体颗粒M；
    S3：将固体颗粒M在惰性氛围中，经过高温碳化处理，得到具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料。
  2. 根据权利要求1所述的具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料的制备方法，其特征在于，所述碳材料选自石墨、软碳、硬碳中的至少一种。
  3. 根据权利要求1所述的具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料的制备方法，其特征在于，所述的锂离子导体是金属离子化合物。
  4. 根据权利要求3所述的具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料的制备方法，其特征在于，所述的金属离子化合物是除Mn、Fe、Co、Ni、Cu、Au、Ag、Zn、Cd、Cr、Cd、Hg、Ge、Pb、Ru、Rh、Pd、Os、Ir、Pt等金属以外的其余金属相应的离子化合物。
  5. 根据权利要求1所述的具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料的制备方法，其特征在于，所述的锂离子导体是选自导锂离子的金属氧化物、金属复合氧化物、金属硫化物、金属氮化物、金属氟化物、金属碳化物、金属磷酸盐、金属硒化物、金属蹄(Te)化物、Li 2CO 3、Li 2TiO 3、Li 4Ti 5O 12、Li 2ZrO 3、LiVO 3、Li 3VO 4、LiNbO 3、Li 3NbO 4、Li 3Ln 3M 2O 12(M＝Te、W；Ln＝Y、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm,Yb,Lu)中的至少一种。
  6. 根据权利要求5所述的具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料的制备方法，其特征在于，所述金属氮化物可以选自Li 3N、Li 3N-LiCl、 Li 9N 2Cl、Li 3AlN 2、LiSi 2N 3、Li 0.85Ca 0.075Si 2N中的至少一种。
  7. 根据权利要求6所述的具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料的制备方法，其特征在于，所述金属磷酸盐选自Li 3PO 4、LiMPO 4(M是Mg 2+、Ca 2+、Sr 2+、Ba 2+中的致少一种)、LiM 2(PO 4) 3(M＝Ge、Ti、Hf)和Li 1+xM xTi 2-x(PO 4) 3(M＝Al、Sc、Y、La)中的至少一种。
  8. 根据权利要求1所述的具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料的制备方法，其特征在于，所述步骤S1中锂离子导体与所述碳材料重量比为1:2～1:100，优选为1：7～1:9。
  9. 根据权利要求1所述的具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料的制备方法，其特征在于，所述步骤S1中有机高分子材料是在碳化后可以转化为碳纤维的有机高分子材料。
  10. 根据权利要求1所述的具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料的制备方法，其特征在于：所述步骤S1中，有机高分子材料选自聚丙烯腈、酚醛树脂、沥青中的至少一种。
  11. 根据权利要求1所述的具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料的制备方法，其特征在于，所述步骤S1中，有机高分子材料的重量占不包括溶剂在内的其它物料总重量的1％～30％,优选为2％～10％。
  12. 根据权利要求1所述的具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料的制备方法，其特征在于，所述步骤S1中，有机溶剂选自能溶解目标高分子材料的液体物质。
  13. 根据权利要求1所述的具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料的制备方法，其特征在于，所述步骤S1中，有机溶剂选自能溶解聚丙烯腈的有机溶剂，如：二甲基甲酰胺(DMF)、N，N-二甲基乙酰胺(DMAc)、二甲基亚砜(DMSO)中至少一种。
  14. 根据权利要求1所述的具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料的制备方法，其特征在于，所述步骤S1中的有机溶剂选自能溶解酚醛树脂的有机溶剂，如甲醇、乙醇、丙醇中至少一种。
  15. 根据权利要求1所述的具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料的制备方法，其特征在于，所述步骤S1中，有机溶剂选自能溶解沥青的有机溶剂选自液体烃类溶剂，如汽油、柴油中的至少一种。
  16. 根据权利要求1所述的具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料的制备方法，其特征在于，所述步骤S3中，材料的碳化处理温度为400-1500℃。
  17. 根据权利要求1所述的具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料的制备方法，其特征在于，所述步骤S3中，材料的碳化处理时间为1-50h。
PCT/CN2019/118250 2018-12-21 2019-11-14 具有碳纤维结构的碳绑定的锂离子导体-碳复合负极材料及其制备方法。 WO2020125282A1 (zh)

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