WO2016192540A1 - Method for manufacturing tin-carbon composite negative electrode material for lithium-ion battery - Google Patents

Method for manufacturing tin-carbon composite negative electrode material for lithium-ion battery Download PDF

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WO2016192540A1
WO2016192540A1 PCT/CN2016/082864 CN2016082864W WO2016192540A1 WO 2016192540 A1 WO2016192540 A1 WO 2016192540A1 CN 2016082864 W CN2016082864 W CN 2016082864W WO 2016192540 A1 WO2016192540 A1 WO 2016192540A1
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tin
nickel
solution
temperature
preparation
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田东
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田东
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387—Tin or alloys based on tin
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention relates to a lithium battery, in particular to a lithium battery anode material, and more particularly to a method for preparing a tin carbon composite anode material.
  • Lithium-ion batteries have been widely used in portable electronic products (such as notebook computers, mobile phones, digital cameras, etc.) because of their high energy density, environmental friendliness, and no memory effect. They are also used in electric vehicles and hybrid vehicles. A huge potential application prospect. With the development of society and the advancement of technology, the demand for high-performance secondary batteries is becoming more and more urgent. However, the theoretical specific capacity of graphite for the negative electrode material of commercial lithium ion batteries is only 372 mAh/g, which cannot meet the requirements of high-capacity power batteries. Therefore, researchers are working hard to find new lithium-ion battery anode materials that can replace carbon materials.
  • metal tin has a high lithium storage capacity (994 mAh / g) and low lithium ion deintercalation platform voltage, etc., is a non-carbon anode material with great development potential.
  • extensive research has been carried out on such materials and some progress has been made.
  • the volume expansion of metallic tin is remarkable, resulting in poor cycle performance and rapid decay of capacity, so it is difficult to meet the requirements of large-scale production.
  • a non-metallic element such as carbon
  • the metal tin is stabilized by alloying or compounding, and the volume expansion of tin is slowed down. Carbon can prevent direct contact between tin particles, inhibit the agglomeration and growth of tin particles, and act as a buffer layer.
  • the heat resistance of the tin-carbon composite material can be improved by introducing a substance having a high melting point.
  • nickel is a metal with good electrical conductivity
  • melting point is 1453 ° C
  • introduced into the tin carbon composite material can improve the heat treatment temperature of the composite material and obtain a negative electrode material with good electrochemical properties.
  • Renzong Hu et al. prepared a core-shell and multi-scale Sn-C-Ni anode material by electron beam evaporation, which exhibited excellent capacity retention and high rate performance.
  • He Chunnian et al. prepared a two-dimensional porous graphitized carbon-coated nickel-tin alloy material by pyrolysis, which has high specific capacity and excellent cycle performance for lithium ion battery anodes (application number 201310715142.1).
  • the purpose of the invention is to solve the problem of large volume expansion of metal tin after high temperature heat treatment and improve the cycle performance of tin carbon composite material, and provide a multi-layer structure lithium battery anode material.
  • the material is uniformly deposited on the surface of a natural flake graphite (NG) having a layered structure by electroless plating.
  • NG natural flake graphite
  • a metal tin is deposited on the surface of the metallic nickel by electroless plating to obtain a Sn-Ni-NG composite material having a layered structure.
  • the combination of metallic nickel and graphite limits the volume effect of the metallic tin, thereby improving the cycle performance of the composite.
  • the lithium battery anode material of the layered structure of the present invention which deposits a nickel layer on the layered structure graphite, and then deposits a tin layer on the surface of the nickel layer to form a Sn-Ni-NG composite material, and the tin particles of the tin layer of the material
  • the size of the material is 90-110 nm, and the mass fraction of tin, nickel, oxygen and graphite in the material is 4% to 12%, 5% to 10%, 30% to 50%, 40% to 50%, respectively.
  • the material metallic nickel and metallic tin are uniformly present in the composite in a tiny layer.
  • the metal agglomeration is effectively relieved by the combination of high melting point nickel and buffering graphite.
  • the size of tin coating particles in Sn-Ni-NG composites is 90-110 nm, which is significantly smaller than the tin particles of 230-250 nm in Sn-NG composites, indicating the high temperature of metallic tin in Sn-Ni-NG composites. After heat treatment, the agglomeration phenomenon was alleviated.
  • the impedance value is smaller than that of the Sn-NG composite material, because the metal tin and the metal nickel are mutually wetted and closely connected to each other, so that the total resistance is reduced.
  • the electrode material exhibits good cycle performance when subjected to a charge and discharge cycle.
  • the present invention also provides a method for preparing a lithium battery anode material of the above layered structure.
  • the method comprises the following steps:
  • step 4) adding the product of step 3) to a stannous sulfate solution or a stannous chloride solution, ultrasonically, washing, and drying for use;
  • step 4) The obtained product of step 4) is under the protection of nitrogen, argon, helium or a mixed gas thereof, and is naturally cooled to room temperature after calcination.
  • step 1) the mass fraction of palladium chloride is from 0.5% to 5%.
  • the stirring time is 0.5 h to 3 h, and the temperature at the time of stirring is 25 to 90 °C.
  • step 2) the concentration of sodium hypophosphite is from 5 g/L to 30 g/L, and the amount is from 30 ml to 60 ml.
  • step 3 the mass ratio of carbon in the activated graphite to the nickel salt in the solution is 3: (1 to 5), the solution concentration is 5 g / L to 40 g / L, the ultrasonic reaction time is 0.5 h to 5 h, and the reaction temperature is 60 to 90 ° C.
  • step 4 the mass ratio of carbon in the activated graphite to the tin salt in the solution is 3: (1 to 3), the solution concentration is 5 g / L to 40 g / L, the ultrasonic reaction time is 0.5 h to 5 h, and the reaction temperature is 60 to 90 ° C.
  • step 5 the gas flow rate is 100-300 ml/min, and the temperature is raised from room temperature to 500-900 ° C at a heating rate of 1 to 10 ° C/min, and then calcined for 1 h to 5 h.
  • the invention adopts a simple electroless plating method to introduce metal nickel into the composite material, which can improve the heat resistance of the composite material in the heat treatment, so that the metal tin body The expansion of the product is alleviated, thereby suppressing the agglomeration of the metal tin.
  • the present invention has the advantage that the present invention successfully deposits metallic nickel and metallic tin onto the surface of graphite using a simple electroless plating process. Among them, metallic nickel is deposited on the graphite with a slight coating, and the metallic tin is deposited with a tiny coating and overlying the metallic nickel layer, thereby obtaining a composite material of the composite layer structure, exhibiting a sandwich layer structure.
  • the Sn-Ni-NG composite material successfully introduces the nickel layer, it not only improves the "non-wetting property" of the metallic tin and the non-metallic carbon, but also improves the heat resistance of the composite material even at 500 ° C to 900 ° C.
  • the heat treatment was carried out at a temperature, and a large amount of agglomeration did not occur in the metal tin, and the agglomeration phenomenon of the metal tin was effectively alleviated.
  • the layered mechanism of graphite and metallic nickel can restrict the expansion of the metallic tin, thereby achieving the purpose of buffering the metallic tin.
  • the composite material has a simple preparation method and excellent morphology, and the metal nickel layer and the metal tin layer are uniformly distributed on the graphite.
  • the composite material has excellent cycle performance when used in the negative electrode of a lithium ion battery.
  • the specific capacity of 410 mAh/g can be maintained by circulating 100 times at a current density of 100 mA/g, and the specific capacity of the electrode is slow with the increase of the number of cycles. Increased trend.
  • a 3 g nickel-plated sample was weighed and added to a 15 g/L 300 ml stannous chloride plating solution, and ultrasonically reacted at 80 ° C for 1 hour, washed and dried to obtain a Sn-Ni-NG composite material.
  • the prepared Sn-Ni-NG composite material, PVDF, conductive carbon black was coated in a copper foil as a negative electrode at a mass ratio of 85:10:5, and a lithium metal plate as a counter electrode, 1 mol/L hexafluorocarbon.
  • Phosphorus lithium is used as an electrolyte to assemble a button battery.
  • the button cell still maintains a specific capacity of 414 mA/g by circulating 100 times at a current density of 100 mA/g.
  • the specific capacity of the Sn-Ni-NG composite has a higher specific capacity than that of the Sn-NG composite obtained by electroless tin plating. After 100 cycles, the specific capacity of the Sn-Ni-NG composite still reaches 410 mAh/g or more.
  • the specific electrode capacity of the Sn-Ni-NG composite material increases slowly with the increase of the number of cycles. This is because The Sn-Ni-NG composite material is completely wetted by the electrolyte, which facilitates the migration of lithium ions into the interior of the material, which is beneficial to increase the lithium insertion capacity and thereby increase the specific capacity of the electrode material.
  • 3 g of the nickel-plated sample was weighed and added to a 15 g/L 300 ml stannous chloride plating solution, and ultrasonically reacted at 80 ° C for 1 hour, washed and dried to obtain a Sn-Ni-NG composite material.
  • a 1 g of Sn-Ni-NG composite was placed in a burning boat and placed in a quartz tube furnace.
  • Ar was introduced as a shielding gas at a gas flow rate of 200 ml/min, and the temperature was raised from room temperature to 600 ° C at a heating rate of 3 ° C/min, and the temperature was kept for 2 hours, and then naturally cooled to room temperature to obtain a calcined product.
  • the test method was the same as in Example 1.
  • the button cell was maintained at a current density of 100 mA/g for 100 times while still maintaining a specific capacity of 427 mA/g.
  • the test method was the same as in Example 1.
  • the button cell was maintained at a current density of 100 mA/g for 100 times while still maintaining a specific capacity of 462 mA/g.
  • 3 g of the nickel-plated sample was weighed and added to a 15 g/L 300 ml stannous chloride plating solution, and ultrasonically reacted at 80 ° C for 2 hours, washed and dried to obtain a Sn-Ni-NG composite material.
  • a 1 g of Sn-Ni-NG composite was placed in a burning boat and placed in a quartz tube furnace.
  • Ar was introduced as a shielding gas at a gas flow rate of 200 ml/min, and the temperature was raised from room temperature to 700 ° C at a heating rate of 5 ° C/min, and the temperature was kept for 2 hours, and then naturally cooled to room temperature to obtain a calcined product.
  • the test method was the same as in Example 1.
  • the button cell maintained a specific capacity of 457 mA/g by circulating 100 times at a current density of 100 mA/g.
  • 3 g of the nickel-plated sample was weighed and added to a 20 g/L 300 ml stannous chloride plating solution, and ultrasonically reacted at 80 ° C for 2 hours, washed and dried to obtain a Sn-Ni-NG composite material.
  • 1 g of Sn-Ni-NG composite material was placed in a burning boat and placed in a quartz tube furnace.
  • Ar was introduced as a shielding gas at a gas flow rate of 300 ml/min, and the temperature was raised from room temperature to 800 ° C at a heating rate of 10 ° C/min, and the temperature was kept for 2 hours, and then naturally cooled to room temperature to obtain a calcined product.
  • the test method was the same as in Example 1.
  • the button cell was maintained at a current density of 100 mA/g for 100 times while still maintaining a specific capacity of 481 mA/g.

Abstract

A tin-carbon composite negative electrode material for a lithium-ion battery in the present invention. A nickel layer is deposited on natural flake graphite that has a layered structure, then a tin layer is deposited on the surface of the nickel layer to form an Sn-Ni-NG composite material, wherein the sizes of tin particles of the tin layer of the material is 90 nm to 110 nm; and the mass fractions of tin, nickel, oxygen and carbon in the material are 4% to 12%, 5% to 10%, 30% to 50% and 40% to 50% respectively. The composite material avoids the phenomenon of huge agglomeration of metal tin after the metal tin is subjected to high-temperature heat treatment, restrains volume expansion and contraction of the metal tin; and after the composite material is subjected to heat treatment at a high temperature, the sizes of the particles are obviously smaller than those of particles of an independent tinned Sn-NG composite material. When the composite material is used as a negative electrode of the lithium-ion battery, the cycling performance is high.

Description

一种锂离子电池锡碳复合负极材料的制备方法Method for preparing tin-carbon composite anode material for lithium ion battery 技术领域Technical field
本发明涉及锂电池，具体是锂电池负极材料，更具体是一种锡碳复合负极材料的制备方法。The invention relates to a lithium battery, in particular to a lithium battery anode material, and more particularly to a method for preparing a tin carbon composite anode material.
背景技术Background technique
锂离子电池因具有能量密度高，环境友好，无记忆效应等优点，已经广泛应用于便携式电子产品中(如笔记本电脑，移动电话，数码相机等)，并在电动汽车以及混合动力汽车领域中拥有巨大的潜在应用前景。随着社会的发展和科技的进步，人们对高性能二次电池的需求日益迫切。然而，当前商用锂离子电池的负极材料石墨的理论比容量仅为372mAh/g，已无法满足高容量动力电池的要求。因此，研究者们正在努力寻找能够替代碳材料的新型锂离子电池负极材料。Lithium-ion batteries have been widely used in portable electronic products (such as notebook computers, mobile phones, digital cameras, etc.) because of their high energy density, environmental friendliness, and no memory effect. They are also used in electric vehicles and hybrid vehicles. A huge potential application prospect. With the development of society and the advancement of technology, the demand for high-performance secondary batteries is becoming more and more urgent. However, the theoretical specific capacity of graphite for the negative electrode material of commercial lithium ion batteries is only 372 mAh/g, which cannot meet the requirements of high-capacity power batteries. Therefore, researchers are working hard to find new lithium-ion battery anode materials that can replace carbon materials.
在众多的可替代材料中，金属锡具有高的储锂容量(994mAh/g)和低的锂离子脱嵌平台电压等优点，是一种极具发展潜力的非碳负极材料。近年来人们对这类材料开展了广泛的研究，并取得了一定的进展。但在可逆储锂过程中，金属锡体积膨胀显著，导致循环性能变差，容量迅速衰减，因此难以满足大规模生产的要求。为此，通过引入碳等非金属元素，以合金化或复合的方式来稳定金属锡，减缓锡的体积膨胀。碳能够阻止锡颗粒间的直接接触，抑制锡颗粒的团聚和长大，起到缓冲层的作用。 Among the many alternative materials, metal tin has a high lithium storage capacity (994 mAh / g) and low lithium ion deintercalation platform voltage, etc., is a non-carbon anode material with great development potential. In recent years, extensive research has been carried out on such materials and some progress has been made. However, in the process of reversible lithium storage, the volume expansion of metallic tin is remarkable, resulting in poor cycle performance and rapid decay of capacity, so it is difficult to meet the requirements of large-scale production. For this reason, by introducing a non-metallic element such as carbon, the metal tin is stabilized by alloying or compounding, and the volume expansion of tin is slowed down. Carbon can prevent direct contact between tin particles, inhibit the agglomeration and growth of tin particles, and act as a buffer layer.
虽然锡碳材料的研究获得了较大的进步，但是金属锡的熔点只有232℃，其在进行高温热处理时不可避免地发生体积膨胀。当前，对锡碳材料进行热处理时，主要面临着以下一些问题。锡碳复合材料在较高温热处理时，锡颗粒较容易融合在一起团聚成大颗粒，在循环过程中电极材料粉化脱落，导致电池容量的迅速降低和循环性能变差；在低温热处理时，锡碳复合材料的电阻大，导电性不好。因此，为了提高锡碳复合材料的导电性以及缓解金属锡颗粒在较高热处理温度下团聚现象，可以通过引入具有高熔点的物质来提高锡碳复合材料的耐热性。其中，镍是具有良好导电性的金属，熔点为1453℃，引入到锡碳复合材料中能够提高复合材料热处理温度并获得具有良好电化学性能的负极材料。Renzong Hu等采用电子束蒸镀法制备了具有核壳以及多尺度的Sn-C-Ni负极材料，该电极材料表现出优异的容量保持率以及高的倍率性能。何春年等采用热解法制备了二维多孔石墨化碳包覆镍锡合金材料，其用于锂离子电池负极具有很高的比容量与极好的循环性能(申请号201310715142.1)。Although the research on tin carbon materials has made great progress, the melting point of metal tin is only 232 ° C, which inevitably causes volume expansion during high temperature heat treatment. At present, when heat treatment of tin carbon materials, the following problems are mainly faced. When the tin-carbon composite material is heat treated at a higher temperature, the tin particles are more easily fused together to form a large particle, and the electrode material is pulverized and detached during the cycle, resulting in rapid decrease in battery capacity and deterioration in cycle performance; in low-temperature heat treatment, tin Carbon composites have large electrical resistance and poor electrical conductivity. Therefore, in order to improve the conductivity of the tin-carbon composite material and to alleviate the agglomeration phenomenon of the metal tin particles at a higher heat treatment temperature, the heat resistance of the tin-carbon composite material can be improved by introducing a substance having a high melting point. Among them, nickel is a metal with good electrical conductivity, melting point is 1453 ° C, introduced into the tin carbon composite material can improve the heat treatment temperature of the composite material and obtain a negative electrode material with good electrochemical properties. Renzong Hu et al. prepared a core-shell and multi-scale Sn-C-Ni anode material by electron beam evaporation, which exhibited excellent capacity retention and high rate performance. He Chunnian et al. prepared a two-dimensional porous graphitized carbon-coated nickel-tin alloy material by pyrolysis, which has high specific capacity and excellent cycle performance for lithium ion battery anodes (application number 201310715142.1).
发明内容Summary of the invention
本发明的目的是为了解决金属锡在高温热处理后发生较大的体积膨胀问题和提高锡碳复合材料的循环性能，提供一种多层次结构的锂电池负极材料。该材料以化学镀的方法把金属镍均匀地的沉积在具有层状结构的天然鳞片石墨(NG)表面上，然 后采用化学镀的方法把金属锡沉积在金属镍的表面上，从而获得具有层状结构的Sn-Ni-NG复合材料。通过金属镍和石墨的共同作用来限制金属锡的体积效应，从而提高复合材料的循环性能。The purpose of the invention is to solve the problem of large volume expansion of metal tin after high temperature heat treatment and improve the cycle performance of tin carbon composite material, and provide a multi-layer structure lithium battery anode material. The material is uniformly deposited on the surface of a natural flake graphite (NG) having a layered structure by electroless plating. Then, a metal tin is deposited on the surface of the metallic nickel by electroless plating to obtain a Sn-Ni-NG composite material having a layered structure. The combination of metallic nickel and graphite limits the volume effect of the metallic tin, thereby improving the cycle performance of the composite.
本发明的层状结构的锂电池负极材料，其在层状结构石墨上沉积镍层，然后再在镍层的表面沉积锡层，构成Sn-Ni-NG复合材料，该材料锡层的锡颗粒尺寸大小为90～110nm，材料中锡、镍、氧、石墨的质量分数分别为4％～12％、5％～10％、30％～50％、40％～50％。The lithium battery anode material of the layered structure of the present invention, which deposits a nickel layer on the layered structure graphite, and then deposits a tin layer on the surface of the nickel layer to form a Sn-Ni-NG composite material, and the tin particles of the tin layer of the material The size of the material is 90-110 nm, and the mass fraction of tin, nickel, oxygen and graphite in the material is 4% to 12%, 5% to 10%, 30% to 50%, 40% to 50%, respectively.
该材料金属镍和金属锡在复合材料中以微小的层均匀地存在石墨表面。金属锡在高熔点的镍和具有缓冲作用的石墨共同作用下，团聚现象明显得到了有效缓解。Sn-Ni-NG复合材料中涂层锡颗粒尺寸大小为90～110nm，明显比Sn-NG复合材料中230～250nm的锡颗粒尺寸小，说明Sn-Ni-NG复合材料中金属锡的在高温热处理后，团聚现象得到了缓解。Sn-Ni-NG复合材料作为电极材料时，阻抗值比Sn-NG复合材料的阻抗值小，这是由于金属锡和金属镍之间相互润湿，相互紧密连接，使得总电阻减小。该电极材料在进行充放电循环时，表现出良好的循环性能。The material metallic nickel and metallic tin are uniformly present in the composite in a tiny layer. The metal agglomeration is effectively relieved by the combination of high melting point nickel and buffering graphite. The size of tin coating particles in Sn-Ni-NG composites is 90-110 nm, which is significantly smaller than the tin particles of 230-250 nm in Sn-NG composites, indicating the high temperature of metallic tin in Sn-Ni-NG composites. After heat treatment, the agglomeration phenomenon was alleviated. When the Sn-Ni-NG composite material is used as an electrode material, the impedance value is smaller than that of the Sn-NG composite material, because the metal tin and the metal nickel are mutually wetted and closely connected to each other, so that the total resistance is reduced. The electrode material exhibits good cycle performance when subjected to a charge and discharge cycle.
本发明还提供上述层状结构的锂电池负极材料的制备方法。该方法包括下述步骤：The present invention also provides a method for preparing a lithium battery anode material of the above layered structure. The method comprises the following steps:
1)将天然鳞片石墨置于氯化钯溶液中并搅拌；1) placing natural flake graphite in a palladium chloride solution and stirring;
2)加入次亚磷酸钠，继续搅拌获得活化石墨； 2) adding sodium hypophosphite and continuing to stir to obtain activated graphite;
3)将活化石墨加入到硝酸镍溶液、硫酸镍溶液或氯化镍溶液中，超声，洗涤干净，烘干备用；3) adding activated graphite to a nickel nitrate solution, a nickel sulfate solution or a nickel chloride solution, ultrasonically, washing, and drying for use;
4)将步骤3)所得物加入到硫酸亚锡溶液或氯化亚锡溶液中，超声，洗涤干净，烘干备用；4) adding the product of step 3) to a stannous sulfate solution or a stannous chloride solution, ultrasonically, washing, and drying for use;
5)将步骤4)所得物在氮气、氩气、氦气或者其混合气体保护下，煅烧后自然降温至室温即得。5) The obtained product of step 4) is under the protection of nitrogen, argon, helium or a mixed gas thereof, and is naturally cooled to room temperature after calcination.
在步骤1)，氯化钯的质量分数浓度为0.5％～5％。In step 1), the mass fraction of palladium chloride is from 0.5% to 5%.
进一步，在步骤1)，搅拌时间为0.5h～3h，搅拌时的温度为25～90℃。Further, in the step 1), the stirring time is 0.5 h to 3 h, and the temperature at the time of stirring is 25 to 90 °C.
在步骤2)，次亚磷酸钠的浓度为5g/L～30g/L，加入量为30ml～60ml。In step 2), the concentration of sodium hypophosphite is from 5 g/L to 30 g/L, and the amount is from 30 ml to 60 ml.
在步骤3)，活化石墨中的碳与溶液中的镍盐质量比为3∶(1～5)，溶液浓度为5g/L～40g/L，超声反应时间为0.5h～5h，反应温度为60～90℃。In step 3), the mass ratio of carbon in the activated graphite to the nickel salt in the solution is 3: (1 to 5), the solution concentration is 5 g / L to 40 g / L, the ultrasonic reaction time is 0.5 h to 5 h, and the reaction temperature is 60 to 90 ° C.
在步骤4)，活化石墨中的碳与溶液中的锡盐质量比为3∶(1～3)，溶液浓度为5g/L～40g/L，超声反应时间为0.5h～5h，反应温度为60～90℃。In step 4), the mass ratio of carbon in the activated graphite to the tin salt in the solution is 3: (1 to 3), the solution concentration is 5 g / L to 40 g / L, the ultrasonic reaction time is 0.5 h to 5 h, and the reaction temperature is 60 to 90 ° C.
在步骤5)，气体流量为100～300ml/min，以1～10℃/min的升温速率从室温升温至500～900℃，然后保温煅烧1h～5h。In step 5), the gas flow rate is 100-300 ml/min, and the temperature is raised from room temperature to 500-900 ° C at a heating rate of 1 to 10 ° C/min, and then calcined for 1 h to 5 h.
本发明采用简单化学镀的方法往复合材料中引入了金属镍，其在热处理中能够提高复合材料的耐热性，使得金属锡体 积膨胀得到缓解，从而起到抑制了金属锡团聚的目的。本发明具有以下优点：本发明利用简单的化学镀的方法成功地把金属镍和金属锡沉积到石墨的表面上。其中，金属镍以微小的涂层沉积在石墨上，而金属锡则以微小的涂层沉积并覆盖在金属镍层上，从而得到复合层结构的复合材料，表现出夹心层结构。由于Sn-Ni-NG复合材料成功地引入了镍层，不仅能够改善金属锡和非金属碳的“不润湿性”，还使得复合材料的耐热性得到提高，即使在500℃～900℃的温度下进行热处理，金属锡也没有发生大量团聚，金属锡的团聚现象得到有效缓解。同时层状机构的石墨和金属镍能够对金属锡的膨胀产生限制作用，从而达到缓冲了金属锡的目的。该复合材料的制备方法简单，形貌优良，金属镍层和金属锡层分布均匀在石墨上。该复合材料用于锂离子电池负极时具有极好的循环性能，在100mA/g的电流密度下循环100次仍能保持410mAh/g的比容量以及电极的比容量随着循环次数的增加有缓慢增加的趋势。The invention adopts a simple electroless plating method to introduce metal nickel into the composite material, which can improve the heat resistance of the composite material in the heat treatment, so that the metal tin body The expansion of the product is alleviated, thereby suppressing the agglomeration of the metal tin. The present invention has the advantage that the present invention successfully deposits metallic nickel and metallic tin onto the surface of graphite using a simple electroless plating process. Among them, metallic nickel is deposited on the graphite with a slight coating, and the metallic tin is deposited with a tiny coating and overlying the metallic nickel layer, thereby obtaining a composite material of the composite layer structure, exhibiting a sandwich layer structure. Since the Sn-Ni-NG composite material successfully introduces the nickel layer, it not only improves the "non-wetting property" of the metallic tin and the non-metallic carbon, but also improves the heat resistance of the composite material even at 500 ° C to 900 ° C. The heat treatment was carried out at a temperature, and a large amount of agglomeration did not occur in the metal tin, and the agglomeration phenomenon of the metal tin was effectively alleviated. At the same time, the layered mechanism of graphite and metallic nickel can restrict the expansion of the metallic tin, thereby achieving the purpose of buffering the metallic tin. The composite material has a simple preparation method and excellent morphology, and the metal nickel layer and the metal tin layer are uniformly distributed on the graphite. The composite material has excellent cycle performance when used in the negative electrode of a lithium ion battery. The specific capacity of 410 mAh/g can be maintained by circulating 100 times at a current density of 100 mA/g, and the specific capacity of the electrode is slow with the increase of the number of cycles. Increased trend.
具体实施方式detailed description
下面结合具体实施例对本发明的内容具体说明如下。The content of the present invention will be specifically described below in conjunction with specific embodiments.
实施例1Example 1
称取5g天然鳞片石墨置于150ml 1％的氯化钯溶液中，加热到55℃磁力搅拌30min，然后加入15g/L 30ml的次亚磷酸钠，再磁力搅拌30min，洗涤干净并烘干，获得活化的石墨。将4g活化的 石墨加入到12g/L 300ml的硫酸镍镀液中，在80℃下超声反应1小时，洗涤干净并烘干，获得镀镍样品。Weigh 5g of natural flake graphite into 150ml 1% palladium chloride solution, heat to 55 ° C magnetic stirring for 30min, then add 15g / L 30ml of sodium hypophosphite, magnetically stirred for 30min, washed and dried, obtained Activated graphite. 4g activated The graphite was added to a 12 g/L 300 ml nickel sulfate plating solution, and ultrasonically reacted at 80 ° C for 1 hour, washed and dried to obtain a nickel plating sample.
称取3g镀镍样品加入到15g/L 300ml的氯化亚锡镀液中，在80℃下超声反应1小时，洗涤干净并烘干，从而获得Sn-Ni-NG复合材料。A 3 g nickel-plated sample was weighed and added to a 15 g/L 300 ml stannous chloride plating solution, and ultrasonically reacted at 80 ° C for 1 hour, washed and dried to obtain a Sn-Ni-NG composite material.
为了作对比试验，称取3g天然鳞片石墨加入到15g/L300ml的氯化亚锡镀液中，在80℃下超声反应1小时，洗涤干净并烘干，获得Sn-NG复合材料。For comparative experiments, 3 g of natural flake graphite was weighed into 15 g/L of 300 ml of stannous chloride plating solution, ultrasonically reacted at 80 ° C for 1 hour, washed and dried to obtain a Sn-NG composite material.
将1g Sn-NG复合材料置于烧舟a中，1gSn-Ni-NG复合材料置于烧舟b中，两者相互紧贴，放入石英管式炉中。通入Ar作为保护气，气体流量为200ml/min，以3℃/min的升温速率从室温升温至600℃，保温2h，然后进行自然降温至室温，从而得到锻烧产物。分别收集得到的煅烧产物，备用。1 g of Sn-NG composite material was placed in a boat a, and 1 g of Sn-Ni-NG composite material was placed in a boat b, which were placed in close contact with each other and placed in a quartz tube furnace. Ar was introduced as a shielding gas at a gas flow rate of 200 ml/min, and the temperature was raised from room temperature to 600 ° C at a heating rate of 3 ° C/min, and the temperature was kept for 2 hours, and then naturally cooled to room temperature to obtain a calcined product. The obtained calcined product was separately collected and used.
以所制得的Sn-Ni-NG复合材料，PVDF，导电碳黑的质量比为85∶10∶5涂覆于铜箔中作为负极，以金属锂片作为对电极，1mol/L的六氟磷锂作为电解液，组装成扣式电池。扣式电池在100mA/g的电流密度下循环100次仍保持414mA/g的比容量。Sn-Ni-NG复合材料的电极比容量比化学镀锡得到的Sn-NG复合材料的电极比容量高，经过100次循环之后Sn-Ni-NG复合材料的比容量仍然达到410mAh/g以上，并且Sn-Ni-NG复合材料的电极比容量随着循环次数的增加有缓慢增加的现象。这是由于 Sn-Ni-NG复合材料被电解液完全润湿，便于锂离子往材料的内部迁移，有利于增加嵌锂容量，从而提高电极材料的比容量。The prepared Sn-Ni-NG composite material, PVDF, conductive carbon black was coated in a copper foil as a negative electrode at a mass ratio of 85:10:5, and a lithium metal plate as a counter electrode, 1 mol/L hexafluorocarbon. Phosphorus lithium is used as an electrolyte to assemble a button battery. The button cell still maintains a specific capacity of 414 mA/g by circulating 100 times at a current density of 100 mA/g. The specific capacity of the Sn-Ni-NG composite has a higher specific capacity than that of the Sn-NG composite obtained by electroless tin plating. After 100 cycles, the specific capacity of the Sn-Ni-NG composite still reaches 410 mAh/g or more. Moreover, the specific electrode capacity of the Sn-Ni-NG composite material increases slowly with the increase of the number of cycles. This is because The Sn-Ni-NG composite material is completely wetted by the electrolyte, which facilitates the migration of lithium ions into the interior of the material, which is beneficial to increase the lithium insertion capacity and thereby increase the specific capacity of the electrode material.
实施例2Example 2
称取5g天然鳞片石墨置于150ml 1％的氯化钯溶液中，加热到70℃磁力搅拌30min，然后加入15g/L 30ml的次亚磷酸钠，再磁力搅拌30min，洗涤干净并烘干，获得活化的石墨。将4g活化的石墨加入到12g/L 300ml的硫酸镍镀液中，在80℃下超声反应1小时，洗涤干净并烘干，获得镀镍样品。称取3g镀镍样品加入到15g/L 300ml的氯化亚锡镀液中，在80℃下超声反应1小时，洗涤干净并烘干，获得Sn-Ni-NG复合材料。将1gSn-Ni-NG复合材料置于烧舟中，放入石英管式炉中。通入Ar作为保护气，气体流量为200ml/min，以3℃/min的升温速率从室温升温至600℃，保温2h，然后进行自然降温至室温，从而得到锻烧产物。Weigh 5g of natural flake graphite into 150ml 1% palladium chloride solution, heat to 70 ° C magnetic stirring for 30min, then add 15g / L 30ml of sodium hypophosphite, then magnetically stirred for 30min, washed and dried, obtained Activated graphite. 4 g of activated graphite was added to a 12 g/L 300 ml nickel sulfate plating solution, and ultrasonically reacted at 80 ° C for 1 hour, washed and dried to obtain a nickel plating sample. 3 g of the nickel-plated sample was weighed and added to a 15 g/L 300 ml stannous chloride plating solution, and ultrasonically reacted at 80 ° C for 1 hour, washed and dried to obtain a Sn-Ni-NG composite material. A 1 g of Sn-Ni-NG composite was placed in a burning boat and placed in a quartz tube furnace. Ar was introduced as a shielding gas at a gas flow rate of 200 ml/min, and the temperature was raised from room temperature to 600 ° C at a heating rate of 3 ° C/min, and the temperature was kept for 2 hours, and then naturally cooled to room temperature to obtain a calcined product.
测试方法同实施例1，扣式电池在100mA/g的电流密度下循环100次仍保持427mA/g的比容量。The test method was the same as in Example 1. The button cell was maintained at a current density of 100 mA/g for 100 times while still maintaining a specific capacity of 427 mA/g.
实施例3Example 3
称取5g天然鳞片石墨置于150ml 1％的氯化钯溶液中，加热到55℃磁力搅拌30min，然后加入15g/L 30ml的次亚磷酸钠，再磁力搅拌30min，洗涤干净并烘干，获得活化的石墨。将4g活化的石墨加入到20g/L 300ml的硫酸镍镀液中，在80℃下超声反应1小时，洗涤干净并烘干，获得镀镍样品。称取3g镀镍样品加入到20g/L 300ml的氯化亚锡镀液中，在80℃下超声反应1 小时，洗涤干净并烘干，获得Sn-Ni-NG复合材料。将1g Sn-Ni-NG复合材料置于烧舟中，放入石英管式炉中。通入Ar作为保护气，气体流量为250ml/min，以3℃/min的升温速率从室温升温至600℃，保温2h，然后进行自然降温至室温，从而得到锻烧产物。Weigh 5g of natural flake graphite into 150ml 1% palladium chloride solution, heat to 55 ° C magnetic stirring for 30min, then add 15g / L 30ml of sodium hypophosphite, magnetically stirred for 30min, washed and dried, obtained Activated graphite. 4 g of activated graphite was added to a 20 g/L 300 ml nickel sulfate plating solution, ultrasonically reacted at 80 ° C for 1 hour, washed and dried to obtain a nickel plating sample. Weigh 3g of nickel-plated sample into 20g / L 300ml of stannous chloride plating solution, ultrasonic reaction at 80 ° C 1 After hours, it was washed and dried to obtain a Sn-Ni-NG composite. 1 g of Sn-Ni-NG composite material was placed in a burning boat and placed in a quartz tube furnace. Ar was introduced as a shielding gas at a gas flow rate of 250 ml/min, and the temperature was raised from room temperature to 600 ° C at a heating rate of 3 ° C/min, and the temperature was kept for 2 hours, and then naturally cooled to room temperature to obtain a calcined product.
测试方法同实施例1，扣式电池在100mA/g的电流密度下循环100次仍保持462mA/g的比容量。The test method was the same as in Example 1. The button cell was maintained at a current density of 100 mA/g for 100 times while still maintaining a specific capacity of 462 mA/g.
实施例4Example 4
称取5g天然鳞片石墨置于150ml 2％的氯化钯溶液中，加热到55℃磁力搅拌30min，然后加入15g/L 30ml的次亚磷酸钠，再磁力搅拌30min，洗涤干净并烘干，获得活化的石墨。将4g活化的石墨加入到20g/L 300ml的氯化镍镀液中，在80℃下超声反应2小时，洗涤干净并烘干，获得镀镍样品。称取3g镀镍样品加入到15g/L 300ml的氯化亚锡镀液中，在80℃下超声反应2小时，洗涤干净并烘干，获得Sn-Ni-NG复合材料。将1gSn-Ni-NG复合材料置于烧舟中，放入石英管式炉中。通入Ar作为保护气，气体流量为200ml/min，以5℃/min的升温速率从室温升温至700℃，保温2h，然后进行自然降温至室温，从而得到锻烧产物。Weigh 5g of natural flake graphite into 150ml 2% palladium chloride solution, heat to 55 ° C magnetic stirring for 30min, then add 15g / L 30ml of sodium hypophosphite, then magnetically stirred for 30min, washed and dried, obtained Activated graphite. 4 g of activated graphite was added to a 20 g/L 300 ml nickel chloride plating solution, ultrasonically reacted at 80 ° C for 2 hours, washed and dried to obtain a nickel plating sample. 3 g of the nickel-plated sample was weighed and added to a 15 g/L 300 ml stannous chloride plating solution, and ultrasonically reacted at 80 ° C for 2 hours, washed and dried to obtain a Sn-Ni-NG composite material. A 1 g of Sn-Ni-NG composite was placed in a burning boat and placed in a quartz tube furnace. Ar was introduced as a shielding gas at a gas flow rate of 200 ml/min, and the temperature was raised from room temperature to 700 ° C at a heating rate of 5 ° C/min, and the temperature was kept for 2 hours, and then naturally cooled to room temperature to obtain a calcined product.
测试方法同实施例1，扣式电池在100mA/g的电流密度下循环100次仍保持457mA/g的比容量。The test method was the same as in Example 1. The button cell maintained a specific capacity of 457 mA/g by circulating 100 times at a current density of 100 mA/g.
实施例5 Example 5
称取5g自制层状石墨置于150ml 2％的氯化钯溶液中，加热到45℃磁力搅拌30min，然后加入15g/L 30ml的次亚磷酸钠，再磁力搅拌30min，洗涤干净并烘干，获得活化的石墨。将4g活化的石墨加入到20g/L 300ml的氯化镍镀液中，在80℃下超声反应2小时，洗涤干净并烘干，获得镀镍样品。称取3g镀镍样品加入到20g/L 300ml的氯化亚锡镀液中，在80℃下超声反应2小时，洗涤干净并烘干，获得Sn-Ni-NG复合材料。将1g Sn-Ni-NG复合材料置于烧舟中，放入石英管式炉中。通入Ar作为保护气，气体流量为300ml/min，以10℃/min的升温速率从室温升温至800℃，保温2h，然后进行自然降温至室温，从而得到锻烧产物。Weigh 5g of homemade layered graphite in 150ml 2% palladium chloride solution, heat to 45 ° C magnetic stirring for 30min, then add 15g / L 30ml of sodium hypophosphite, magnetically stirred for 30min, washed and dried, Activated graphite is obtained. 4 g of activated graphite was added to a 20 g/L 300 ml nickel chloride plating solution, ultrasonically reacted at 80 ° C for 2 hours, washed and dried to obtain a nickel plating sample. 3 g of the nickel-plated sample was weighed and added to a 20 g/L 300 ml stannous chloride plating solution, and ultrasonically reacted at 80 ° C for 2 hours, washed and dried to obtain a Sn-Ni-NG composite material. 1 g of Sn-Ni-NG composite material was placed in a burning boat and placed in a quartz tube furnace. Ar was introduced as a shielding gas at a gas flow rate of 300 ml/min, and the temperature was raised from room temperature to 800 ° C at a heating rate of 10 ° C/min, and the temperature was kept for 2 hours, and then naturally cooled to room temperature to obtain a calcined product.
测试方法同实施例1，扣式电池在100mA/g的电流密度下循环100次仍保持481mA/g的比容量。 The test method was the same as in Example 1. The button cell was maintained at a current density of 100 mA/g for 100 times while still maintaining a specific capacity of 481 mA/g.

Claims (7)

  1. 一种锂离子电池锡碳复合负极材料的制备方法，包括下述步骤：A preparation method of a tin-carbon composite anode material for a lithium ion battery, comprising the following steps:
    1)将层状石墨置于氯化钯溶液中并搅拌；1) placing the layered graphite in a palladium chloride solution and stirring;
    2)加入次亚磷酸钠，继续搅拌获得活化石墨；2) adding sodium hypophosphite and continuing to stir to obtain activated graphite;
    3)将活化石墨加入到硝酸镍溶液、硫酸镍溶液或氯化镍溶液中，超声，洗涤干净，烘干备用；3) adding activated graphite to a nickel nitrate solution, a nickel sulfate solution or a nickel chloride solution, ultrasonically, washing, and drying for use;
    4)将步骤3)所得物加入到硫酸亚锡溶液或氯化亚锡溶液中，超声，洗涤干净，烘干备用；4) adding the product of step 3) to a stannous sulfate solution or a stannous chloride solution, ultrasonically, washing, and drying for use;
    5)将步骤4)所得物在氮气、氩气、氦气或者其混合气体保护下，煅烧后自然降温至室温即得。5) The obtained product of step 4) is under the protection of nitrogen, argon, helium or a mixed gas thereof, and is naturally cooled to room temperature after calcination.
  2. 根据权利要求1所述的制备方法，其特征在于：在步骤1)，氯化钯质量分数浓度为0.5％～5％。The preparation method according to claim 1, wherein in the step 1), the palladium chloride mass fraction concentration is from 0.5% to 5%.
  3. 根据权利要求1所述的制备方法，其特征在于：在步骤1)，搅拌时间为0.5h～3h，搅拌时的温度为25～90℃。The preparation method according to claim 1, wherein in the step 1), the stirring time is 0.5 h to 3 h, and the temperature at the time of stirring is 25 to 90 °C.
  4. 根据权利要求1所述的制备方法，其特征在于：在步骤2)，次亚磷酸钠的浓度为5g/L～30g/L，加入量为30ml～60ml。The preparation method according to claim 1, wherein in the step 2), the concentration of sodium hypophosphite is from 5 g/L to 30 g/L, and the amount is from 30 ml to 60 ml.
  5. 根据权利要求1所述的制备方法，其特征在于：在步骤3)，活化石墨中的碳与溶液中的镍盐质量比为3∶(1～5)，溶液浓度为5g/L～40g/L，超声反应时间为0.5h～5h，反应温度为60～90℃。 The preparation method according to claim 1, wherein in the step 3), the mass ratio of the carbon in the activated graphite to the nickel salt in the solution is 3: (1 to 5), and the solution concentration is 5 g/L to 40 g/ L, the ultrasonic reaction time is 0.5 h to 5 h, and the reaction temperature is 60 to 90 ° C.
  6. 根据权利要求1所述的制备方法，其特征在于：在步骤4)，活化石墨中的碳与溶液中的锡盐质量比为3∶(1～3)，溶液浓度为5g/L～40g/L，超声反应时间为0.5h～5h，反应温度为60～90℃。The preparation method according to claim 1, wherein in the step 4), the mass ratio of the carbon in the activated graphite to the tin salt in the solution is 3: (1 to 3), and the solution concentration is 5 g/L to 40 g/ L, the ultrasonic reaction time is 0.5 h to 5 h, and the reaction temperature is 60 to 90 ° C.
  7. 根据权利要求1所述的制备方法，其特征在于：在步骤5)，气体流量为100～300ml/min，以1～10℃/min的升温速率从室温升温至500～900℃，然后保温煅烧1h～5h。 The preparation method according to claim 1, wherein in step 5), the gas flow rate is 100 to 300 ml/min, and the temperature is raised from room temperature to 500 to 900 ° C at a temperature increase rate of 1 to 10 ° C / min, and then the temperature is calcined. 1h ~ 5h.
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