WO2019127031A1 - Energy composite material for lithium battery and preparation method therefor - Google Patents

Energy composite material for lithium battery and preparation method therefor Download PDF

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Publication number
WO2019127031A1
WO2019127031A1 PCT/CN2017/118676 CN2017118676W WO2019127031A1 WO 2019127031 A1 WO2019127031 A1 WO 2019127031A1 CN 2017118676 W CN2017118676 W CN 2017118676W WO 2019127031 A1 WO2019127031 A1 WO 2019127031A1
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Prior art keywords
composite material
plant
carbon matrix
energy composite
lithium battery
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PCT/CN2017/118676
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French (fr)
Chinese (zh)
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徐琳
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四川金色未来科技有限公司
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Priority to PCT/CN2017/118676 priority Critical patent/WO2019127031A1/en
Priority to CN201780098263.2A priority patent/CN115943121A/en
Publication of WO2019127031A1 publication Critical patent/WO2019127031A1/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G19/00—Compounds of tin
    • C01G19/02—Oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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 the technical field of functional composite materials, and more particularly to an energy composite material for a lithium battery and a preparation method thereof.
  • lithium batteries Since its commercial use in the 1990s, lithium batteries have been widely used in electronic devices such as mobile phones, flat panels, cameras, and new energy power vehicles due to their high energy density and high charge-discharge cycle efficiency.
  • the electrodes of the lithium battery are mainly made of graphite materials, and the theoretical capacity of the electrode materials made of the graphite materials is limited.
  • the research and development of high-capacity anode materials has been a common pursuit of those skilled in the art. More practice has proved that materials with higher theoretical capacity show poor cycle performance in electrode reactions, such as tin oxide materials, theoretical capacity of 790 mA / g, self-discharge voltage ⁇ 1.5V, but The tin oxide material is prone to agglomeration during charging and discharging, affecting the structure of the electrode material, causing volume change of the battery, reducing battery capacity, and poor cycle stability.
  • the object of the present invention is to overcome the deficiencies of the prior art, and to provide an energy composite material for a lithium battery and a preparation method thereof, which can reduce the raw material cost of the energy composite material and reduce the process by using the plant as a raw material for preparing the energy composite material.
  • the requirements of the equipment, simplifying the process flow, and reducing the process modification engineering of the processed pore structure can reduce the production cost of the energy composite material.
  • the pore structure based on the plant itself can be used for efficiently transporting the electrolyte liquid, which helps to improve the efficiency of the conductive ion circulation. Conducive to the efficient circulation of conductive liquid.
  • a method for preparing an energy composite material for a lithium battery comprising the following steps:
  • the plant carbon substrate obtained in the step (3) is mixed with a strong acid solution having a mass concentration of 65% to 75% to carry out a carboxylation treatment to obtain a plant carbon substrate having a mass concentration of 0.6000 g/L to 0.8000 g/L.
  • a strong acid solution having a mass concentration of 65% to 75% to carry out a carboxylation treatment to obtain a plant carbon substrate having a mass concentration of 0.6000 g/L to 0.8000 g/L.
  • Mixing the solution reacting the plant carbon matrix mixed solution at 85 ° C ⁇ 90 ° C for 180 ⁇ 270 min, filtering, washing with water until the solution is neutral, vacuum drying, to obtain the carboxylated plant carbon matrix powder material;
  • step (4) mixing the plant carbon matrix powder material in step (4) with stannous oxide at a mass ratio of 1:3, adding ethanol and distilled water for stirring, sonicating for 4.5 to 6.5 hours, suction filtration, and vacuum drying to obtain a composite material. ;
  • the composite material obtained in the step (5) is placed in a tube furnace, and the tube furnace is evacuated.
  • the pressure in the tube furnace is ⁇ 0.08 MPa
  • the temperature control power source is turned on, first at 5 ° C / min ⁇ Heating at a heating rate of 8 ° C / min to 400 ° C ⁇ 500 ° C, nitrogen gas, heat for 3.5 ⁇ 4.5h, and finally cooled to 300 ° C at a rate of 1 ° C / min ⁇ 2 ° C / min, turn off the power, naturally cooled to room temperature , get energy composite materials.
  • the plant is at least one of reed and water hyacinth.
  • the vacuum drying temperature is 50 ° C to 60 ° C, and the drying time is 12 to 36 h.
  • the temperature is raised to 450 ° C to 460 ° C at a temperature increase rate of 6.5 ° C / min to 6.8 ° C / min.
  • the cooling rate in the step (6) is from 1 ° C / min to 1.5 ° C / min.
  • the present invention adopts a reed plant or the like, carbonizes it, extracts a carbon matrix material, and performs an activation treatment on the extracted carbon matrix material by sodium hydroxide mixed calcination, and then the activated carbon matrix material and
  • the iron oxide mixture is calcined at a high temperature, and the iron oxide is used as a catalyst to induce the transformation of the carbon matrix material into a network structure of graphite and graphene-like materials at a high temperature, and the electron transport capacity of the graphite and graphene-like network structures.
  • the present invention directly utilizes a liquid transport channel formed by a plant based on material exchange and energy flow to transport conductive ions, reduces complicated pore modification engineering, and reduces processing and manufacturing costs of the pore material in the energy composite material.
  • the present invention carboxylates a plant carbon matrix material in a strong acid solution, and utilizes the strong oxidizing property of a strong acid to increase the activity of the reaction site of the plant carbon matrix material, and enhance the activation energy of the reaction site, in the stannous oxide
  • the strong acid solution may be a nitric acid solution or a concentrated sulfuric acid solution. Wait.
  • a method for preparing an energy composite material for a lithium battery comprising the steps of:
  • the mixture obtained by calcining in the step (2) is mixed with iron oxide according to a mass ratio of 1:1, calcined in a nitrogen atmosphere at 650 ° C for 3 hours, and after cooling, 11 wt% of a dilute hydrochloric acid solution is added for washing and deoxidation.
  • Iron impurities a mixed solution having a mass concentration of 9 g / L, the mixed solution was heated at 70 ° C while stirring in a water bath for 3.5 h, washed with water until the solution was neutral, filtered and dried to obtain a plant carbon matrix material;
  • the plant carbon matrix material obtained in the step (3) is mixed with a strong acid solution having a mass concentration of 70% for carboxylation treatment to enhance the activation energy of the plant carbon matrix material, and the mass concentration is 0.7000 g/L.
  • Plant carbon matrix mixed solution the plant carbon matrix mixed solution is reacted at 87 ° C for 220 min, filtered, washed with water until the solution is neutral, vacuum dried to obtain a carboxylated plant carbon matrix powder material;
  • step (4) mixing the plant carbon matrix powder material in step (4) with stannous oxide at a mass ratio of 1:3, adding ethanol and distilled water for stirring, sonicating for 5 hours, suction filtration, and vacuum drying to obtain a composite material, which can be improved.
  • Cyclic stability of stannous oxide
  • the composite material obtained in the step (5) is placed in a tube furnace, and the tube furnace is evacuated.
  • the pressure in the tube furnace is ⁇ 0.08 MPa
  • the temperature control power source is turned on, first at 6 ° C / min.
  • the heating rate was heated to 450 ° C, nitrogen gas was introduced, the temperature was kept for 4 hours, and finally the temperature was lowered to 300 ° C at a rate of 1.5 ° C / min.
  • the power was turned off and naturally cooled to room temperature to obtain an energy composite material.
  • a method for preparing an energy composite material for a lithium battery comprising the steps of:
  • the mixture obtained by calcining in the step (2) is mixed with iron oxide according to a mass ratio of 1:1, calcined in a nitrogen atmosphere at 700 ° C for 3 hours, and after cooling, 11 wt% of a dilute hydrochloric acid solution is added for washing and deoxidation.
  • Iron impurities a mixed solution having a mass concentration of 9 g / L, the mixed solution was heated at 80 ° C while stirring in a water bath for 3.5 h, washed with water until the solution was neutral, filtered and dried to obtain a plant carbon matrix material;
  • the plant carbon matrix material obtained in the step (3) is mixed with a strong acid solution having a mass concentration of 70% for carboxylation treatment to enhance the activation energy of the plant carbon matrix material, and the mass concentration is 0.7000 g/L.
  • Plant carbon matrix mixed solution the plant carbon matrix mixed solution is reacted at 90 ° C for 220 min, filtered, washed with water until the solution is neutral, vacuum dried to obtain a carboxylated plant carbon matrix powder material;
  • step (4) mixing the plant carbon matrix powder material in step (4) with stannous oxide at a mass ratio of 1:3, adding ethanol and distilled water for stirring, sonicating for 5 hours, suction filtration, and vacuum drying to obtain a composite material, which can be improved.
  • Cyclic stability of stannous oxide
  • the composite material obtained in the step (5) is placed in a tube furnace, and the tube furnace is evacuated.
  • the pressure in the tube furnace is ⁇ 0.08 MPa
  • the temperature control power source is turned on, first at 6 ° C / min.
  • the heating rate was heated to 450 ° C, nitrogen gas was introduced, the temperature was kept for 4 hours, and finally the temperature was lowered to 300 ° C at a rate of 1.5 ° C / min.
  • the power was turned off and naturally cooled to room temperature to obtain an energy composite material.
  • a method for preparing an energy composite material for a lithium battery comprising the steps of:
  • the mixture obtained by calcining in the step (2) is mixed with iron oxide according to a mass ratio of 1:1, calcined in a nitrogen atmosphere at 600 ° C for 3 hours, and after cooling, 11 wt% of a dilute hydrochloric acid solution is added for washing and deoxidation.
  • Iron impurities a mixed solution having a mass concentration of 9 g / L, the mixed solution was heated at 60 ° C while stirring in a water bath for 3.5 h, washed with water until the solution was neutral, filtered and dried to obtain a plant carbon matrix material;
  • the plant carbon matrix material obtained in the step (3) is mixed with a strong acid solution having a mass concentration of 70% for carboxylation treatment to enhance the activation energy of the plant carbon matrix material, and the mass concentration is 0.7000 g/L.
  • Plant carbon matrix mixed solution the plant carbon matrix mixed solution is reacted at 85 ° C for 220 min, filtered, washed with water until the solution is neutral, vacuum dried to obtain a carboxylated plant carbon matrix powder material;
  • step (4) mixing the plant carbon matrix powder material in step (4) with stannous oxide at a mass ratio of 1:3, adding ethanol and distilled water for stirring, sonicating for 5 hours, suction filtration, and vacuum drying to obtain a composite material, which can be improved.
  • Cyclic stability of stannous oxide
  • the composite material obtained in the step (5) is placed in a tube furnace, and the tube furnace is evacuated.
  • the pressure in the tube furnace is ⁇ 0.08 MPa
  • the temperature control power source is turned on, first at 6 ° C / min.
  • the heating rate was heated to 450 ° C, nitrogen gas was introduced, the temperature was kept for 4 hours, and finally the temperature was lowered to 300 ° C at a rate of 1.5 ° C / min.
  • the power was turned off and naturally cooled to room temperature to obtain an energy composite material.
  • a method for preparing an energy composite material for a lithium battery comprising the steps of:
  • the mixture obtained by calcining in the step (2) is mixed with iron oxide according to a mass ratio of 1:1, calcined in a nitrogen atmosphere at 700 ° C for 4 hours, and after cooling, 11 wt% of a dilute hydrochloric acid solution is added for washing and deoxidation.
  • Iron impurities a mixed solution of mass concentration of 9g / L, the mixed solution was heated at 80 ° C while stirring in a water bath for 4 h, washed with water until the solution was neutral, filtered and dried to obtain a plant carbon matrix material;
  • the plant carbon matrix material obtained in the step (3) is mixed with a strong acid solution having a mass concentration of 70% for carboxylation treatment to enhance the activation energy of the plant carbon matrix material, and the mass concentration is 0.7000 g/L.
  • Plant carbon matrix mixed solution the plant carbon matrix mixed solution is reacted at 90 ° C for 270 min, filtered, washed with water until the solution is neutral, vacuum dried to obtain a carboxylated plant carbon matrix powder material;
  • step (4) mixing the plant carbon matrix powder material in step (4) with stannous oxide at a mass ratio of 1:3, adding ethanol and distilled water for stirring, sonicating for 6.5 hours, suction filtration, and vacuum drying to obtain a composite material.
  • stannous oxide improves the cycle stability of stannous oxide
  • the composite material obtained in the step (5) is placed in a tube furnace, and the tube furnace is evacuated.
  • the pressure in the tube furnace is ⁇ 0.08 MPa
  • the temperature control power source is turned on, first at 6 ° C / min.
  • the heating rate was heated to 450 ° C, nitrogen gas was introduced, the temperature was maintained for 4.5 h, and finally the temperature was lowered to 300 ° C at a rate of 1.5 ° C / min.
  • the power was turned off and naturally cooled to room temperature to obtain an energy composite material.
  • a method for preparing an energy composite material for a lithium battery comprising the steps of:
  • the mixture obtained by calcining in the step (2) is mixed with iron oxide according to a mass ratio of 1:1, calcined in a nitrogen atmosphere at 600 ° C for 2 h, and after cooling, 11 wt% of a dilute hydrochloric acid solution is added for washing and deoxidation.
  • Iron impurities a mixed solution having a mass concentration of 9 g / L, the mixed solution was heated at 60 ° C with a water bath for 3 h, washed with water until the solution was neutral, filtered and dried to obtain a plant carbon matrix material;
  • the plant carbon matrix material obtained in the step (3) is mixed with a strong acid solution having a mass concentration of 70% for carboxylation treatment to enhance the activation energy of the plant carbon matrix material, and the mass concentration is 0.7000 g/L.
  • Plant carbon matrix mixed solution the plant carbon matrix mixed solution is reacted at 85 ° C for 180 min, filtered, washed with water until the solution is neutral, vacuum dried to obtain a carboxylated plant carbon matrix powder material;
  • step (4) mixing the plant carbon matrix powder material in step (4) with stannous oxide at a mass ratio of 1:3, adding ethanol and distilled water for stirring, sonicating for 4.5 hours, suction filtration, and vacuum drying to obtain a composite material.
  • stannous oxide improves the cycle stability of stannous oxide
  • the composite material obtained in the step (5) is placed in a tube furnace, and the tube furnace is evacuated.
  • the pressure in the tube furnace is ⁇ 0.08 MPa
  • the temperature control power source is turned on, first at 6 ° C / min.
  • the heating rate was heated to 450 ° C, nitrogen was introduced, the temperature was kept for 3.5 h, and finally the temperature was lowered to 300 ° C at a rate of 1.5 ° C / min.
  • the power was turned off and naturally cooled to room temperature to obtain an energy composite material.
  • a method for preparing an energy composite material for a lithium battery comprising the steps of:
  • the mixture obtained by calcining in the step (2) is mixed with iron oxide according to a mass ratio of 1:1, calcined in a nitrogen atmosphere at 650 ° C for 3 hours, and after cooling, 11 wt% of a dilute hydrochloric acid solution is added for washing and deoxidation.
  • Iron impurities a mixed solution having a mass concentration of 9 g / L, the mixed solution was heated at 70 ° C while stirring in a water bath for 3.5 h, washed with water until the solution was neutral, filtered and dried to obtain a plant carbon matrix material;
  • the plant carbon matrix material obtained in the step (3) is mixed with a strong acid solution having a mass concentration of 70% for carboxylation treatment to enhance the activation energy of the plant carbon matrix material, and the mass concentration is 0.7000 g/L.
  • Plant carbon matrix mixed solution the plant carbon matrix mixed solution is reacted at 87 ° C for 220 min, filtered, washed with water until the solution is neutral, vacuum dried to obtain a carboxylated plant carbon matrix powder material;
  • step (4) mixing the plant carbon matrix powder material in step (4) with stannous oxide at a mass ratio of 1:3, adding ethanol and distilled water for stirring, sonicating for 5 hours, suction filtration, and vacuum drying to obtain a composite material, which can be improved.
  • Cyclic stability of stannous oxide
  • the composite material obtained in the step (5) is placed in a tube furnace, and the tube furnace is evacuated.
  • the pressure in the tube furnace is ⁇ 0.08 MPa
  • the temperature control power source is turned on, first at 6 ° C / min.
  • the heating rate was heated to 450 ° C, nitrogen gas was introduced, the temperature was kept for 4 hours, and finally the temperature was lowered to 300 ° C at a rate of 1.5 ° C / min.
  • the power was turned off and naturally cooled to room temperature to obtain an energy composite material.

Abstract

Disclosed are an energy composite material for a lithium battery and a preparation method therefor, comprising the steps of preparing a plant matrix material, activating the plant matrix material, carrying out high-temperature calcination and catalysis on the activated material, and compounding the material subjected to high-temperature calcination. By means of the present invention, the raw material acquisition cost of the energy composite material is reduced, the requirements on process equipment are reduced, the process flow is simplified, the aperture modification engineering of the raw material in the preparation of the energy composite material is reduced, and the manufacturing cost of the energy composite material is reduced; by means of a plant-based natural pore channel structure, an electrolyte can be efficiently conveyed, the circulation efficiency of conductive ions can be improved, and the high-efficiency circulation of conductive liquid is facilitated.

Description

用于锂电池的能源复合材料及其制备方法Energy composite material for lithium battery and preparation method thereof 技术领域Technical field
本发明涉及功能复合材料技术领域，更为具体地，涉及一种用于锂电池的能源复合材料及其制备方法。The invention relates to the technical field of functional composite materials, and more particularly to an energy composite material for a lithium battery and a preparation method thereof.
背景技术Background technique
锂电池自二十世纪九十年代商用以来，凭借能量密度高，充放电循环效率高等特点，被广泛应用于电子装置中，例如手机，平板，相机，新能源动力汽车等。Since its commercial use in the 1990s, lithium batteries have been widely used in electronic devices such as mobile phones, flat panels, cameras, and new energy power vehicles due to their high energy density and high charge-discharge cycle efficiency.
现有技术中，锂电池的电极主要采用石墨材料制作，而石墨材料制作的电极材料理论容量有限，对高容量负极材料的研究和开发一直是本领域技术人员的普遍追求。较多的实践证明，对于具备较高的理论容量的材料，在电极反应中却表现出循环性能较差的问题，例如氧化锡材料，理论容量达790mA/g，自放电电压<1.5V，但是氧化锡材料在充放电的过程中容易发生团聚，影响电极材料的结构，造成电池的体积变化，降低电池容量，循环稳定性较差。碳材料虽然理论容量较低，但是具有较高的循环稳定性，对碳材料进行功能设计一直是本领域技术人员普遍努力的方向。例如，公开号为CN103840137B的中国专利公开了一种利用水葫芦制得的Fe 3O 4/C复合材料及其应用，该专利的说明书公开的制备方法在改善环境重金属污染的同时具有原材料来源广泛、易于工业化实施、制备工艺简单、对环境友好的特点，制得的Fe 3O 4/C复合材料作为锂离子电池负极材料应用具有良好的循环性能和库伦效率。例如，《Aavanced Materials》，(《先进材料》)，在2009年，21期，2536页上发表的“Designed Synthesis of Coaxial SnO 2carbon Hollow Nanospheres for Highly Reversible Lithium Storage”(“高可逆性锂电池用碳包覆二氧化锡纳米空心球的设计组装)，能够制备包覆有碳层的二氧化锡纳米空心球，可以缓解充放电过程中二氧化锡材料的体积变化。 In the prior art, the electrodes of the lithium battery are mainly made of graphite materials, and the theoretical capacity of the electrode materials made of the graphite materials is limited. The research and development of high-capacity anode materials has been a common pursuit of those skilled in the art. More practice has proved that materials with higher theoretical capacity show poor cycle performance in electrode reactions, such as tin oxide materials, theoretical capacity of 790 mA / g, self-discharge voltage <1.5V, but The tin oxide material is prone to agglomeration during charging and discharging, affecting the structure of the electrode material, causing volume change of the battery, reducing battery capacity, and poor cycle stability. Although the carbon material has a low theoretical capacity, it has high cycle stability, and functional design of carbon materials has been a common direction for those skilled in the art. For example, Chinese Patent Publication No. CN103840137B discloses a Fe 3 O 4 /C composite material prepared by using water hyacinth and its application, and the preparation method disclosed in the specification of the patent has a wide range of raw materials while improving environmental heavy metal pollution. The invention is easy to industrialize, simple in preparation process and environmentally friendly. The obtained Fe 3 O 4 /C composite material has good cycle performance and coulombic efficiency as a negative electrode material for lithium ion battery. For example, "Aavanced Materials", "Advanced Materials", "Designed Synthesis of Coaxial SnO 2 carbon Hollow Nanospheres for Highly Reversible Lithium Storage", 2009, 21, 2536 ("High Reversible Lithium Battery" The design and assembly of carbon-coated tin dioxide nano-hollow spheres can prepare tin dioxide nano-hollow spheres coated with carbon layer, which can alleviate the volume change of tin dioxide material during charging and discharging.
在锂电池的充、放电过程中，在脱锂和嵌锂的过程中，电极材料的比表面积和导电性成为影响能量效率的至关重要的因素。常规的碳材料，在一定程度上能够保证锂离子的良好导通，且热力学和化学稳定性较好。但是，目前对碳材料进行功能结构设计的工艺存在原材料较少、制备工艺步骤较多、制备成本较高等难题。总之，在现有技术中，很少有直接利用植物自身结构进行能源功能复合材料制备，人类对大自然给予的资源并没有充分利用起来。During the charging and discharging process of lithium batteries, the specific surface area and conductivity of the electrode materials become a crucial factor affecting energy efficiency during delithiation and lithium intercalation. Conventional carbon materials can ensure good conduction of lithium ions to a certain extent, and have good thermodynamic and chemical stability. However, at present, the process of designing the functional structure of carbon materials has problems such as less raw materials, more preparation steps, and higher preparation costs. In short, in the prior art, there are few direct use of the plant's own structure for the preparation of energy functional composite materials, and the resources given by humans to nature are not fully utilized.
发明内容Summary of the invention
本发明的目的在于克服现有技术的不足，提供一种用于锂电池的能源复合材料及其制备方法，利用植物作为制备能源复合材料的原材料，能够降低能源复合材料的原材料成本，降低对工艺设备的需求，简化工艺流程，减少加工孔径结构的工艺修饰工程，能够降低能源复合材料的制作成本，基于植物本身的孔道结构能够用于高效输送电解液液，有助于提高导电 离子循环效率，有利于导电液的高效流通。The object of the present invention is to overcome the deficiencies of the prior art, and to provide an energy composite material for a lithium battery and a preparation method thereof, which can reduce the raw material cost of the energy composite material and reduce the process by using the plant as a raw material for preparing the energy composite material. The requirements of the equipment, simplifying the process flow, and reducing the process modification engineering of the processed pore structure can reduce the production cost of the energy composite material. The pore structure based on the plant itself can be used for efficiently transporting the electrolyte liquid, which helps to improve the efficiency of the conductive ion circulation. Conducive to the efficient circulation of conductive liquid.
本发明的目的是通过以下技术方案来实现的：一种用于锂电池的能源复合材料的制备方法，包括以下步骤：The object of the present invention is achieved by the following technical solutions: a method for preparing an energy composite material for a lithium battery, comprising the following steps:
(1)选择具有多孔结构的植物的茎或叶作为原材料，干燥，然后将干燥后的茎或叶在660℃～720℃下进行碳化处理；(1) selecting a stem or a leaf of a plant having a porous structure as a raw material, drying, and then subjecting the dried stem or leaf to carbonization at 660 ° C to 720 ° C;
(2)取碳化处理后的茎或叶的粉末，加氢氧化钠粉末，按照质量比1:3混合，得到混合粉末，将混合粉末在氮气气氛、810℃～1000℃下煅烧1～2h，冷却至室温；(2) taking the powder of the stem or leaf after the carbonization treatment, adding sodium hydroxide powder, mixing at a mass ratio of 1:3 to obtain a mixed powder, and calcining the mixed powder in a nitrogen atmosphere at 810 ° C to 1000 ° C for 1 to 2 hours. Cool to room temperature;
(3)将步骤(2)煅烧后得到的混合物与氧化铁按照质量比1:1进行混合，在氮气气氛、600℃～700℃下煅烧2～4h，冷却后加10wt％～12wt％的稀盐酸溶液，洗去氧化铁杂质，得到质量浓度为8g/L～11g/L的混合溶液，将混合溶液在60℃～80℃下边搅拌边水浴加热3～4h，水洗，直至溶液呈中性，过滤、干燥，得到植物碳基体材料；(3) mixing the mixture obtained by calcining in the step (2) with iron oxide according to a mass ratio of 1:1, calcining in a nitrogen atmosphere at 600 ° C to 700 ° C for 2 to 4 hours, and adding 10 wt% to 12 wt% of the rarex after cooling. Hydrochloric acid solution, wash away iron oxide impurities, to obtain a mixed solution with a mass concentration of 8g / L ~ 11g / L, the mixed solution is heated at 60 ° C ~ 80 ° C while stirring in a water bath for 3 ~ 4h, washed with water until the solution is neutral, Filtering and drying to obtain a plant carbon matrix material;
(4)将步骤(3)得到的植物碳基体材料，与质量浓度为65％～75％的强酸溶液混合进行羧基化处理，得到质量浓度为0.6000g/L～0.8000g/L的植物碳基体混合溶液，待植物碳基体混合溶液在85℃～90℃下反应180～270min，过滤，水洗，直至溶液呈中性，真空干燥，得到羧基化处理后的植物碳基体粉末材料；(4) The plant carbon substrate obtained in the step (3) is mixed with a strong acid solution having a mass concentration of 65% to 75% to carry out a carboxylation treatment to obtain a plant carbon substrate having a mass concentration of 0.6000 g/L to 0.8000 g/L. Mixing the solution, reacting the plant carbon matrix mixed solution at 85 ° C ~ 90 ° C for 180 ~ 270 min, filtering, washing with water until the solution is neutral, vacuum drying, to obtain the carboxylated plant carbon matrix powder material;
(5)将步骤(4)中的植物碳基体粉末材料与氧化亚锡按照质量比1:3混合，加乙醇和蒸馏水进行搅拌，超声处理4.5～6.5h，抽滤，真空干燥，得到复合材料；(5) mixing the plant carbon matrix powder material in step (4) with stannous oxide at a mass ratio of 1:3, adding ethanol and distilled water for stirring, sonicating for 4.5 to 6.5 hours, suction filtration, and vacuum drying to obtain a composite material. ;
(6)将步骤(5)得到的复合材料放入管式炉中，对管式炉进行抽真空，当管式炉中压力＜0.08MPa时，开启温控电源，先以5℃/min～8℃/min的升温速率加热至400℃～500℃，通入氮气，保温3.5～4.5h，最后以1℃/min～2℃/min的速率降温至300℃，关闭电源，自然冷却至室温，得到能源复合材料。(6) The composite material obtained in the step (5) is placed in a tube furnace, and the tube furnace is evacuated. When the pressure in the tube furnace is <0.08 MPa, the temperature control power source is turned on, first at 5 ° C / min ～ Heating at a heating rate of 8 ° C / min to 400 ° C ~ 500 ° C, nitrogen gas, heat for 3.5 ~ 4.5h, and finally cooled to 300 ° C at a rate of 1 ° C / min ~ 2 ° C / min, turn off the power, naturally cooled to room temperature , get energy composite materials.
进一步地，在步骤(1)中，所述植物为芦苇、凤眼莲中的至少一种。Further, in the step (1), the plant is at least one of reed and water hyacinth.
进一步地，在步骤(4)中，真空干燥温度为50℃～60℃，干燥时间为12～36h。Further, in the step (4), the vacuum drying temperature is 50 ° C to 60 ° C, and the drying time is 12 to 36 h.
进一步地，在步骤(6)中以6.5℃/min～6.8℃/min的升温速率升温至450℃～460℃。Further, in the step (6), the temperature is raised to 450 ° C to 460 ° C at a temperature increase rate of 6.5 ° C / min to 6.8 ° C / min.
进一步地，在步骤(6)中所述降温速率为1℃/min～1.5℃/min。Further, the cooling rate in the step (6) is from 1 ° C / min to 1.5 ° C / min.
以及，使用如上技术方案中任一种所述制备方法制备得到的用于锂电池的能源复合材料。And an energy composite material for a lithium battery prepared by the preparation method according to any one of the above aspects.
本发明的有益效果是：The beneficial effects of the invention are:
(1)本发明首次采用芦苇植物等，对其进行碳化处理，提取碳基质材料，并对提取的碳基质材料通过氢氧化钠混合煅烧，进行活化处理，然后将活化处理后的碳基质材料与氧化铁混合在高温下进行煅烧处理，氧化铁作为催化剂，在高温下诱导碳基质材料转变为石墨和类石墨烯的网状结构材料，石墨和类石墨烯的网状结构对电子的输运能力比无定形碳强，在高 温煅烧和催化剂共同作用后，提高了碳基质材料的导电性能，而碳基质材料本身由于植物通过蒸腾作用将根吸收的水分输送到叶子，茎、叶在整个植物的生长代谢中起着输送物质和能量交换的作用，这种生命体结构本身有利于液体的高效流通，在碳化、活化和高温煅烧催化后的这种植物碳基质材料能够高效输送电解液中的导电离子，有助于提高导电离子循环效率，使用这种材料制作电池的电极，有利于导电液的高效流通。(1) For the first time, the present invention adopts a reed plant or the like, carbonizes it, extracts a carbon matrix material, and performs an activation treatment on the extracted carbon matrix material by sodium hydroxide mixed calcination, and then the activated carbon matrix material and The iron oxide mixture is calcined at a high temperature, and the iron oxide is used as a catalyst to induce the transformation of the carbon matrix material into a network structure of graphite and graphene-like materials at a high temperature, and the electron transport capacity of the graphite and graphene-like network structures. Stronger than amorphous carbon, after the high temperature calcination and the catalyst work together, the conductivity of the carbon matrix material is improved, and the carbon matrix material itself transports the water absorbed by the root to the leaves, stems and leaves throughout the plant due to transpiration of the plant. Growth metabolism plays a role in transporting substances and energy. This living body structure is beneficial to the efficient circulation of liquid. The plant carbon matrix material can be efficiently transported in the electrolyte after carbonization, activation and high temperature calcination. Ions, which help to improve the efficiency of conductive ion recycling, using this material to make the electrodes of the battery, there are Conducive to the efficient circulation of conductive liquid.
(2)本发明直接利用植物基于物质交换和能量流动形成的液体输送通道来传输导电离子，减少了复杂的孔径修饰工程，降低了在能源复合材料中对孔隙材料的加工制造成本。(2) The present invention directly utilizes a liquid transport channel formed by a plant based on material exchange and energy flow to transport conductive ions, reduces complicated pore modification engineering, and reduces processing and manufacturing costs of the pore material in the energy composite material.
(3)本发明在强酸溶液中对植物碳基质材料进行羧基化处理，利用强酸的强氧化性提高植物碳基质材料的反应位点的活性，增强反应位点的活化能，在将氧化亚锡与植物碳基质材料进行复合时，有利于促进氧化亚锡材料在植物碳基质材料上进行较均匀地分布，促进植物碳基质材料与氧化亚锡地复合，强酸溶液可以是硝酸溶液，浓硫酸溶液等。(3) The present invention carboxylates a plant carbon matrix material in a strong acid solution, and utilizes the strong oxidizing property of a strong acid to increase the activity of the reaction site of the plant carbon matrix material, and enhance the activation energy of the reaction site, in the stannous oxide When compounded with the plant carbon matrix material, it is beneficial to promote the uniform distribution of the stannous oxide material on the plant carbon matrix material, and promote the compounding of the plant carbon matrix material and the stannous oxide. The strong acid solution may be a nitric acid solution or a concentrated sulfuric acid solution. Wait.
本发明的技术效果不限于如上所述，以上技术效果仅仅是示例性说明，本发明的其他特征及其作用等将在随后的具体实施方式部分予以详细说明。本领域技术人员可以根据本申请的说明书可以直接或间接地知悉其余的技术效果等，不再赘述。The technical effects of the present invention are not limited to the above, and the above technical effects are merely illustrative, and other features, functions, and the like of the present invention will be described in detail in the following detailed description. Those skilled in the art may directly or indirectly know the remaining technical effects and the like according to the description of the present application, and will not be described again.
具体实施方式Detailed ways
下面将详细描述本发明的具体实施例，本说明书中公开的所有特征，或隐含公开的所有方法或过程中的步骤，除了互相排斥的特征和/或步骤以外，可以以任何方式组合。这里描述的实施例只用于举例说明，并不用于限制本发明。在以下描述中，对于本领域普通技术人员显而易见的是：不必采用这些特定细节来实行本发明。在其他实例中，为了避免混淆本发明，未具体描述公知的工艺，公知的辅助添加剂或公知的实施设备等。The specific embodiments of the present invention are described in detail below, and all the features disclosed in the specification, or the steps of all methods or processes disclosed in the specification, may be combined in any manner except for mutually exclusive features and/or steps. The embodiments described herein are for illustrative purposes only and are not intended to limit the invention. In the following description, it will be apparent to those skilled in the art that In other instances, well-known processes, well-known auxiliary additives or well-known implementation equipment and the like have not been specifically described in order to avoid obscuring the present invention.
【实施例一】[Embodiment 1]
一种用于锂电池的能源复合材料的制备方法，包括以下步骤：A method for preparing an energy composite material for a lithium battery, comprising the steps of:
(1)选择芦苇的茎或叶作为原材料，干燥，然后将干燥后的茎或叶在700℃下进行碳化处理，提取碳基质材料；(1) selecting the stem or leaf of the reed as a raw material, drying, and then carbonizing the dried stem or leaf at 700 ° C to extract the carbon matrix material;
(2)取碳化处理后的茎或叶的粉末，加氢氧化钠粉末，按照质量比1:3混合，得到混合粉末，将混合粉末在氮气气氛、900℃下煅烧1.5h，进行活化处理，冷却至室温；(2) taking the powder of the stem or leaf after the carbonization treatment, adding sodium hydroxide powder, mixing at a mass ratio of 1:3 to obtain a mixed powder, and calcining the mixed powder in a nitrogen atmosphere at 900 ° C for 1.5 h to carry out activation treatment. Cool to room temperature;
(3)将步骤(2)煅烧后得到的混合物与氧化铁按照质量比1:1进行混合，在氮气气氛、650℃下煅烧3h，冷却后加11wt％的稀盐酸溶液，用于洗去氧化铁杂质，得到质量浓度为9g/L的混合溶液，将混合溶液在70℃下边搅拌边水浴加热3.5h，水洗，直至溶液呈中性，过滤、干燥，得到植物碳基体材料；(3) The mixture obtained by calcining in the step (2) is mixed with iron oxide according to a mass ratio of 1:1, calcined in a nitrogen atmosphere at 650 ° C for 3 hours, and after cooling, 11 wt% of a dilute hydrochloric acid solution is added for washing and deoxidation. Iron impurities, a mixed solution having a mass concentration of 9 g / L, the mixed solution was heated at 70 ° C while stirring in a water bath for 3.5 h, washed with water until the solution was neutral, filtered and dried to obtain a plant carbon matrix material;
(4)将步骤(3)得到的植物碳基体材料，与质量浓度为70％的强酸溶液混合进行羧基 化处理，用于增强植物碳基体材料的活化能，得到质量浓度为0.7000g/L的植物碳基体混合溶液，待植物碳基体混合溶液在87℃下反应220min，过滤，水洗，直至溶液呈中性，真空干燥，得到羧基化处理后的植物碳基体粉末材料；(4) The plant carbon matrix material obtained in the step (3) is mixed with a strong acid solution having a mass concentration of 70% for carboxylation treatment to enhance the activation energy of the plant carbon matrix material, and the mass concentration is 0.7000 g/L. Plant carbon matrix mixed solution, the plant carbon matrix mixed solution is reacted at 87 ° C for 220 min, filtered, washed with water until the solution is neutral, vacuum dried to obtain a carboxylated plant carbon matrix powder material;
(5)将步骤(4)中的植物碳基体粉末材料与氧化亚锡按照质量比1:3混合，加乙醇和蒸馏水进行搅拌，超声处理5h，抽滤，真空干燥，得到复合材料，能够提高氧化亚锡的循环稳定性；(5) mixing the plant carbon matrix powder material in step (4) with stannous oxide at a mass ratio of 1:3, adding ethanol and distilled water for stirring, sonicating for 5 hours, suction filtration, and vacuum drying to obtain a composite material, which can be improved. Cyclic stability of stannous oxide;
(6)将步骤(5)得到的复合材料放入管式炉中，对管式炉进行抽真空，当管式炉中压力＜0.08MPa时，开启温控电源，先以6℃/min的升温速率加热至450℃，通入氮气，保温4h，最后以1.5℃/min的速率降温至300℃，关闭电源，自然冷却至室温，得到能源复合材料。(6) The composite material obtained in the step (5) is placed in a tube furnace, and the tube furnace is evacuated. When the pressure in the tube furnace is <0.08 MPa, the temperature control power source is turned on, first at 6 ° C / min. The heating rate was heated to 450 ° C, nitrogen gas was introduced, the temperature was kept for 4 hours, and finally the temperature was lowered to 300 ° C at a rate of 1.5 ° C / min. The power was turned off and naturally cooled to room temperature to obtain an energy composite material.
【实施例二】[Embodiment 2]
一种用于锂电池的能源复合材料的制备方法，包括以下步骤：A method for preparing an energy composite material for a lithium battery, comprising the steps of:
(1)选择芦苇的茎或叶作为原材料，干燥，然后将干燥后的茎或叶在720℃下进行碳化处理，提取碳基质材料；(1) selecting the stem or leaf of the reed as a raw material, drying, and then carbonizing the dried stem or leaf at 720 ° C to extract the carbon matrix material;
(2)取碳化处理后的茎或叶的粉末，加氢氧化钠粉末，按照质量比1:3混合，得到混合粉末，将混合粉末在氮气气氛、1000℃下煅烧1.5h，进行活化处理，冷却至室温；(2) taking the powder of the stem or leaf after the carbonization treatment, adding sodium hydroxide powder, mixing at a mass ratio of 1:3 to obtain a mixed powder, and calcining the mixed powder in a nitrogen atmosphere at 1000 ° C for 1.5 h, and performing activation treatment. Cool to room temperature;
(3)将步骤(2)煅烧后得到的混合物与氧化铁按照质量比1:1进行混合，在氮气气氛、700℃下煅烧3h，冷却后加11wt％的稀盐酸溶液，用于洗去氧化铁杂质，得到质量浓度为9g/L的混合溶液，将混合溶液在80℃下边搅拌边水浴加热3.5h，水洗，直至溶液呈中性，过滤、干燥，得到植物碳基体材料；(3) The mixture obtained by calcining in the step (2) is mixed with iron oxide according to a mass ratio of 1:1, calcined in a nitrogen atmosphere at 700 ° C for 3 hours, and after cooling, 11 wt% of a dilute hydrochloric acid solution is added for washing and deoxidation. Iron impurities, a mixed solution having a mass concentration of 9 g / L, the mixed solution was heated at 80 ° C while stirring in a water bath for 3.5 h, washed with water until the solution was neutral, filtered and dried to obtain a plant carbon matrix material;
(4)将步骤(3)得到的植物碳基体材料，与质量浓度为70％的强酸溶液混合进行羧基化处理，用于增强植物碳基体材料的活化能，得到质量浓度为0.7000g/L的植物碳基体混合溶液，待植物碳基体混合溶液在90℃下反应220min，过滤，水洗，直至溶液呈中性，真空干燥，得到羧基化处理后的植物碳基体粉末材料；(4) The plant carbon matrix material obtained in the step (3) is mixed with a strong acid solution having a mass concentration of 70% for carboxylation treatment to enhance the activation energy of the plant carbon matrix material, and the mass concentration is 0.7000 g/L. Plant carbon matrix mixed solution, the plant carbon matrix mixed solution is reacted at 90 ° C for 220 min, filtered, washed with water until the solution is neutral, vacuum dried to obtain a carboxylated plant carbon matrix powder material;
(5)将步骤(4)中的植物碳基体粉末材料与氧化亚锡按照质量比1:3混合，加乙醇和蒸馏水进行搅拌，超声处理5h，抽滤，真空干燥，得到复合材料，能够提高氧化亚锡的循环稳定性；(5) mixing the plant carbon matrix powder material in step (4) with stannous oxide at a mass ratio of 1:3, adding ethanol and distilled water for stirring, sonicating for 5 hours, suction filtration, and vacuum drying to obtain a composite material, which can be improved. Cyclic stability of stannous oxide;
(6)将步骤(5)得到的复合材料放入管式炉中，对管式炉进行抽真空，当管式炉中压力＜0.08MPa时，开启温控电源，先以6℃/min的升温速率加热至450℃，通入氮气，保温4h，最后以1.5℃/min的速率降温至300℃，关闭电源，自然冷却至室温，得到能源复合材料。(6) The composite material obtained in the step (5) is placed in a tube furnace, and the tube furnace is evacuated. When the pressure in the tube furnace is <0.08 MPa, the temperature control power source is turned on, first at 6 ° C / min. The heating rate was heated to 450 ° C, nitrogen gas was introduced, the temperature was kept for 4 hours, and finally the temperature was lowered to 300 ° C at a rate of 1.5 ° C / min. The power was turned off and naturally cooled to room temperature to obtain an energy composite material.
【实施例三】[Embodiment 3]
一种用于锂电池的能源复合材料的制备方法，包括以下步骤：A method for preparing an energy composite material for a lithium battery, comprising the steps of:
(1)选择芦苇的茎或叶作为原材料，干燥，然后将干燥后的茎或叶在660℃下进行碳化处理，提取碳基质材料；(1) selecting the stem or leaf of the reed as a raw material, drying, and then carbonizing the dried stem or leaf at 660 ° C to extract the carbon matrix material;
(2)取碳化处理后的茎或叶的粉末，加氢氧化钠粉末，按照质量比1:3混合，得到混合粉末，将混合粉末在氮气气氛、810℃下煅烧1.5h，进行活化处理，冷却至室温；(2) taking the powder of the stem or leaf after the carbonization treatment, adding sodium hydroxide powder, mixing at a mass ratio of 1:3 to obtain a mixed powder, and calcining the mixed powder in a nitrogen atmosphere at 810 ° C for 1.5 h to carry out activation treatment. Cool to room temperature;
(3)将步骤(2)煅烧后得到的混合物与氧化铁按照质量比1:1进行混合，在氮气气氛、600℃下煅烧3h，冷却后加11wt％的稀盐酸溶液，用于洗去氧化铁杂质，得到质量浓度为9g/L的混合溶液，将混合溶液在60℃下边搅拌边水浴加热3.5h，水洗，直至溶液呈中性，过滤、干燥，得到植物碳基体材料；(3) The mixture obtained by calcining in the step (2) is mixed with iron oxide according to a mass ratio of 1:1, calcined in a nitrogen atmosphere at 600 ° C for 3 hours, and after cooling, 11 wt% of a dilute hydrochloric acid solution is added for washing and deoxidation. Iron impurities, a mixed solution having a mass concentration of 9 g / L, the mixed solution was heated at 60 ° C while stirring in a water bath for 3.5 h, washed with water until the solution was neutral, filtered and dried to obtain a plant carbon matrix material;
(4)将步骤(3)得到的植物碳基体材料，与质量浓度为70％的强酸溶液混合进行羧基化处理，用于增强植物碳基体材料的活化能，得到质量浓度为0.7000g/L的植物碳基体混合溶液，待植物碳基体混合溶液在85℃下反应220min，过滤，水洗，直至溶液呈中性，真空干燥，得到羧基化处理后的植物碳基体粉末材料；(4) The plant carbon matrix material obtained in the step (3) is mixed with a strong acid solution having a mass concentration of 70% for carboxylation treatment to enhance the activation energy of the plant carbon matrix material, and the mass concentration is 0.7000 g/L. Plant carbon matrix mixed solution, the plant carbon matrix mixed solution is reacted at 85 ° C for 220 min, filtered, washed with water until the solution is neutral, vacuum dried to obtain a carboxylated plant carbon matrix powder material;
(5)将步骤(4)中的植物碳基体粉末材料与氧化亚锡按照质量比1:3混合，加乙醇和蒸馏水进行搅拌，超声处理5h，抽滤，真空干燥，得到复合材料，能够提高氧化亚锡的循环稳定性；(5) mixing the plant carbon matrix powder material in step (4) with stannous oxide at a mass ratio of 1:3, adding ethanol and distilled water for stirring, sonicating for 5 hours, suction filtration, and vacuum drying to obtain a composite material, which can be improved. Cyclic stability of stannous oxide;
(6)将步骤(5)得到的复合材料放入管式炉中，对管式炉进行抽真空，当管式炉中压力＜0.08MPa时，开启温控电源，先以6℃/min的升温速率加热至450℃，通入氮气，保温4h，最后以1.5℃/min的速率降温至300℃，关闭电源，自然冷却至室温，得到能源复合材料。(6) The composite material obtained in the step (5) is placed in a tube furnace, and the tube furnace is evacuated. When the pressure in the tube furnace is <0.08 MPa, the temperature control power source is turned on, first at 6 ° C / min. The heating rate was heated to 450 ° C, nitrogen gas was introduced, the temperature was kept for 4 hours, and finally the temperature was lowered to 300 ° C at a rate of 1.5 ° C / min. The power was turned off and naturally cooled to room temperature to obtain an energy composite material.
【实施例四】[Embodiment 4]
一种用于锂电池的能源复合材料的制备方法，包括以下步骤：A method for preparing an energy composite material for a lithium battery, comprising the steps of:
(1)选择芦苇的茎或叶作为原材料，干燥，然后将干燥后的茎或叶在720℃下进行碳化处理，提取碳基质材料；(1) selecting the stem or leaf of the reed as a raw material, drying, and then carbonizing the dried stem or leaf at 720 ° C to extract the carbon matrix material;
(2)取碳化处理后的茎或叶的粉末，加氢氧化钠粉末，按照质量比1:3混合，得到混合粉末，将混合粉末在氮气气氛、1000℃下煅烧2h，进行活化处理，冷却至室温；(2) taking the powder of the stem or leaf after the carbonization treatment, adding sodium hydroxide powder, mixing at a mass ratio of 1:3 to obtain a mixed powder, and calcining the mixed powder in a nitrogen atmosphere at 1000 ° C for 2 hours, performing activation treatment, and cooling To room temperature;
(3)将步骤(2)煅烧后得到的混合物与氧化铁按照质量比1:1进行混合，在氮气气氛、700℃下煅烧4h，冷却后加11wt％的稀盐酸溶液，用于洗去氧化铁杂质，得到质量浓度为9g/L的混合溶液，将混合溶液在80℃下边搅拌边水浴加热4h，水洗，直至溶液呈中性，过滤、干燥，得到植物碳基体材料；(3) The mixture obtained by calcining in the step (2) is mixed with iron oxide according to a mass ratio of 1:1, calcined in a nitrogen atmosphere at 700 ° C for 4 hours, and after cooling, 11 wt% of a dilute hydrochloric acid solution is added for washing and deoxidation. Iron impurities, a mixed solution of mass concentration of 9g / L, the mixed solution was heated at 80 ° C while stirring in a water bath for 4 h, washed with water until the solution was neutral, filtered and dried to obtain a plant carbon matrix material;
(4)将步骤(3)得到的植物碳基体材料，与质量浓度为70％的强酸溶液混合进行羧基化处理，用于增强植物碳基体材料的活化能，得到质量浓度为0.7000g/L的植物碳基体混合溶液，待植物碳基体混合溶液在90℃下反应270min，过滤，水洗，直至溶液呈中性，真空干燥， 得到羧基化处理后的植物碳基体粉末材料；(4) The plant carbon matrix material obtained in the step (3) is mixed with a strong acid solution having a mass concentration of 70% for carboxylation treatment to enhance the activation energy of the plant carbon matrix material, and the mass concentration is 0.7000 g/L. Plant carbon matrix mixed solution, the plant carbon matrix mixed solution is reacted at 90 ° C for 270 min, filtered, washed with water until the solution is neutral, vacuum dried to obtain a carboxylated plant carbon matrix powder material;
(5)将步骤(4)中的植物碳基体粉末材料与氧化亚锡按照质量比1:3混合，加乙醇和蒸馏水进行搅拌，超声处理6.5h，抽滤，真空干燥，得到复合材料，能够提高氧化亚锡的循环稳定性；(5) mixing the plant carbon matrix powder material in step (4) with stannous oxide at a mass ratio of 1:3, adding ethanol and distilled water for stirring, sonicating for 6.5 hours, suction filtration, and vacuum drying to obtain a composite material. Improve the cycle stability of stannous oxide;
(6)将步骤(5)得到的复合材料放入管式炉中，对管式炉进行抽真空，当管式炉中压力＜0.08MPa时，开启温控电源，先以6℃/min的升温速率加热至450℃，通入氮气，保温4.5h，最后以1.5℃/min的速率降温至300℃，关闭电源，自然冷却至室温，得到能源复合材料。(6) The composite material obtained in the step (5) is placed in a tube furnace, and the tube furnace is evacuated. When the pressure in the tube furnace is <0.08 MPa, the temperature control power source is turned on, first at 6 ° C / min. The heating rate was heated to 450 ° C, nitrogen gas was introduced, the temperature was maintained for 4.5 h, and finally the temperature was lowered to 300 ° C at a rate of 1.5 ° C / min. The power was turned off and naturally cooled to room temperature to obtain an energy composite material.
【实施例五】[Embodiment 5]
一种用于锂电池的能源复合材料的制备方法，包括以下步骤：A method for preparing an energy composite material for a lithium battery, comprising the steps of:
(1)选择芦苇的茎或叶作为原材料，干燥，然后将干燥后的茎或叶在660℃下进行碳化处理，提取碳基质材料；(1) selecting the stem or leaf of the reed as a raw material, drying, and then carbonizing the dried stem or leaf at 660 ° C to extract the carbon matrix material;
(2)取碳化处理后的茎或叶的粉末，加氢氧化钠粉末，按照质量比1:3混合，得到混合粉末，将混合粉末在氮气气氛、810℃下煅烧1h，进行活化处理，冷却至室温；(2) taking the powder of the stem or leaf after the carbonization treatment, adding sodium hydroxide powder, mixing at a mass ratio of 1:3 to obtain a mixed powder, and calcining the mixed powder in a nitrogen atmosphere at 810 ° C for 1 h, performing activation treatment, and cooling To room temperature;
(3)将步骤(2)煅烧后得到的混合物与氧化铁按照质量比1:1进行混合，在氮气气氛、600℃下煅烧2h，冷却后加11wt％的稀盐酸溶液，用于洗去氧化铁杂质，得到质量浓度为9g/L的混合溶液，将混合溶液在60℃下边搅拌边水浴加热3h，水洗，直至溶液呈中性，过滤、干燥，得到植物碳基体材料；(3) The mixture obtained by calcining in the step (2) is mixed with iron oxide according to a mass ratio of 1:1, calcined in a nitrogen atmosphere at 600 ° C for 2 h, and after cooling, 11 wt% of a dilute hydrochloric acid solution is added for washing and deoxidation. Iron impurities, a mixed solution having a mass concentration of 9 g / L, the mixed solution was heated at 60 ° C with a water bath for 3 h, washed with water until the solution was neutral, filtered and dried to obtain a plant carbon matrix material;
(4)将步骤(3)得到的植物碳基体材料，与质量浓度为70％的强酸溶液混合进行羧基化处理，用于增强植物碳基体材料的活化能，得到质量浓度为0.7000g/L的植物碳基体混合溶液，待植物碳基体混合溶液在85℃下反应180min，过滤，水洗，直至溶液呈中性，真空干燥，得到羧基化处理后的植物碳基体粉末材料；(4) The plant carbon matrix material obtained in the step (3) is mixed with a strong acid solution having a mass concentration of 70% for carboxylation treatment to enhance the activation energy of the plant carbon matrix material, and the mass concentration is 0.7000 g/L. Plant carbon matrix mixed solution, the plant carbon matrix mixed solution is reacted at 85 ° C for 180 min, filtered, washed with water until the solution is neutral, vacuum dried to obtain a carboxylated plant carbon matrix powder material;
(5)将步骤(4)中的植物碳基体粉末材料与氧化亚锡按照质量比1:3混合，加乙醇和蒸馏水进行搅拌，超声处理4.5h，抽滤，真空干燥，得到复合材料，能够提高氧化亚锡的循环稳定性；(5) mixing the plant carbon matrix powder material in step (4) with stannous oxide at a mass ratio of 1:3, adding ethanol and distilled water for stirring, sonicating for 4.5 hours, suction filtration, and vacuum drying to obtain a composite material. Improve the cycle stability of stannous oxide;
(6)将步骤(5)得到的复合材料放入管式炉中，对管式炉进行抽真空，当管式炉中压力＜0.08MPa时，开启温控电源，先以6℃/min的升温速率加热至450℃，通入氮气，保温3.5h，最后以1.5℃/min的速率降温至300℃，关闭电源，自然冷却至室温，得到能源复合材料。(6) The composite material obtained in the step (5) is placed in a tube furnace, and the tube furnace is evacuated. When the pressure in the tube furnace is <0.08 MPa, the temperature control power source is turned on, first at 6 ° C / min. The heating rate was heated to 450 ° C, nitrogen was introduced, the temperature was kept for 3.5 h, and finally the temperature was lowered to 300 ° C at a rate of 1.5 ° C / min. The power was turned off and naturally cooled to room temperature to obtain an energy composite material.
【实施例六】[Embodiment 6]
一种用于锂电池的能源复合材料的制备方法，包括以下步骤：A method for preparing an energy composite material for a lithium battery, comprising the steps of:
(1)选择凤眼莲的茎或叶作为原材料，干燥，然后将干燥后的茎或叶在700℃下进行碳化处理，提取碳基质材料；(1) selecting the stem or leaf of the water hyacinth as a raw material, drying, and then carbonizing the dried stem or leaf at 700 ° C to extract the carbon matrix material;
(2)取碳化处理后的茎或叶的粉末，加氢氧化钠粉末，按照质量比1:3混合，得到混合粉末，将混合粉末在氮气气氛、900℃下煅烧1.5h，进行活化处理，冷却至室温；(2) taking the powder of the stem or leaf after the carbonization treatment, adding sodium hydroxide powder, mixing at a mass ratio of 1:3 to obtain a mixed powder, and calcining the mixed powder in a nitrogen atmosphere at 900 ° C for 1.5 h to carry out activation treatment. Cool to room temperature;
(3)将步骤(2)煅烧后得到的混合物与氧化铁按照质量比1:1进行混合，在氮气气氛、650℃下煅烧3h，冷却后加11wt％的稀盐酸溶液，用于洗去氧化铁杂质，得到质量浓度为9g/L的混合溶液，将混合溶液在70℃下边搅拌边水浴加热3.5h，水洗，直至溶液呈中性，过滤、干燥，得到植物碳基体材料；(3) The mixture obtained by calcining in the step (2) is mixed with iron oxide according to a mass ratio of 1:1, calcined in a nitrogen atmosphere at 650 ° C for 3 hours, and after cooling, 11 wt% of a dilute hydrochloric acid solution is added for washing and deoxidation. Iron impurities, a mixed solution having a mass concentration of 9 g / L, the mixed solution was heated at 70 ° C while stirring in a water bath for 3.5 h, washed with water until the solution was neutral, filtered and dried to obtain a plant carbon matrix material;
(4)将步骤(3)得到的植物碳基体材料，与质量浓度为70％的强酸溶液混合进行羧基化处理，用于增强植物碳基体材料的活化能，得到质量浓度为0.7000g/L的植物碳基体混合溶液，待植物碳基体混合溶液在87℃下反应220min，过滤，水洗，直至溶液呈中性，真空干燥，得到羧基化处理后的植物碳基体粉末材料；(4) The plant carbon matrix material obtained in the step (3) is mixed with a strong acid solution having a mass concentration of 70% for carboxylation treatment to enhance the activation energy of the plant carbon matrix material, and the mass concentration is 0.7000 g/L. Plant carbon matrix mixed solution, the plant carbon matrix mixed solution is reacted at 87 ° C for 220 min, filtered, washed with water until the solution is neutral, vacuum dried to obtain a carboxylated plant carbon matrix powder material;
(5)将步骤(4)中的植物碳基体粉末材料与氧化亚锡按照质量比1:3混合，加乙醇和蒸馏水进行搅拌，超声处理5h，抽滤，真空干燥，得到复合材料，能够提高氧化亚锡的循环稳定性；(5) mixing the plant carbon matrix powder material in step (4) with stannous oxide at a mass ratio of 1:3, adding ethanol and distilled water for stirring, sonicating for 5 hours, suction filtration, and vacuum drying to obtain a composite material, which can be improved. Cyclic stability of stannous oxide;
(6)将步骤(5)得到的复合材料放入管式炉中，对管式炉进行抽真空，当管式炉中压力＜0.08MPa时，开启温控电源，先以6℃/min的升温速率加热至450℃，通入氮气，保温4h，最后以1.5℃/min的速率降温至300℃，关闭电源，自然冷却至室温，得到能源复合材料。(6) The composite material obtained in the step (5) is placed in a tube furnace, and the tube furnace is evacuated. When the pressure in the tube furnace is <0.08 MPa, the temperature control power source is turned on, first at 6 ° C / min. The heating rate was heated to 450 ° C, nitrogen gas was introduced, the temperature was kept for 4 hours, and finally the temperature was lowered to 300 ° C at a rate of 1.5 ° C / min. The power was turned off and naturally cooled to room temperature to obtain an energy composite material.
在以上实施例中的其余技术特征，本领域技术人员均可以根据实际情况进行灵活选用和以满足不同的具体实际需求。然而，对于本领域普通技术人员显而易见的是：不必采用这些特定细节来实行本发明。在其他实例中，为了避免混淆本发明，未具体描述公知的工艺，公知的辅助添加剂、公知的工艺实施设备、公知的材料结构、公知的数据和图表等，均在本发明的权利要求书请求保护的技术方案限定技术保护范围之内。In the remaining technical features in the above embodiments, those skilled in the art can flexibly select and meet different specific practical requirements according to actual conditions. However, it will be apparent to those skilled in the art that the invention In other instances, well-known processes have not been specifically described in order to avoid obscuring the present invention. Known auxiliary additives, well-known process implementation equipment, well-known material structures, well-known data and figures, etc. are all claimed in the claims of the present invention. The technical solution of protection limits the scope of technical protection.
以上所述仅是本发明的优选实施方式，应当理解本发明并非局限于本文所披露的形式，不应看作是对其他实施例的排除，而可用于各种其他组合、修改和环境，并能够在本文所述构想范围内，通过上述教导或相关领域的技术或知识进行改动。而本领域人员所进行的改动和变化不脱离本发明的精神和范围，则都应在本发明所附权利要求的保护范围内。The above is only a preferred embodiment of the present invention, and it should be understood that the present invention is not limited to the forms disclosed herein, and is not to be construed as being limited to the other embodiments, but may be used in various other combinations, modifications and environments. Modifications can be made by the techniques or knowledge of the above teachings or related art within the scope of the teachings herein. All changes and modifications made by those skilled in the art are intended to be within the scope of the appended claims.

Claims (6)

  1. 一种用于锂电池的能源复合材料的制备方法，其特征在于，包括以下步骤：A method for preparing an energy composite material for a lithium battery, comprising the steps of:
    (1)选择具有多孔结构的植物的茎或叶作为原材料，干燥，然后将干燥后的茎或叶在660℃～720℃下进行碳化处理；(1) selecting a stem or a leaf of a plant having a porous structure as a raw material, drying, and then subjecting the dried stem or leaf to carbonization at 660 ° C to 720 ° C;
    (2)取碳化处理后的茎或叶的粉末，加氢氧化钠粉末，按照质量比1:3混合，得到混合粉末，将混合粉末在氮气气氛、810℃～1000℃下煅烧1～2h，冷却至室温；(2) taking the powder of the stem or leaf after the carbonization treatment, adding sodium hydroxide powder, mixing at a mass ratio of 1:3 to obtain a mixed powder, and calcining the mixed powder in a nitrogen atmosphere at 810 ° C to 1000 ° C for 1 to 2 hours. Cool to room temperature;
    (3)将步骤(2)煅烧后得到的混合物与氧化铁按照质量比1:1进行混合，在氮气气氛、600℃～700℃下煅烧2～4h，冷却后加10wt％～12wt％的稀盐酸溶液，洗去氧化铁杂质，得到质量浓度为8g/L～11g/L的混合溶液，将混合溶液在60℃～80℃下边搅拌边水浴加热3～4h，水洗，直至溶液呈中性，过滤、干燥，得到植物碳基体材料；(3) mixing the mixture obtained by calcining in the step (2) with iron oxide according to a mass ratio of 1:1, calcining in a nitrogen atmosphere at 600 ° C to 700 ° C for 2 to 4 hours, and adding 10 wt% to 12 wt% of the rarex after cooling. Hydrochloric acid solution, wash away iron oxide impurities, to obtain a mixed solution with a mass concentration of 8g / L ~ 11g / L, the mixed solution is heated at 60 ° C ~ 80 ° C while stirring in a water bath for 3 ~ 4h, washed with water until the solution is neutral, Filtering and drying to obtain a plant carbon matrix material;
    (4)将步骤(3)得到的植物碳基体材料，与质量浓度为65％～75％的强酸溶液混合进行羧基化处理，得到质量浓度为0.6000g/L～0.8000g/L的植物碳基体混合溶液，待植物碳基体混合溶液在85℃～90℃下反应180～270min，过滤，水洗，直至溶液呈中性，真空干燥，得到羧基化处理后的植物碳基体粉末材料；(4) The plant carbon substrate obtained in the step (3) is mixed with a strong acid solution having a mass concentration of 65% to 75% to carry out a carboxylation treatment to obtain a plant carbon substrate having a mass concentration of 0.6000 g/L to 0.8000 g/L. Mixing the solution, reacting the plant carbon matrix mixed solution at 85 ° C ~ 90 ° C for 180 ~ 270 min, filtering, washing with water until the solution is neutral, vacuum drying, to obtain the carboxylated plant carbon matrix powder material;
    (5)将步骤(4)中的植物碳基体粉末材料与氧化亚锡按照质量比1:3混合，加乙醇和蒸馏水进行搅拌，超声处理4.5～6.5h，抽滤，真空干燥，得到复合材料；(5) mixing the plant carbon matrix powder material in step (4) with stannous oxide at a mass ratio of 1:3, adding ethanol and distilled water for stirring, sonicating for 4.5 to 6.5 hours, suction filtration, and vacuum drying to obtain a composite material. ;
    (6)将步骤(5)得到的复合材料放入管式炉中，对管式炉进行抽真空，当管式炉中压力＜0.08MPa时，开启温控电源，先以5℃/min～8℃/min的升温速率加热至400℃～500℃，通入氮气，保温3.5～4.5h，最后以1℃/min～2℃/min的速率降温至300℃，关闭电源，自然冷却至室温，得到能源复合材料。(6) The composite material obtained in the step (5) is placed in a tube furnace, and the tube furnace is evacuated. When the pressure in the tube furnace is <0.08 MPa, the temperature control power source is turned on, first at 5 ° C / min ～ Heating at a heating rate of 8 ° C / min to 400 ° C ~ 500 ° C, nitrogen gas, heat for 3.5 ~ 4.5h, and finally cooled to 300 ° C at a rate of 1 ° C / min ~ 2 ° C / min, turn off the power, naturally cooled to room temperature , get energy composite materials.
  2. 根据权利要求1所述的一种用于锂电池的能源复合材料的制备方法，其特征在于，在步骤(1)中，所述植物为芦苇、凤眼莲中的至少一种。The method for preparing an energy composite material for a lithium battery according to claim 1, wherein in the step (1), the plant is at least one of reed and water hyacinth.
  3. 根据权利要求1所述的一种用于锂电池的能源复合材料的制备方法，其特征在于，在步骤(4)中，真空干燥温度为50℃～60℃，干燥时间为12～36h。The method for preparing an energy composite material for a lithium battery according to claim 1, wherein in the step (4), the vacuum drying temperature is 50 ° C to 60 ° C, and the drying time is 12 to 36 h.
  4. 根据权利要求1所述的一种用于锂电池的能源复合材料的制备方法，其特征在于，在步骤(6)中以6.5℃/min～6.8℃/min的升温速率升温至450℃～460℃。The method for preparing an energy composite material for a lithium battery according to claim 1, wherein in step (6), the temperature is raised to 450 ° C to 460 at a temperature increase rate of 6.5 ° C / min to 6.8 ° C / min. °C.
  5. 根据权利要求1所述的一种用于锂电池的能源复合材料的制备方法，其特征在于，在步骤(6)中所述降温速率为1℃/min～1.5℃/min。The method for preparing an energy composite material for a lithium battery according to claim 1, wherein the temperature reduction rate in the step (6) is from 1 ° C/min to 1.5 ° C/min.
  6. 权利要求1～5任一项所述制备方法制备得到的用于锂电池的能源复合材料。The energy composite material for a lithium battery prepared by the preparation method according to any one of claims 1 to 5.
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