WO2017117839A1 - Method for preparing graphene by using anode material of waste aluminum-ion secondary battery - Google Patents

Method for preparing graphene by using anode material of waste aluminum-ion secondary battery Download PDF

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WO2017117839A1
WO2017117839A1 PCT/CN2016/072875 CN2016072875W WO2017117839A1 WO 2017117839 A1 WO2017117839 A1 WO 2017117839A1 CN 2016072875 W CN2016072875 W CN 2016072875W WO 2017117839 A1 WO2017117839 A1 WO 2017117839A1
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battery
ion secondary
secondary battery
electrolysis
aluminum
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PCT/CN2016/072875
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French (fr)
Chinese (zh)
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焦树强
雷海萍
涂继国
王俊香
李海滨
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北京金吕能源科技有限公司
甘肃鑫吕能源材料有限公司
北京科技大学
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Definitions

  • the invention relates to the field of waste battery recycling and high-end material preparation, and in particular to a method for preparing graphene by using a waste aluminum ion secondary battery.
  • Jiao Shuqiang's research group has carried out a lot of research on aluminum ion secondary batteries, and proposed the use of aluminum metal and aluminum alloy as anode materials for aluminum ion secondary batteries, graphite materials as cathode materials, and applied for a number of patents.
  • CN201510188866.4 a rechargeable aluminum ion battery and a preparation method thereof
  • CN201510269862.9 A non-aqueous aluminum ion secondary battery and a preparation method thereof.
  • Such batteries have good cycle performance, and the price of positive and negative materials is low.
  • Such batteries can be applied on a large scale, but how to recycle used batteries after application is a technical problem to be solved.
  • the physical method is to prepare a single layer or a plurality of graphenes by a micro mechanical peeling method, a liquid phase or a gas phase direct stripping method.
  • Chemical methods include chemical vapor deposition (CVD), crystal epitaxial growth (SiC high temperature annealing), oxidation-reduction, and the like.
  • the oxidation-reduction method is the main method for preparing graphene in large quantities, but this method requires concentrated sulfuric acid, potassium permanganate and other oxidants, which are often carried out at high temperatures. The above methods have potential safety hazards and generate a large amount of waste liquid, resulting in Environmental pollution.
  • the purpose of the invention is to recycle the positive electrode material of the aluminum ion battery, and prepare the graphene by using the positive electrode material of the aluminum ion battery, turning waste into treasure.
  • the complete battery provides a channel for the electroplated graphite material, so that the aluminum complex ions in the electrolyte are continuously embedded in the graphite layer. This continuous intercalation of the ions will cause van der Waals force between the nano carbon layers and peel off. Disperse and form graphene.
  • the method has simple process steps and low raw material cost. It has played a very important role in the large-scale industrial application and recycling of aluminum ion batteries.
  • the technical solution of the present invention is: a method for preparing graphene by using a waste aluminum ion secondary battery cathode material, comprising the following steps:
  • Step 1 Select raw materials: use a cathode material with a graphite content of 40% or more, and a waste aluminum ion secondary battery containing an aluminum complex ion in the electrolyte, and reserve;
  • Step 2 Electrolysis: The secondary aluminum ion secondary battery selected in step 1 is charged with constant current or constant voltage for electrolysis, electrolyzed for a certain period of time, then discharged to 0.3V, and then charged, cycled 5 times or more, and completed electrolysis. spare;
  • Step 3 The positive electrode material of the battery treated in step 2 is taken out and placed in a beaker containing absolute ethanol, ultrasonically sonicated for 20-30 minutes, and the impurities are removed and dried in a blast drying oven to obtain graphene.
  • the current electrolysis has a current density of 10 to 500 mAg -1 ; and the voltage electrolysis has a voltage of 1.8 V to 2.7 V.
  • the electrolysis time is 2-60 hours.
  • drying temperature is 50-200 °C.
  • the aluminum complex ion is: [AlCl 4 ] - or [Al 2 Cl 7 ] - or a mixture of the two.
  • the composition of the electrolyte contains a non-aqueous solution of Al 3+ ions
  • the non-aqueous solution containing Al 3+ ions includes an aluminum halide and an ionic liquid
  • the anions of the ionic liquid include F - , Cl - , Br - , I - , PF 6- , CN - , SCN - , [N(CF 3 SO 2 )] - or [N(CN) 2 ] - ions
  • cations include imidazolium ions, pyridinium ions, pyrrole ions, piperidinium ions, Morpholinium ion, quaternary ammonium ion, quaternary phosphonium ion or tertiary sulfur salt ion.
  • the invention has the advantages that the invention utilizes an aluminum ion battery containing a graphite material, and the aluminum complex ions are contained in the electrolyte, and the ions are continuously embedded in the graphite layer under the continuous electrolysis, and finally the graphite layer is dispersed and stripped to form graphene. .
  • the process is simple, the cost is low, and the waste aluminum ion secondary battery can be recycled, which is green and environmentally friendly. This method of efficiently recovering an aluminum ion secondary battery has great significance for the industrial application of an aluminum ion battery.
  • Fig. 1 is a graph showing the electrolysis process of an aluminum ion secondary battery of Example 4 at 2.3 V.
  • Example 2 is a topographical view of a transmission electron microscope of the graphene product prepared in Example 4.
  • Fig. 3 is a graph showing the electrolysis process of the aluminum ion secondary battery of Example 7 at 2.0V.
  • the positive electrode material of the aluminum ion secondary battery to be recovered by the invention is a high-purity graphite sheet, the electrolyte contains aluminum complex ions, and the constant current (current density 10mAg -1 ) of the waste aluminum ion battery is charged to 2.3V, and then at 2.0.
  • the graphite sheet of constant pressure electrolysis was placed under V for 2 hours, and then discharged to 0.3 V, and the cycle was repeated 5 times or more. When the battery is removed, its status is undischarged.
  • the battery was disassembled at least five times, and the positive electrode material of the battery was ultrasonicated for 20 minutes to remove impurities, and then dried in a 70 ° C blast oven to obtain a graphene ratio of 20%.
  • the positive electrode material of the aluminum ion secondary battery to be recovered by the invention is a high-purity graphite sheet containing aluminum complex ions, and the constant current (current density 100mAg -1 ) of the waste aluminum ion battery is charged to 2.3V, and then at 2.5.
  • the constant pressure electroplated graphite sheet was subjected to V for 4 hours, and then discharged to 0.3 V, and the cycle was repeated 5 times or more. Remove the battery status to the undischarged state.
  • the battery was disassembled at least five times, and the positive electrode material of the battery was ultrasonicated for 40 minutes, and the impurities were removed and dried in a 70 ° C blast oven to obtain a graphene ratio of 30%.
  • the positive electrode material of the aluminum ion secondary battery to be recovered by the invention is a high-purity graphite sheet containing aluminum complex ions, and the constant current (current density 500mAg -1 ) of the waste aluminum ion battery is charged to 2.3V, and then at 2.7.
  • the graphite sheet was continuously pressed at V for 6 hours, and then discharged to 0.3 V, and the cycle was repeated 5 times or more. Remove the battery status to the undischarged state.
  • the battery was circulated at least five times, and the battery positive electrode material was ultrasonically sonicated for 60 minutes to remove impurities, and then dried in a 70 ° C blast drying oven to obtain a graphene ratio of 35%.
  • the positive electrode material of the aluminum ion secondary battery to be recovered by the invention is a high-purity graphite sheet containing aluminum complex ions, and the constant current (current density 10mAg -1 ) of the waste aluminum ion battery is charged to 2.3V, and then at 2.3.
  • the constant pressure electrolytic graphite sheet was placed under V for 10 hours, and then discharged to 0.3 V for 5 times or more.
  • the electrolytic cycle curve is shown in Fig. 1. Remove the battery status to the undischarged state. The battery was circulated at least five times, and the positive electrode material of the battery was ultrasonicated for 20 minutes, and the impurities were removed and dried in a blast oven at 80 ° C to obtain a graphene ratio of 40%.
  • Fig. 2 for a transmission electron microscope (TEM) topographical view of the three-layer graphene material obtained by the present invention.
  • TEM transmission electron microscope
  • the positive electrode material of the aluminum ion secondary battery to be recovered by the invention is a high-purity graphite sheet, the electrolyte contains aluminum complex ions, and the constant current (current density 100mAg -1 ) of the waste aluminum ion battery is charged to 2.3V, and then in 2.3.
  • the graph of the constant pressure electrolyzed graphite was placed under V for 20 hours, and then discharged to 0.3 V, and the cycle was repeated 5 times or more. Remove the battery status to the undischarged state.
  • the battery was circulated at least five times, and the positive electrode material of the battery was ultrasonically sonicated for 40 minutes to remove impurities and dried in a blast oven at 80 ° C to obtain a graphene ratio of 45%.
  • the positive electrode material of the aluminum ion secondary battery to be recovered by the invention is a high-purity graphite sheet, the electrolyte contains aluminum complex ions, and the constant current (current density 200mAg -1 ) of the waste aluminum ion battery is charged to 2.3V, and then in 2.3.
  • the constant pressure electroplated graphite sheet was subjected to V for 40 hours, and then discharged to 0.3 V, and the cycle was repeated 5 times or more. Remove the battery status to the undischarged state.
  • the battery was disassembled at least five times, and the positive electrode material of the battery was ultrasonicated for 60 minutes, and the impurities were removed and dried in a blast oven at 80 ° C to obtain a graphene ratio of 50%.
  • the positive electrode material of the aluminum ion secondary battery to be recovered by the invention is a high-purity graphite sheet, the electrolyte contains aluminum complex ions, and the constant current (current density 10mAg -1 ) of the waste aluminum ion battery is charged to 2.3V, and then at 2.0.
  • the constant pressure electrolytic graphite sheet was placed under V for 10 hours, and then discharged to 0.3 V, and the cycle was repeated 5 times or more.
  • the test cycle curve is shown in Fig. 3. Remove the battery status to the undischarged state. The battery was circulated at least five times, and the battery positive electrode material was ultrasonically sonicated for 60 minutes to remove impurities and dried in a blast oven at 120 ° C to obtain a graphene ratio of 40%.
  • the positive electrode material of the aluminum ion secondary battery to be recovered by the invention is a high-purity graphite sheet, the electrolyte contains aluminum complex ions, and the constant current (current density 300mAg -1 ) of the waste aluminum ion battery is charged to 2.3V, and then at 2.0. Constant pressure electrolytic graphite carbon paper was placed under V for 40 hours, and then discharged to 0.3 V. Cycle more than 5 times. Remove the battery status to the undischarged state. The battery was circulated at least five times, and the positive electrode material of the battery was ultrasonicated for 60 minutes, and the impurities were removed and dried in a blast oven at 120 ° C to obtain a graphene ratio of 50%.
  • the positive electrode material of the aluminum ion secondary battery to be recovered by the invention is a high-purity graphite sheet containing aluminum complex ions, and the constant current (current density 400mAg -1 ) of the waste aluminum ion battery is charged to 2.3V, and then at 1.8. Constant pressure electrolytic graphite carbon paper under V for 10 hours, and then discharged to 0.3V. Cycle more than 5 times, the test cycle curve is shown in Figure 3. Remove the battery status to the undischarged state. The battery was circulated at least five times, and the positive electrode material of the battery was ultrasonically ultrasonically washed for 60 minutes to remove impurities and dried in a blast oven at 120 ° C to obtain a graphene ratio of 35%.
  • the positive electrode material of the aluminum ion secondary battery to be recovered by the invention is a high-purity graphite sheet, and the constant current (current density 500mAg -1 ) of the waste aluminum ion battery is charged to 2.3V, and then the constant pressure electrolytic graphite carbon paper 40 is at 1.8V. After hours, discharge to 0.3V. Cycle 5 times or more, and remove the battery state to the undischarged state.
  • the battery was circulated at least five times, and the battery positive electrode material was ultrasonically sonicated for 60 minutes to remove impurities and dried in a blast oven at 120 ° C to obtain a graphene ratio of 45%.

Abstract

The present invention relates to a method for preparing graphene by using an anode material of a waste aluminum-ion secondary battery. The method is highly efficient at recycling graphite from the anode material of a waste aluminum-ion secondary battery, and belongs to the fields of waste battery recycling and preparation of advanced materials. The method comprises utilizing a waste aluminum-ion battery having a graphite structure material as an anode, and by means of electrolysis directly converting the graphite anode of the waste battery into graphene for recycling. The method is based on the principle that under a high electric potential, aluminum complex ions in an ionic liquid are caused to be embedded into a carbon layer continuously, such that a layered structure of the graphite collapses and splits, thus generating graphene with a high added value.

Description

利用废旧铝离子二次电池的正极材料制备石墨烯的方法Method for preparing graphene by using cathode material of waste aluminum ion secondary battery 技术领域Technical field
本发明涉及废旧电池回收及高端材料制备领域，尤其是涉及一种利用废旧铝离子二次电池制备石墨烯的方法。The invention relates to the field of waste battery recycling and high-end material preparation, and in particular to a method for preparing graphene by using a waste aluminum ion secondary battery.
背景技术Background technique
焦树强课题组对铝离子二次电池进行了大量的研究，提出了采用铝金属、合金铝作为铝离子二次电池的负极材料，石墨类材料作为正极材料，且申请了多项专利。如CN201510188866.4一种可充电铝离子电池及其制备方法；CN201510269862.9一种非水溶液铝离子二次电池及其制备方法等。这类电池具有很好的循环性能，且正负极材料价钱低廉，这类电池可大规模应用，但是如何将应用后的废旧电池回收是亟待要解决的技术问题。Jiao Shuqiang's research group has carried out a lot of research on aluminum ion secondary batteries, and proposed the use of aluminum metal and aluminum alloy as anode materials for aluminum ion secondary batteries, graphite materials as cathode materials, and applied for a number of patents. For example, CN201510188866.4 a rechargeable aluminum ion battery and a preparation method thereof; CN201510269862.9 A non-aqueous aluminum ion secondary battery and a preparation method thereof. Such batteries have good cycle performance, and the price of positive and negative materials is low. Such batteries can be applied on a large scale, but how to recycle used batteries after application is a technical problem to be solved.
目前，国内外有非常多有关石墨烯的制备方法，主要有物理方法和化学方法。物理方法是通过微机械剥离法、液相或者气相直接剥离法来制备单层或多层石墨烯。化学方法包括化学气相沉积法(CVD)、晶体外延生长法(SiC高温退火)、氧化-还原法等。而氧化-还原法是实现大批量制备石墨烯的主要方法，但是这种方法需要浓硫酸、高锰酸钾等氧化剂，经常会在高温下进行，上述方法存在安全隐患，产生大量废液，造成环境污染。At present, there are many methods for preparing graphene at home and abroad, mainly including physical methods and chemical methods. The physical method is to prepare a single layer or a plurality of graphenes by a micro mechanical peeling method, a liquid phase or a gas phase direct stripping method. Chemical methods include chemical vapor deposition (CVD), crystal epitaxial growth (SiC high temperature annealing), oxidation-reduction, and the like. The oxidation-reduction method is the main method for preparing graphene in large quantities, but this method requires concentrated sulfuric acid, potassium permanganate and other oxidants, which are often carried out at high temperatures. The above methods have potential safety hazards and generate a large amount of waste liquid, resulting in Environmental pollution.
由此可见，为了铝离子二次电池的可持续发展，其电池的回收是亟待解决的技术问题；其次，现有的石墨烯的制备方法成本高、环境污染严重、安全性差。因而，采用电化学方法对废旧铝离子电池的正极石墨材料进行电解处理并得到高附加值的石墨烯，因其操作简便、不额外添加其他化学试剂等原因，是非常有前景的一种回收方式。 It can be seen that for the sustainable development of the aluminum ion secondary battery, the recovery of the battery is a technical problem to be solved urgently. Secondly, the existing method for preparing graphene has high cost, serious environmental pollution and poor safety. Therefore, electrochemical method is used to electrolyze the cathode graphite material of waste aluminum ion battery and obtain high value-added graphene. It is a promising recycling method because of its simple operation and no additional chemical reagents. .
发明内容Summary of the invention
本发明的目的在于：对铝离子电池正极材料做回收处理，利用铝离子电池的正极材料制备石墨烯，变废为宝。完整的电池提供了电解石墨类材料的通道，从而使电解液中的铝配合物离子持续不断的嵌入石墨层中，这种持续的配离子的嵌入会使纳米碳层间失去范德华力，进而剥离、分散，形成石墨烯。该方法工艺步骤简单、原料成本低。对铝离子电池的大规模产业化应用及回收起到了非常大的作用。The purpose of the invention is to recycle the positive electrode material of the aluminum ion battery, and prepare the graphene by using the positive electrode material of the aluminum ion battery, turning waste into treasure. The complete battery provides a channel for the electroplated graphite material, so that the aluminum complex ions in the electrolyte are continuously embedded in the graphite layer. This continuous intercalation of the ions will cause van der Waals force between the nano carbon layers and peel off. Disperse and form graphene. The method has simple process steps and low raw material cost. It has played a very important role in the large-scale industrial application and recycling of aluminum ion batteries.
为解决上述技术问题，本发明的技术方案是：利用废旧铝离子二次电池正极材料制备石墨烯的方法，包括以下步骤：In order to solve the above technical problem, the technical solution of the present invention is: a method for preparing graphene by using a waste aluminum ion secondary battery cathode material, comprising the following steps:
步骤一.选取原料：采用石墨含量为40％以上的正极材料，电解液中含有铝配合物离子的废旧铝离子二次电池，备用；Step 1. Select raw materials: use a cathode material with a graphite content of 40% or more, and a waste aluminum ion secondary battery containing an aluminum complex ion in the electrolyte, and reserve;
步骤二.电解：对步骤1选取好的废旧铝离子二次电池充入恒电流或恒电压进行电解，电解一定的时间，然后放电至0.3V，再进行充电，循环5次以上，完成电解，备用； Step 2. Electrolysis: The secondary aluminum ion secondary battery selected in step 1 is charged with constant current or constant voltage for electrolysis, electrolyzed for a certain period of time, then discharged to 0.3V, and then charged, cycled 5 times or more, and completed electrolysis. spare;
步骤三：将经过步骤2处理的电池正极材料取出置于装有无水乙醇的烧杯中，超声波超声20-30分钟洗净，去除杂质后在鼓风干燥箱中烘干，得到石墨烯。Step 3: The positive electrode material of the battery treated in step 2 is taken out and placed in a beaker containing absolute ethanol, ultrasonically sonicated for 20-30 minutes, and the impurities are removed and dried in a blast drying oven to obtain graphene.
进一步，所述电流电解的电流密度为10-500mAg-1；所述电压电解的电压为1.8V-2.7V。Further, the current electrolysis has a current density of 10 to 500 mAg -1 ; and the voltage electrolysis has a voltage of 1.8 V to 2.7 V.
进一步，所述电解时间为2-60小时。Further, the electrolysis time is 2-60 hours.
进一步，所述的烘干温度为50-200℃。Further, the drying temperature is 50-200 °C.
进一步，所述铝配合物离子为：[AlCl4]-或[Al2Cl7]-或二者的混合物。Further, the aluminum complex ion is: [AlCl 4 ] - or [Al 2 Cl 7 ] - or a mixture of the two.
进一步，电解液的成分含有Al3+离子的非水溶液，含Al3+离子的 非水溶液中包括卤化铝和离子液体，所述离子液体的阴离子包括F-，Cl-，Br-，I-，PF6-，CN-，SCN-，[N(CF3SO2)]-或[N(CN)2]-离子；阳离子包括咪唑嗡离子、吡啶嗡离子、吡咯嗡离子、哌啶嗡离子、吗啉嗡离子、季铵盐离子、季磷盐离子或叔硫盐离子。Further, the composition of the electrolyte contains a non-aqueous solution of Al 3+ ions, and the non-aqueous solution containing Al 3+ ions includes an aluminum halide and an ionic liquid, and the anions of the ionic liquid include F - , Cl - , Br - , I - , PF 6- , CN - , SCN - , [N(CF 3 SO 2 )] - or [N(CN) 2 ] - ions; cations include imidazolium ions, pyridinium ions, pyrrole ions, piperidinium ions, Morpholinium ion, quaternary ammonium ion, quaternary phosphonium ion or tertiary sulfur salt ion.
本发明的优点在于：本发明利用含石墨材料的铝离子电池，通过电解液中含有铝配合物离子在持续电解作用下，使配离子不断嵌入石墨层间，最终使石墨层分散剥离形成石墨烯。其工艺简单，成本较低，能够回收废旧铝离子二次电池，绿色环保。这种高效回收铝离子二次电池的方法对铝离子电池的工业化应用具有非常大的意义。The invention has the advantages that the invention utilizes an aluminum ion battery containing a graphite material, and the aluminum complex ions are contained in the electrolyte, and the ions are continuously embedded in the graphite layer under the continuous electrolysis, and finally the graphite layer is dispersed and stripped to form graphene. . The process is simple, the cost is low, and the waste aluminum ion secondary battery can be recycled, which is green and environmentally friendly. This method of efficiently recovering an aluminum ion secondary battery has great significance for the industrial application of an aluminum ion battery.
附图说明DRAWINGS
图1为实施例4中铝离子二次电池2.3V下电解过程的曲线图。BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a graph showing the electrolysis process of an aluminum ion secondary battery of Example 4 at 2.3 V.
图2为实施例4中制备的石墨烯产品的透射电子显微镜的形貌图。2 is a topographical view of a transmission electron microscope of the graphene product prepared in Example 4.
图3为实施例7中铝离子二次电池2.0V下电解过程曲线图。Fig. 3 is a graph showing the electrolysis process of the aluminum ion secondary battery of Example 7 at 2.0V.
具体实施方式detailed description
本发明将通过具体实施例进行更详细的描述，但本发明的保护范围并不受限制于这些实施例。The invention will be described in more detail by way of specific examples, but the scope of the invention is not limited thereto.
实施例1Example 1
本发明要回收的铝离子二次电池的正极材料是高纯石墨片，电解液中含有铝配合物离子，将废旧铝离子电池恒流(电流密度10mAg-1)充电至2.3V，然后在2.0V下恒压电解石墨片2小时，后放电至0.3V，循环5次以上。拆下电池时其状态为未放电状态。将循环至少五次的电池拆卸，将电池正极材料用超声波超声20分钟洗净，去除杂质后在70℃鼓风干燥箱中烘干，得到石墨烯比例 为20％。The positive electrode material of the aluminum ion secondary battery to be recovered by the invention is a high-purity graphite sheet, the electrolyte contains aluminum complex ions, and the constant current (current density 10mAg -1 ) of the waste aluminum ion battery is charged to 2.3V, and then at 2.0. The graphite sheet of constant pressure electrolysis was placed under V for 2 hours, and then discharged to 0.3 V, and the cycle was repeated 5 times or more. When the battery is removed, its status is undischarged. The battery was disassembled at least five times, and the positive electrode material of the battery was ultrasonicated for 20 minutes to remove impurities, and then dried in a 70 ° C blast oven to obtain a graphene ratio of 20%.
实施例2Example 2
本发明要回收的铝离子二次电池的正极材料是高纯石墨片，电解液中含有铝配合物离子，将废旧铝离子电池恒流(电流密度100mAg-1)充电至2.3V，然后在2.5V下恒压电解石墨片4小时，后放电至0.3V，循环5次以上。拆下电池状态为未放电状态。将循环至少五次的电池拆卸，将电池正极材料用超声波超声40分钟洗净，去除杂质后在70℃鼓风干燥箱中烘干，得到石墨烯比例为30％。The positive electrode material of the aluminum ion secondary battery to be recovered by the invention is a high-purity graphite sheet containing aluminum complex ions, and the constant current (current density 100mAg -1 ) of the waste aluminum ion battery is charged to 2.3V, and then at 2.5. The constant pressure electroplated graphite sheet was subjected to V for 4 hours, and then discharged to 0.3 V, and the cycle was repeated 5 times or more. Remove the battery status to the undischarged state. The battery was disassembled at least five times, and the positive electrode material of the battery was ultrasonicated for 40 minutes, and the impurities were removed and dried in a 70 ° C blast oven to obtain a graphene ratio of 30%.
实施例3Example 3
本发明要回收的铝离子二次电池的正极材料是高纯石墨片，电解液中含有铝配合物离子，将废旧铝离子电池恒流(电流密度500mAg-1)充电至2.3V，然后在2.7V下恒压电解石墨片6小时，后放电至0.3V，循环5次以上。拆下电池状态为未放电状态。将循环至少五次的电池拆卸，将电池正极材料用超声波超声60分钟洗净，去除杂质后在70℃鼓风干燥箱中烘干，得到石墨烯比例为35％。The positive electrode material of the aluminum ion secondary battery to be recovered by the invention is a high-purity graphite sheet containing aluminum complex ions, and the constant current (current density 500mAg -1 ) of the waste aluminum ion battery is charged to 2.3V, and then at 2.7. The graphite sheet was continuously pressed at V for 6 hours, and then discharged to 0.3 V, and the cycle was repeated 5 times or more. Remove the battery status to the undischarged state. The battery was circulated at least five times, and the battery positive electrode material was ultrasonically sonicated for 60 minutes to remove impurities, and then dried in a 70 ° C blast drying oven to obtain a graphene ratio of 35%.
实施例4Example 4
本发明要回收的铝离子二次电池的正极材料是高纯石墨片，电解液中含有铝配合物离子，将废旧铝离子电池恒流(电流密度10mAg-1)充电至2.3V，然后在2.3V下恒压电解石墨片10小时，后放电至0.3V，循环5次以上，其电解循环曲线如图1。拆下电池状态为未放电状态。将循环至少五次的电池拆卸，将电池正极材料用超声波超声20分钟洗净，去除杂质在80℃鼓风干燥箱中烘干，得到石墨烯比例为40％。请配合参阅图2所示，本发明得到的 三层石墨烯材料的透射电子显微镜(TEM)的形貌图。The positive electrode material of the aluminum ion secondary battery to be recovered by the invention is a high-purity graphite sheet containing aluminum complex ions, and the constant current (current density 10mAg -1 ) of the waste aluminum ion battery is charged to 2.3V, and then at 2.3. The constant pressure electrolytic graphite sheet was placed under V for 10 hours, and then discharged to 0.3 V for 5 times or more. The electrolytic cycle curve is shown in Fig. 1. Remove the battery status to the undischarged state. The battery was circulated at least five times, and the positive electrode material of the battery was ultrasonicated for 20 minutes, and the impurities were removed and dried in a blast oven at 80 ° C to obtain a graphene ratio of 40%. Please refer to Fig. 2 for a transmission electron microscope (TEM) topographical view of the three-layer graphene material obtained by the present invention.
实施例5Example 5
本发明要回收的铝离子二次电池的正极材料是高纯石墨片，电解液中含有铝配合物离子，将废旧铝离子电池恒流(电流密度100mAg-1)充电至2.3V，然后在2.3V下恒压电解石墨片20小时，后放电至0.3V，循环5次以上。拆下电池状态为未放电状态。将循环至少五次的电池拆卸，将电池正极材料用超声波超声40分钟洗净，去除杂质在80℃鼓风干燥箱中烘干，得到石墨烯比例为45％。The positive electrode material of the aluminum ion secondary battery to be recovered by the invention is a high-purity graphite sheet, the electrolyte contains aluminum complex ions, and the constant current (current density 100mAg -1 ) of the waste aluminum ion battery is charged to 2.3V, and then in 2.3. The graph of the constant pressure electrolyzed graphite was placed under V for 20 hours, and then discharged to 0.3 V, and the cycle was repeated 5 times or more. Remove the battery status to the undischarged state. The battery was circulated at least five times, and the positive electrode material of the battery was ultrasonically sonicated for 40 minutes to remove impurities and dried in a blast oven at 80 ° C to obtain a graphene ratio of 45%.
实施例6Example 6
本发明要回收的铝离子二次电池的正极材料是高纯石墨片，电解液中含有铝配合物离子，将废旧铝离子电池恒流(电流密度200mAg-1)充电至2.3V，然后在2.3V下恒压电解石墨片40小时，后放电至0.3V，循环5次以上。拆下电池状态为未放电状态。将循环至少五次的电池拆卸，将电池正极材料用超声波超声60分钟洗净，去除杂质在80℃鼓风干燥箱中烘干，得到石墨烯比例为50％。The positive electrode material of the aluminum ion secondary battery to be recovered by the invention is a high-purity graphite sheet, the electrolyte contains aluminum complex ions, and the constant current (current density 200mAg -1 ) of the waste aluminum ion battery is charged to 2.3V, and then in 2.3. The constant pressure electroplated graphite sheet was subjected to V for 40 hours, and then discharged to 0.3 V, and the cycle was repeated 5 times or more. Remove the battery status to the undischarged state. The battery was disassembled at least five times, and the positive electrode material of the battery was ultrasonicated for 60 minutes, and the impurities were removed and dried in a blast oven at 80 ° C to obtain a graphene ratio of 50%.
实施例7Example 7
本发明要回收的铝离子二次电池的正极材料是高纯石墨片，电解液中含有铝配合物离子，将废旧铝离子电池恒流(电流密度10mAg-1)充电至2.3V，然后在2.0V下恒压电解石墨片10小时，后放电至0.3V，循环5次以上，其测试循环曲线如图3。拆下电池状态为未放电状态。将循环至少五次的电池拆卸，将电池正极材料用超声波超声60分钟洗净，去除杂质在120℃鼓风干燥箱中烘干，得到石墨烯比例为40％。The positive electrode material of the aluminum ion secondary battery to be recovered by the invention is a high-purity graphite sheet, the electrolyte contains aluminum complex ions, and the constant current (current density 10mAg -1 ) of the waste aluminum ion battery is charged to 2.3V, and then at 2.0. The constant pressure electrolytic graphite sheet was placed under V for 10 hours, and then discharged to 0.3 V, and the cycle was repeated 5 times or more. The test cycle curve is shown in Fig. 3. Remove the battery status to the undischarged state. The battery was circulated at least five times, and the battery positive electrode material was ultrasonically sonicated for 60 minutes to remove impurities and dried in a blast oven at 120 ° C to obtain a graphene ratio of 40%.
实施例8Example 8
本发明要回收的铝离子二次电池的正极材料是高纯石墨片， 电解液中含有铝配合物离子，将废旧铝离子电池恒流(电流密度300mAg-1)充电至2.3V，然后在2.0V下恒压电解石墨碳纸40小时，后放电至0.3V。循环5次以上。拆下电池状态为未放电状态。将循环至少五次的电池拆卸，将电池正极材料用超声波超声60分钟洗净，去除杂质在120℃鼓风干燥箱中烘干，得到石墨烯比例为50％。The positive electrode material of the aluminum ion secondary battery to be recovered by the invention is a high-purity graphite sheet, the electrolyte contains aluminum complex ions, and the constant current (current density 300mAg -1 ) of the waste aluminum ion battery is charged to 2.3V, and then at 2.0. Constant pressure electrolytic graphite carbon paper was placed under V for 40 hours, and then discharged to 0.3 V. Cycle more than 5 times. Remove the battery status to the undischarged state. The battery was circulated at least five times, and the positive electrode material of the battery was ultrasonicated for 60 minutes, and the impurities were removed and dried in a blast oven at 120 ° C to obtain a graphene ratio of 50%.
实施例9Example 9
本发明要回收的铝离子二次电池的正极材料是高纯石墨片，电解液中含有铝配合物离子，将废旧铝离子电池恒流(电流密度400mAg-1)充电至2.3V，然后在1.8V下恒压电解石墨碳纸10小时，后放电至0.3V。循环5次以上，其测试循环曲线如图3。拆下电池状态为未放电状态。将循环至少五次的电池拆卸，将电池正极材料用超声波超声60分钟洗净，去除杂质在120℃鼓风干燥箱中烘干，得到石墨烯比例为35％。The positive electrode material of the aluminum ion secondary battery to be recovered by the invention is a high-purity graphite sheet containing aluminum complex ions, and the constant current (current density 400mAg -1 ) of the waste aluminum ion battery is charged to 2.3V, and then at 1.8. Constant pressure electrolytic graphite carbon paper under V for 10 hours, and then discharged to 0.3V. Cycle more than 5 times, the test cycle curve is shown in Figure 3. Remove the battery status to the undischarged state. The battery was circulated at least five times, and the positive electrode material of the battery was ultrasonically ultrasonically washed for 60 minutes to remove impurities and dried in a blast oven at 120 ° C to obtain a graphene ratio of 35%.
实施例10Example 10
本发明要回收的铝离子二次电池的正极材料是高纯石墨片，将废旧铝离子电池恒流(电流密度500mAg-1)充电至2.3V，然后在1.8V下恒压电解石墨碳纸40小时，后放电至0.3V。循环5次以上，拆下电池状态为未放电状态。将循环至少五次的电池拆卸，将电池正极材料用超声波超声60分钟洗净，去除杂质在120℃鼓风干燥箱中烘干，得到石墨烯比例为45％。The positive electrode material of the aluminum ion secondary battery to be recovered by the invention is a high-purity graphite sheet, and the constant current (current density 500mAg -1 ) of the waste aluminum ion battery is charged to 2.3V, and then the constant pressure electrolytic graphite carbon paper 40 is at 1.8V. After hours, discharge to 0.3V. Cycle 5 times or more, and remove the battery state to the undischarged state. The battery was circulated at least five times, and the battery positive electrode material was ultrasonically sonicated for 60 minutes to remove impurities and dried in a blast oven at 120 ° C to obtain a graphene ratio of 45%.
以上仅为本发明的较佳实施例，当不得以此限定本发明实施的技术范围，因此凡参考本发明的说明书内容所作的简单等效变化与修饰，皆应仍属本发明的保护范围。 The above is only the preferred embodiment of the present invention, and the technical equivalents of the present invention should not be limited thereto. Therefore, the simple equivalent changes and modifications made with reference to the contents of the specification of the present invention should still fall within the scope of the present invention.

Claims (5)

  1. 一种利用废旧铝离子二次电池正极材料制备石墨烯的方法，其特征在于包括以下步骤：A method for preparing graphene using a waste aluminum ion secondary battery cathode material, characterized in that the method comprises the following steps:
    步骤一.选取原料：采用石墨含量为40％以上的正极材料，电解液中含有铝配合物离子的废旧铝离子二次电池，备用；Step 1. Select raw materials: use a cathode material with a graphite content of 40% or more, and a waste aluminum ion secondary battery containing an aluminum complex ion in the electrolyte, and reserve;
    步骤二.电解：对步骤1选取好的废旧铝离子二次电池充入恒电流或恒电压进行电解，电解一定的时间，然后放电至0.3V，再进行充电，循环5次以上，完成电解，备用；Step 2. Electrolysis: The secondary aluminum ion secondary battery selected in step 1 is charged with constant current or constant voltage for electrolysis, electrolyzed for a certain period of time, then discharged to 0.3V, and then charged, cycled 5 times or more, and completed electrolysis. spare;
    步骤三：将经过步骤2处理的电池正极材料取出置于装有无水乙醇的烧杯中，超声波超声20-30分钟洗净，去除杂质后在鼓风干燥箱中烘干，得到石墨烯。Step 3: The positive electrode material of the battery treated in step 2 is taken out and placed in a beaker containing absolute ethanol, ultrasonically sonicated for 20-30 minutes, and the impurities are removed and dried in a blast drying oven to obtain graphene.
  2. 根据权利要求1所述的方法，其特征在于：所述步骤二中，所述电流电解的电流密度为10-500mA g-1；所述电压电解的电压为1.8V-2.7V。The method according to claim 1, wherein in the second step, the current density of the current electrolysis is 10-500 mA g -1 ; and the voltage of the voltage electrolysis is 1.8 V-2.7 V.
  3. 根据权利要求1所述的方法，其特征在于：所述步骤二中，所述电解时间为2-60小时。The method according to claim 1, wherein in the second step, the electrolysis time is from 2 to 60 hours.
  4. 根据权利要求1所述的方法，其特征在于：所述步骤三中，所述的烘干温度为50-200℃。The method according to claim 1, wherein in the third step, the drying temperature is 50-200 °C.
  5. 根据权利要求1所述的方法，其特征在于：所述步骤一种，所述铝配合物离子为：[AlCl4]-或[Al2Cl7]-或二者的混合物。 The method according to claim 1, wherein in said step, said aluminum complex ion is: [AlCl 4 ] - or [Al 2 Cl 7 ] - or a mixture of the two.
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