WO2018028507A1 - 一种铝离子电池正极材料的制备方法 - Google Patents

一种铝离子电池正极材料的制备方法 Download PDF

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WO2018028507A1
WO2018028507A1 PCT/CN2017/095880 CN2017095880W WO2018028507A1 WO 2018028507 A1 WO2018028507 A1 WO 2018028507A1 CN 2017095880 W CN2017095880 W CN 2017095880W WO 2018028507 A1 WO2018028507 A1 WO 2018028507A1
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graphene
pmma
nickel
foam
ion battery
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French (fr)
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许志
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福建新峰二维材料科技有限公司
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—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
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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 aluminum ion batteries, and in particular to a method for preparing a positive electrode material for an aluminum ion battery.
  • Lithium-ion batteries are widely used in portable electronic products and network storage due to their relatively high discharge voltage, energy density, and good power performance.
  • LIBs Lithium-ion batteries
  • aluminum-ion batteries have the following characteristics: aluminum resources are abundant, low in price, and widely distributed.
  • Aluminum-ion batteries have the advantages of safety, high performance and low cost, so they have broad application prospects in large-scale electric energy storage.
  • the present invention provides an ultra-high capacity and ultra-stable aluminum ion battery.
  • a method of preparing a polar material is a method of preparing a polar material.
  • the technical solution adopted by the present invention is: a method for preparing a positive electrode material for an aluminum ion battery, the method comprising the following steps:
  • Graphene is grown on the surface of the pretreated nickel foam to form a graphene/foam nickel structure
  • the surface of the graphene/foam nickel after the etching treatment is coated with a PMMA solvent and baked to form a PMMA/graphene/foam nickel structure;
  • PMMA in PMMA/graphene is removed to obtain graphene based on foam structure.
  • the etching process is at least one of a plasma etching method, a chemical etching method, and a laser etching method
  • the gas used in the plasma etching method is Ar, H 2 , He, N 2 , At least one of NH 3 .
  • the foamed nickel is subjected to Ar + plasma etching, and the nickel foam is placed in a plasma etching reactor at a selected power of 30-50 W, and the treatment time with Ar + plasma is 10-20 min.
  • the nickel foam is pretreated by placing the nickel foam into a tube furnace, introducing Ar (flow rate of 300-600 sccm) and H 2 (flow rate of 100-300 sccm), and heating to 800-1200 ° C, Annealing was carried out for 10-20 min.
  • Ar flow rate of 300-600 sccm
  • H 2 flow rate of 100-300 sccm
  • the method for growing graphene on the surface of the foamed nickel is to pass a flow of 10-30 sccm of methane into a tube furnace, and the corresponding total gas flow volume fraction is 1%-5%, and the reaction time is 10-30 minutes. Then, the sample was rapidly cooled to room temperature, and the gas atmosphere was Ar (flow rate of 300-600 sccm.) and H 2 (flow rate of 100-300 sccm.), and the cooling rate was 200-500 ° C / min.
  • Ar flow rate of 300-600 sccm.
  • H 2 flow rate of 100-300 sccm.
  • the graphene/foam nickel is subjected to Ar + plasma etching, and the graphene/foam nickel is placed in a plasma etching reactor with a selected power of 20-50 w, and the processing time with Ar + plasma is 5-30min.
  • the surface of the graphene/foam nickel after the etching treatment is coated with a PMMA solvent, and the PMMA is dissolved in ethyl acetate at a concentration of 4.5%, and baked at 100-120 ° C for 0.5-1 h.
  • a PMMA/graphene/foam nickel structure was obtained.
  • the acid treatment method is to immerse the obtained PMMA/graphene/foam nickel structure in a HCl solution having a concentration of 3 mol/L, the temperature is controlled at 60-80 ° C, and the soaking time is 2-3 hours.
  • the PMMA removal method is to soak the PMMA/graphene in acetone at a temperature of 40-55 ° C for 0.5-1 hour, and then perform an annealing treatment under the condition that the gas used is Ar/H 2 (80-100 sccm.
  • the temperature is 600 ° - 700 C, and the time is 1-3 hours.
  • the present invention has the following advantages over the prior art:
  • the positive electrode material of the aluminum battery of the present invention is a three-dimensional graphene with a graphene nanopore zone, and the high porosity three-dimensional graphene foam has a large number of uniformly distributed nanopores such that AlCl 4 - throughout the graphite positive electrode It is easier to embed and deintercalate, which not only overcomes the limited problem of graphite edge in the past, but also increases the capacity, and also achieves a lower charging threshold voltage, so that there is no side reaction in the cycle (previous charging threshold voltage is 2.45V, which is higher than the decomposition voltage of the ionic electrolyte), improves its cycle stability.
  • the invention realizes the synthesis of a binderless cathode material for an aluminum ion battery by chemical vapor deposition and etching technology, the material has a porous structure, a large specific surface area, and the graphene surface has a large number of nano-voids, and has a large capacity. At the same time, it has a lower charging voltage, and its critical voltage is only 2.3V, which can effectively avoid the decomposition of ions and avoid the volume expansion of the material during charging and discharging, so that the aluminum ion battery has excellent cycle stability and has an extremely long life.
  • the present invention has good flexibility, can not be broken even under strong bending conditions, can maintain structural integrity, and the material does not need a binder.
  • the conductive agent can be directly applied to the positive electrode material of the aluminum ion battery or the flexible aluminum ion battery.
  • the aluminum ion battery prepared by the invention exhibits excellent electrochemical performance, high capacity, unique properties of fast charging and slow discharging, and excellent temperature characteristics.
  • FIG. 1 is a flow chart of a method for preparing a positive electrode material for an aluminum ion battery according to the present invention
  • FIG. 3 is a graph showing electrochemical performance of an aluminum ion battery according to Embodiment 3 of the present invention.
  • FIG. 5 is a comparison diagram of the appearance of a soft pack battery and a soft three-dimensional graphene-based soft pack battery according to the present invention after a period of charge and discharge cycles.
  • a method for preparing a positive electrode material for an aluminum ion battery comprising the following steps:
  • the foamed nickel is treated by Ar + plasma etching, and the nickel foam is placed in a plasma etching reactor, the selected power is 50w, and the processing time is 10 min with Ar + plasma;
  • the positive electrode material of the aluminum battery of the invention is a three-dimensional graphene with a graphene nanopore zone, and the high porosity three-dimensional graphene foam has a large number of uniformly distributed nanopores so that AlCl 4 - in the entire graphite positive electrode Easy to embed and de-embed, which not only overcomes the limited problem of graphite edge in the past, but also increases the capacity, while also achieving a lower charging threshold voltage, so that there is no side reaction in the cycle (previous charging threshold voltage is 2.45V , higher than the decomposition voltage of the ionic electrolyte), which improves the cycle stability.
  • the invention realizes the synthesis as a binderless cathode material for an aluminum ion battery by chemical vapor deposition and etching technology, the material has a porous structure, a large specific surface area, and the graphene surface has a large number of nano-voids, and has a large capacity, and at the same time
  • the threshold voltage is only 2.3V, which can effectively avoid the decomposition of ions and avoid the volume expansion of the material during charging and discharging, so that the aluminum ion battery has excellent cycle stability and has an extremely long life.
  • the material Compared with the conventional electrode materials of other ion batteries, the material has good flexibility, can not be broken even under strong bending conditions, and can maintain the structural integrity. In addition, the material does not need adhesive and conductive.
  • the agent can be directly applied to an aluminum ion battery or a flexible aluminum ion battery Positive electrode material.
  • a method for preparing a positive electrode material for an ultra-stable aluminum ion battery comprising the following steps:
  • the PMMA treatment method is to coat the graphene/foam nickel surface with a layer of PMMA solvent (PMMA is dissolved in ethyl acetate, the concentration is 4.5%), and bake at 110 ° C for 1 h to obtain PMMA / graphene / Foam nickel structure.
  • PMMA solvent PMMA is dissolved in ethyl acetate, the concentration is 4.5%
  • a method for preparing a positive electrode material for an aluminum ion battery comprising the following steps:
  • a step of adding a plasma etching treatment to the nickel foam, which further increases the surface porosity of the foamed nickel, is further performed before the pretreatment of the foamed nickel.
  • the specific surface area is increased, thereby increasing the capacity of the aluminum ion battery.
  • the anion penetration distance also makes the cut-off voltage of the aluminum ion battery during charging relatively low, avoiding the electrolyte being decomposed at a high cut-off voltage, releasing the gas, and rapidly expanding the flatulence volume of the battery, resulting in poor cycle life.
  • the three-dimensional graphene with graphene nanopore zone formed by etching technology is used as a positive electrode material for an aluminum ion battery, exhibiting high capacity, long cycle life, excellent rate performance and temperature characteristics.
  • the aluminum ion battery prepared by the present invention exhibits excellent electrochemical performance, high capacity, unique properties of fast charging and slow discharging, and excellent temperature characteristics.
  • Figure 3a is a cyclic voltammetry curve of an aluminum ion battery prepared in Example 3 of the present invention, at a scanning rate of 30 mV/s, a graphene nanoribbon structure on the surface of a three-dimensional graphene foam.
  • Figures 4a) and b) are photographs showing a graphene nanoribbon structure of an aluminum ion battery based on a high porosity three-dimensional graphene surface, which illuminate the LED indicator at 0 ° C and 80 ° C, respectively.
  • c) Charging and discharging curves of graphene nanoribbon structured soft-packed cells on the surface of aluminum/three-dimensional graphene foam at a current density of 5000 mA/g, charge and discharge curves at different temperatures;
  • the aluminum ion battery prepared by the invention exhibits excellent electrochemical performance and has high capacity: the capacity is up to 123 mAh/g at a current density of 5000 mA/g; excellent cycle stability: no capacity decay after 10,000 cycles; In addition, there is good rate performance, and the reversible capacity at a large current density of 8000 mA/g is 111 mAh/g.
  • the aluminum ion battery prepared by the invention exhibits the unique performance of fast charging and slow discharging, and the battery can be charged and discharged in excess of 3700S in 80s, and the cycle stability is excellent in the use process.
  • the aluminum ion battery prepared by the invention has excellent temperature characteristics: high capacity at high temperature (The capacity at a current density of 5000 mA/g is constant at 123 mAh/g in the range of 20-80 ° C) and cycle stability); high coulombic efficiency (100%) and cycle stability at low temperatures.
  • the three-dimensional graphene soft pack battery with a graphene nanopore strip provided by the present invention has no flatulence after 10 days of charge and discharge cycle at a large current density of 5000 mA/g;
  • the three-dimensional graphene soft pack battery was charged and discharged for one day under the same conditions, and the battery volume expanded significantly, and the battery flatulence phenomenon was obvious.
  • the cut-off voltage of the three-dimensional graphene with the graphene nanopore strip provided by the invention is reduced to 2.3V, which can effectively prevent the ionic electrolyte from being decomposed and avoid the flatulence phenomenon of the battery, so that the battery has good cycle stability.

Abstract

一种铝离子电池正极材料的制备方法，所述方法包括以下步骤：首先用刻蚀法处理泡沫镍（S101）；再对泡沫镍进行表面预处理（S102）；然后在泡沫镍表面生长石墨烯，形成石墨烯/泡沫镍结构（S103）；再对石墨烯/泡沫镍进行刻蚀法处理（S104）；在石墨烯/泡沫镍表面涂覆一层PMMA溶剂，烘烤成膜，得到PMMA/石墨烯/泡沫镍结构（S105）；再对PMMA/石墨烯/泡沫镍进行酸处理，溶解泡沫镍，得到PMMA/石墨烯结构（S106）；最后去除PMMA/石墨烯中的PMMA，得到基于泡沫结构的石墨烯（S107）。通过化学气相沉积和刻蚀技术实现了作为铝离子电池无粘结剂正极材料的合成，具有超大容量，较低充电电压，避免充放电过程中材料的体积膨胀，具有优良的循环稳定性。

Description

一种铝离子电池正极材料的制备方法 技术领域
本发明涉及铝离子电池技术领域，尤其涉及一种铝离子电池正极材料的制备方法。
背景技术
在如今这个能源时代，开发具有高能量密度的储能设备非常重要。锂离子电池(LIBs)由于其相对较高的放电电压、能量密度和很好的功率性能，所以被广泛地应用于便携式电子产品和网络存储。但是，因为其成本较高以及原材料锂的缺乏，促使了新型的同类可替代产品的出现，比如铝离子电池)。相比较锂离子电池，铝离子电池具有以下特点：铝资源丰富，价格低廉，分布广泛，铝离子电池具有安全、高性能、低成本优势，因此在大规模电能存储中有着广阔的应用前景。
其实铝离子电池很早就被研究者发现，但是它无法用于充电电池，因此其商业化发展并不顺利。究其原因，主要有三个：一是循环寿命差；二是充电速度太慢，容量低；第三，其致命缺点是电解液里面的铝离子不稳定，很容易发生化学反应，有严重的安全隐患，这些弱点让铝离子电池一直没有实现实用化。因此，要解决以上问题，必须找到一种新的正极材料和新的性能稳定的电解液用于铝离子电池。
发明内容
针对上述问题，本发明提供了一种超高容量和超稳定的铝离子电池正 极材料的制备方法。
为解决上述技术问题，本发明所采用的技术方案是：一种铝离子电池正极材料的制备方法，所述方法包括以下步骤：
用刻蚀法处理泡沫镍；
对刻蚀法处理后的泡沫镍进行表面预处理，清洁表面及去除表面氧化物；
在预处理后的泡沫镍表面生长石墨烯，形成石墨烯/泡沫镍结构；
对石墨烯/泡沫镍进行刻蚀法处理，诱导在石墨烯表面形成纳米带；
在刻蚀法处理后的石墨烯/泡沫镍表面涂覆一层PMMA溶剂，烘烤成膜，得到PMMA/石墨烯/泡沫镍结构；
对PMMA/石墨烯/泡沫镍进行酸处理，充分溶解泡沫镍，得到PMMA/石墨烯结构；
去除PMMA/石墨烯中的PMMA，得到基于泡沫结构的石墨烯。
优选的，所述刻蚀法处理为等离子刻蚀法、化学刻蚀法、激光刻蚀法中的至少一种，所述等离子刻蚀法所用的气体为Ar、H2、He、N2、NH3中的至少一种。
优选的，所述泡沫镍采用Ar+等离子体刻蚀法，将泡沫镍放入等离子体刻蚀反应器，所选功率为30-50w，用Ar+等离子体处理时间为10-20min。
优选的，所述泡沫镍进行预处理方法为将泡沫镍放入管式炉中，通入Ar(流量为300-600sccm)和H2(流量为100-300sccm)，加热到800-1200℃，进行退火处理10-20min。
优选的，所述在泡沫镍表面生长石墨烯的方法为将10-30sccm流量甲烷 通入管式炉进行反应，对应的总气体流量体积分数为1％-5％，反应时间为10-30分钟，然后样品迅速冷却至室温，气体氛围为Ar(流量为300-600sccm.)和H2(流量为100-300sccm.)，冷却速度为200-500℃/min。
优选的，所述石墨烯/泡沫镍采用Ar+等离子体刻蚀法，将石墨烯/泡沫镍放入等离子体刻蚀反应器，所选功率为20-50w，用Ar+等离子体处理时间为5-30min。
优选的，所述在刻蚀法处理后的石墨烯/泡沫镍表面涂覆一层PMMA溶剂，PMMA溶解于乙酸乙酯，浓度为4.5％，于100-120℃条件下烘烤0.5-1h，得到PMMA/石墨烯/泡沫镍结构。
优选的，所述酸处理方法为将得到的PMMA/石墨烯/泡沫镍结构浸入浓度为3mol/L的HCl溶液中，温度控制在60-80℃，浸泡时间为2-3小时。
优选的，所述PMMA去除方法为将PMMA/石墨烯浸泡在温度为40-55℃的丙酮中0.5-1小时，再进行退火处理，处理条件为，所用气体Ar/H2(80-100sccm.)温度为600°-700C，时间为1-3小时。
由上述对本发明结构的描述可知，和现有技术相比，本发明具有如下优点：
1、本发明铝电池正极材料是一种带有石墨烯纳米孔隙带的三维石墨烯，这种高孔隙率的三维石墨烯泡沫具有大量的、均匀分布的纳米孔洞使得AlCl4–在整个石墨正极中更容易嵌入和脱嵌，这不仅克服了以往的石墨边缘有限问题，并提高了容量，同时也取得了较低的充电临界电压，从而在循环中没有任何副反应(以前的充电临界电压为2.45V，高于离子电解质的分解电压)，提高了其循环稳定性。
2、本发明通过化学气相沉积和刻蚀技术实现了作为铝离子电池无粘结剂正极材料的合成，该材料具有多孔结构，超大比表面积，而且石墨烯表面具有大量的纳米空隙，具有超大容量，同时具有较低充电电压，其临界电压仅为2.3V，能有效避免离子的电解质分解，避免充放电过程中材料的体积膨胀，使得铝离子电池具有优良的循环稳定性即有超长寿命。
3、本发明与其它离子电池的传统电极材料相比，该材料具有很好的柔韧性，即使在强弯曲条件下，不会断裂，能够保持结构的完整性，另外，该材料无需粘结剂和导电剂就可以直接应用于铝离子电池或柔性铝离子电池的正极材料。
4、采用本发明制备的铝离子电池表现出优异的电化学性能，具有高的容量，快速充电和慢速放电的独特性能，卓越的温度特性。
附图说明
构成本申请的一部分的附图用来提供对本发明的进一步理解，本发明的示意性实施例及其说明用于解释本发明，并不构成对本发明的不当限定。在附图中：
图1为本发明一种铝离子电池正极材料的制备方法的流程图；
图2为本发明实施例3流程图；
图3为本发明实施例3铝离子电池的电化学性能曲线图；
图4为本发明实施例3铝离子电池不同温度的性能曲线图；
图5为本发明提供的软包电池和基于纯三维石墨烯的软包电池经过一段时间的充放电循环的外形对比图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
实施例1
参考图1，一种铝离子电池正极材料的制备方法，所述方法包括以下步骤：
S101、用Ar+等离子体刻蚀法处理泡沫镍，将泡沫镍放入等离子体刻蚀反应器，所选功率为50w，用Ar+等离子体处理时间为10min；
S102、对Ar+等离子体刻蚀法处理后的泡沫镍进行表面预处理，将泡沫镍放入管式炉中，通入Ar(流量为500sccm)和H2(流量为200sccm)，加热到1000℃，进行退火处理20min，清洁表面及去除表面氧化物；
S103、用CVD法在预处理后的泡沫镍表面生长石墨烯，将10sccm流量甲烷通入管式炉进行反应，对应的总气体流量体积分数为1.4％，反应时间为10分钟，然后样品迅速冷却至室温，气体氛围为Ar(流量为500sccm.)和H2(流量为200sccm.)，冷却速度为300℃/min，形成石墨烯/泡沫镍结构；
S104、对石墨烯/泡沫镍进行Ar+等离子体刻蚀法处理，将石墨烯/泡沫镍放入等离子体刻蚀反应器，所选功率为40w，用Ar+等离子体处理时间为5-20min，诱导在石墨烯表面形成纳米带；
S105、在Ar+等离子体刻蚀法处理后的石墨烯/泡沫镍表面涂覆一层PMMA溶剂，PMMA溶解于乙酸乙酯，浓度为4.5％，于110℃条件下烘烤 0.5h，烘烤成膜，得到PMMA/石墨烯/泡沫镍结构；
S106、对PMMA/石墨烯/泡沫镍进行酸处理，将得到的PMMA/石墨烯/泡沫镍结构浸入浓度为3mol/L的HCl溶液中，温度控制在80℃，浸泡时间为3小时，充分溶解泡沫镍，得到PMMA/石墨烯结构；
S107、去除PMMA/石墨烯中的PMMA，将PMMA/石墨烯浸泡在温度为4温度为55℃的丙酮中1小时，再进行退火处理，处理条件为，所用气体Ar/H2(80sccm.)温度为650C，时间为2小时，得到基于泡沫结构的石墨烯。
本发明铝电池正极材料是一种带有石墨烯纳米孔隙带的三维石墨烯，这种高孔隙率的三维石墨烯泡沫具有大量的、均匀分布的纳米孔洞使得AlCl4–在整个石墨正极中更容易嵌入和脱嵌，这不仅克服了以往的石墨边缘有限问题，并提高了容量，同时也取得了较低的充电临界电压，从而在循环中没有任何副反应(以前的充电临界电压为2.45V，高于离子电解质的分解电压)，提高了其循环稳定性。
本发明通过化学气相沉积和刻蚀技术实现了作为铝离子电池无粘结剂正极材料的合成，该材料具有多孔结构，超大比表面积，而且石墨烯表面具有大量的纳米空隙，具有超大容量，同时具有较低充电电压，其临界电压仅为2.3V，能有效避免离子的电解质分解，避免充放电过程中材料的体积膨胀，使得铝离子电池具有优良的循环稳定性即有超长寿命。
本发明与其它离子电池的传统电极材料相比，该材料具有很好的柔韧性，即使在强弯曲条件下，不会断裂，能够保持结构的完整性，另外，该材料无需粘结剂和导电剂就可以直接应用于铝离子电池或柔性铝离子电池 的正极材料。
实施例2
参考图1，一种超稳定铝离子电池正极材料的制备方法，所述方法包括以下步骤：
S101、用Ar+等离子体刻蚀法处理泡沫镍，将泡沫镍放入等离子体刻蚀反应器，所选功率为40w，用Ar+等离子体处理时间为10min，在泡沫镍孔壁上形成纳米孔隙带；接着用化学刻蚀方法对泡沫镍进行处理，进一步增长纳米孔隙的尺寸，利于
Figure PCTCN2017095880-appb-000001
阴离子在电极材料中的扩散渗透。
S102、对刻蚀法处理后的泡沫镍进行表面预处理，将泡沫镍放入管式炉中，通入Ar(流量为400sccm)和H2(流量为200sccm)，加热到1000℃，进行退火处理30min，清洁表面及去除表面氧化物。
S103、用CVD法在预处理后的泡沫镍表面生长石墨烯，将20sccm流量甲烷通入管式炉进行反应，对应的总气体流量体积分数为1.4％，反应时间为10分钟，然后样品迅速冷却至室温，气体氛围为Ar+(流量为500sccm.)和H2(流量为200sccm.)，冷却速度为300℃/min，形成石墨烯/泡沫镍结构。
S104、对石墨烯/泡沫镍进行Ar+等离子体刻蚀法处理，将石墨烯/泡沫镍放入等离子体刻蚀反应器，所选功率为40w，用Ar+等离子体处理时间为20min，诱导在石墨烯表面形成纳米带。
S105、所述PMMA处理方法为将石墨烯/泡沫镍表面涂覆一层PMMA溶剂(PMMA溶解于乙酸乙酯，浓度为4.5％)，于110℃条件下烘烤1h，得到PMMA/石墨烯/泡沫镍结构。
S106、对PMMA/石墨烯/泡沫镍进行酸处理，将得到的PMMA/石墨烯 /泡沫镍结构浸入浓度为3mol/L的HCl溶液中，温度控制在80℃，浸泡时间为3小时，充分溶解泡沫镍，得到PMMA/石墨烯结构。
S107、去除PMMA/石墨烯中的PMMA，将PMMA/石墨烯浸泡在温度为55℃的丙酮中0.5小时，再进行退火处理，处理条件为，所用气体Ar/H2(80sccm.)温度为650C，时间为2小时，得到基于泡沫结构的石墨烯。
实施例3
参考图2，一种铝离子电池正极材料的制备方法，所述方法包括以下步骤：
S101、对泡沫镍进行表面预处理，将泡沫镍放入管式炉中，通入Ar(流量为500sccm)和H2(流量为200sccm)，加热到1000℃，进行退火处理20min，清洁表面及去除表面氧化物；
S102、用CVD法在预处理后的泡沫镍表面生长石墨烯，将10sccm流量甲烷通入管式炉进行反应，对应的总气体流量体积分数为1.4％，反应时间为10分钟，然后样品迅速冷却至室温，气体氛围为Ar(流量为500sccm.)和H2(流量为200sccm.)，冷却速度为300℃/min，形成石墨烯/泡沫镍结构；
S103、对石墨烯/泡沫镍进行Ar+等离子体刻蚀法处理，将石墨烯/泡沫镍放入等离子体刻蚀反应器，所选功率为40w，用Ar+等离子体处理时间为5-20min，诱导在石墨烯表面形成纳米带；
S104、在Ar+等离子体刻蚀法处理后的石墨烯/泡沫镍表面涂覆一层PMMA溶剂，PMMA溶解于乙酸乙酯，浓度为4.5％，于110℃条件下烘烤0.5h，烘烤成膜，得到PMMA/石墨烯/泡沫镍结构；
S105、对PMMA/石墨烯/泡沫镍进行酸处理，将得到的PMMA/石墨烯 /泡沫镍结构浸入浓度为3mol/L的HCl溶液中，温度控制在80℃，浸泡时间为3小时，充分溶解泡沫镍，得到PMMA/石墨烯结构；
S106、去除PMMA/石墨烯中的PMMA，将PMMA/石墨烯浸泡在温度为4温度为55℃的丙酮中1小时，再进行退火处理，处理条件为，所用气体Ar/H2(80sccm.)温度为650C，时间为2小时，得到基于泡沫结构的石墨烯。
与实施例3相比，实施例1和实施例2中工艺过程在对泡沫镍进行预处理前，增加步骤，对泡沫镍进行等离子体刻蚀处理，该步骤能够进一步增加泡沫镍表面孔隙率，进而增大其比表面积，进而提升铝离子电池的容量。
在
Figure PCTCN2017095880-appb-000002
阴离子扩散渗透到石墨电极的过程中，石墨电极上积累的电荷会形成一个内建电场，从而阻止更多的
Figure PCTCN2017095880-appb-000003
阴离子进一步更深入地渗透到石墨中，这种情况就像一个硼掺杂的硅片和一个磷掺杂的硅片紧贴着放在一起会形成一个二极管一样。截止充电电压跟其自生成电位有关。这样即使穿透深度有限，当整个石墨表面均匀、且大量地分布有纳米孔洞时，
Figure PCTCN2017095880-appb-000004
阴离子可以从各个孔隙位置扩散渗透，增加嵌入到整个石墨电极的
Figure PCTCN2017095880-appb-000005
阴离子数量。从而大幅度提升大幅度提升铝离子电池容量。再者，较短的
Figure PCTCN2017095880-appb-000006
阴离子渗透距离也会使得铝离子电池充电过程中的截止电压相对较低，避免电解液在高的截止电压下被分解，释放气体，电池胀气体积快速膨胀，从而导致循环寿命差。总而言之，通过刻蚀技术形成的带有石墨烯纳米孔隙带的三维石墨烯作为铝离子电池的正极材料，表现出高容量、长循环寿命、优异的倍率性能及温度特性。
参考图3、图4，采用本发明制备的铝离子电池表现出优异的电化学性能，具有高的容量，快速充电和慢速放电的独特性能，卓越的温度特性。
图3a)本发明实施例3制备的铝离子电池的循环伏安曲线，在扫描速率为30mV/s下，三维石墨烯泡沫表面的石墨烯纳米带结构。b)充电和放电曲线；c)一个铝/在三维石墨烯泡沫表面的石墨烯纳米带结构袋电池在5000mA/g电流密度下的循环性能；d)软包电池在2000、4000、5000、6000、7000和8000mA/g下充电和放电的倍率性能；e)软包电池的快速充电和慢速放电性能，在5000mA/g的电流密度下充电，在电流密度范围从100到5000mA/g下放电。
图4a)和b)照片显示了基于高孔隙率的三维石墨烯表面的石墨烯纳米带结构的铝离子电池，分别在0℃和80℃点亮LED指示灯。c)充电和放电曲线的铝/三维石墨烯泡沫表面的石墨烯纳米带结构的软包电池在5000mA/g的电流密度下，在不同温度下的充电和放电曲线；d)和e)软包电池分别在低温(0℃)和高温(40，60，和80℃)下的循环性能。
采用本发明制备的铝离子电池表现出优异的电化学性能，具有高的容量：在电流密度5000mA/g下的容量高达123mAh/g；优异的循环稳定性：经过10000次循环后没有容量衰减；另外，还有良好的倍率性能，在8000mA/g的大电流密度仍下的可逆容量达到111mAh/g。
采用本发明制备的铝离子电池表现出快速充电和慢速放电的独特性能，电池可以在80s完成充电和放电超过3700S以上，及使用过程优异循环稳定性。
采用本发明制备的铝离子电池具有卓越的温度特性：在高温的高容量 (在20-80℃范围，在电流密度5000mA/g下的容量恒定在123mAh/g)和循环稳定性)；在低温下的高库仑效率(100％)和循环稳定性。
参考图5，可以看出，本发明提供的基于带有石墨烯纳米孔隙带的三维石墨烯软包电池在大电流密度5000mA/g下充放电循环10天后，软包电池没有胀气现象；而基于三维石墨烯的软包电池在一样的条件下充放电循环1天后，电池体积明显膨胀，电池胀气现象明显。本发明提供的带有石墨烯纳米孔隙带的三维石墨烯的截止电压降到2.3V，能有效避免了离子电解质被分解，避免电池出现胀气现象，使得电池具有很好的循环稳定性。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (9)

  1. 一种铝离子电池正极材料的制备方法，其特征在于：所述方法包括以下步骤：
    用刻蚀法处理泡沫镍；
    对刻蚀法处理后的泡沫镍进行表面预处理，清洁表面及去除表面氧化物；
    在预处理后的泡沫镍表面生长石墨烯，形成石墨烯/泡沫镍结构；
    对石墨烯/泡沫镍进行刻蚀法处理，诱导在石墨烯表面形成纳米孔隙带；
    在刻蚀法处理后的石墨烯/泡沫镍表面涂覆一层PMMA溶剂，烘烤成膜，得到PMMA/石墨烯/泡沫镍结构；
    对PMMA/石墨烯/泡沫镍进行酸处理，充分溶解泡沫镍，得到PMMA/石墨烯结构；
    去除PMMA/石墨烯中的PMMA，得到基于泡沫结构的石墨烯。
  2. 根据权利要求1所述一种铝离子电池正极材料的制备方法，其特征在于：所述刻蚀法处理为等离子刻蚀法、化学刻蚀法、激光刻蚀法中的至少一种，所述等离子刻蚀法所用的气体为Ar、H2、He、N2、NH3中的至少一种。
  3. 根据权利要求1所述一种铝离子电池正极材料的制备方法，其特征在于：所述泡沫镍采用Ar+等离子体刻蚀法，将泡沫镍放入等离子体刻蚀反应器，所选功率为30-50w，用Ar+等离子体处理时间为10-20min。
  4. 根据权利要求1所述一种铝离子电池正极材料的制备方法，其特征在于：所述泡沫镍进行预处理方法为将泡沫镍放入管式炉中，通入Ar(流量为300-600sccm)和H2(流量为100-300sccm)，加热到800-1200℃，进行退火 处理10-20min。
  5. 根据权利要求1所述一种铝离子电池正极材料的制备方法，其特征在于：所述在泡沫镍表面生长石墨烯的方法为将10-30sccm流量甲烷通入管式炉进行反应，对应的总气体流量体积分数为1％-5％，反应时间为10-30分钟，然后样品迅速冷却至室温，气体氛围为Ar(流量为300-600sccm.)和H2(流量为100-300sccm.)，冷却速度为200-500℃/min。
  6. 根据权利要求1所述一种铝离子电池正极材料的制备方法，其特征在于：所述石墨烯/泡沫镍采用Ar+等离子体刻蚀法，将石墨烯/泡沫镍放入等离子体刻蚀反应器，所选功率为20-50w，用Ar+等离子体处理时间为5-30min。
  7. 根据权利要求1所述一种铝离子电池正极材料的制备方法，其特征在于：所述在刻蚀法处理后的石墨烯/泡沫镍表面涂覆一层PMMA溶剂，PMMA溶解于乙酸乙酯，浓度为4.5％，于100-120℃条件下烘烤0.5-1h，得到PMMA/石墨烯/泡沫镍结构。
  8. 根据权利要求1所述一种铝离子电池正极材料的制备方法，其特征在于：所述酸处理方法为将得到的PMMA/石墨烯/泡沫镍结构浸入浓度为3mol/L的HCl溶液中，温度控制在60-80℃，浸泡时间为2-3小时。
  9. 根据权利要求1所述一种铝离子电池正极材料的制备方法，其特征在于：所述PMMA去除方法为将PMMA/石墨烯浸泡在温度为40-55℃的丙酮中0.5-1小时，再进行退火处理，处理条件为，所用气体Ar/H2(80-100sccm.)温度为600°-700C，时间为1-3小时。
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