WO2019029192A1 - 一种铝电池 - Google Patents

一种铝电池 Download PDF

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Publication number
WO2019029192A1
WO2019029192A1 PCT/CN2018/084350 CN2018084350W WO2019029192A1 WO 2019029192 A1 WO2019029192 A1 WO 2019029192A1 CN 2018084350 W CN2018084350 W CN 2018084350W WO 2019029192 A1 WO2019029192 A1 WO 2019029192A1
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Prior art keywords
aluminum
positive electrode
expanded graphite
film
separator
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PCT/CN2018/084350
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English (en)
French (fr)
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高超
董晓忠
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杭州高烯科技有限公司
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Priority claimed from CN201710685752.XA external-priority patent/CN107464932A/zh
Priority claimed from CN201710684938.3A external-priority patent/CN107492631A/zh
Priority claimed from CN201710685751.5A external-priority patent/CN107482219A/zh
Priority claimed from CN201710685318.1A external-priority patent/CN107546390A/zh
Application filed by 杭州高烯科技有限公司 filed Critical 杭州高烯科技有限公司
Publication of WO2019029192A1 publication Critical patent/WO2019029192A1/zh

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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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • 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 belongs to the field of novel batteries and relates to an aluminum battery.
  • a nickel-cobalt-manganese ternary material and lithium iron phosphate are mainly used as a positive electrode material, and a carbonate-based ester is used as a main solvent of an electrolytic solution.
  • the power lithium-ion battery charge and discharge capacity is usually up to 1.5A / g or more, about 0.5A / g in actual use, to meet the driving needs of electric vehicles.
  • the energy density of the power lithium ion battery is between 120-220 Wh/kg, and the energy density of the battery pack is about 100 Wh/kg.
  • the main problems of the power lithium-ion battery are: (1) The capacity of the cathode material has been maintained at around 150 mAh/g, and it is difficult to make breakthroughs in the current technology; (2) the price of the cathode material has remained high, limiting the promotion of electric vehicles. Popularization; (3) In the process of high-current charging and discharging, the stability of the positive electrode material is poor, and the safety of the battery is greatly reduced due to the use of the carbonated ester as the main solvent of the electrolyte. At present, the battery explosion accident of the electric vehicle has been reported.
  • the aluminum ion battery uses the ionic liquid as the electrolyte, the safety of the battery is greatly improved, and the combustion explosion accident occurring during the use of the lithium ion battery can be avoided.
  • the pyrolytic graphite cathode material is prepared by chemical vapor deposition of methane gas on the foamed nickel. After the pyrolytic graphite deposition is completed, the nickel foam is also removed by hydrochloric acid, and the whole process is complicated and difficult to industrialize.
  • an aluminum foil is usually used as a current collector of a positive electrode material.
  • glassy carbon is used as the current collector of the pyrolytic graphite cathode material. The main function of the current collector is to reduce the internal resistance of the battery.
  • the object of the present invention is to provide an aluminum battery without a current collector positive electrode, which solves the problem that the preparation process of the positive electrode of the existing aluminum ion battery is complicated, and at the same time, the positive current collector is omitted, and the specific capacity and rate performance of the aluminum ion battery are improved. .
  • the positive electrode is a current collectorless self-supporting expanded graphite film
  • the electrolyte is 1-ethyl-3-methylimidazolium chloride and aluminum chloride according to a molar ratio of 1:1.0 a mixture of ⁇ 1:1.6
  • the fluid-free, self-supporting expanded graphite film is formed into a film from expanded graphite by a pressure of 1-30 MPa, and is directly contacted with the positive electrode shell in a button battery, in a soft pack battery. Directly connected to the tabs by conductive paste.
  • a separator is provided between the positive electrode and the negative electrode, and the separator is composed of 1-5 layers of glass fibers.
  • the negative electrode is an aluminum foil, an aluminum sheet or the like.
  • the expanded graphite is inexpensive, and the electrode is formed conveniently.
  • the positive electrode which is pressed into the film can also save the current collecting body in the battery assembly process, and greatly reduce the cost of the power battery.
  • the expanded graphite cathode material can also greatly improve the specific capacity and rate performance of the power battery, and has the potential to replace the power lithium ion battery.
  • An aluminum ion battery with high graphitization positive electrode the positive electrode is a high graphitization expanded graphite film
  • the electrolyte is 1-ethyl-3-methylimidazolium chloride and aluminum trichloride according to a molar ratio of 1:1.0 ⁇ 1:1.6 composition of the mixture;
  • the high graphitization degree expanded graphite film is incubated by expanded graphite at a temperature of 2000-3000 ° C for 5 minutes to 10 hours, and then pressed to a film by a pressure of 1.5-35 MPa.
  • a separator is provided between the positive electrode and the negative electrode, and the separator is composed of 1-6 layers of glass fibers.
  • the negative electrode is an aluminum foil, an aluminum sheet or the like.
  • the beneficial effects are that the expanded graphite which is subjected to high temperature graphitization can remove the original non-carbon hetero atoms in the expanded graphite and improve the degree of graphitization of the expanded graphite.
  • Graphitized expanded graphite is used as a positive electrode material for aluminum ion batteries. Compared with pyrolytic graphite cathode materials and graphene aerogel cathode materials, it is not only inexpensive, but also has a simple electrode forming process and good battery specific capacity and rate performance. Conducive to the commercial application of aluminum ion batteries.
  • the positive electrode is a self-supporting expanded graphite film
  • the electrolyte is a mixture of triethylamine hydrochloride and aluminum trichloride in a molar ratio of 1:1.0 to 1:1.8; the self-supporting
  • the expanded graphite film was formed into a film from expanded graphite by a pressure of 1-35 MPa.
  • a separator is provided between the positive electrode and the negative electrode, and the separator is composed of 1-5 layers of glass fibers.
  • the negative electrode is an aluminum foil, an aluminum sheet or the like.
  • the beneficial effects are: low price of expanded graphite, convenient electrode forming of aluminum ion battery; triethylamine hydrochloride as electrolyte of aluminum ion battery, relatively cheap; aluminum ion battery using expanded graphite and triethylamine hydrochloride system has higher The battery's specific capacity and rate performance, cost-effective.
  • the positive electrode is a self-supporting expanded graphite film
  • the electrolyte is a mixture of triethylamine hydrochloride and aluminum trichloride in a molar ratio of 1:1.0 to 1:1.8; the self-supporting
  • the expanded graphite film is kept from expanded graphite at a temperature of 2000-3000 ° C for 5 minutes to 12 hours, and then pressed at a pressure of 1 to 30 MPa to form a film.
  • a separator is provided between the positive electrode and the negative electrode, and the separator is composed of 1-6 layers of glass fibers.
  • the negative electrode is an aluminum foil, an aluminum sheet or the like.
  • the beneficial effects are that the expanded graphite which is subjected to high temperature graphitization can increase the degree of graphitization of the expanded graphite and increase the active site of the aluminum ion battery material, thereby increasing the capacity of the battery.
  • the aluminum ion battery using graphitized expanded graphite and triethylamine hydrochloride system has higher specific capacity and rate performance, and the material preparation process is simple and the price is relatively cheap.
  • Example 1 is a cycle performance diagram of a button cell of the current collector-free expanded graphite positive electrode prepared in Example 1.
  • Example 2 is a cycle performance diagram of a button cell of the current collector-free expanded graphite positive electrode prepared in Example 2.
  • FIG. 3 is a cycle performance diagram of a soft pack battery without a current collector expanded graphite positive electrode prepared in Example 3.
  • FIG. 3 is a cycle performance diagram of a soft pack battery without a current collector expanded graphite positive electrode prepared in Example 3.
  • Example 4 is a Raman spectrum of the expanded graphite of Example 4 before and after graphitization at 2500 °C.
  • Example 5 is a cycle performance diagram of a button-type aluminum ion battery of a graphitized expanded graphite positive electrode prepared in Example 4.
  • FIG. 6 is a cycle performance diagram of a button-type aluminum ion battery of a graphitized expanded graphite positive electrode prepared in Example 5.
  • FIG. 7 is a cycle performance diagram of a soft-packed aluminum ion battery of graphitized expanded graphite positive electrode prepared in Example 6.
  • Figure 8 is a graph showing the cycle performance of the low cost button-type aluminum ion battery prepared in Example 7.
  • Figure 9 is a graph showing the cycle performance of the high performance button-type aluminum ion battery prepared in Example 10.
  • the molar ratio of 1-ethyl-3-methylimidazolium chloride to aluminum trichloride is 1: 1.0;
  • the button cell is assembled in the following order: the expanded graphite positive electrode film prepared in the above (1) is placed in the positive electrode case (CR2025), and the two are in direct contact; then, on the expanded graphite positive electrode film, 5 layers of glass are placed. Fiber membrane (Whatman), add an appropriate amount of 1:1.0 electrolyte; then place the negative aluminum foil on the glass fiber diaphragm (Whatman), align and compact, cover the negative shell, and finally use the button battery packaging machine package.
  • the button cell is assembled in the following order: the expanded graphite positive electrode film prepared in the above (1) is placed in the positive electrode case (CR2025), and the two are in direct contact; then, on the expanded graphite positive electrode film, three layers of glass are placed. Fiber membrane (Whatman), add an appropriate amount of 1:1.4 electrolyte; then place the negative aluminum sheet on the glass fiber diaphragm (Whatman), align and compact, cover the negative shell, and finally use the button battery package .
  • the molar ratio of 1-ethyl-3-methylimidazolium chloride to aluminum trichloride is 1: 1.6;
  • the expanded graphite positive electrode film prepared in the above (1) is directly connected with the nickel tab as the positive electrode of the soft pack battery; and the aluminum foil is directly used as the negative electrode of the soft pack battery; Between the expanded graphite positive film and the aluminum foil negative electrode, place a layer of glass fiber separator (Whatman), align and fix it, put it into the soft pack battery bag, add an appropriate amount of electrolyte with a mixing ratio of 1:1.6, and finally use the soft pack battery.
  • the commercial expanded graphite is placed in a high temperature graphitization furnace and kept at a temperature of 2500 ° C for 5 minutes. As shown in Fig. 4, the degree of graphitization of the expanded graphite is greatly improved after being treated at a high temperature of 2500 ° C;
  • the molar ratio of 1-ethyl-3-methylimidazolium chloride to aluminum trichloride is 1: 1.0;
  • the button cell is assembled in the following order: the graphitized expanded graphite positive electrode film prepared in the above (2) is placed in the positive electrode shell (CR2025); and the four-layer glass fiber separator is placed on the graphitized expanded graphite positive electrode film. (Whatman), add an appropriate amount of 1:1.0 electrolyte; then place the negative aluminum foil on the glass fiber diaphragm (Whatman), align and compact, cover the negative shell, and finally use the button battery packer.
  • the above-mentioned assembled button battery was subjected to a 5 A/g constant current charge and discharge experiment, and it was found that the capacity of the button-type aluminum ion battery of the graphitized expanded graphite positive electrode can be maintained at 92 mAh/g. As shown in Figure 5.
  • the molar ratio of 1-ethyl-3-methylimidazolium chloride to aluminum trichloride is 1: 1.4;
  • the button cell is assembled in the following order: the graphitized expanded graphite positive electrode film prepared in the above (2) is placed in the positive electrode case (CR2025); and the one layer of the glass fiber separator is placed on the graphitized expanded graphite positive electrode film. (Whatman), add an appropriate amount of 1:1.4 electrolyte; then place the negative aluminum sheet on the glass fiber diaphragm (Whatman), align and compact, cover the negative shell, and finally use the button battery packaging machine.
  • the above-mentioned assembled button battery was subjected to a 5 A/g constant current charge and discharge test, and it was found that the capacity of the button-type aluminum ion battery of the graphitized expanded graphite positive electrode can be maintained at 93 mAh/g. As shown in Figure 6.
  • the molar ratio of 1-ethyl-3-methylimidazolium chloride to aluminum trichloride is 1: 1.6;
  • the button battery is assembled in the following order: the expanded graphite positive electrode film prepared in the above (1) is placed in the positive electrode case (CR2025); and the first layer of the glass fiber separator (Whatman) is placed on the expanded graphite positive electrode film.
  • An appropriate amount of an electrolyte solution having a mixing ratio of 1:1.3 was added dropwise; then a negative aluminum foil was placed on a glass fiber separator (Whatman), aligned and compacted, covered with a negative electrode can, and finally packaged using a button cell packaging machine.
  • the button cell is assembled in the following order: the expanded graphite positive electrode film prepared in the above (1) is placed in the positive electrode shell (CR2025); on the expanded graphite positive electrode film, a 3-layer glass fiber separator (Whatman) is placed, An appropriate amount of an electrolyte solution having a mixing ratio of 1:1.8 was added dropwise; then, a negative electrode aluminum piece was placed on a glass fiber separator (Whatman), aligned and compacted, covered with a negative electrode case, and finally packaged using a button cell packaging machine.
  • the button cell is assembled in the following order: the graphitized expanded graphite positive electrode film prepared in the above (2) is placed in the positive electrode case (CR2025); and the one layer of the glass fiber separator is placed on the graphitized expanded graphite positive electrode film. (Whatman), add an appropriate amount of 1:1.0 electrolyte; then place the negative aluminum foil on the glass fiber diaphragm (Whatman), align and compact, cover the negative shell, and finally use the button battery packer.
  • the button cell is assembled in the following order: the graphitized expanded graphite positive electrode film prepared in the above (2) is placed in the positive electrode shell (CR2025); and the four-layer glass fiber separator is placed on the graphitized expanded graphite positive electrode film. (Whatman), add an appropriate amount of 1:1.5 electrolyte; then place the negative aluminum sheet on the glass fiber diaphragm (Whatman), align and compact, cover the negative shell, and finally use the button battery packer.
  • the above-mentioned assembled button battery was subjected to a 5 A/g constant current charge and discharge test, and it was found that the capacity of the high performance button type aluminum ion battery of the graphitized expanded graphite positive electrode can be maintained at 98 mAh/g.

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Abstract

本发明公开了一种铝电池，该电池正极为膨胀石墨膜。使用1-乙基-3-甲基咪唑氯化物与三氯化铝的混合物或三乙胺盐酸盐与三氯化铝的混合物为电解液；按照无集流体的原则组装扣式和软包电池。本发明所采用的膨胀石墨价格低廉，方便电极成型，极大的降低动力电池的成本。同时，膨胀石墨正极材料，还可以极大提高动力电池的比容量和倍率性能，有潜力取代动力锂离子电池。

Description

一种铝电池 技术领域
本发明属于新型电池领域，涉及一种铝电池。
背景技术
随着应对全球气候变化的《巴黎协定》的签署，世界各国都在致力于节能减排。欧洲、美国相继推出了严格的燃油汽车排放标准以及新能源汽车的补贴政策，中国政府也在积极推动新能源汽车的发展。受政策驱动，自2015年以来，世界各大汽车制造商都加速推出了各自品牌的电动汽车，其中特斯拉Model3广受关注。
作为驱动电动汽车的动力锂离子电池，主要是由镍钴锰三元材料、磷酸铁锂作为正极材料，碳酸烯类酯作为电解液主要溶剂。动力锂离子电池充放电能力通常会高达1.5A/g以上，实际使用过程中约0.5A/g左右，以满足电动汽车的驱动需求。目前动力锂离子电池的能量密度在120-220Wh/kg之间，电池组能量密度约100Wh/kg。动力锂离子电池主要存在的问题是：(1)正极材料的容量一直保持在150mAh/g左右，目前技术很难有所突破；(2)正极材料的价格一直居高不下，限制电动汽车的推广普及；(3)在大电流充放过程中，正极材料的稳定性差，同时由于采用碳酸烯类酯作为电解液主要溶剂，电池的安全性大大降低，目前电动汽车的电池爆燃事故时有报道。
斯坦福大学戴宏杰教授研究了一种以热解石墨为正极、金属铝为负极、离子液体为电解质的铝离子电池，具有超快的充放电能力，可以在4A/g的电流密度下连续充放电，容量保持60mAh/g左右。经过计算，其能量密度达到40Wh/kg，与铅酸、镍氢电池能量密度相当；其功率密度达到3kW/kg，与超级电容器的功率密度相近。另外，由于铝离子电池使用了离子液体作为电解质，电池的安全性大大提高，可以避免锂离子电池使用过程中出现的燃烧爆炸事故。但是，热解石墨正极材料是通过甲烷气体在泡沫镍上发生化学气相沉积方法制备的，热解石墨沉积完成后还需要将泡沫镍用盐酸除去，整个工艺流程复杂，不易工业化。
在动力锂离子电池的组装过程中，通常是使用铝箔作为正极材料的集流体。在戴宏杰教授研究的铝离子电池中，则使用玻璃碳作为热解石墨正极材料的集流体。集流体的主要作用是降低电池的内阻。
发明内容
本发明的目的是，提供一种无集流体正极的铝电池，解决现有铝离子电池正电极制备工艺复杂的问题，同时省去了正极集流体，提高了铝离子电池的比容量和倍率性能。
本发明所采用的技术方案如下：
一种无集流体正极的铝电池，正极为无集流体的、自支撑的膨胀石墨膜，电解液为1-乙基-3-甲基咪唑氯化物与三氯化铝按照摩尔比1:1.0～1:1.6组成的混合物；所述无集流体的、自支撑的膨胀石墨膜由膨胀石墨经1-30MPa的压力压制成膜，在扣式电池中与正极壳直接接触，在软包电池中通过导电胶与极耳直接相连。
进一步地，所述正极与负极之间具有隔膜，所述隔膜由1-5层的玻璃纤维构成。
进一步地，所述负极为铝箔、铝片等。
有益效果在于：膨胀石墨价格低廉，方便电极成型，压制成膜的正电极还可以省去电池组装过程中的集流体，极大的降低动力电池的成本。同时，膨胀石墨正极材料，还可以极大提高动力电池的比容量和倍率性能，有潜力取代动力锂离子电池。
一种高石墨化度正极的铝离子电池，正极为高石墨化度的膨胀石墨膜，电解液为1-乙基-3-甲基咪唑氯化物与三氯化铝按照摩尔比1:1.0～1:1.6组成的混合物；所述高石墨化度的膨胀石墨膜由膨胀石墨经2000-3000℃温度下保温5分钟-10小时后，再经1.5-35MPa的压力压制成膜。
进一步地，所述正极与负极之间具有隔膜，所述隔膜由1-6层的玻璃纤维构成。
进一步地，所述负极为铝箔、铝片等。
有益效果在于：经高温石墨化处理的膨胀石墨，可以除去膨胀石墨中原有的非碳杂原子，提高膨胀石墨的石墨化度。石墨化膨胀石墨作为铝离子电池正极材料，与热解石墨正极材料、石墨烯气凝胶正极材料相比，不仅价格低廉，电极成型工艺简单，而且具有很好的电池比容量和倍率性能，有利于铝离子电池的商业化应用。
一种低成本铝离子电池，正极为自支撑的膨胀石墨膜，电解液为三乙胺盐酸盐与三氯化铝按照摩尔比1:1.0～1:1.8组成的混合物；所述自支撑的膨胀石墨膜由膨胀石墨经1-35MPa的压力压制成膜。
进一步地，所述正极与负极之间具有隔膜，所述隔膜由1-5层的玻璃纤维构成。
进一步地，所述负极为铝箔、铝片等。
有益效果在于：膨胀石墨价格低，方便铝离子电池电极成型；三乙胺盐酸盐作为铝离子电池电解质，价格相对便宜；使用膨胀石墨和三乙胺盐酸盐体系的铝离子电池具有较高的电池比容量和倍率性能，性价比高。
一种高性能铝离子电池，正极为自支撑的膨胀石墨膜，电解液为三乙胺盐酸盐与三氯化铝按照摩尔比1:1.0～1:1.8组成的混合物；所述自支撑的膨胀石墨膜由膨胀石墨经2000-3000℃温度下保温5分钟-12小时后，再经1-30MPa的压力压制成膜。
进一步地，所述正极与负极之间具有隔膜，所述隔膜由1-6层的玻璃纤维构成。
进一步地，所述负极为铝箔、铝片等。
有益效果在于：经高温石墨化处理的膨胀石墨，可以提高膨胀石墨的石墨化度，增加铝离子电池材料的活性位，从而提高电池的容量。使用石墨化膨胀石墨与三乙胺盐酸盐体系的铝离子电池具有较高的电池比容量和倍率性能，材料制备工艺简单，价格相对便宜。
附图说明
图1是实施例1制备的无集流体膨胀石墨正极的扣式电池的循环性能图。
图2是实施例2制备的无集流体膨胀石墨正极的扣式电池的循环性能图。
图3是实施例3制备的无集流体膨胀石墨正极的软包电池的循环性能图。
图4是实施例4中膨胀石墨经2500℃石墨化处理前后的拉曼光谱图。
图5是实施例4制备的、石墨化膨胀石墨正极的扣式铝离子电池的循环性能图。
图6是实施例5制备的、石墨化膨胀石墨正极的扣式铝离子电池的循环性能图。
图7是实施例6制备的、石墨化膨胀石墨正极的软包铝离子电池的循环性能图。
图8是实施例7制备的低成本扣式铝离子电池的循环性能图。
图9是实施例10制备的高性能扣式铝离子电池的循环性能图。
具体实施方式
下面结合实施例，对本发明做进一步阐述。
应注意，此处实施例仅用于说明本发明，而不是限制本发明的范围。
还应注意，在阅读本发明的内容后，本领域技术人员对本发明所做的各种改动和修改，这些等价形式同样属于本发明权利要求书的限定范围。
实施例1：
(1)使用1MPa的压力将商业膨胀石墨压制成膜，作为正极；
(2)使用5层玻璃纤维(Whatman)作为正极与负极铝箔之间的隔膜；
(3)使用三氯化铝与1-乙基-3-甲基咪唑氯化物的混合物为电解液，1-乙基-3-甲基咪唑氯化物与三氯化铝混合摩尔比为1:1.0；
(4)按照以下顺序装配扣式电池：在正极壳(CR2025)中放入上述(1)中制备的膨胀石墨正极膜，两者直接接触；接着在膨胀石墨正极膜上，放5层的玻璃纤维隔膜(Whatman)，滴加适量的混合比例1:1.0的电解液；然后在玻璃纤维隔膜(Whatman)上放负极铝箔，对齐压实，盖上负极壳，最后使用扣式电池封装机封装。
使用蓝电测试系统，对上述组装的扣式电池进行5A/g恒流充放电实验，发现这种无集流体膨胀石墨正极的扣式电池的容量可以保持在70mAh/g。如图1所示。
实施例2：
(1)使用20MPa的压力将商业膨胀石墨压制成膜，作为正极；
(2)使用3层玻璃纤维(Whatman)作为正极与负极铝片之间的隔膜；
(3)使用三氯化铝与1-乙基-3-甲基咪唑氯化物的混合物为电解液，1-乙基-3-甲基咪唑氯化物与三氯化铝混合摩尔比为1:1.4；
(4)按照以下顺序装配扣式电池：在正极壳(CR2025)中放入上述(1)中制备的膨胀石墨正极膜，两者直接接触；接着在膨胀石墨正极膜上，放3层的玻璃纤维隔膜(Whatman)，滴加适量的混合比例1:1.4的电解液；然后在玻璃纤维隔膜(Whatman)上放负极铝片，对齐压实，盖上负极壳，最后使用扣式电池封装机封装。
使用蓝电测试系统，对上述组装的扣式电池进行5A/g恒流充放电实验，发现这种无集流体膨胀石墨正极的扣式电池的容量可以保持在80mAh/g。如图2所示。
实施例3：
(1)使用30MPa的压力将商业膨胀石墨压制成膜，作为正极；
(2)使用1层玻璃纤维(Whatman)作为正极与负极铝箔之间的隔膜；
(3)使用三氯化铝与1-乙基-3-甲基咪唑氯化物的混合物为电解液，1-乙基-3-甲基咪唑氯化物与三氯化铝混合摩尔比为1:1.6；
(4)按照以下顺序装配软包电池：使用导电胶将上述(1)中制备的膨胀石墨正极膜与镍极耳直接相连，作为软包电池的正极；以铝箔直接作为软包电池的负极；在膨胀石墨正极膜与铝箔负极之间，放置1层的玻璃纤维隔膜(Whatman)，对齐固定，放入软包电池袋中，加入适量的混合比例1:1.6的电解液，最后使用软包电池封装机封装。
使用蓝电测试系统，对上述组装的软包电池进行5A/g恒流充放电实验，发现这种无集流体膨胀石墨正极的软包电池的容量可以保持在85mAh/g。如图3所示。
实施例4：
(1)将商业膨胀石墨放入高温石墨化炉，在2500℃温度下保温5分钟，如图4所示，膨胀石墨经2500℃高温处理后，石墨化度大幅提高；
(2)使用1.5MPa的压力将上述经石墨化处理的膨胀石墨压制成膜，作为正极；
(3)使用4层的玻璃纤维(Whatman)作为正极与负极铝箔之间的隔膜；
(4)使用三氯化铝与1-乙基-3-甲基咪唑氯化物的混合物为电解液，1-乙基-3-甲基咪唑氯化物与三氯化铝混合摩尔比为1:1.0；
(5)按照以下顺序装配扣式电池：在正极壳(CR2025)中放入上述(2)中制备的石墨化膨胀石墨正极膜；在石墨化膨胀石墨正极膜上，放4层的玻璃纤维隔膜(Whatman)，滴加适量的混合比例1:1.0的电解液；然后在玻璃纤维隔膜(Whatman)上放负极铝箔，对齐压实，盖上负极壳，最后使用扣式电池封装机封装。
使用蓝电测试系统，对上述组装的扣式电池进行5A/g恒流充放电实验，发现这种石墨化膨胀石墨正极的扣式铝离子电池的容量可以保持在92mAh/g。如图5所示。
实施例5：
(1)使用15MPa的压力将商业膨胀石墨压制成膜；
(2)将上述(1)中压制的膨胀石墨膜放入高温石墨化炉，在2000℃温度下保温2小时,得到石墨化膨胀石墨膜，作为正极；
(3)使用1层的玻璃纤维(Whatman)作为正极与负极铝片之间的隔膜；
(4)使用三氯化铝与1-乙基-3-甲基咪唑氯化物的混合物为电解液，1-乙基 -3-甲基咪唑氯化物与三氯化铝混合摩尔比为1:1.4；
(5)按照以下顺序装配扣式电池：在正极壳(CR2025)中放入上述(2)中制备的石墨化膨胀石墨正极膜；在石墨化膨胀石墨正极膜上，放1层的玻璃纤维隔膜(Whatman)，滴加适量的混合比例1:1.4的电解液；然后在玻璃纤维隔膜(Whatman)上放负极铝片，对齐压实，盖上负极壳，最后使用扣式电池封装机封装。
使用蓝电测试系统，对上述组装的扣式电池进行5A/g恒流充放电实验，发现这种石墨化膨胀石墨正极的扣式铝离子电池的容量可以保持在93mAh/g。如图6所示。
实施例6：
(1)将商业膨胀石墨放入高温石墨化炉，在3000℃温度下保温10小时；
(2)使用35MPa的压力将上述经石墨化处理的膨胀石墨压制成膜，作为正极；
(3)使用6层的玻璃纤维(Whatman)作为正极与负极铝箔之间的隔膜；
(4)使用三氯化铝与1-乙基-3-甲基咪唑氯化物的混合物为电解液，1-乙基-3-甲基咪唑氯化物与三氯化铝混合摩尔比为1:1.6；
(5)按照以下顺序装配软包电池：使用上述(2)中制备的石墨化膨胀石墨正极膜，作为软包电池的正极；以铝箔作为软包电池的负极；在石墨化膨胀石墨正极膜与铝箔负极之间，放置6层的玻璃纤维隔膜(Whatman)，对齐固定，放入软包电池袋中，加入适量的混合比例1:1.6的电解液，最后使用软包电池封装机封装。
使用蓝电测试系统，对上述组装的软包电池进行5A/g恒流充放电实验，发现这种石墨化膨胀石墨正极的软包铝离子电池的容量可以保持在88mAh/g。如图7所示。
实施例7：
(1)使用15MPa的压力将商业膨胀石墨压制成膜，作为正极；
(2)使用1层的玻璃纤维(Whatman)作为正极与负极铝箔之间的隔膜；
(3)使用三氯化铝与三乙胺盐酸盐的混合物为电解液，三乙胺盐酸盐与三氯化铝的混合摩尔比为1:1.3；
(4)按照以下顺序装配扣式电池：在正极壳(CR2025)中放入上述(1)中制备的膨胀石墨正极膜；在膨胀石墨正极膜上，放1层的玻璃纤维隔膜(Whatman)，滴加适量的混合比例1:1.3的电解液；然后在玻璃纤维隔膜(Whatman)上放负极铝箔，对齐压实，盖上负极壳，最后使用扣式电池封装机 封装。
使用蓝电测试系统，对上述组装的扣式电池进行5A/g恒流充放电实验，发现这种低成本扣式铝离子电池的容量可以保持在110mAh/g。如图8所示。
实施例8：
(1)使用35MPa的压力将商业膨胀石墨压制成膜，作为正极；
(2)使用3层的玻璃纤维(Whatman)作为正极与负极铝片之间的隔膜；
(3)使用三氯化铝与三乙胺盐酸盐的混合物为电解液，三乙胺盐酸盐与三氯化铝的混合摩尔比为1:1.8；
(4)按照以下顺序装配扣式电池：在正极壳(CR2025)中放入上述(1)中制备的膨胀石墨正极膜；在膨胀石墨正极膜上，放3层的玻璃纤维隔膜(Whatman)，滴加适量的混合比例1:1.8的电解液；然后在玻璃纤维隔膜(Whatman)上放负极铝片，对齐压实，盖上负极壳，最后使用扣式电池封装机封装。
使用蓝电测试系统，对上述组装的扣式电池进行5A/g恒流充放电实验，发现这种低成本扣式铝离子电池的容量可以保持在105mAh/g。
实施例9：
(1)使用1MPa的压力将商业膨胀石墨压制成膜，作为正极；
(2)使用5层的玻璃纤维(Whatman)作为正极与负极铝箔之间的隔膜；
(3)使用三氯化铝与三乙胺盐酸盐的混合物为电解液，三乙胺盐酸盐与三氯化铝的混合摩尔比为1:1.0；
(4)按照以下顺序装配软包电池：使用上述(1)中制备的膨胀石墨正极膜，作为软包电池的正极；以铝箔作为软包电池的负极；在膨胀石墨正极膜与铝箔负极之间，放置5层的玻璃纤维隔膜(Whatman)，对齐固定，放入软包电池袋中，加入适量的混合比例1:1.0的电解液，最后使用软包电池封装机封装。
使用蓝电测试系统，对上述组装的软包电池进行5A/g恒流充放电实验，发现这种低成本软包铝离子电池的容量可以保持在108mAh/g。
实施例10：
(1)将商业膨胀石墨放入高温石墨化炉，在2600℃温度下保温5分钟；
(2)使用1MPa的压力将上述经石墨化处理的膨胀石墨压制成膜，作为正极；
(3)使用1层的玻璃纤维(Whatman)作为正极与负极铝箔之间的隔膜；
(4)使用三氯化铝与三乙胺盐酸盐的混合物为电解液，三乙胺盐酸盐与三氯化铝的混合摩尔比为1:1.0；
(5)按照以下顺序装配扣式电池：在正极壳(CR2025)中放入上述(2)中制备的石墨化膨胀石墨正极膜；在石墨化膨胀石墨正极膜上，放1层的玻璃纤维隔膜(Whatman)，滴加适量的混合比例1:1.0的电解液；然后在玻璃纤维隔膜(Whatman)上放负极铝箔，对齐压实，盖上负极壳，最后使用扣式电池封装机封装。
使用蓝电测试系统，对上述组装的扣式电池进行5A/g恒流充放电实验，发现这种石墨化膨胀石墨正极的高性能扣式铝离子电池的容量可以保持在100mAh/g。如图9所示。
实施例11：
(1)使用12MPa的压力将商业膨胀石墨压制成膜，；
(2)将上述(1)中压制的膨胀石墨膜放入高温石墨化炉，在2000℃温度下保温12小时,得到石墨化膨胀石墨膜，作为正极；
(3)使用4层的玻璃纤维(Whatman)作为正极与负极铝片之间的隔膜；
(4)使用三氯化铝与三乙胺盐酸盐的混合物为电解液，三乙胺盐酸盐与三氯化铝的混合摩尔比为1:1.5；
(5)按照以下顺序装配扣式电池：在正极壳(CR2025)中放入上述(2)中制备的石墨化膨胀石墨正极膜；在石墨化膨胀石墨正极膜上，放4层的玻璃纤维隔膜(Whatman)，滴加适量的混合比例1:1.5的电解液；然后在玻璃纤维隔膜(Whatman)上放负极铝片，对齐压实，盖上负极壳，最后使用扣式电池封装机封装。
使用蓝电测试系统，对上述组装的扣式电池进行5A/g恒流充放电实验，发现这种石墨化膨胀石墨正极的高性能扣式铝离子电池的容量可以保持在98mAh/g。
实施例12：
(1)将商业膨胀石墨放入高温石墨化炉，在3000℃温度下保温2小时；
(2)使用30MPa的压力将上述经石墨化处理的膨胀石墨压制成膜，作为正极；
(3)使用6层的玻璃纤维(Whatman)作为正极与负极铝箔之间的隔膜；
(4)使用三氯化铝与三乙胺盐酸盐的混合物为电解液，三乙胺盐酸盐与三氯化铝的混合摩尔比为1:1.8；
(5)按照以下顺序装配软包电池：使用上述(2)中制备的石墨化膨胀石墨正极膜，作为软包电池的正极；以铝箔作为软包电池的负极；在石墨化膨胀石墨正极膜与铝箔负极之间，放置6层的玻璃纤维隔膜(Whatman)，对齐固定， 放入软包电池袋中，加入适量的混合比例1:1.8的电解液，最后使用软包电池封装机封装。
使用蓝电测试系统，对上述组装的软包电池进行5A/g恒流充放电实验，发现这种石墨化膨胀石墨正极的高性能软包铝离子电池的容量可以保持在96mAh/g。

Claims (12)

  1. 一种无集流体正极的铝电池，其特征在于，正极为无集流体的、自支撑的膨胀石墨膜，电解液为1-乙基-3-甲基咪唑氯化物与三氯化铝按照摩尔比1:1.0～1:1.6组成的混合物；所述无集流体的、自支撑的膨胀石墨膜由膨胀石墨经1-30MPa的压力压制成膜，在扣式电池中与正极壳直接接触，在软包电池中通过导电胶与极耳直接相连。
  2. 根据权利要求1所述的铝电池，其特征在于，所述正极与负极之间具有隔膜，所述隔膜由1-5层的玻璃纤维构成。
  3. 根据权利要求1所述的铝电池，其特征在于，所述负极为铝箔、铝片。
  4. 一种高石墨化度正极的铝离子电池，其特征在于，正极为高石墨化度的膨胀石墨膜，电解液为1-乙基-3-甲基咪唑氯化物与三氯化铝按照摩尔比1:1.0～1:1.6组成的混合物；所述高石墨化度的膨胀石墨膜由膨胀石墨经2000-3000℃温度下保温5分钟-10小时后，再经1.5-35MPa的压力压制成膜。
  5. 根据权利要求4所述的铝电池，其特征在于，所述正极与负极之间具有隔膜，所述隔膜由1-6层的玻璃纤维构成。
  6. 根据权利要求4所述的铝电池，其特征在于，所述负极为铝箔、铝片。
  7. 一种低成本铝离子电池，其特征在于，正极为自支撑的膨胀石墨膜，电解液为三乙胺盐酸盐与三氯化铝按照摩尔比1:1.0～1:1.8组成的混合物；所述自支撑的膨胀石墨膜由膨胀石墨经1-35MPa的压力压制成膜。
  8. 根据权利要求7所述的铝离子电池，其特征在于，所述正极与负极之间具有隔膜，所述隔膜由1-5层的玻璃纤维构成。
  9. 根据权利要求7所述的铝离子电池，其特征在于，所述负极为铝箔、铝片。
  10. 一种高性能铝离子电池，其特征在于，正极为自支撑的膨胀石墨膜，电解液为三乙胺盐酸盐与三氯化铝按照摩尔比1:1.0～1:1.8组成的混合物；所述自支撑的膨胀石墨膜由膨胀石墨经2000-3000℃温度下保温5分钟-12小时后，再经1-30MPa的压力压制成膜。
  11. 根据权利要求10所述的铝离子电池，其特征在于，所述正极与负极之间具有隔膜，所述隔膜由1-6层的玻璃纤维构成。
  12. 根据权利要求10所述的铝离子电池，其特征在于，所述负极为铝箔、铝片。
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014222609A (ja) * 2013-05-13 2014-11-27 学校法人 関西大学 アルミニウム二次電池
CN104810544A (zh) * 2015-04-20 2015-07-29 北京科技大学 一种可充电铝离子电池及其制备方法
CN105810947A (zh) * 2016-04-29 2016-07-27 深圳博磊达新能源科技有限公司 一种铝离子电池正极材料、电极及铝离子电池
CN105977526A (zh) * 2016-06-15 2016-09-28 昆明理工大学 一种可充电铝碳电池及其制备方法
CN106887637A (zh) * 2015-12-15 2017-06-23 中国科学院苏州纳米技术与纳米仿生研究所 自支撑铝离子电池及其制备方法
CN107464932A (zh) * 2017-08-11 2017-12-12 杭州高烯科技有限公司 一种低成本铝离子电池
CN107482219A (zh) * 2017-08-11 2017-12-15 杭州高烯科技有限公司 一种高性能铝离子电池
CN107492631A (zh) * 2017-08-11 2017-12-19 杭州高烯科技有限公司 一种无集流体正极的铝电池
CN107546390A (zh) * 2017-08-11 2018-01-05 杭州高烯科技有限公司 一种高石墨化度正极的铝离子电池

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014222609A (ja) * 2013-05-13 2014-11-27 学校法人 関西大学 アルミニウム二次電池
CN104810544A (zh) * 2015-04-20 2015-07-29 北京科技大学 一种可充电铝离子电池及其制备方法
CN106887637A (zh) * 2015-12-15 2017-06-23 中国科学院苏州纳米技术与纳米仿生研究所 自支撑铝离子电池及其制备方法
CN105810947A (zh) * 2016-04-29 2016-07-27 深圳博磊达新能源科技有限公司 一种铝离子电池正极材料、电极及铝离子电池
CN105977526A (zh) * 2016-06-15 2016-09-28 昆明理工大学 一种可充电铝碳电池及其制备方法
CN107464932A (zh) * 2017-08-11 2017-12-12 杭州高烯科技有限公司 一种低成本铝离子电池
CN107482219A (zh) * 2017-08-11 2017-12-15 杭州高烯科技有限公司 一种高性能铝离子电池
CN107492631A (zh) * 2017-08-11 2017-12-19 杭州高烯科技有限公司 一种无集流体正极的铝电池
CN107546390A (zh) * 2017-08-11 2018-01-05 杭州高烯科技有限公司 一种高石墨化度正极的铝离子电池

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