WO2018170926A1 - 一种负极和隔膜一体化结构及其制备方法和电池 - Google Patents

一种负极和隔膜一体化结构及其制备方法和电池 Download PDF

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WO2018170926A1
WO2018170926A1 PCT/CN2017/078204 CN2017078204W WO2018170926A1 WO 2018170926 A1 WO2018170926 A1 WO 2018170926A1 CN 2017078204 W CN2017078204 W CN 2017078204W WO 2018170926 A1 WO2018170926 A1 WO 2018170926A1
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aluminum
negative electrode
alloy foil
integrated structure
aluminum alloy
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PCT/CN2017/078204
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English (en)
French (fr)
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唐永炳
秦盼盼
王蒙
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深圳先进技术研究院
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    • 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

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  • the invention relates to the technical field of secondary batteries, in particular to an integrated structure of a negative electrode and a diaphragm, a preparation method thereof and a battery.
  • the secondary battery is widely used in various portable electronic devices because it can be repeatedly charged and discharged, can greatly reduce the use cost, and has less environmental pollution.
  • a commercial secondary battery often uses a graphite-based material as a negative electrode, and a copper foil serves as a negative electrode current collector and a polyolefin-based material as a separator.
  • a battery structure hinders the improvement of the energy density of the secondary lithium ion battery, simplifies the production process, and reduces the cost.
  • the theoretical specific capacity of the graphite negative electrode is low (372 mAh g -1 ), and the compacted density is low, which is not conducive to increasing the energy density of the battery; the negative active material needs to be composited with a binder, a conductive carbon black, and the like.
  • the production process is cumbersome, and the negative active material and the current collector are easy to fall off; the polyolefin diaphragm material used at the present stage is poor in thermal stability and mechanical properties, and is prone to thermal runaway and puncture, resulting in A certain security risk.
  • the present invention provides an integrated structure of a negative electrode and a diaphragm, which can effectively reduce the volume and weight of the battery, simplify the production process, increase the overall capacity and energy density of the battery, and improve the high rate performance of the battery. And high temperature performance for improved safety.
  • the present invention provides an integrated structure of a negative electrode and a diaphragm, including aluminum or aluminum An alloy foil, and an aluminum oxide layer formed on the surface of the aluminum or aluminum alloy foil, which simultaneously serves as a negative electrode current collector and a negative electrode active material, the aluminum oxide layer serving as a separator.
  • the aluminum oxide layer may be formed on one side surface of the aluminum or aluminum alloy foil, or may be formed on the entire surface of the aluminum or aluminum alloy foil, depending on the specific application.
  • one electrode unit When formed on one side surface, one electrode unit may be formed with the positive electrode to form a button type battery or the like; when formed on the entire surface, a plurality of stacked electrode units may be formed with the positive electrode to form a wound type commercial battery or the like.
  • the aluminum oxide layer has a porous structure, and the porous pores have a pore diameter of 10 to 3000 nm and a porosity of 85% or less. Further, the porous pores have a pore diameter of 200 to 1000 nm and a porosity of 10% to 85%.
  • the porous structure of the aluminum oxide layer facilitates the alloying reaction of the metal ions in the electrolyte with the aluminum or aluminum alloy foil.
  • the thickness of the aluminum oxide layer is 10% to 200% of the thickness of the aluminum or aluminum alloy foil; the thickness of the aluminum oxide layer is 5 to 50 ⁇ m.
  • the suitable thickness of the aluminum oxide layer can ensure good mechanical properties, prevent the occurrence of puncture, and ensure that the electrons of the positive and negative electrodes are short-circuited and the ions are turned on.
  • the aluminum or aluminum alloy foil has a thickness of 10 to 200 ⁇ m, and further, the thickness may be 50 to 200 ⁇ m. A suitable thickness ensures that it functions as both a negative current collector and a negative active material.
  • the aluminum or aluminum alloy foil is a dense aluminum or aluminum alloy foil or a porous aluminum or aluminum alloy foil.
  • the aluminum alloy foil may be an aluminum-copper alloy foil, an aluminum-manganese alloy foil, an aluminum-magnesium alloy foil, an aluminum-silicon alloy foil, or the like.
  • the integrated structure of the negative electrode and the separator provided by the first aspect of the present invention can significantly reduce the weight and volume of the battery by integrating the negative electrode current collector, the negative electrode active material and the separator, and is beneficial to increasing the proportion of active materials in the battery. Improve the energy density of the battery; help to simplify the battery production process and reduce the cost; the aluminum oxide layer in the structure acts as a diaphragm, has excellent mechanical strength, can effectively prevent the occurrence of thermal runaway and puncture, and improve the safety performance of the battery; When the integrated structure is applied to the battery system, the metal aluminum realizes the battery reaction by alloying/de-alloying, and has higher specific volume than the conventional graphite material. the amount.
  • the present invention provides a method for preparing an integrated structure of a negative electrode and a separator, comprising the following steps:
  • the aluminum or aluminum alloy foil simultaneously serving as a negative current collector and a negative active material
  • the organic polymer film coated on one side of the aluminum or aluminum alloy foil is removed by calcination under an inert atmosphere or by chemical dissolution to obtain an integrated structure of the negative electrode and the separator.
  • the aluminum or aluminum alloy foil has a thickness of 10 to 600 ⁇ m, and further, the thickness may be 50 to 200 ⁇ m.
  • the aluminum or aluminum alloy foil is a dense aluminum or aluminum alloy foil, or a porous aluminum or aluminum alloy foil, and the aluminum or aluminum alloy foil has a porosity of 0-85%.
  • the organic polymer solution comprises one or more of the following organic polymers: polyacrylonitrile, polyvinylidene fluoride, polyacrylic acid, polyurethane, polyvinyl butyral, polytetrafluoroethylene, polyurethane, polyethylene, Polypropylene, polymethylpyrrolidone, polyvinyl chloride, polysulfone, polyethersulfone, polyethylene oxide, polymethyl methacrylate, polyvinylidene fluoride-hexafluoropropylene, polyoxypropylene, polyvinyl acetal, poly Vinyl pyrrolidone, sulfonylurea polymer, polyphenylenesulfone sulfonic acid polymer, polyethylene oxide, styrene butadiene rubber, polybutadiene, polyvinyl chloride, polystyrene, acrylate, chitosan, polyethylene Alcohol, polyvinyl butyral, polyethylene glycol, polyether acrylate, phosphat
  • the organic solvent in the organic polymer solution includes methanol, ethanol, ethylene glycol, acetone, dimethylformamide, propylene glycol methyl ether, propylene carbonate, ethylene carbonate, dimethyl carbonate, dipropyl carbonate , Ethyl propyl carbonate, vinylene carbonate, ethyl isopropyl carbonate, methylbutyl carbonate, dibutyl carbonate, ethyl butyl carbonate, ethyl methyl carbonate, diethyl carbonate, ⁇ -butyrolactone and N- One of methyl pyrrolidone Or a plurality of; the organic polymer solution has a mass concentration of 0.1 to 100 mg/mL.
  • the anodic oxidation includes constant voltage anodization or constant current anodization, the voltage of the constant voltage anodization is 5 to 200 V, and further may be 10 to 40 V; and the current of the constant current anodization is 0.01 to 6 A cm -2 .
  • the anodic oxidation time is 0.1 to 240 min, and further may be 30 to 180 min.
  • the anodizing electrolyte is not particularly limited, and various well-known anodized electrolytes suitable for light metal materials can be used.
  • the electrolyte may be an electrolyte of an oxalate, phosphate or silicate system; the electrolyte of the phosphate system may be an aqueous solution containing a phosphate and a hydroxide; The electrolyte may be an aqueous solution containing a silicate and a hydroxide.
  • the temperature of the anodizing electrolyte is 0 to 40 ° C, and further preferably 1 to 25 ° C.
  • the gas used for the plasma oxidation is oxygen, the flow rate is 10-300 sccm, the power is 10-150 W, the time is 1-360 min, and the temperature is 25-400 °C.
  • the aluminum oxide layer may be an oxide layer of a dense structure or a porous structure having a pore diameter of 10 to 3000 nm and a porosity of 85% or less.
  • an anodizing method is adopted, and the process parameters are controlled, and an aluminum oxide layer having a porous structure can be obtained.
  • the porous pore size of the aluminum oxide layer is about several tens to A few hundred nanometers.
  • both anodization and plasma oxidation can be used to obtain an alumina layer having a porous structure, and the pore size is not much different from that of the aluminum or aluminum alloy foil substrate.
  • the porous inner wall is also coated with an organic polymer solution when the organic polymer solution is applied.
  • the chemical dissolution method may specifically be: treating the anodized aluminum or aluminum alloy foil in an organic solvent at a certain temperature for a period of time to dissolve the organic polymer film.
  • the organic solvent Including methanol, ethanol, ethylene glycol, acetone, dimethylformamide, propylene glycol methyl ether, propylene carbonate, ethylene carbonate, dimethyl carbonate, dipropyl carbonate, ethylene propyl carbonate, vinylene carbonate, carbonic acid
  • ethyl isopropyl ester methylbutyl carbonate, dibutyl carbonate, ethyl butyl carbonate, ethyl methyl carbonate, diethyl carbonate, ⁇ -butyrolactone, and N-methylpyrrolidone.
  • the temperature can be set according to the needs of different solvents.
  • the preparation method of the integrated structure of the negative electrode and the separator provided by the second aspect of the invention has the advantages of simple process, easy availability of raw materials, environmental friendliness, and is suitable for commercial production.
  • the present invention provides a battery comprising a positive electrode, an electrolyte, and a negative electrode and separator integrated structure according to the first aspect of the present invention, the positive electrode including a positive electrode current collector and a positive electrode current collector A positive active material layer on the positive electrode active material layer including a positive electrode active material.
  • the positive electrode is adjacent to the side of the aluminum oxide layer of the integrated structure of the negative electrode and the separator.
  • the positive electrode material includes LiCoO 2 , LiMnO 2 , LiNiO 2 , LiFeO 2 , LiFePO 4 , (Li(Ni x Co y Mn 1-xy )O 2 , Li(Ni x Co y Al 1-xy )O 2 ), One or more of Na 3 V 2 (PO 4 ) 2 F 3 , Na 2 FePO 4 F, natural graphite, expanded graphite, mesocarbon microbeads.
  • the electrolyte salt in the electrolyte includes one or more of a lithium salt, a sodium salt, a potassium salt, a calcium salt, and a magnesium salt.
  • the preparation process of the battery provided by the present invention may include the following steps:
  • Step 1 The integrated structure of the negative electrode and the separator is prepared according to the preparation method of the second aspect of the embodiment of the present invention.
  • Step 2 preparing a positive electrode of the battery: dispersing the positive electrode active material, the conductive agent, and the binder in a suitable ratio in a suitable solvent to form a positive electrode slurry; applying the positive electrode slurry to the surface of the positive electrode current collector, drying and then cutting Cut into the required size to obtain a positive electrode;
  • Step 3 Prepare the electrolyte: weigh the appropriate amount of electrolyte salt into a volume of solvent, stir well After dissolving, a certain amount of additives are selectively added, and the mixture is stirred evenly;
  • the electrolyte salt in the step 3 is one or more of a lithium salt, a sodium salt, a potassium salt, a calcium salt and a magnesium salt;
  • the solvent is one of an ester, a sulfone, an ether, a nitrile or an olefin.
  • the additive includes one or more of an organic additive such as an ester, a sulfone, an ether, a nitrile or an olefin.
  • steps 1-3 can be carried out simultaneously or in any order.
  • Step 4 Assembling the battery: stacking or winding the integrated structure of the positive electrode, the negative electrode and the separator of the battery in sequence under an inert gas or an anhydrous oxygen-free environment, and adding an appropriate amount of electrolyte to the battery. In the housing, the assembly of the battery is completed.
  • FIG. 1 is a schematic structural view of a porous aluminum foil according to an embodiment of the present invention.
  • FIG. 2 is a schematic structural view of an integrated structure of a negative electrode and a separator according to an embodiment of the present invention.
  • a method for preparing an integrated structure of a negative electrode and a separator comprises the following steps:
  • the heating temperature is 70-80 ° C
  • the polyacrylonitrile solution is solidified to form a polyacrylonitrile film
  • the glass piece is removed to obtain a porous aluminum foil coated with a polyacrylonitrile film on one side;
  • an aqueous solution of oxalic acid is used as an electrolyte (concentration: 0.3 mol/L)
  • a porous aluminum foil coated with a polyacrylonitrile film on one side is used as an anode
  • graphite is used as a cathode for constant voltage anodization.
  • the other side of the porous aluminum foil was oxidized to form an aluminum oxide layer, and the voltage of the anodization was 20 V for 60 minutes.
  • FIG. 2 is a schematic view showing an integrated structure of a negative electrode and a separator according to Embodiment 1 of the present invention; in the figure, 10 is an aluminum foil, 11 is a porous hole, and 20 is an aluminum oxide layer.
  • Example 2 The integrated structure of the negative electrode and the separator prepared in Example 1 of the present invention is cut into a disk having a diameter of 12 mm, and placed in a glove box as a battery negative electrode;
  • Examples 2-11 differ only in the materials and processing conditions in Step (1) and Step (2) in Example 1, and the anodizing treatment conditions in Step (3), steps The post-calcination treatment conditions in (4) were replaced with the same as in Table 1 and Table 2, and the other operations were the same as in Example 1.
  • Example 3 of the present invention The integrated structure of the negative electrode and the separator prepared in Example 3 of the present invention is cut into a disk having a diameter of 12 mm, and placed in a glove box as a battery negative electrode;
  • the integrated structure of the negative electrode and the diaphragm provided by the embodiment of the invention can effectively reduce the volume and weight of the battery, simplify the production process, increase the overall capacity and energy density of the battery, and improve the high rate performance and high temperature performance of the battery, and solve the present problem.
  • There are problems in the secondary battery production process large initial investment, poor battery safety performance, low energy density, and difficult design and assembly.

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Abstract

一种负极和隔膜一体化结构，包括铝或铝合金箔（10），以及形成在所述铝或铝合金箔表面的氧化铝层（20），所述铝或铝合金箔（10）同时充当负极集流体和负极活性材料，所述氧化铝层（20）充当隔膜。该一体化设计可有效减小电池的体积及重量，简化生产过程，增加电池的整体容量以及能量密度，同时提高电池的高倍率性能和高温性能，提高安全性，解决了现有二次电池生产工艺复杂、前期投入大、电池安全性能差、能量密度低、设计组装困难等问题。还提供了该负极和隔膜一体化结构的制备方法以及包含该一体化结构的电池。

Description

一种负极和隔膜一体化结构及其制备方法和电池 技术领域
本发明涉及二次电池技术领域，特别是涉及一种负极和隔膜一体化结构及其制备方法和电池。
背景技术
近年来，随着人口的不断增加，人们对能源的消耗及需求不断增长，寻找新型的能源供给方式及高效的能源存储方式成为当今社会的迫切需求。二次电池，因其可重复充放电，可以大幅度降低使用成本，并对环境污染小，而被广泛应用于各种便携式电子设备。
目前，商用二次电池多使用石墨类材料作为负极，铜箔作为负极集流体、聚烯烃类材料作为隔膜。然而，这样的电池结构对于提高二次锂离子电池的能量密度、简化生产工艺、降低成本存在阻碍。例如，石墨负极的理论比容量较低(372mAh g-1)，且压实密度低，不利于提高电池的能量密度；负极活性材料需要和粘结剂、导电炭黑等相复合，并涂覆在铜箔集流体上，生产工艺较为繁琐，且负极活性材料与集流体之间容易脱落；现阶段使用的聚烯烃隔膜材料热稳定及机械性能较差，容易发生热失控及穿刺现象，从而造成一定的安全隐患。
发明内容
鉴于此，本发明提供了一种负极和隔膜一体化结构，该一体化设计可有效减小电池的体积及重量，简化生产过程，增加电池的整体容量以及能量密度，同时提高电池的高倍率性能和高温性能，提高安全性。
具体地，第一方面，本发明提供了一种负极和隔膜一体化结构，包括铝或铝 合金箔，以及形成在所述铝或铝合金箔表面的氧化铝层，所述铝或铝合金箔同时充当负极集流体和负极活性材料，所述氧化铝层充当隔膜。
本发明实施方式中，根据具体的应用情况，所述氧化铝层可以是形成在所述铝或铝合金箔的一侧表面，也可以是形成在所述铝或铝合金箔的整个表面。当形成在一侧表面时，可与正极构成一个电极单元，制作成扣式电池等；当形成在整个表面时，可与正极形成多个叠加的电极单元，制作成卷绕式商用电池等。
所述氧化铝层具有多孔结构，所述多孔的孔径为10-3000nm，孔隙率小于等于85％。进一步地，所述多孔的孔径为200-1000nm，孔隙率为10％-85％。氧化铝层的多孔结构有利于电解液中的金属离子与铝或铝合金箔发生合金化反应。
所述氧化铝层的厚度为铝或铝合金箔厚度的10％-200％；所述氧化铝层的厚度为5-50μm。适合的氧化铝层厚度能够保证良好的机械性能，防止穿刺现象的产生，并确保正负极的电子短路，离子导通。
所述铝或铝合金箔的厚度为10-200μm，进一步地，厚度可为50-200μm。适合的厚度可保证其同时作为负极集流体和负极活性材料性能的发挥。
所述铝或铝合金箔为致密的铝或铝合金箔，或者为多孔的铝或铝合金箔。当所述铝或铝合金箔为多孔时，可有效缓解电池的膨胀效应，提高循环性能。所述铝合金箔可以是铝铜合金箔、铝锰合金箔、铝镁合金箔、铝硅合金箔等。
本发明第一方面提供的负极和隔膜一体化结构，通过将负极集流体、负极活性材料和隔膜进行一体化设计，可显著降低电池的重量和体积，有利于增加电池中的活性物质占比，提高电池能量密度；有利于简化电池生产工艺，降低成本；结构中的氧化铝层起到隔膜作用，具有优异的机械强度，可有效防止热失控及穿刺现象的产生，提高电池安全性能；将该一体化结构应用到电池体系时，金属铝通过合金化/去合金化实现电池反应，相对于传统石墨材料具有更高比容 量。
第二方面，本发明提供了一种负极和隔膜一体化结构的制备方法，包括以下步骤：
取铝或铝合金箔，所述铝或铝合金箔同时充当负极集流体和负极活性材料；
在所述铝或铝合金箔的一面涂覆有机聚合物溶液，待固化形成有机聚合物膜之后，采用阳极氧化或等离子体氧化的方式对所述铝或铝合金箔的另一面进行可控氧化，使所述铝或铝合金箔的另一面形成氧化铝层；
再在惰性气氛下煅烧或采用化学溶解的方法去掉包覆在所述铝或铝合金箔一面的所述有机聚合物膜，得到负极和隔膜一体化结构。
其中，所述铝或铝合金箔的厚度为10-600μm，进一步地，厚度可为50-200μm。所述铝或铝合金箔为致密的铝或铝合金箔，或者为多孔的铝或铝合金箔，铝或铝合金箔的孔隙率为0-85％。
所述有机聚合物溶液包含如下有机聚合物中的一种或多种：聚丙烯腈、聚偏氟乙烯、聚丙烯酸、聚氨酯、聚乙烯醇缩丁醛、聚四氟乙烯、聚氨酯、聚乙烯、聚丙烯，聚甲基吡咯烷酮，聚氯乙烯、聚砜、聚醚砜、聚氧化乙烯、聚甲基丙烯酸甲酯、聚偏氟乙烯-六氟丙烯、聚氧丙烯、聚乙烯醇缩醛、聚乙烯吡咯烷酮、磺脲聚合物、聚亚苯基砜磺酸聚合物、聚环氧乙烷、丁苯橡胶、聚丁二烯、聚氯乙烯、聚苯乙烯、丙烯酸酯、壳糖酸、聚乙烯醇、聚乙烯醇缩丁醛、聚乙二醇、聚醚丙烯酸乙二醇酯、磷酸酯类聚合物。
其中，所述有机聚合物溶液中的有机溶剂包括甲醇、乙醇、乙二醇、丙酮、二甲基甲酰胺、丙二醇甲醚、碳酸丙烯脂、碳酸乙烯脂、碳酸二甲脂、碳酸二丙酯、碳酸乙丙酯、碳酸亚乙烯酯、碳酸乙异丙酯、碳酸甲丁酯、碳酸二丁酯、碳酸乙丁酯、碳酸甲乙酯、碳酸二乙酯、γ-丁内酯和N-甲基吡咯烷酮中的一种 或多种；所述有机聚合物溶液的质量浓度为0.1-100mg/mL。
所述阳极氧化包括恒电压阳极氧化或恒电流阳极氧化，所述恒电压阳极氧化的电压为5～200V，进一步可为10～40V；所述恒电流阳极氧化的电流为0.01～6A cm-2，所述阳极氧化的时间为0.1～240min，进一步可为30～180min。
所述阳极氧化电解液没有特别的限制，可以使用各种公知的适合轻金属材料的阳极氧化的电解液。例如，所述电解液可以为草酸盐、磷酸盐或硅酸盐体系的电解液；所述磷酸盐体系的电解液可以为含有磷酸盐和氢氧化物的水溶液；所述硅酸盐体系的电解液可以为含有硅酸盐和氢氧化物的水溶液。所述的阳极氧化电解液的温度为0～40℃，进一步地可为1～25℃。
所述等离子体氧化所用气体为氧气，流量为10-300sccm，功率为10-150W，时间为1-360min，温度为25-400℃。
所述氧化铝层可以是致密结构的氧化层，也可以是具有多孔结构，所述多孔的孔径为10-3000nm，孔隙率小于等于85％。当铝或铝合金箔本身是致密结构时，使用阳极氧化的方式，并控制好工艺参数，可以获得具有多孔结构的氧化铝层，此种情况下，氧化铝层的多孔孔径约为几十到几百纳米。而当铝或铝合金箔本身具有多孔时，使用阳极氧化和等离子体氧化均能获得具有多孔结构的氧化铝层，多孔尺寸与铝或铝合金箔基底的孔尺寸相差不大。当铝或铝合金箔本身具有多孔时，在涂覆有机聚合物溶液时，使多孔内壁也附上一层有机聚合物溶液。
所述惰性气氛下煅烧，其中惰性气氛可以是氢气、氩气、氮气中的至少一种，煅烧温度可以是200-700℃，进一步地可以是300-650℃；煅烧时间可以是0.5-4小时。所述化学溶解的方法具体可以是，将经阳极氧化后的铝或铝合金箔置于一定温度下的有机溶剂中处理一段时间，使有机聚合物膜溶解。所述有机溶剂 包括甲醇、乙醇、乙二醇、丙酮、二甲基甲酰胺、丙二醇甲醚、碳酸丙烯脂、碳酸乙烯脂、碳酸二甲脂、碳酸二丙酯、碳酸乙丙酯、碳酸亚乙烯酯、碳酸乙异丙酯、碳酸甲丁酯、碳酸二丁酯、碳酸乙丁酯、碳酸甲乙酯、碳酸二乙酯、γ-丁内酯和N-甲基吡咯烷酮中的一种或多种。所述温度可根据不同溶剂的需要设定。
本发明第二方面提供的负极和隔膜一体化结构的制备方法，工艺简单，原料易得，环境友好，适于商业化生产。
第三方面，本发明提供了一种电池，包括正极，电解液，以及如本发明第一方面所述的负极和隔膜一体化结构，所述正极包括正极集流体和设置在所述正极集流体上的正极活性材料层，所述正极活性材料层包括正极活性材料。所述正极靠近所述负极和隔膜一体化结构的氧化铝层一侧。
所述正极材料包括LiCoO2、LiMnO2、LiNiO2、LiFeO2、LiFePO4、(Li(NixCoyMn1-x-y)O2、Li(NixCoyAl1-x-y)O2)、Na3V2(PO4)2F3、Na2FePO4F、天然石墨、膨胀石墨、中间相碳微球中的一种或多种。
所述电解液中的电解质盐包括锂盐、钠盐、钾盐、钙盐和镁盐中的一种或多种。
本发明上述提供的电池的制备过程可以包括如下步骤：
步骤1、按本发明实施例第二方面所述的制备方法制得负极和隔膜一体化结构；
步骤2、制备电池正极：将正极活性材料、导电剂、粘结剂按照合适比例分散于适当溶剂中，配置成正极浆料；将所述正极浆料涂覆于正极集流体表面，干燥后裁切成所需尺寸，得到正极；
步骤3、配制电解液：称取适量电解质盐加入到一定体积溶剂中，充分搅拌 溶解后，再选择性加入一定量添加剂，搅拌均匀后备用；
步骤3中所述电解质盐为锂盐、钠盐、钾盐、钙盐和镁盐中的一种或几种；溶剂为酯类、砜类、醚类、腈类、烯烃类中的一种或几种；添加剂包括酯类、砜类、醚类、腈类或烯烃类有机添加剂中的一种或几种。
步骤1-3的制备可以同时或者按照任意顺序执行。
步骤4、组装电池：在惰性气体或无水无氧环境下，将所述电池正极、负极和隔膜一体化结构依次堆叠或卷绕成电芯，滴加适量电解液，并封装于所述电池壳体内，完成电池的组装。
本发明的优点将会在下面的说明书中部分阐明，一部分根据说明书是显而易见的，或者可以通过本发明实施例的实施而获知。
附图说明
图1为本发明实施例的多孔铝箔的结构示意图；
图2为本发明实施例的负极和隔膜一体化结构的结构示意图。
具体实施方式
以下所述是本发明实施例的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明实施例原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也视为本发明实施例的保护范围。
实施例1
一种负极和隔膜一体化结构的制备方法，包括以下步骤：
(1)取一块玻璃片，采用丙酮超声清洗15min后，晾干备用；取孔隙率为85％的多孔铝箔(如图1所示)，采用乙醇和丙酮分别清洗10min后，晾干备 用。
(2)称取50mg聚丙烯腈(PAN)溶于10mL二甲基甲酰胺(DMF)中，然后加热到50℃，保持5min以上，使PAN完全溶解，得到聚丙烯腈溶液；取500μL上述聚丙烯腈溶液滴涂在玻璃基底上，待溶液均匀分散后，把多孔铝箔放置在上面，让聚丙烯腈溶液均匀浸没多孔铝箔(仅露出上表面)，晾干后，再将玻璃片连同多孔铝箔一同放在加热器上加热，加热温度为70～80℃，聚丙烯腈溶液固化形成聚丙烯腈膜后，移除玻璃片，得到一侧表面包覆有聚丙烯腈膜的多孔铝箔；
(3)在4℃下，以草酸水溶液做电解液(浓度0.3mol/L)，所述一侧表面包覆有聚丙烯腈膜的多孔铝箔为阳极，石墨为阴极进行恒电压阳极氧化，使所述多孔铝箔的另一面发生氧化生成氧化铝层，阳极氧化的电压为20V，时间为60min。
(4)在氢氩混合气氛围下，将阳极氧化过后的多孔铝箔在650℃下热处理3h，去除聚丙烯腈膜层，得到负极和隔膜一体化结构。
图2为本发明实施例1提供的负极和隔膜一体化结构的示意图；图中，10为铝箔，11为多孔孔洞，20为氧化铝层。
二次电池的制备
(1)制备电池正极：将0.4g钴酸锂、0.05g导电碳黑、0.05g聚偏氟乙烯加入到3mL氮甲基吡咯烷酮溶剂中，充分研磨获得均匀浆料；然后将浆料均匀涂覆于铝箔表面，80℃真空干燥12h。对干燥所得电极片裁切成直径为10mm的圆片，置于手套箱中作为电池正极备用；
(2)将本发明实施例1制备得到的负极和隔膜一体化结构裁切成直径为12mm的圆片，置于手套箱中作为电池负极备用；
(3)配制电解液：在手套箱中配制1mol/L六氟磷酸锂-碳酸亚乙酯(EC)： 碳酸二甲酯(DMC)：碳酸甲乙酯(EMC)(v/v/v＝1:1:1)，并加入5wt％的碳酸亚乙烯酯作为添加剂作为电解液备用；
(4)二次电池组装：在氩气保护的手套箱中，将上述制备好的电池正极、电池负极依次排放、卷绕，再经过电解液注入、封口等工艺完成二次电池组装。
实施例2-11
与实施例1相比，实施例2-11的区别仅在于，将实施例1中步骤(1)和步骤(2)中的物料和处理条件，以及步骤(3)的阳极氧化处理条件，步骤(4)中的煅烧后处理条件替换成如表1和表2所示，其他操作与实施例1相同。
表1 实施例2-11的步骤(1)和步骤(2)中的物料及处理条件
Figure PCTCN2017078204-appb-000001
表2 实施例2-11的阳极氧化处理及后处理条件
Figure PCTCN2017078204-appb-000002
二次电池制备
(1)制备电池正极：将0.4g人造石墨、0.05g导电碳黑、0.05g聚四氟乙烯加入到3mL氮甲基吡咯烷酮溶剂中，充分研磨获得均匀浆料；然后将浆料均匀涂覆于铝箔表面，80℃真空干燥12h。对干燥所得电极片裁切成直径为10mm的圆片，置于手套箱中作为电池正极备用；
(2)将本发明实施例2制备得到的负极和隔膜一体化结构裁切成直径为12mm的圆片，置于手套箱中作为电池负极备用；
(3)配制电解液：在手套箱中配制4mol/L六氟磷酸锂碳酸甲乙酯(EMC)，再加入5wt％的碳酸亚乙烯酯添加剂，作为电解液备用；
(4)二次电池组装：在氩气保护的手套箱中，将上述制备好的电池正极、 电池负极依次排放、卷绕，再经过电解液注入、封口等工艺完成二次电池组装。
二次电池制备
(1)制备电池正极：将0.4g磷酸铁锂、0.05g导电石墨、0.05g聚四氟乙烯加入到3mL氮甲基吡咯烷酮溶剂中，充分研磨获得均匀浆料；然后将浆料均匀涂覆于铝箔表面，80℃真空干燥12h。对干燥所得电极片裁切成直径为10mm的圆片，置于手套箱中作为电池正极备用；
(2)将本发明实施例3制备得到的负极和隔膜一体化结构裁切成直径为12mm的圆片，置于手套箱中作为电池负极备用；
(3)配制电解液：在手套箱中配制1mol/L六氟磷酸锂-碳酸亚乙酯(EC)：碳酸二乙酯(DEC)(v/v＝1:1)，并加入5wt％的碳酸亚乙烯酯添加剂，作为电解液备用；
(4)二次电池组装：在氩气保护的手套箱中，将上述制备好的电池正极、电池负极依次排放、卷绕，再经过电解液注入、封口等工艺完成二次电池组装。
实施例12-21
分别将本发明实施例2-11的步骤(3)的氧化处理条件，以及步骤(4)中的煅烧或化学溶解的后处理条件替换成如表3所示，得到本发明实施例12-21。
表3 实施例12-21中的等离子体氧化处理及后处理条件
Figure PCTCN2017078204-appb-000004
本发明实施例提供的负极和隔膜一体化结构，可有效减小电池的体积及重量，简化生产过程，增加电池的整体容量以及能量密度，同时提高电池的高倍率性能和高温性能，解决了现有二次电池生产工艺复杂、前期投入大、电池安全性能差、能量密度低、设计组装困难等问题。

Claims (12)

  1. 一种负极和隔膜一体化结构，其特征在于，包括铝或铝合金箔，以及形成在所述铝或铝合金箔表面的氧化铝层，所述铝或铝合金箔同时充当负极集流体和负极活性材料，所述氧化铝层充当隔膜。
  2. 如权利要求1所述的负极和隔膜一体化结构，其特征在于，所述氧化铝层具有多孔结构，所述多孔的孔径为10-3000nm，孔隙率小于等于85％。
  3. 如权利要求1所述的负极和隔膜一体化结构，其特征在于，所述氧化铝层的厚度为5-50μm；所述铝或铝合金箔的厚度为10-200μm。
  4. 如权利要求1所述的负极和隔膜一体化结构，其特征在于，所述氧化铝层的厚度为所述铝或铝合金箔厚度的10％-200％。
  5. 如权利要求1所述的负极和隔膜一体化结构，其特征在于，所述铝或铝合金箔为致密的铝或铝合金箔，或者为多孔的铝或铝合金箔。
  6. 一种负极和隔膜一体化结构的制备方法，其特征在于，包括以下步骤：
    取铝或铝合金箔，所述铝或铝合金箔同时充当负极集流体和负极活性材料；
    在所述铝或铝合金箔的一面涂覆有机聚合物溶液，待固化形成有机聚合物膜之后，采用阳极氧化或等离子体氧化的方式对所述铝或铝合金箔的另一面进行可控氧化，使所述铝或铝合金箔的另一面形成氧化铝层；
    再在惰性气氛下煅烧或采用化学溶解的方法去掉包覆在所述铝或铝合金箔一面的所述有机聚合物膜，得到负极和隔膜一体化结构。
  7. 如权利要求6所述的负极和隔膜一体化结构的制备方法，其特征在于，所述有机聚合物溶液包含如下有机聚合物中的一种或多种：聚丙烯腈、聚偏氟乙烯、聚丙烯酸、聚氨酯、聚乙烯醇缩丁醛、聚四氟乙烯、聚氨酯、聚乙烯、 聚丙烯，聚甲基吡咯烷酮，聚氯乙烯、聚砜、聚醚砜、聚氧化乙烯、聚甲基丙烯酸甲酯、聚偏氟乙烯-六氟丙烯、聚氧丙烯、聚乙烯醇缩醛、聚乙烯吡咯烷酮、磺脲聚合物、聚亚苯基砜磺酸聚合物、聚环氧乙烷、丁苯橡胶、聚丁二烯、聚氯乙烯、聚苯乙烯、丙烯酸酯、壳糖酸、聚乙烯醇、聚乙烯醇缩丁醛、聚乙二醇、聚醚丙烯酸乙二醇酯、磷酸酯类聚合物。
  8. 如权利要求6所述的负极和隔膜一体化结构的制备方法，其特征在于，所述有机聚合物溶液中的有机溶剂包括甲醇、乙醇、乙二醇、丙酮、二甲基甲酰胺、丙二醇甲醚、碳酸丙烯脂、碳酸乙烯脂、碳酸二甲脂、碳酸二丙酯、碳酸乙丙酯、碳酸亚乙烯酯、碳酸乙异丙酯、碳酸甲丁酯、碳酸二丁酯、碳酸乙丁酯、碳酸甲乙酯、碳酸二乙酯、γ-丁内酯和N-甲基吡咯烷酮中的一种或多种；所述有机聚合物溶液的质量浓度为0.1-100mg/mL。
  9. 如权利要求6所述的负极和隔膜一体化结构的制备方法，其特征在于，所述阳极氧化包括恒电压阳极氧化或恒电流阳极氧化，所述恒电压阳极氧化的电压为5～200V，所述恒电流阳极氧化的电流为0.01～6A cm-2，所述阳极氧化的时间为0.1～240min，所述阳极氧化电解液的温度为0～40℃。
  10. 如权利要求6所述的负极和隔膜一体化结构的制备方法，其特征在于，所述等离子体氧化所用气体为氧气，流量为10-300sccm，功率为10-150W，时间为1-360min，温度为25-400℃。
  11. 一种电池，其特征在于，包括正极，电解液，以及如权利要求1-5任一项所述的负极和隔膜一体化结构，所述正极包括正极集流体和设置在所述正极集流体上的正极活性材料层，所述正极活性材料层包括正极活性材料。
  12. 如权利要求11所述的电池，其特征在于，所述电解液中的电解质盐包括锂盐、钠盐、钾盐、钙盐和镁盐中的一种或多种。
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