WO2017084128A1 - 一种新型二次电池及其制备方法 - Google Patents

一种新型二次电池及其制备方法 Download PDF

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WO2017084128A1
WO2017084128A1 PCT/CN2015/096887 CN2015096887W WO2017084128A1 WO 2017084128 A1 WO2017084128 A1 WO 2017084128A1 CN 2015096887 W CN2015096887 W CN 2015096887W WO 2017084128 A1 WO2017084128 A1 WO 2017084128A1
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battery
positive electrode
secondary battery
negative electrode
novel secondary
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PCT/CN2015/096887
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English (en)
French (fr)
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唐永炳
张小龙
李振声
樊建平
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中国科学院深圳先进技术研究院
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Definitions

  • the invention belongs to the technical field of secondary batteries, and particularly relates to a novel secondary battery which uses a layered graphite-like material as a positive electrode material and does not contain a negative electrode material and a preparation method thereof.
  • a secondary battery also called a rechargeable battery, is a battery that can be repeatedly charged and discharged and used multiple times. Compared with a non-reusable primary battery, the secondary battery has the advantages of low cost of use and low environmental pollution.
  • the main secondary battery technologies are lead-acid batteries, nickel-chromium batteries, nickel-hydrogen batteries, and lithium-ion batteries. Among them, lithium-ion batteries are the most widely used, and daily use of mobile phones, notebook computers, digital cameras, etc. are all powered by lithium-ion batteries.
  • the core component of a lithium ion battery usually comprises a positive electrode, a negative electrode and an electrolyte, which realizes electrical energy storage and release by a redox reaction in which ion transport and electron transport phase separation occurs at the interface between the positive electrode, the negative electrode and the electrolyte.
  • a redox reaction in which ion transport and electron transport phase separation occurs at the interface between the positive electrode, the negative electrode and the electrolyte.
  • the commercial lithium ion battery is a transition metal oxide (LiCoO 2 , LiNiMnCoO 2 , LiMn 2 O 4 ) or a polyanionic metal compound (LiFePO 4 ) as a positive electrode active material, graphite or carbon as a negative electrode active material, and ester electrolysis.
  • the liquid or polymer gel is an electrolyte.
  • the positive active material contains a transition metal element, which increases the cost of preparing the material, and on the other hand, increases the potential environmental hazard after the battery is discarded.
  • the industry is actively developing new secondary battery technologies that are environmentally friendly and have high energy density.
  • One of the two carbon batteries is of particular concern.
  • the battery uses graphite or carbon as the active material for the positive and negative electrodes and is completely free of transition metal elements.
  • the anion in the electrolyte is embedded in the cathode graphite material, and the lithium ions are embedded in the anode carbon material; when discharging, the anion is released from the cathode material, and lithium ions are released from the anode material.
  • Read and Xu of the US Army Lab Energy Environ.Sci.
  • a double-graphite secondary battery was developed, which uses a graphite material as both a negative electrode and a positive electrode active material, and a fluorinated modified ester as an electrolyte solvent to realize a reversible charge and discharge experiment of the battery system.
  • Rothermel and Placke et al. (Energy Environ. Sci. 2014, 7, 3412) of the University of Weg, Germany, developed a dual graphite battery based on an ionic liquid electrolyte, which also achieved reversible charge and discharge of a dual graphite battery system.
  • the graphite material has a limited embedding capacity for anions, so the battery capacity cannot be comparable to that of a conventional lithium ion battery; 2.
  • the fluorinated modified ester electrolyte and the ionic liquid electrolyte The cost of preparation is very high, thus reducing the cost advantage of dual carbon batteries.
  • the object of the present invention is to overcome the deficiencies of the prior art, and to provide a novel secondary battery using graphite as a positive electrode material and no negative electrode material, wherein the electrolyte solution can be formulated with a high-concentration ester electrolyte modified by an additive.
  • the invention solves the defects of large environmental pollution, high manufacturing cost, and low energy density of the existing secondary battery.
  • the present invention provides a novel secondary battery comprising: a battery negative electrode 1, an electrolyte 2, a separator 3, a battery positive electrode 4, and a battery case for packaging; wherein the battery negative electrode 1 includes a negative electrode current collector Excluding the negative electrode active material; the electrolyte 2 is an electrolyte containing an organic additive of an ester, a sulfone, an ether, a nitrile or an olefin; the battery positive electrode 4 includes a positive active material layer, wherein the positive active material has a layered shape A graphite-based material, a sulfide, a nitride, an oxide, or a carbide having a crystal structure.
  • the present invention provides a method for preparing the novel secondary battery of claim 1, comprising: preparing a battery negative electrode; preparing an electrolyte; preparing a separator; preparing a battery positive electrode; using the battery negative electrode, an electrolyte, and a separator
  • the battery positive electrode is assembled with a new secondary battery.
  • the main active component of the novel secondary battery proposed by the invention is a graphite-like material having a layered crystal structure, which is environmentally friendly and low in cost.
  • the new secondary battery system of the present invention does not require a negative electrode material, thereby significantly reducing the battery weight and cost, and improving the energy density of the battery.
  • FIG. 1 is a schematic view showing the structure of a novel secondary battery according to an embodiment of the present invention.
  • FIG. 2 is a second embodiment of graphite according to an embodiment of the present invention, which comprises graphite as a positive electrode material and does not contain a negative electrode material.
  • the novel secondary battery includes a battery negative electrode 1, an electrolyte 2, a separator 3, a battery positive electrode 4, and a battery case (not shown) for packaging.
  • the battery negative electrode 1 includes a negative electrode current collector, does not include a negative electrode active material, and the negative electrode current collector is a conductive material, and the conductive material is one of aluminum, copper, iron, tin, zinc, nickel, titanium, manganese or the foregoing alloy. .
  • the components of the electrolyte 2 include a solvent, an electrolyte, and an additive;
  • the solvent is an ester, sulfone or ether organic solvent, and one or more of diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, dimethyl sulfone, and dimethyl ether may be used;
  • the electrolyte is a lithium salt, one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, and lithium perchlorate may be used, and the concentration ranges from 0.1 to 10 mol/L;
  • the additive is an organic additive containing an ester, a sulfone, an ether, a nitrile or an olefin, and may be selected from vinylene carbonate, ethylene sulfite, propylene sulfite, ethylene sulfoxide, cyclobutyl sulfone, 1 One or more of 3-dioxol cyclopentane, acetonitrile, long-chain olefin, and added in an amount of 0.1-40% by weight.
  • the separator 3 is made of an insulating porous polymer film or an inorganic porous film, and a porous polypropylene film, a porous polyethylene film, a porous composite polymer film, a glass fiber paper or a porous ceramic separator may be used.
  • the battery positive electrode 4 includes a positive electrode active material layer 41 and a positive electrode current collector 42.
  • the positive electrode active material layer 41 includes a positive electrode active material, a conductive agent, and a binder, and the positive electrode current collector 42 is a conductive material, and the conductive material is one of aluminum, copper, iron, tin, zinc, nickel, titanium, manganese, or the foregoing. Alloy.
  • the amount of the positive electrode active material is 50 - 90% by weight, the content of the conductive agent is 30 - 0.1% by weight, and the content of the binder is 10 - 0.1% by weight.
  • the positive electrode active material is composed of a graphite-based material, a sulfide, a nitride, an oxide, and a carbide having a layered crystal structure, wherein the graphite-based material is one selected from natural graphite, artificial graphite, and graphite flakes.
  • Sulfide one or more selected from the group consisting of molybdenum disulfide, tungsten disulfide, vanadium disulfide and titanium disulfide;
  • Nitride one or more of hexagonal boron nitride and carbon doped hexagonal boron nitride;
  • oxide one or more of molybdenum trioxide, tungsten trioxide, vanadium pentoxide, and titanium dioxide;
  • titanium carbide tantalum carbide, molybdenum carbide, and silicon carbide are used.
  • the conductive agent is one or more of conductive acetylene black, Super P conductive carbon sphere, conductive graphite KS6, carbon nanotube, and graphene.
  • the binder is one or more of polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, SBR rubber, and polyolefin.
  • FIG. 2 is a schematic view showing the working principle of a novel secondary battery using graphite as a positive electrode material and containing no negative electrode material according to an embodiment of the present invention.
  • the secondary battery of the present invention operates differently from a conventional lithium ion battery.
  • a conventional lithium ion battery When a conventional lithium ion battery is charged, lithium ions are extracted from the positive electrode material and then embedded in the negative electrode material; when discharged, lithium ions are extracted from the negative electrode material and embedded in the positive electrode material.
  • lithium ions 100 (Li + ) in the electrolytic solution 2 are deposited on the surface of the negative electrode current collector 1, while the anion 200 in the electrolytic solution 2 is embedded in the positive electrode of the graphite-based battery;
  • the lithium ions 100 deposited on the fluid 1 are returned to the electrolyte 2, and the anion 200 embedded in the positive electrode of the graphite-based battery is also released and returned to the electrolyte 2.
  • the main active component of the novel secondary battery proposed by the present invention is a graphite-like material having a layered crystal structure, and thus is environmentally friendly and low in cost.
  • the new secondary battery system of the present invention does not require a negative electrode material, thereby significantly reducing the battery weight and cost, and improving the energy density of the battery.
  • the invention has prepared a button type analog battery, and the battery system test shows that the reversible charge and discharge can be realized, and the battery preparation process is significantly simplified, the material cost can be reduced by 40%, the battery active component weight is reduced by 50%, and the capacity can be compared with the ordinary lithium ion battery. .
  • Step 1 preparing a battery negative electrode
  • the negative electrode of the battery comprises a negative current collector, and does not comprise a negative active material
  • the preparation process is to cut metal foils such as copper, iron, tin, aluminum, etc. into a desired size, and clean the surface for use.
  • Step 2 preparing an electrolyte
  • Step 3 preparing a separator
  • porous polymer film or the inorganic porous film is cut into a desired size, cleaned and used.
  • Step 4 preparing a positive electrode of the battery
  • the positive electrode of the battery is a positive electrode of a graphite battery, and includes a positive active material layer and a positive current collector.
  • the preparation process is to weigh the active material, the conductive agent, and the binder in a certain ratio, and fully grind into a uniform slurry by adding a suitable solvent, and then uniformly apply to the surface of the cathode current collector, that is, formed on the surface of the cathode current collector.
  • the positive electrode active material layer after the slurry is completely dried, it is cut to obtain a battery positive electrode of a desired size.
  • steps 1-4 describe the operation of the preparation method of the present invention in a specific order, it is not required or implied that these operations must be performed in this particular order.
  • the preparation of steps 1-4 can be carried out simultaneously or in any order.
  • Step 5 assembling the new secondary battery by using the battery negative electrode, the electrolyte, the separator, and the battery positive electrode;
  • the battery is assembled in an inert gas or waterless environment, and the prepared negative electrode current collector, separator, and battery positive electrode are closely stacked in sequence, and the electrolyte is dripped to completely infiltrate the separator, and then the stacked portion is packaged into the battery case to complete the battery. Assembly.
  • the invention optimizes the selection of the solvent type, the selection of the electrolyte concentration, and the type and amount of the additive.
  • a structure of a positive electrode of a battery comprising a positive electrode current collector and a positive electrode active material layer coated on the surface of the current collector, and the positive electrode active material layer comprises a graphite-like material having a layered crystal structure, a conductive agent and a binder
  • a negative current collector matched with the electrolyte and the positive electrode of the battery was selected.
  • Preparation of battery negative electrode Take a copper foil with a thickness of 0.5 mm, cut into a 12 mm diameter disk, wash the copper piece with ethanol, and dry it as a negative electrode current collector for use.
  • the Celgard 2400 porous polymer film was cut into a 16 mm diameter disc, washed with acetone, dried and used as a separator.
  • Preparation of battery positive electrode 0.8g artificial graphite, 0.1g carbon black, 0.1g polyvinylidene fluoride was added to 2ml of nitromethylpyrrolidone solution, fully ground to obtain a uniform slurry; then the slurry was uniformly applied to the surface of the aluminum foil (ie , positive current collector) and vacuum dried.
  • the electrode sheet obtained by drying was cut into a disk having a diameter of 10 mm, and was used as a battery positive electrode after being pressed.
  • the prepared negative electrode current collector, separator, and battery positive electrode are closely stacked in sequence, and the electrolyte is dripped to completely infiltrate the separator, and then the stacked portion is packaged into the button battery case. , complete battery assembly.
  • Preparation of battery negative electrode Take aluminum foil with a thickness of 0.3 mm, cut into a 12 mm diameter disk, wash the copper piece with ethanol, and dry it as a negative current collector for use.
  • the glass fiber paper was cut into a 16 mm diameter disc, washed with acetone, dried and used as a separator.
  • Preparation of battery positive electrode 0.7g artificial graphite, 0.2g carbon black, 0.1g polyvinylidene fluoride was added to 2ml of nitromethylpyrrolidone solution, fully ground to obtain a uniform slurry; then the slurry was uniformly coated on the surface of aluminum foil and vacuum dry.
  • the electrode sheet obtained by drying was cut into a disk having a diameter of 10 mm, and was used as a battery positive electrode after being pressed.
  • the prepared negative electrode current collector, separator, and battery positive electrode are closely stacked in sequence, and the electrolyte is dripped to completely infiltrate the separator, and then the stacked portion is packaged into the button battery case. , complete battery assembly.
  • Preparation of battery negative electrode Take aluminum foil with a thickness of 0.3 mm, cut into a 12 mm diameter disk, wash the copper piece with ethanol, and dry it as a negative current collector for use.
  • the glass fiber paper was cut into a 16 mm diameter disc, washed with acetone, dried and used as a separator.
  • Formulation of electrolyte 2g of lithium tetrafluoroborate is added to 5ml of ethyl methyl carbonate, stirred until lithium tetrafluoroborate is completely dissolved, then ethylene carbonate of 3% by mass is added as an additive, fully stirred and then used as electrolysis Liquid spare.
  • Preparation of battery positive electrode 0.8g artificial graphite, 0.15g carbon black, 0.05g polyvinylidene fluoride was added to 2ml of nitromethylpyrrolidone solution, fully ground to obtain a uniform slurry; then the slurry was uniformly coated on the surface of the aluminum foil and vacuum dry.
  • the electrode sheet obtained by drying was cut into a disk having a diameter of 10 mm, and was used as a battery positive electrode after being pressed.
  • the prepared negative electrode current collector, separator, and battery positive electrode are closely stacked in sequence, and the electrolyte is dripped to completely infiltrate the separator, and then the stacked portion is packaged into the button battery case. , complete battery assembly.
  • Preparation of battery negative electrode Take an iron piece with a thickness of 0.3 mm, cut into a 12 mm diameter disk, wash the copper piece with ethanol, and dry it as a negative electrode current collector for use.
  • the glass fiber paper was cut into a 16 mm diameter disc, washed with acetone, dried and used as a separator.
  • Preparation of battery positive electrode 1 g of titanium carbide, 0.15 g of carbon black, 0.05 g of polyvinylidene fluoride was added to 2 ml of nitromethylpyrrolidone solution, and fully ground to obtain a uniform slurry; then the slurry was uniformly coated on the surface of the aluminum foil and vacuum dried. .
  • the electrode sheet obtained by drying was cut into a disk having a diameter of 10 mm, and was used as a battery positive electrode after being pressed.
  • the prepared negative electrode current collector, separator, and battery positive electrode are closely stacked in sequence, and the electrolyte is dripped to completely infiltrate the separator, and then the stacked portion is packaged into the button battery case. , complete battery assembly.
  • Preparation of battery negative electrode Take a copper foil with a thickness of 0.3 mm, cut into a disk having a diameter of 12 mm, clean the copper piece with ethanol, and dry it as a negative electrode current collector for use.
  • the porous polypropylene film was cut into a 16 mm-diameter wafer, washed with acetone, dried and used as a separator.
  • Preparation of battery positive electrode 1 g of titanium carbide, 0.15 g of carbon black, 0.05 g of polyvinylidene fluoride was added to 2 ml of nitromethylpyrrolidone solution, and fully ground to obtain a uniform slurry; then the slurry was uniformly coated on the surface of the aluminum foil and vacuum dried. .
  • the electrode sheet obtained by drying was cut into a disk having a diameter of 10 mm, and was used as a battery positive electrode after being pressed.
  • the prepared negative electrode current collector, separator, and battery positive electrode are closely stacked in sequence, and the electrolyte is dripped to completely infiltrate the separator, and then the stacked portion is packaged into the button battery case. , complete battery assembly.
  • Preparation of battery negative electrode Take aluminum foil with a thickness of 0.3 mm, cut into a 12 mm diameter disk, wash the copper piece with ethanol, and dry it as a negative current collector for use.
  • the porous polypropylene film was cut into a 16 mm-diameter wafer, washed with acetone, dried and used as a separator.
  • Preparation of battery positive electrode 1 g of molybdenum disulfide, 0.15 g of carbon black, 0.05 g of polyvinylidene fluoride was added to 2 ml of nitromethylpyrrolidone solution, and fully ground to obtain a uniform slurry; then the slurry was uniformly coated on the surface of the aluminum foil and vacuumed dry.
  • the electrode sheet obtained by drying was cut into a disk having a diameter of 10 mm, and was used as a battery positive electrode after being pressed.
  • the prepared negative electrode current collector, separator, and battery positive electrode are closely stacked in sequence, and the electrolyte is dripped to completely infiltrate the separator, and then the stacked portion is packaged into the button battery case. , complete battery assembly.
  • the form of the secondary battery according to the present invention is not limited to the button type battery, and may be designed in the form of a flat battery or a cylindrical battery depending on the core component.
  • the main active component of the novel secondary battery proposed by the invention is graphite-like graphite having a layered crystal structure Material, environmentally friendly and low cost.
  • the new secondary battery system of the present invention does not require a negative electrode material, thereby significantly reducing the battery weight and cost, and improving the energy density of the battery.

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Abstract

本发明公开了一种新型二次电池及其制备方法，其中，该新型二次电池包括：电池负极、电解液、隔膜、电池正极以及用于封装的电池壳体；其中，电池负极包括负极集流体，不包含负极活性材料；电解液为含酯类、砜类、醚类、腈类或烯烃类有机添加剂的电解液；电池正极包括正极活性材料层，其中，正极活性材料由具有层状晶体结构的石墨类材料、硫化物、氮化物、氧化物、碳化物组成。本发明提出的新型二次电池主要活性成分为具有层状晶体结构的类石墨材料，环境友好且成本低。同时，本发明的新型二次电池体系中无需负极材料，因而显著降低电池自重和成本，提升电池能量密度。

Description

一种新型二次电池及其制备方法
优先权声明
本申请要求2015年11月18日递交的、申请号为CN201510796123.5、发明名称为“一种新型二次电池及其制备方法”的中国发明专利的优先权，该发明专利的所有内容在此全部引入。
技术领域
本发明属于二次电池技术领域，具体涉及一种以层状类石墨材料为正极材料且不含负极材料的新型二次电池及其制备方法。
背景技术
二次电池也称为可充电电池，是一种可重复充放电、使用多次的电池。相比于不可重复使用的一次电池，二次电池具有使用成本低、对环境污染小的优点。目前主要的二次电池技术有铅酸电池、镍铬电池、镍氢电池、锂离子电池。其中尤其以锂离子电池应用最为广泛，日常使用的手机、笔记本电脑、数码相机等都是以锂离子电池为电源。锂离子电池的核心组成部件通常包含正极、负极和电解液，它通过发生在正极、负极与电解液界面上的离子传输与电子传输相分离的氧化还原反应来实现电能存储与释放。充电时，锂离子从正极活性材料中脱出，嵌入负极活性材料；放电时，锂离子从负极活性材料脱出而嵌入到正极活性材料中。商用的锂离子电池是以过渡金属氧化物(LiCoO2、LiNiMnCoO2、LiMn2O4)或聚阴离子型金属化合物(LiFePO4)为正极活性材料，以石墨或碳为负极活性材料，酯类电解液或聚合物凝胶为电解液。正极活性材料中包含过渡金属元素，这一方面使得材料的制备成本增加，另一方面也使得电池废弃后对环境的潜在危害加大。
当前业内正在积极研发环境友好、能量密度高的新型二次电池技术。其中一种双碳电池尤其值得关注，这种电池以石墨或碳材料作为正极和负极活性材料，完全不含过渡金属元素。充电时，电解液中的阴离子嵌入正极石墨材料中，锂离子则嵌入负极碳材料中；放电时，阴离子从正极材料脱出，锂离子从负极材料脱出。例如，美国陆军实验室的Read和Xu等(Energy Environ.Sci.2014,7,617) 开发了一种双石墨二次电池，其以石墨材料同时作为负极和正极活性材料，以氟化改性酯类作为电解液溶剂，实现了该电池体系的可逆充放电实验。德国明斯特大学的Rothermel和Placke等(Energy Environ.Sci.2014,7,3412)研发了一种基于离子液体电解液的双石墨电池，亦实现了双石墨电池体系的可逆充放电。
但是，上述两项研究工作还面临如下问题：1.石墨材料对阴离子的嵌入容量有限，因此电池容量无法与常规锂离子电池媲美；2.氟化改性酯类电解液和离子液体电解液的制备成本非常高，因而削弱了双碳电池的成本优势。
发明内容
本发明的目的在于克服现有技术的不足，提供了一种以石墨为正极材料且不含负极材料的新型二次电池，其中的电解液可以利用添加剂改性的高浓度酯类电解液配方，以解决现有二次电池存在的环境污染大、制造成本高、能量密度低等缺陷。
为达到上述目的，本发明提出了一种新型二次电池，包括：电池负极1、电解液2、隔膜3、电池正极4以及用于封装的电池壳体；其中，电池负极1包括负极集流体，不包含负极活性材料；电解液2为含酯类、砜类、醚类、腈类或烯烃类有机添加剂的电解液；电池正极4包括正极活性材料层，其中，正极活性材料由具有层状晶体结构的石墨类材料、硫化物、氮化物、氧化物、碳化物组成。
为达到上述目的，本发明提出了一种制备权利要求1的新型二次电池的方法，包括：制备电池负极；配制电解液；制备隔膜；制备电池正极；利用所述电池负极、电解液、隔膜、电池正极进行新型二次电池的组装。
本发明提出的新型二次电池主要活性成分为具有层状晶体结构的类石墨材料，环境友好且成本低。同时，本发明的新型二次电池体系中无需负极材料，因而显著降低电池自重和成本，提升电池能量密度。
附图说明
此处所说明的附图用来提供对本发明的进一步理解，构成本申请的一部分，并不构成对本发明的限定。在附图中：
图1为本发明一实施例的新型二次电池的结构示意图。
图2为本发明一实施例的以石墨为正极材料且不含负极材料的新型二次 电池的工作原理示意图。
具体实施方式
以下配合图示及本发明的较佳实施例，进一步阐述本发明为达成预定发明目的所采取的技术手段。
图1为本发明一实施例的新型二次电池的结构示意图。如图1所示，该新型二次电池包括：电池负极1、电解液2、隔膜3、电池正极4以及用于封装的电池壳体(图未绘示)。
其中，电池负极1包括负极集流体，不包含负极活性材料，负极集流体为导电材料，该导电材料为铝、铜、铁、锡、锌、镍、钛、锰中的一种或前述的合金。
电解液2的组分包含溶剂、电解质、添加剂；其中，
所述溶剂为酯类、砜类或醚类有机溶剂，可以选用碳酸二乙酯、碳酸二甲酯、碳酸甲乙酯、二甲基砜、二甲醚中的一种或多种；
所述电解质为锂盐，可以选用六氟磷酸锂、四氟硼酸锂、高氯酸锂中的一种或多种，且浓度范围为0.1–10mol/L；
所述添加剂为含酯类、砜类、醚类、腈类或烯烃类有机添加剂，可以选用碳酸亚乙烯酯、亚硫酸亚乙酯、亚硫酸丙烯酯、硫酸亚乙酯环丁基砜、1,3-二氧环戊烷、乙腈、长链烯烃中的一种或多种，且添加量为0.1-40％wt。
隔膜3的成分为绝缘的多孔聚合物薄膜或无机多孔薄膜，可以选用多孔聚丙烯薄膜、多孔聚乙烯薄膜、多孔复合聚合物薄膜、玻璃纤维纸或多孔陶瓷隔膜。
电池正极4包括正极活性材料层41及正极集流体42。正极活性材料层41包括正极活性材料、导电剂、粘结剂，正极集流体42为导电材料，该导电材料为铝、铜、铁、锡、锌、镍、钛、锰中的一种或前述的合金。
在正极活性材料层41中，正极活性材料的份量为50–90％wt，导电剂的含量为30–0.1％wt，粘结剂的含量为10–0.1％wt。
进一步的，正极活性材料由具有层状晶体结构的石墨类材料、硫化物、氮化物、氧化物、碳化物组成，其中，石墨类材料，选用天然石墨、人造石墨、石墨片中的一种或多种；
硫化物，选用二硫化钼、二硫化钨、二硫化钒、二硫化钛中的一种或多种；
氮化物，选用六方氮化硼、碳掺杂六方氮化硼中的一种或多种；
氧化物，选用三氧化钼、三氧化钨、五氧化二钒、二氧化钛中的一种或多种；
碳化物，选用碳化钛、碳化钽、碳化钼、碳化硅中的一种或多种。
导电剂为导电乙炔黑、Super P导电碳球、导电石墨KS6、碳纳米管、石墨烯中的一种或多种。
粘结剂为聚偏氟乙烯、聚四氟乙烯、聚乙烯醇、羧甲基纤维素、SBR橡胶、聚烯烃类中的一种或多种。
图2为本发明一实施例的以石墨为正极材料且不含负极材料的新型二次电池的工作原理示意图。如图2所示，本发明所述的二次电池工作原理与传统锂离子电池不同。传统锂离子电池充电时，锂离子从正极材料脱出，然后嵌入负极材料中；放电时，锂离子则从负极材料脱出，嵌入正极材料。本发明的二次电池充电时，电解液2中的锂离子100(Li+)沉积到负极集流体1表面，同时电解液2中的阴离子200则嵌入石墨类电池正极中；放电时，负极集流体1上沉积的锂离子100回到电解液2中，嵌入石墨类电池正极的阴离子200也脱出，回到电解液2中。
相比于现有二次电池技术，本发明提出的新型二次电池主要活性成分为具有层状晶体结构的类石墨材料，因此环境友好且成本低。同时，本发明的新型二次电池体系中无需负极材料，因而显著降低电池自重和成本，提升电池能量密度。
本发明已制备出扣式模拟电池，通过电池系统测试表明能够实现可逆充放电，且电池制备过程显著简化，材料成本可降低40％，电池活性成分自重降低50％，容量可比拟普通锂离子电池。
对于本发明提出的新型二次电池，相应的制备方法如下：
步骤1、制备电池负极；
其中，电池负极包括负极集流体，不包含负极活性材料；
具体的，制备过程是将铜、铁、锡、铝等金属箔片裁切成所需尺寸，将表面清洗干净备用。
步骤2、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，再加入一定量电解液添加剂，搅拌均匀后备用。
步骤3、制备隔膜；
将多孔聚合物薄膜或无机多孔薄膜裁切成所需尺寸，清洗干净后备用。
步骤4、制备电池正极；
其中，电池正极为石墨类电池正极，包括正极活性材料层及正极集流体。
具体的，制备过程是按一定比例称取活性材料、导电剂、粘结剂，加入适当溶剂中充分研磨成均匀浆料，然后均匀涂覆于正极集流体表面，即在正极集流体表面形成了正极活性材料层；待浆料完全干燥后进行裁切，得所需尺寸的电池正极。
尽管上述步骤1-4是以特定顺序描述了本发明制备方法的操作，但是，这并非要求或者暗示必须按照该特定顺序来执行这些操作。步骤1-4的制备可以同时或者任意先后执行。
步骤5、利用所述电池负极、电解液、隔膜、电池正极进行新型二次电池的组装；
在惰性气体或无水环境下组装电池，将上述制备好的负极集流体、隔膜、电池正极依次紧密堆叠，滴加电解液使隔膜完全浸润，然后将上述堆叠部分封装入电池壳体，完成电池组装。
本发明在制备新型二次电池时，优化了溶剂种类的选择、电解质浓度的选择和添加剂种类与分量。还提出了一种电池正极的结构，包括正极集流体以及涂覆于该集流体表面的正极活性材料层，且正极活性材料层包括具有层状晶体结构的类石墨材料、导电剂和粘结剂，同时选择了与该电解液和电池正极相匹配的负极集流体。
为了对新型二次电池进行更为清楚的解释，下面结合一个具体的实施例来进行说明，然而值得注意的是该实施例仅是为了更好地说明本发明，并不构成对本发明不当的限定。
实施例1
制备电池负极：取厚度为0.5mm的铜箔，裁切成直径12mm的圆片，用乙醇清洗铜片，晾干作为负极集流体备用。
制备隔膜：将Celgard2400多孔聚合物薄膜裁切成直径16mm的圆片，用丙酮清洗，晾干后作为隔膜备用。
配制电解液：称取3g六氟磷酸锂加入到5ml碳酸甲乙酯中，搅拌至六氟磷酸锂完全溶解，然后加入质量分数为2％的碳酸亚乙烯酯作为添加剂，充分搅拌均匀后作为电解液备用。
制备电池正极：将0.8g人造石墨、0.1g碳黑、0.1g聚偏氟乙烯加入到2ml氮甲基吡咯烷酮溶液中，充分研磨获得均匀浆料；然后将浆料均匀涂覆于铝箔表面(即，正极集流体)并真空干燥。对干燥所得电极片裁切成直径10mm的圆片，压死后作为电池正极备用。
电池组装：在惰性气体保护的手套箱中，将上述制备好的负极集流体、隔膜、电池正极依次紧密堆叠，滴加电解液使隔膜完全浸润，然后将上述堆叠部分封装入扣式电池壳体，完成电池组装。
实施例2
制备电池负极：取厚度为0.3mm的铝箔，裁切成直径12mm的圆片，用乙醇清洗铜片，晾干作为负极集流体备用。
制备隔膜：将玻璃纤维纸裁切成直径16mm的圆片，用丙酮清洗，晾干后作为隔膜备用。
配制电解液：称取3g六氟磷酸锂加入到5ml碳酸甲乙酯中，搅拌至六氟磷酸锂完全溶解，然后加入质量分数为3％的亚硫酸亚乙酯作为添加剂，充分搅拌均匀后作为电解液备用。
制备电池正极：将0.7g人造石墨、0.2g碳黑、0.1g聚偏氟乙烯加入到2ml氮甲基吡咯烷酮溶液中，充分研磨获得均匀浆料；然后将浆料均匀涂覆于铝箔表面并真空干燥。对干燥所得电极片裁切成直径10mm的圆片，压死后作为电池正极备用。
电池组装：在惰性气体保护的手套箱中，将上述制备好的负极集流体、隔膜、电池正极依次紧密堆叠，滴加电解液使隔膜完全浸润，然后将上述堆叠部分封装入扣式电池壳体，完成电池组装。
实施例3
制备电池负极：取厚度为0.3mm的铝箔，裁切成直径12mm的圆片，用乙醇清洗铜片，晾干作为负极集流体备用。
制备隔膜：将玻璃纤维纸裁切成直径16mm的圆片，用丙酮清洗，晾干后作为隔膜备用。
配制电解液：称取2g四氟硼酸锂加入到5ml碳酸甲乙酯中，搅拌至四氟硼酸锂完全溶解，然后加入质量分数为3％的碳酸亚乙烯酯作为添加剂，充分搅拌均匀后作为电解液备用。
制备电池正极：将0.8g人造石墨、0.15g碳黑、0.05g聚偏氟乙烯加入到2ml氮甲基吡咯烷酮溶液中，充分研磨获得均匀浆料；然后将浆料均匀涂覆于铝箔表面并真空干燥。对干燥所得电极片裁切成直径10mm的圆片，压死后作为电池正极备用。
电池组装：在惰性气体保护的手套箱中，将上述制备好的负极集流体、隔膜、电池正极依次紧密堆叠，滴加电解液使隔膜完全浸润，然后将上述堆叠部分封装入扣式电池壳体，完成电池组装。
实施例4
制备电池负极：取厚度为0.3mm的铁片，裁切成直径12mm的圆片，用乙醇清洗铜片，晾干作为负极集流体备用。
制备隔膜：将玻璃纤维纸裁切成直径16mm的圆片，用丙酮清洗，晾干后作为隔膜备用。
配制电解液：称取3g六氟磷酸锂加入到5ml碳酸甲乙酯中，搅拌至六氟磷酸锂完全溶解，然后加入质量分数为2％的硫酸亚乙酯作为添加剂，充分搅拌均匀后作为电解液备用。
制备电池正极：将1g碳化钛、0.15g碳黑、0.05g聚偏氟乙烯加入到2ml氮甲基吡咯烷酮溶液中，充分研磨获得均匀浆料；然后将浆料均匀涂覆于铝箔表面并真空干燥。对干燥所得电极片裁切成直径10mm的圆片，压死后作为电池正极备用。
电池组装：在惰性气体保护的手套箱中，将上述制备好的负极集流体、隔膜、电池正极依次紧密堆叠，滴加电解液使隔膜完全浸润，然后将上述堆叠部分封装入扣式电池壳体，完成电池组装。
实施例5
制备电池负极：取厚度为0.3mm的铜箔，裁切成直径12mm的圆片，用乙醇清洗铜片，晾干作为负极集流体备用。
制备隔膜：将多孔聚丙烯薄膜裁切成直径16mm的圆片，用丙酮清洗，晾干后作为隔膜备用。
配制电解液：称取3g六氟磷酸锂加入到5ml碳酸甲乙酯中，搅拌至六氟磷酸锂完全溶解，然后加入质量分数为2％的环丁基砜作为添加剂，充分搅拌均匀后作为电解液备用。
制备电池正极：将1g碳化钛、0.15g碳黑、0.05g聚偏氟乙烯加入到2ml氮甲基吡咯烷酮溶液中，充分研磨获得均匀浆料；然后将浆料均匀涂覆于铝箔表面并真空干燥。对干燥所得电极片裁切成直径10mm的圆片，压死后作为电池正极备用。
电池组装：在惰性气体保护的手套箱中，将上述制备好的负极集流体、隔膜、电池正极依次紧密堆叠，滴加电解液使隔膜完全浸润，然后将上述堆叠部分封装入扣式电池壳体，完成电池组装。
实施例6
制备电池负极：取厚度为0.3mm的铝箔，裁切成直径12mm的圆片，用乙醇清洗铜片，晾干作为负极集流体备用。
制备隔膜：将多孔聚丙烯薄膜裁切成直径16mm的圆片，用丙酮清洗，晾干后作为隔膜备用。
配制电解液：称取3g高氯酸锂加入到5ml碳酸甲乙酯中，搅拌至高氯酸锂完全溶解，然后加入质量分数为2％的亚硫酸亚乙酯作为添加剂，充分搅拌均匀后作为电解液备用。
制备电池正极：将1g二硫化钼、0.15g碳黑、0.05g聚偏氟乙烯加入到2ml氮甲基吡咯烷酮溶液中，充分研磨获得均匀浆料；然后将浆料均匀涂覆于铝箔表面并真空干燥。对干燥所得电极片裁切成直径10mm的圆片，压死后作为电池正极备用。
电池组装：在惰性气体保护的手套箱中，将上述制备好的负极集流体、隔膜、电池正极依次紧密堆叠，滴加电解液使隔膜完全浸润，然后将上述堆叠部分封装入扣式电池壳体，完成电池组装。
本发明涉及的二次电池形态不局限于扣式电池，也可根据核心成分设计成平板电池、圆柱电池等形态。
本发明提出的新型二次电池主要活性成分为具有层状晶体结构的类石墨 材料，环境友好且成本低。同时，本发明的新型二次电池体系中无需负极材料，因而显著降低电池自重和成本，提升电池能量密度。
以上所述的具体实施例，对本发明的目的、技术方案和有益效果进行了进一步详细说明，所应理解的是，以上所述仅为本发明的具体实施例而已，并不用于限定本发明的保护范围，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (11)

  1. 一种新型二次电池，其特征在于，包括：电池负极(1)、电解液(2)、隔膜(3)、电池正极(4)以及用于封装的电池壳体；其中，
    电池负极(1)包括负极集流体，不包含负极活性材料；
    电解液(2)包含酯类、砜类、醚类、腈类或烯烃类有机添加剂；
    电池正极(4)包括正极活性材料层，其中，正极活性材料由具有层状晶体结构的石墨类材料、硫化物、氮化物、氧化物、碳化物组成。
  2. 根据权利要求1所述的新型二次电池，其特征在于，电池负极(1)的负极集流体为导电材料，该导电材料为铝、铜、铁、锡、锌、镍、钛、锰中的一种或前述的合金。
  3. 根据权利要求1所述的新型二次电池，其特征在于，电解液(2)的组分还包含溶剂、电解质；其中，
    所述溶剂为酯类、砜类或醚类有机溶剂，选用碳酸二乙酯、碳酸二甲酯、碳酸甲乙酯、二甲基砜、二甲醚中的一种或多种；
    所述电解质为锂盐，选用六氟磷酸锂、四氟硼酸锂、高氯酸锂中的一种或多种，且浓度范围为0.1–10mol/L；
    所述酯类、砜类、醚类、腈类或烯烃类有机添加剂，选用碳酸亚乙烯酯、亚硫酸亚乙酯、亚硫酸丙烯酯、硫酸亚乙酯环丁基砜、1,3-二氧环戊烷、乙腈、长链烯烃中的一种或多种，且在电解液中的添加量为0.1-40％wt。
  4. 根据权利要求1所述的新型二次电池，其特征在于，隔膜(3)的成分为绝缘的多孔聚合物薄膜或无机多孔薄膜。
  5. 根据权利要求4所述的新型二次电池，其特征在于，隔膜(3)选用多孔聚丙烯薄膜、多孔聚乙烯薄膜、多孔复合聚合物薄膜、玻璃纤维纸或多孔陶瓷隔膜。
  6. 根据权利要求1所述的新型二次电池，其特征在于，电池正极(4)还包括正极集流体，该正极集流体为导电材料，该导电材料为铝、铜、铁、锡、锌、镍、钛、锰中的一种或前述的合金。
  7. 根据权利要求1所述的新型二次电池，其特征在于，电池正极(4)的正极活性材料层还包括导电剂、粘结剂，其中正极活性材料的份量为50–90％wt， 导电剂的含量为30–0.1％wt，粘结剂的含量为10–0.1％wt。
  8. 根据权利要求7所述的新型二次电池，其特征在于，在所述正极活性材料中的石墨类材料，选用天然石墨、人造石墨、石墨片中的一种或多种；
    硫化物，选用二硫化钼、二硫化钨、二硫化钒、二硫化钛中的一种或多种；
    氮化物，选用六方氮化硼、碳掺杂六方氮化硼中的一种或多种；
    氧化物，选用三氧化钼、三氧化钨、五氧化二钒、二氧化钛中的一种或多种；
    碳化物，选用碳化钛、碳化钽、碳化钼、碳化硅中的一种或多种。
  9. 根据权利要求7所述的新型二次电池，其特征在于，所述导电剂为导电乙炔黑、Super P导电碳球、导电石墨KS6、碳纳米管、导电碳纤维、石墨烯中的一种或多种。
  10. 根据权利要求7所述的新型二次电池，其特征在于，所述粘结剂为聚偏氟乙烯、聚四氟乙烯、聚乙烯醇、羧甲基纤维素、SBR橡胶、聚烯烃类中的一种或多种。
  11. 一种制备权利要求1至10中任一项所述的新型二次电池的方法，其特征在于，包括：
    制备电池负极；
    配制电解液；
    制备隔膜；
    制备电池正极；
    利用所述电池负极、电解液、隔膜、电池正极进行新型二次电池的组装。
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