WO2020124328A1

WO2020124328A1 - Pre-lithiated negative electrode fabrication method, fabricated pre-lithiated negative electrode, energy storage device, energy storage system, and electrical device

Info

Publication number: WO2020124328A1
Application number: PCT/CN2018/121573
Authority: WO
Inventors: 唐永炳; 张阁; 欧学武
Original assignee: 深圳先进技术研究院
Priority date: 2018-12-17
Filing date: 2018-12-17
Publication date: 2020-06-25

Abstract

The present application relates to the field of new energy. Specifically, a pre-lithiated negative electrode fabrication method, a fabricated pre-lithiated negative electrode, an energy storage device, an energy storage system, and an electrical device are provided. The pre-lithiated negative electrode fabrication method comprises: providing a half-cell, and charging or discharging the half-cell. An operation electrode of the half-cell is a metal material, and a counter electrode is a material capable of providing a lithium source. An electrolyte is a lithium salt solution containing additives. The metal material is a metal, an alloy, or a metal composite material capable of reacting with lithium ions to form an alloy. The additives comprise a substance capable of decomposing and forming an SEI film on a surface of the metal material. The method has a simple process, and is low-cost. The method forms an SEI passivation film on the surface of the metal material to prevent volume expansion and pulverization of the negative electrode, thereby improving the stability of the negative electrode. In addition, the alloy formed by means of pre-lithiation improves Coulombic efficiency, thereby improving discharging capacity and cycling performance.

Description

预嵌锂负极的制备方法及制备得到的预嵌锂负极、储能器件、储能***及用电设备Preparation method of pre-embedded lithium negative electrode and prepared pre-embedded lithium negative electrode, energy storage device, energy storage system and electrical equipment

技术领域Technical field

本申请涉及新能源领域，具体而言，涉及一种预嵌锂负极的制备方法及制备得到的预嵌锂负极、储能器件、储能***及用电设备。The present application relates to the field of new energy, and in particular, to a method for preparing a pre-embedded lithium negative electrode and the prepared pre-embedded lithium negative electrode, an energy storage device, an energy storage system, and electrical equipment.

背景技术Background technique

作为绿色储能器件，以锂离子电池为代表的二次电池通过电能与化学能之间的可逆转化实现储电和放电，被广泛应用于各个领域。锂离子电池主要由正负极活性材料、集流体、电解液环和隔膜等主要部分组成。锂离子电池依靠锂离子在正极与负极之间来回移动(嵌入和脱嵌过程)实现电池的充放电过程(因此又称为“摇椅式电池”)，具体而言，在充电时，锂离子从正极脱出，经过电解液嵌入负极；放电过程则相反。由于受到正负极材料理论比容量的限制，商用锂离子电池的能量密度十分有限。其中，负极材料目前主要采用改性天然石墨和人造石墨等，然而，石墨电极的比容量有限(372mAh/g)并且已经几乎达到了极限；同时石墨负极压实密度较低，极大地限制了电池高体积能量密度的获得。因此，对于更加廉价、高效以及低成本的负极材料关键技术的研发显得尤为迫切。As a green energy storage device, a secondary battery represented by a lithium ion battery realizes electricity storage and discharge through reversible conversion between electrical energy and chemical energy, and is widely used in various fields. Lithium ion batteries are mainly composed of positive and negative active materials, current collectors, electrolyte rings and separators. Lithium-ion batteries rely on lithium ions to move back and forth between the positive and negative electrodes (the process of insertion and extraction) to achieve the battery's charge and discharge process (hence the name "rocker battery"). Specifically, during charging, lithium ions The positive electrode comes out and is inserted into the negative electrode through the electrolyte; the discharge process is reversed. Due to the limitation of the theoretical specific capacity of positive and negative materials, the energy density of commercial lithium-ion batteries is very limited. Among them, the anode material currently mainly uses modified natural graphite and artificial graphite. However, the specific capacity of the graphite electrode is limited (372mAh/g) and has almost reached the limit; at the same time, the compact density of the graphite anode is low, which greatly limits the battery Achievement of high volume energy density. Therefore, the research and development of key technologies for cheaper, more efficient and lower-cost anode materials are particularly urgent.

初步研究表明，以高容量和低成本的廉价金属箔材作为电池负极，利用金属与锂离子的合金化/去合金化过程实现电池的充放电反应，可以获得高比容量及高能量密度的新型锂离子电池。相比于传统商用石墨类负极，金属负极在提高电池容量方面具有非常明显的优势。以金属铝为例，其理论比容量高达993mAh/g(合金化形成LiAl)，约为石墨负极容量的3倍。此外，廉价金属铝具有优异的导电性，可以同时充当电池的负极活性材料和负极集流体，从而有利于减小电池体积重量，降低生产成本，同时增加锂离子电池的能量密度。中国科学院深圳先进技术研究院曾利用金属铝的高比容量和良好的导电特性，以金属铝箔同时作为负极活性材料和集流体，传统的钴酸锂、磷酸铁锂和三元材料为正极活性材料，组建了新型电池体系，并申请了相关的专利(CN106654289A；PCT/CN2016/081346)。这一体系可以极大提高锂离子电池的能量密度，显著降低电池的综合成本，因此具有良好的商业化前景；然而金属铝箔在发生合金化/去合金化的过程中，体积会发生膨胀，造成粉化，导致电池库伦效率不高，容量衰减快。Preliminary research shows that using low-cost metal foil with high capacity and low cost as the negative electrode of the battery, the alloying/dealloying process of metal and lithium ion is used to realize the charge and discharge reaction of the battery, and a new type with high specific capacity and high energy density can be obtained. Lithium Ion Battery. Compared with traditional commercial graphite anodes, metal anodes have very obvious advantages in improving battery capacity. Taking metal aluminum as an example, its theoretical specific capacity is as high as 993mAh/g (alloyed to form LiAl), which is about 3 times the capacity of graphite anode. In addition, the cheap metal aluminum has excellent conductivity and can serve as both the negative electrode active material and the negative electrode current collector of the battery, thereby helping to reduce the battery weight and production cost, while increasing the energy density of the lithium ion battery. The Shenzhen Institute of Advanced Technology of the Chinese Academy of Sciences used the high specific capacity and good electrical conductivity of aluminum metal to simultaneously use aluminum foil as the negative electrode active material and current collector. Traditional lithium cobalt oxide, lithium iron phosphate, and ternary materials were used as positive electrode active materials. , Set up a new battery system, and applied for related patents (CN106654289A; PCT/CN2016/081346). This system can greatly increase the energy density of lithium ion batteries and significantly reduce the overall cost of the battery, so it has good commercial prospects; however, the volume of aluminum foil will expand during the alloying/dealloying process, causing Pulverization results in low battery coulombic efficiency and rapid capacity decay.

为了充分利用廉价、容量高和制备工艺简单的金属箔材作为电池负极，同时解决金属箔材作为电池负极而产生的库伦效率低以及容易粉化的问题，通常采用的办法是对箔材进行多孔化设计或者对其进行表面包覆。例如，专利PCT/CN2016/081344和PCT/CN2016/081345中提出，通过对金属铝箔进行多孔化设计，同时采用表面碳包覆的手段，能够有效抑制铝负极在充放电过程中的粉化，提高电池的循环使用寿命以及充放电倍率性能。然而，上述的方法需要采用比较复杂的工艺手段，譬如激光穿孔、电化学腐蚀和高温碳化等，从而增加了电池的整体成本。In order to make full use of the cheap, high-capacity and simple preparation of metal foils as battery anodes, and at the same time solve the problems of low coulombic efficiency and easy powdering caused by metal foils as battery negatives, the usual method is to make the foil porous Design or surface coating. For example, the patents PCT/CN2016/081344 and PCT/CN2016/081345 propose that through the porous design of metal aluminum foil and the use of surface carbon coating, it can effectively suppress the powdering of the aluminum anode during the charge and discharge process and improve Battery cycle life and charge-discharge rate performance. However, the above-mentioned methods require the use of more complicated process methods, such as laser perforation, electrochemical corrosion, and high-temperature carbonization, which increase the overall cost of the battery.

有鉴于此，特提出本申请。In view of this, this application is hereby submitted.

发明内容Summary of the invention

本申请的第一目的在于提供一种预嵌锂负极的制备方法，该方法工艺简单且成本低廉，该方法能够在金属材料表面形成SEI钝化膜，避免负极产生体积膨胀和被粉化，从而提高负极的稳定性，而预嵌锂形成的合金有助于提高库伦效率，从而提高放电容量和循环性能。The first objective of the present application is to provide a method for preparing a pre-embedded lithium negative electrode. This method is simple in process and low in cost. This method can form a SEI passivation film on the surface of a metal material to avoid volume expansion and pulverization of the negative electrode. Improve the stability of the negative electrode, and the alloy formed by pre-intercalating lithium helps to improve the Coulomb efficiency, thereby improving the discharge capacity and cycle performance.

本申请的第二目的在于提供一种采用上述预嵌锂负极的制备方法制备得到的预嵌锂负极，该负极具有成本低廉、稳定性高、自重低、能量密度高、比容量高、库仑效果高和循环性能好的优点。The second object of the present application is to provide a pre-intercalated lithium anode prepared by using the above pre-intercalated lithium negative electrode preparation method, which has low cost, high stability, low dead weight, high energy density, high specific capacity, and coulombic effect High and good cycle performance advantages.

本申请的第三目的在于提供一种储能器件，该储能器件包括采用上述预嵌锂负极的制备方法制备而成的预嵌锂负极，具有器件成本低廉、结构稳定、库仑效率高、放电容量高、能量密度高和循环性能好的优点。The third object of the present application is to provide an energy storage device including a pre-lithium-embedded negative electrode prepared by the above-mentioned method for preparing a pre-embedded lithium anode, which has low device cost, stable structure, high coulomb efficiency, and discharge The advantages of high capacity, high energy density and good cycle performance.

本申请的第四目的在于提供一种储能***，该储能***包括上述储能器件，具有成本低廉、结构稳定、库仑效率高、比容量高、能量密度高和循环性能好的优点。The fourth object of the present application is to provide an energy storage system including the above energy storage device, which has the advantages of low cost, stable structure, high coulomb efficiency, high specific capacity, high energy density and good cycle performance.

本申请的第五目的在于提供一种用电设备，该用电设备包括上述储能器件，具有成本低廉、比容量高、能量密度高和循环性能好的优点，该用电设备在相同的充放电电流以及相同环境下使用时，使用寿命更长。The fifth object of the present application is to provide an electrical equipment including the above energy storage device, which has the advantages of low cost, high specific capacity, high energy density and good cycle performance. The electrical equipment is charged at the same The discharge current and the service life are longer when used in the same environment.

为了实现本申请的上述目的，特采用以下技术方案：In order to achieve the above purpose of this application, the following technical solutions are specifically adopted:

第一方面，本申请提供了一种预嵌锂负极的制备方法，提供一半电池，对所述半电池进行充电或放电；In the first aspect, the present application provides a method for preparing a pre-embedded lithium negative electrode, providing a half battery, and charging or discharging the half battery;

其中，所述半电池的工作电极为金属材料，对电极为能够提供锂源的材料，电解液为含有添加剂的锂盐溶液；Wherein, the working electrode of the half-cell is a metal material, the counter electrode is a material capable of providing a lithium source, and the electrolyte is a lithium salt solution containing additives;

所述金属材料包括能够与锂离子发生合金化反应的金属、合金或金属复合材料；The metal material includes a metal, alloy or metal composite material capable of alloying reaction with lithium ions;

所述添加剂包括能够分解并在所述金属材料表面形成SEI膜的物质。The additive includes a substance capable of decomposing and forming an SEI film on the surface of the metal material.

作为进一步优选的技术方案，所述金属为铝、锡、镁、锌、铜、铁、镍、钛、锰、锑或铋中的任意一种；As a further preferred technical solution, the metal is any one of aluminum, tin, magnesium, zinc, copper, iron, nickel, titanium, manganese, antimony or bismuth;

或，所述合金为至少包括铝、锡、镁、锌、铜、铁、镍、钛、锰、锑或铋中的任意一种的合金；Or, the alloy is an alloy including at least any one of aluminum, tin, magnesium, zinc, copper, iron, nickel, titanium, manganese, antimony or bismuth;

或，所述金属复合材料为至少包括铝、锡、镁、锌、铜、铁、镍、钛、锰、锑或铋中的任意一种的复合材料；Or, the metal composite material is a composite material including at least any one of aluminum, tin, magnesium, zinc, copper, iron, nickel, titanium, manganese, antimony or bismuth;

优选地，所述金属材料的厚度为10-1000μm。Preferably, the thickness of the metal material is 10-1000 μm.

作为进一步优选的技术方案，所述能够提供锂源的材料包括金属锂或锂的化合物；As a further preferred technical solution, the material capable of providing a lithium source includes metallic lithium or a lithium compound;

优选地，所述锂的化合物包括硫化锂、氧化锂、硒化锂、氟化锂、草酸锂、钴酸锂、碳酸锂或磷酸铁锂中的至少一种；Preferably, the lithium compound includes at least one of lithium sulfide, lithium oxide, lithium selenide, lithium fluoride, lithium oxalate, lithium cobaltate, lithium carbonate, or lithium iron phosphate;

优选地，所述对电极为金属锂，对以金属锂作为对电极的半电池进行放电；Preferably, the counter electrode is metallic lithium, and the half-cell with metallic lithium as the counter electrode is discharged;

优选地，所述对电极为锂的化合物，对以锂的化合物作为对电极的半电池进行充电。Preferably, the counter electrode is a lithium compound, and a half-cell using the lithium compound as a counter electrode is charged.

作为进一步优选的技术方案，所述添加剂包括LiBOB、LiODFB、LiPO ₂F ₂、LiDFOP、LiBMB、LiDFMFMB、LiDFEFMB、LiDFPFMB或LiTFOP中的至少一种； As a further preferred technical solution, the additive includes at least one of LiBOB, LiODFB, LiPO ₂ F ₂ , LiDFOP, LiBMB, LiDFMFMB, LiDFEFMB, LiDFPFMB or LiTFOP;

优选地，所述添加剂在电解液中的质量分数为0.1％-30％，优选为8％-15％；Preferably, the mass fraction of the additive in the electrolyte is 0.1%-30%, preferably 8%-15%;

优选地，电解液中的锂盐包括六氟磷酸锂、四氟硼酸锂、氯化锂、碳酸锂、硫酸锂、硝酸锂、氟化锂、三氟甲磺酸锂、双(三氟甲基磺酰基)亚胺锂、双氟磺酰亚胺锂或高氯酸锂中的至少一种；Preferably, the lithium salt in the electrolyte includes lithium hexafluorophosphate, lithium tetrafluoroborate, lithium chloride, lithium carbonate, lithium sulfate, lithium nitrate, lithium fluoride, lithium trifluoromethanesulfonate, bis(trifluoromethylsulfonyl) At least one of lithium imide, lithium difluorosulfonimide, or lithium perchlorate;

优选地，所述电解液中，锂盐的浓度为0.1-10mol/L；Preferably, the concentration of the lithium salt in the electrolyte is 0.1-10mol/L;

优选地，所述电解液的溶剂包括酯类、砜类、醚类、腈类或烯烃类中的至少一种；Preferably, the solvent of the electrolyte includes at least one of esters, sulfones, ethers, nitriles or olefins;

优选地，所述电解液的溶剂包括碳酸丙烯酯(PC)、碳酸乙烯酯(EC)、碳酸二乙酯(DEC)、碳酸二甲酯(DMC)、碳酸甲乙酯(EMC)、甲酸甲酯(MF)、乙酸甲酯(MA)、N,N-二甲基乙酰胺(DMA)、氟代碳酸乙烯酯(FEC)、丙酸甲酯(MP)、丙酸乙酯(EP)、乙酸乙酯(EA)、γ-丁内酯(GBL)、四氢呋喃(THF)、2-甲基四氢呋喃(2MeTHF)、1,3-二氧环戊烷(DOL)、4-甲基-1,3-二氧环戊烷(4MeDOL)、二甲氧甲烷(DMM)、1,2-二甲氧丙烷(DMP)、三乙二醇二甲醚(DG)、二甲基砜(MSM)、二甲醚(DME)、亚硫酸乙烯酯(ES)、亚硫酸丙烯脂(PS)、亚硫酸二甲脂(DMS)、亚硫酸二乙脂(DES)或冠醚(12-冠-4)中的至少一种。Preferably, the solvent of the electrolyte includes propylene carbonate (PC), ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), methyl formate Ester (MF), methyl acetate (MA), N,N-dimethylacetamide (DMA), fluoroethylene carbonate (FEC), methyl propionate (MP), ethyl propionate (EP), Ethyl acetate (EA), γ-butyrolactone (GBL), tetrahydrofuran (THF), 2-methyltetrahydrofuran (2MeTHF), 1,3-dioxolane (DOL), 4-methyl-1, 3-dioxolane (4MeDOL), dimethoxymethane (DMM), 1,2-dimethoxypropane (DMP), triethylene glycol dimethyl ether (DG), dimethyl sulfone (MSM), Dimethyl ether (DME), vinyl sulfite (ES), propylene sulfite (PS), dimethyl sulfite (DMS), diethyl sulfite (DES) or crown ether (12-crown-4) At least one of them.

作为进一步优选的技术方案，充电或放电的电流为0.01-1mA/cm ²，充电或放电的时间为100-1小时； As a further preferred technical solution, the current for charging or discharging is 0.01-1 mA/cm ² , and the time for charging or discharging is 100-1 hours;

优选地，所述半电池还包括隔膜，所述隔膜包括玻璃纤维、聚乙烯隔膜、聚丙烯隔膜、或聚丙烯/聚乙烯/聚丙烯隔膜中的至少一种。Preferably, the half-cell further includes a separator including at least one of glass fiber, polyethylene separator, polypropylene separator, or polypropylene/polyethylene/polypropylene separator.

第二方面，本申请提供了一种采用上述预嵌锂负极的制备方法制备得到的预嵌锂负极。In a second aspect, the present application provides a pre-lithium-embedded negative electrode prepared by using the above method for preparing a pre-embedded lithium anode.

第三方面，本申请提供了一种储能器件，包括采用上述预嵌锂负极的制备方法制备而成的预嵌锂负极。In a third aspect, the present application provides an energy storage device, including a pre-lithium-embedded negative electrode prepared by using the above method for preparing a pre-embedded lithium anode.

作为进一步优选的技术方案，所述储能器件还包括正极材料；As a further preferred technical solution, the energy storage device further includes a cathode material;

优选地，储能器件为锂离子电池，正极材料包括锰酸锂、钴酸锂、磷酸铁锂或三元材料中的至少一种；Preferably, the energy storage device is a lithium ion battery, and the positive electrode material includes at least one of lithium manganate, lithium cobaltate, lithium iron phosphate, or ternary material;

优选地，储能器件为锂离子电容器，正极材料包括活性炭、碳纳米管、活性碳纤维、石墨烯、介孔碳、碳分子筛或炭泡沫中的至少一种；Preferably, the energy storage device is a lithium ion capacitor, and the positive electrode material includes at least one of activated carbon, carbon nanotubes, activated carbon fiber, graphene, mesoporous carbon, carbon molecular sieve, or carbon foam;

优选地，储能器件为双离子电池，正极材料包括天然石墨和/或膨胀石墨。Preferably, the energy storage device is a dual ion battery, and the positive electrode material includes natural graphite and/or expanded graphite.

第四方面，本申请提供了一种储能***，包括上述储能器件。In a fourth aspect, the present application provides an energy storage system, including the above energy storage device.

第五方面，本申请提供了一种用电设备，包括上述储能器件。According to a fifth aspect, the present application provides an electrical equipment, including the above energy storage device.

与现有技术相比，本申请的有益效果为：Compared with the prior art, the beneficial effects of this application are:

本申请所提供的预嵌锂负极的制备方法中采用金属材料作为工作电极、能够提供锂源的材料作为对电极和含有添加剂的锂盐溶液作为电解液组装而成的半电池进行充电或放电即可。上述预嵌锂的工作机理为：在充电或放电过程中，电解液中的添加剂首先分解，从而在金属材料表面形成SEI钝化膜，在进一步进行充电或放电过程中，锂离子通过钝化膜与金属材料发生合金化反应，形成金属材料与锂的合金，从而完成预嵌锂的过程。对电极主要是为了提供预嵌锂的锂源；采用金属材料的工作电极在预嵌锂完成后即为预嵌锂负极。In the method for preparing a pre-intercalated lithium anode provided in this application, a metal battery is used as a working electrode, a material capable of providing a lithium source is used as a counter electrode, and a lithium salt solution containing additives is used as an electrolyte to charge or discharge a half-cell assembled can. The working mechanism of the above pre-intercalated lithium is: during charging or discharging, the additives in the electrolyte are first decomposed, thereby forming a SEI passivation film on the surface of the metal material, and during further charging or discharging, lithium ions pass through the passivation film An alloying reaction occurs with the metal material to form an alloy of the metal material and lithium, thereby completing the process of pre-intercalating lithium. The counter electrode is mainly to provide a lithium source for pre-intercalating lithium; the working electrode using a metal material is a pre-intercalating lithium anode after the pre-intercalation of lithium is completed.

上述方法工艺简单且成本低廉。上述预嵌锂过程中形成的SEI钝化膜有利于提高负极的稳定性，减少负极在与锂离子发生合金化/去合金化的过程中而产生的体积膨胀，避免负极被粉化，而预嵌锂形成的合金有助于提高库伦效率，提高放电容量和循环性能。另外，由于负极为预嵌锂的金属材料，金属材料同时作为负极活性材料和负极集流体，能够有效减轻负极的自重，进一步增加储能器件的能量密度和比容量。The above method is simple in process and low in cost. The SEI passivation film formed during the above lithium pre-intercalation process is beneficial to improve the stability of the negative electrode, reduce the volume expansion of the negative electrode during alloying/dealloying with lithium ions, and prevent the negative electrode from being powdered. The alloy formed by intercalating lithium helps to improve the Coulomb efficiency, improve the discharge capacity and cycle performance. In addition, since the negative electrode is a metal material pre-intercalated with lithium, the metal material serves as both the negative electrode active material and the negative electrode current collector, which can effectively reduce the weight of the negative electrode and further increase the energy density and specific capacity of the energy storage device.

采用上述预嵌锂负极的制备方法得到的预嵌锂负极成本较低，且具有较高的稳定性，其在与锂离子发生合金化/去合金化的过程中而产生的体积膨胀小，不易被粉化，库仑效果高且循环性能好，且该负极具有自重低的优点，能够进一步增加储能器件的能量密度和比容量。The pre-lithium-embedded negative electrode prepared by the above method of pre-embedded lithium anode has low cost and high stability. Its volume expansion during alloying/dealloying with lithium ions is small, which is not easy After being powdered, the Coulomb effect is high and the cycle performance is good, and the negative electrode has the advantage of low self-weight, which can further increase the energy density and specific capacity of the energy storage device.

本申请提供的储能器件包括采用上述预嵌锂负极的制备方法制备而成的预嵌锂负极，因而具有器件成本低廉、结构稳定、库仑效率高、放电容量高、能量密度高和循环性能好的优点。The energy storage device provided by the present application includes the pre-intercalated lithium negative electrode prepared by the above pre-intercalated lithium negative electrode preparation method, and thus has low device cost, stable structure, high coulomb efficiency, high discharge capacity, high energy density and good cycle performance The advantages.

本申请提供的储能***包括上述储能器件，因而至少具有与上述储能器件相同的优势，具有成本低廉、结构稳定、库仑效率高、比容量高、能量密度高和循环性能好的优点。The energy storage system provided by the present application includes the above energy storage device, and therefore has at least the same advantages as the above energy storage device, and has the advantages of low cost, stable structure, high coulomb efficiency, high specific capacity, high energy density, and good cycle performance.

本申请提供的用电设备包括上述储能器件，因而至少具有与上述储能器件相同的优势，具有成本低廉、比容量高、能量密度高和循环性能好的优点，该用电设备在相同的充放电电流以及相同环境下使用时，使用寿命更长。The electrical equipment provided by the present application includes the above energy storage device, and therefore has at least the same advantages as the above energy storage device, and has the advantages of low cost, high specific capacity, high energy density, and good cycle performance. The electrical equipment is in the same When the charge and discharge current and the same environment are used, the service life is longer.

附图说明BRIEF DESCRIPTION

图1为本申请一种实施方式的预嵌锂负极的制备方法中半电池的结构示意图；1 is a schematic structural diagram of a half-cell in a method for preparing a pre-intercalated lithium anode according to an embodiment of the present application;

图2为本申请一种实施方式的储能器件的结构示意图；2 is a schematic structural diagram of an energy storage device according to an embodiment of the present application;

图3为实施例1和对比例1预嵌锂放电曲线；3 is a discharge curve of pre-intercalated lithium of Example 1 and Comparative Example 1;

图4(a)为对比例1得到的预嵌锂负极的表面形貌；4(a) is the surface morphology of the pre-lithium-embedded negative electrode obtained in Comparative Example 1;

图4(b)为实施例1得到的预嵌锂负极的表面形貌。FIG. 4(b) is the surface morphology of the lithium pre-doped negative electrode obtained in Example 1. FIG.

图标：1-工作电极；2-对电极；3-半电池电解液；5-半电池隔膜；6-预嵌锂负极；7-储能器件电解液；9-储能器件隔膜；10-正极活性物质；11-正极集流体。Pictograms: 1- working electrode; 2- counter electrode; 3- half-cell electrolyte; 5- half-cell separator; 6- pre-embedded lithium anode; 7- energy storage device electrolyte; 9- energy storage device separator; 10- positive electrode Active material; 11- positive electrode current collector.

具体实施方式detailed description

下面将结合实施例对本申请的实施方案进行详细描述，但是本领域技术人员将会理解，下列实施例仅用于说明本申请，而不应视为限制本申请的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。The embodiments of the present application will be described in detail below in conjunction with examples, but those skilled in the art will understand that the following examples are only used to illustrate the present application and should not be considered as limiting the scope of the present application. If no specific conditions are indicated in the examples, the conventional conditions or the conditions recommended by the manufacturer shall be used.

需要说明的是：It should be noted:

本申请中，如果没有特别的说明，本文所提到的所有实施方式以及优选实施方法可以相互组合形成新的技术方案。In this application, unless otherwise specified, all the embodiments and preferred implementation methods mentioned herein can be combined with each other to form a new technical solution.

本申请中，如果没有特别的说明，本文所提到的所有技术特征以及优选特征可以相互组合形成新的技术方案。In this application, if there is no special description, all the technical features and preferred features mentioned in this document can be combined with each other to form a new technical solution.

本申请中，如果没有特别的说明，百分数(％)或者份指的是相对于组合物的重量百分数或重量份。In this application, unless otherwise specified, the percentage (%) or part refers to the weight percentage or part by weight relative to the composition.

本申请中，如果没有特别的说明，所涉及的各组分或其优选组分可以相互组合形成新的技术方案。In this application, unless otherwise specified, the involved components or their preferred components can be combined with each other to form a new technical solution.

本申请中，除非有其他说明，数值范围“a-b”表示a到b之间的任意实数组合的缩略表示，其中a和b都是实数。例如数值范围“0.01-1”表示本文中已经全部列出了“0.01-1”之间的全部实数，“0.01-1”只是这些数值组合的缩略表示。In this application, unless otherwise stated, the numerical range "a-b" represents an abbreviated representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "0.01-1" means that all real numbers between "0.01-1" have been listed in this article, and "0.01-1" is just an abbreviated representation of these numerical combinations.

本申请所公开的“范围”以下限和上限的形式，可以分别为一个或多个下限，和一个或多个上限。The forms of the "lower limit" and the upper limit disclosed in the "range" of this application may be one or more lower limits and one or more upper limits, respectively.

本申请中，除非另有说明，各个反应或操作步骤可以顺序进行，也可以按照顺序进行。优选地，本文中的反应方法是顺序进行的。In this application, unless otherwise stated, each reaction or operation step may be performed sequentially or in order. Preferably, the reaction methods herein are performed sequentially.

除非另有说明，本文中所用的专业与科学术语与本领域熟练人员所熟悉的意义相同。此外，任何与所记载内容相似或均等的方法或材料也可应用于本申请中。Unless otherwise stated, the technical and scientific terms used in this article have the same meaning as those familiar to those skilled in the art. In addition, any method or material similar to or equivalent to the described content can also be applied to this application.

第一方面，在至少一个实施例中提供了一种预嵌锂负极的制备方法，提供一半电池，对所述半电池进行充电或放电；In the first aspect, in at least one embodiment, a method for preparing a pre-intercalated lithium negative electrode is provided, which provides half a battery and charges or discharges the half battery;

需要说明的是：It should be noted:

“能够与锂离子发生合金化反应的金属、合金或金属复合材料”是指能够与锂离子发生合金化反应的金属、能够与锂离子发生合金化反应的合金材料或能够与锂离子发生合金化反应的金属复合导电材料。"Metal, alloy or metal composite material capable of alloying reaction with lithium ions" means a metal capable of alloying reaction with lithium ions, an alloy material capable of alloying reaction with lithium ions or alloying with lithium ions Reactive metal composite conductive material.

“合金”是指由两种或两种以上的金属与金属或非金属经一定方法所合成的具有金属特性的物质。"Alloy" refers to a substance with metallic properties synthesized by two or more metals and metals or non-metals through a certain method.

“金属复合材料”是指金属与其他非金属材料结合所形成的金属基复合导电材料。典型但非限制性的金属复合材料包括石墨烯-金属复合材料、碳纤维-金属复合材料或陶瓷-金属复合材料等。"Metal composite material" refers to a metal-based composite conductive material formed by combining metals with other non-metallic materials. Typical but non-limiting metal composite materials include graphene-metal composite materials, carbon fiber-metal composite materials or ceramic-metal composite materials.

“能够提供锂源的材料”是指含有锂的材料，并且材料中的锂在半电池充电或放电过程中能够以锂离子的形式进入电解液中，进而与工作电极发生合金化反应形成金属材料与锂的合金。"Material capable of providing a lithium source" refers to a material containing lithium, and the lithium in the material can enter the electrolyte in the form of lithium ions during the charging or discharging of the half-cell, and then alloy with the working electrode to form a metal material Alloy with lithium.

应当理解的是，不同的“能够提供锂源的材料”的标准电极电位不同，当标准电极电位低于工作电极时，该对电极作为半电池的负极，对半电池进行放电从而实现金属材料的预嵌锂；当标准电极电位高于工作电极时，该对电极作为半电池的正极，对半电池进行充电从而实现金属材料的预嵌锂。It should be understood that different "materials capable of providing a lithium source" have different standard electrode potentials. When the standard electrode potential is lower than the working electrode, the pair of electrodes serves as the negative electrode of the half-cell, and the half-cell is discharged to realize the metal material. Lithium pre-insertion; when the standard electrode potential is higher than the working electrode, the pair of electrodes serves as the positive electrode of the half-cell, which charges the half-cell to realize the pre-lithium intercalation of metal materials.

“能够分解并在所述金属材料表面形成SEI膜”是指能够在半电池充电或放电过程中分解，然后在所述金属材料表面形成SEI钝化膜。"Able to decompose and form an SEI film on the surface of the metal material" means to be able to decompose during charging or discharging of the half-cell, and then form an SEI passivation film on the surface of the metal material.

上述预嵌锂负极的制备方法中采用金属材料作为工作电极、能够提供锂源的材料作为对电极和含有添加剂的锂盐溶液作为电解液组装而成的半电池进行充电或放电即可。上述预嵌锂的工作机理为：在充电或放电过程中，电解液中的添加剂首先分解，从而在金属材料表面形成SEI钝化膜，在进一步进行充电或放电过程中，锂离子通过钝化膜与金属材料发生合金化反应，形成金属材料与锂的合金，从而完成预嵌锂的过程。对电极主要是为了提供预嵌锂的锂源；采用金属材料的工作电极在预嵌锂完成后即为预嵌锂负极。In the above method for preparing a pre-intercalated lithium anode, a metal material is used as a working electrode, a material capable of providing a lithium source is used as a counter electrode, and a lithium salt solution containing additives is used as an electrolyte to charge or discharge a half-cell. The working mechanism of the above pre-intercalated lithium is: during charging or discharging, the additives in the electrolyte are first decomposed, thereby forming a SEI passivation film on the surface of the metal material, and during further charging or discharging, lithium ions pass through the passivation film An alloying reaction occurs with the metal material to form an alloy of the metal material and lithium, thereby completing the process of pre-intercalating lithium. The counter electrode is mainly to provide a lithium source for pre-intercalating lithium; the working electrode using a metal material is a pre-intercalating lithium anode after the pre-intercalation of lithium is completed.

SEI(Solid Electrolyte Interface)膜是指“固体电解质界面膜”，其形成于储能器件首次放电过程中，是电极材料与电解液在固液相界面上发生反应，从而形成的一层覆盖于电极材料表面的钝化层。SEI膜能在有机溶剂中稳定存在，并且能有效阻止溶剂分子的通过，避免溶剂分子与电极材料反应造成电极材料的破坏；而Li ⁺却可以经过该SEI膜自由地嵌入和脱出，不会对电池的充放电以及循环性能产生不良影响。 SEI (Solid Electrolyte Interface) film refers to the "solid electrolyte interface film", which is formed during the first discharge of the energy storage device. It is the reaction between the electrode material and the electrolyte at the solid-liquid interface, thus forming a layer covering the electrode Passivation layer on the surface of the material. The SEI film can stably exist in organic solvents, and can effectively prevent the passage of solvent molecules to avoid the destruction of the electrode material caused by the reaction of the solvent molecules with the electrode material; while Li ⁺ can freely insert and extract through the SEI film, it will not The battery's charge and discharge and cycle performance have an adverse effect.

上述方法工艺简单且成本低廉。上述预嵌锂过程中形成的SEI钝化膜有利于提高负极的稳定性，减少负极在与锂离子发生合金化/去合金化的过程中而产生的体积膨胀，避免负极被粉化，而预嵌锂形成的合金有助于提高负极的库伦效率，提高放电容量和循环性能。另外，由于负极为预嵌锂的金属材料，金属材料同时作为负极活性材料和负极集流体，能够有效减轻负极的自重，进一步增加储能器件的能量密度和比容量。The above method is simple in process and low in cost. The SEI passivation film formed during the above lithium pre-intercalation process is beneficial to improve the stability of the negative electrode, reduce the volume expansion of the negative electrode during alloying/dealloying with lithium ions, and prevent the negative electrode from being powdered. The alloy formed by intercalating lithium helps to improve the Coulomb efficiency of the negative electrode and improve the discharge capacity and cycle performance. In addition, since the negative electrode is a metal material pre-intercalated with lithium, the metal material serves as both the negative electrode active material and the negative electrode current collector, which can effectively reduce the weight of the negative electrode and further increase the energy density and specific capacity of the energy storage device.

在一种优选的实施方式中，所述金属为铝、锡、镁、锌、铜、铁、镍、钛、锰、锑或铋中的任意一种；In a preferred embodiment, the metal is any one of aluminum, tin, magnesium, zinc, copper, iron, nickel, titanium, manganese, antimony or bismuth;

或，所述金属复合材料为至少包括铝、锡、镁、锌、铜、铁、镍、钛、锰、锑或铋中的任意一种的复合材料。Or, the metal composite material is a composite material including at least any one of aluminum, tin, magnesium, zinc, copper, iron, nickel, titanium, manganese, antimony or bismuth.

上述合金典型但非限制性的为铝锡合金、镁锌合金、铜铁合金、镍钛合金、锰锑合金、锑铋合金、铝锡镁合金、锌铜铁合金、镍钛锰合金或锰锑铋合金等。上述金属复合材料典型但非限制性的为铝/石墨烯复合箔片、锡/石墨烯复合箔片、镁/石墨烯复合箔片或锌/石墨烯复合箔片等。Typical but non-limiting alloys are aluminum-tin alloy, magnesium-zinc alloy, copper-iron alloy, nickel-titanium alloy, manganese-antimony alloy, antimony-bismuth alloy, aluminum-tin-magnesium alloy, zinc-copper-iron alloy, nickel-titanium-manganese alloy, or manganese-antimony-bismuth alloy Wait. Typical but non-limiting metal composite materials are aluminum/graphene composite foil, tin/graphene composite foil, magnesium/graphene composite foil or zinc/graphene composite foil.

进一步地，所述金属材料的厚度为10～1000μm。上述金属材料的厚度典型但非限制性的为10μm、50μm、100μm、150μm、200μm、250μm、300μm、350μm、400μm、450μm、500μm、550μm、600μm、650μm、700μm、750μm、800μm、850μm、900μm、950μm或1000μm。Further, the thickness of the metal material is 10-1000 μm. Typical but non-limiting thicknesses of the above metal materials are 10 μm, 50 μm, 100 μm, 150 μm, 200 μm, 250 μm, 300 μm, 350 μm, 400 μm, 450 μm, 500 μm, 550 μm, 600 μm, 650 μm, 700 μm, 750 μm, 800 μm, 850 μm, 900 μm, 950μm or 1000μm.

需要说明的是，上述金属材料的形态优选为箔材，制备得到的预嵌锂负极的形态优选为片状。It should be noted that the form of the metal material is preferably a foil, and the form of the prepared lithium pre-doped negative electrode is preferably a sheet.

在一种优选的实施方式中，所述能够提供锂源的材料包括金属锂或锂的化合物。上述“锂的化合物”是指锂与其他一种或两种以上元素组成的物质。In a preferred embodiment, the material capable of providing the lithium source includes metallic lithium or lithium compounds. The above "lithium compound" refers to a substance composed of lithium and one or more elements.

优选地，所述锂的化合物包括硫化锂、氧化锂、硒化锂、氟化锂、草酸锂、钴酸锂、碳酸锂或磷酸铁锂中的至少一种。上述锂的化合物典型但非限制性的为硫化锂，氧化锂，硒化锂，氟化锂，草酸锂，钴酸锂，碳酸锂，磷酸铁锂，硫化锂和氧化锂的组合，硒化锂和氟化锂的组合，草酸锂和钴酸锂的组合，碳酸锂和磷酸铁锂的组合，硫化锂、氧化锂和硒化锂的组合，氟化锂、草酸锂和钴酸锂的组合，或，钴酸锂、碳酸锂和磷酸铁锂的组合等。Preferably, the lithium compound includes at least one of lithium sulfide, lithium oxide, lithium selenide, lithium fluoride, lithium oxalate, lithium cobaltate, lithium carbonate, or lithium iron phosphate. Typical but non-limiting lithium compounds are lithium sulfide, lithium oxide, lithium selenide, lithium fluoride, lithium oxalate, lithium cobaltate, lithium carbonate, lithium iron phosphate, a combination of lithium sulfide and lithium oxide, lithium selenide Combination with lithium fluoride, combination of lithium oxalate and lithium cobaltate, combination of lithium carbonate and lithium iron phosphate, combination of lithium sulfide, lithium oxide and lithium selenide, combination of lithium fluoride, lithium oxalate and lithium cobaltate, Or, a combination of lithium cobaltate, lithium carbonate, and lithium iron phosphate.

优选地，所述对电极为金属锂，对以金属锂作为对电极的半电池进行放电。金属锂的标准电极电位低于工作电极的标准电极电位，因此以金属锂作为对电极在半电池中实际为负极，对该半电池进行放电，金属锂中的锂离子即可溶入电解液中，对工作电极的金属材料进行预嵌锂。Preferably, the counter electrode is metallic lithium, and the half-cell with metallic lithium as the counter electrode is discharged. The standard electrode potential of metal lithium is lower than the standard electrode potential of the working electrode, so using metal lithium as the counter electrode is actually the negative electrode in the half-cell, and the half-cell is discharged, and the lithium ions in the metal lithium can be dissolved into the electrolyte , Pre-intercalate lithium on the metal material of the working electrode.

优选地，所述对电极为锂的化合物，对以锂的化合物作为对电极的半电池进行充电。锂的化合物的标准电极电位高于工作电极的标准电极电位，因此以锂的化合物作为对电极在半电池中实际为正极，对该半电池进行充电，锂的化合物中的锂离子即可脱出进入电解液中，对工作电极的金属材料进行预嵌锂。Preferably, the counter electrode is a lithium compound, and a half-cell using the lithium compound as a counter electrode is charged. The standard electrode potential of the lithium compound is higher than the standard electrode potential of the working electrode, so the lithium compound as the counter electrode is actually the positive electrode in the half-cell, and the half-cell is charged, and the lithium ions in the lithium compound can be taken out into the In the electrolyte, the metal material of the working electrode is pre-doped with lithium.

需要说明的是，当以锂的化合物作为对电极时，对电极中包括电极材料和电极集流体，电极材料包括电极活性物质、溶剂、导电剂和粘结剂等，其中电极活性物质为上述锂的化合物，本申请对上述电极集流体、溶剂、导电剂和粘结剂不做特别限制，采用现有技术中的即可。It should be noted that when a compound of lithium is used as the counter electrode, the counter electrode includes an electrode material and an electrode current collector, and the electrode material includes an electrode active material, a solvent, a conductive agent, a binder, etc., wherein the electrode active material is the above lithium In this application, the present application does not specifically limit the above-mentioned electrode current collector, solvent, conductive agent and binder, and only those in the prior art may be used.

在一种优选的实施方式中，所述添加剂包括LiBOB、LiODFB、LiPO ₂F ₂、LiDFOP、LiBMB、LiDFMFMB、LiDFEFMB、LiDFPFMB或LiTFOP中的至少一种。LiBOB为二草酸硼酸锂，LiODFB为二氟草酸硼酸锂，LiPO ₂F ₂为二氟磷酸锂，LiDFOP为二氟双草酸磷酸锂，LiBMB双丙二酸硼酸锂，LiDFMFMB为二氟-2-甲基-2-氟代丙二酸锂，LiDFEFMB为二氟-2-乙基-2-氟代丙二酸锂，LiDFPFMB为二氟-2-丙基-2-氟代丙二酸锂，LiTFOP为四氟草酸磷酸锂。上述添加剂在半电池充电或放电时易于分解，且分解后能在金属材料表面形成稳定且性能优良的SEI钝化膜。 In a preferred embodiment, the additive includes at least one of LiBOB, LiODFB, LiPO ₂ F ₂ , LiDFOP, LiBMB, LiDFMFMB, LiDFEFMB, LiDFPFMB or LiTFOP. LiBOB is lithium dioxalate borate, LiODFB is lithium difluorooxalate borate, LiPO ₂ F ₂ is lithium difluorophosphate, LiDFOP is lithium difluorobisoxalate phosphate, LiBMB lithium dimalonate borate, and LiDFMFMB is difluoro-2-methyl Lithium-2-fluoromalonate, LiDFEFMB is lithium difluoro-2-ethyl-2-fluoromalonate, LiDFPFMB is lithium difluoro-2-propyl-2-fluoromalonate, LiTFOP Lithium tetrafluorooxalate phosphate. The above additives are easily decomposed when the half-cell is charged or discharged, and after decomposition, a stable and excellent SEI passivation film can be formed on the surface of the metal material.

上述添加剂典型但非限制性的为LiBOB，LiODFB，LiPO ₂F ₂，LiDFOP，LiBMB，LiDFMFMB，LiDFEFMB，LiDFPFMB，LiTFOP，LiBOB和LiODFB的组合，LiPO ₂F ₂和LiDFOP的组合，LiBMB和LiDFMFMB的组合，LiDFEFMB和LiDFPFMB的组合，LiDFPFMB和LiTFOP的组合，LiBOB、LiODFB和LiPO ₂F ₂的组合，LiDFOP、LiBMB和LiDFMFMB的组合，或，LiDFEFMB、LiDFPFMB和LiTFOP的组合等。 Typical but non-limiting additives are LiBOB, LiODFB, LiPO ₂ F ₂ , LiDFOP, LiBMB, LiDFMFMB, LiDFEFMB, LiDFPFMB, LiTFOP, the combination of LiBOB and LiODFB, the combination of LiPO ₂ F ₂ and LiDFOP, the combination of LiBMB and LiDFMFMB , The combination of LiDFEFMB and LiDFPFMB, the combination of LiDFPFMB and LiTFOP, the combination of LiBOB, LiODFB and LiPO ₂ F ₂ , the combination of LiDFOP, LiBMB and LiDFMFMB, or the combination of LiDFEFMB, LiDFPFMB and LiTFOP, etc.

在一种优选的实施方式中，所述添加剂在电解液中的质量分数为0.1％-30％，优选为8％-15％。上述质量分数典型但非限制性的为0.1％、0.5％、1％、2％、4％、6％、8％、10％、12％、14％、16％、18％、20％、22％、24％、26％、28％或30％。通过调节添加剂的质量份数，可以调控SEI膜的厚度。当添加剂的质量分数为0.1％-30％时，SEI膜的厚度较为合理，减少负极在首次放电时的不可逆的容量损失，保证负极具有良好的稳定性，同时不会影响负极的电化学性能。In a preferred embodiment, the mass fraction of the additive in the electrolyte is 0.1%-30%, preferably 8%-15%. Typical but non-limiting quality scores above are 0.1%, 0.5%, 1%, 2%, 4%, 6%, 8%, 10%, 12%, 14%, 16%, 18%, 20%, 22 %, 24%, 26%, 28% or 30%. By adjusting the mass fraction of additives, the thickness of the SEI film can be adjusted. When the mass fraction of the additive is 0.1%-30%, the thickness of the SEI film is more reasonable, reducing the irreversible capacity loss of the negative electrode during the first discharge, ensuring the negative electrode has good stability, and does not affect the electrochemical performance of the negative electrode.

进一步地，上述锂盐包括六氟磷酸锂、四氟硼酸锂、氯化锂、碳酸锂、硫酸锂、硝酸锂、氟化锂、三氟甲磺酸锂、双(三氟甲基磺酰基)亚胺锂、双氟磺酰亚胺锂或高氯酸锂中的至少一种。上述锂盐典型但非限制性的为六氟磷酸锂，四氟硼酸锂，氯化锂，碳酸锂，硫酸锂，硝酸锂，氟化锂，三氟甲磺酸锂，双(三氟甲基磺酰基)亚胺锂，双氟磺酰亚胺锂，高氯酸锂，六氟磷酸锂和四氟硼酸锂的组合，氯化锂和碳酸锂的组合，硫酸锂和硝酸锂的组合，氟化锂和三氟甲磺酸锂的组合，双(三氟甲基磺酰基)亚胺锂和双氟磺酰亚胺锂的组合，六氟磷酸锂、四氟硼酸锂和氯化锂的组合，碳酸锂、硫酸锂和硝酸锂的组合，氟化锂、三氟甲磺酸锂和双(三氟甲基磺酰基)亚胺锂的组合，或，双(三氟甲基磺酰基)亚胺锂、双氟磺酰亚胺锂和高氯酸锂的组合等。Further, the lithium salt includes lithium hexafluorophosphate, lithium tetrafluoroborate, lithium chloride, lithium carbonate, lithium sulfate, lithium nitrate, lithium fluoride, lithium trifluoromethanesulfonate, lithium bis(trifluoromethylsulfonyl)imide , At least one of lithium bisfluorosulfonimide or lithium perchlorate. Typical but non-limiting lithium salts are lithium hexafluorophosphate, lithium tetrafluoroborate, lithium chloride, lithium carbonate, lithium sulfate, lithium nitrate, lithium fluoride, lithium trifluoromethanesulfonate, bis(trifluoromethylsulfonyl) Lithium imide, lithium difluorosulfonylimide, lithium perchlorate, lithium hexafluorophosphate and lithium tetrafluoroborate, lithium chloride and lithium carbonate, lithium sulfate and lithium nitrate, lithium fluoride and trifluoromethane Combination of lithium sulfonate, combination of lithium bis(trifluoromethylsulfonyl)imide and lithium bisfluorosulfonimide, combination of lithium hexafluorophosphate, lithium tetrafluoroborate and lithium chloride, lithium carbonate, lithium sulfate and lithium nitrate Combination of lithium fluoride, lithium trifluoromethanesulfonate and lithium bis(trifluoromethylsulfonyl)imide, or lithium bis(trifluoromethylsulfonyl)imide, difluorosulfonimide Combination of lithium and lithium perchlorate.

进一步地，所述电解液中，锂盐的浓度为0.1-10mol/L。上述锂盐的浓度典型但非限制性的为0.1mol/L、0.5mol/L、1mol/L、1.5mol/L、2mol/L、2.5mol/L、3mol/L、3.5mol/L、4mol/L、4.5mol/L、5mol/L、5.5mol/L、6mol/L、6.5mol/L、7mol/L、7.5mol/L、8mol/L、8.5mol/L、9mol/L、9.5mol/L或10mol/L。Further, in the electrolyte, the lithium salt concentration is 0.1-10 mol/L. Typical but non-limiting concentrations of the above lithium salts are 0.1mol/L, 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, 3.5mol/L, 4mol /L, 4.5mol/L, 5mol/L, 5.5mol/L, 6mol/L, 6.5mol/L, 7mol/L, 7.5mol/L, 8mol/L, 8.5mol/L, 9mol/L, 9.5mol /L or 10mol/L.

进一步地，电解液的溶剂包括碳酸丙烯酯(PC)、碳酸乙烯酯(EC)、碳酸二乙酯(DEC)、碳酸二甲酯(DMC)、碳酸甲乙酯(EMC)、甲酸甲酯(MF)、乙酸甲酯(MA)、N,N-二甲基乙酰胺(DMA)、氟代碳酸乙烯酯(FEC)、丙酸甲酯(MP)、丙酸乙酯(EP)、乙酸乙酯(EA)、γ-丁内酯(GBL)、四氢呋喃(THF)、2-甲基四氢呋喃(2MeTHF)、1,3-二氧环戊烷(DOL)、4-甲基-1,3-二氧环戊烷(4MeDOL)、二甲氧甲烷(DMM)、1,2-二甲氧丙烷(DMP)、三乙二醇二甲醚(DG)、二甲基砜(MSM)、二甲醚(DME)、亚硫酸乙烯酯(ES)、亚硫酸丙烯脂(PS)、亚硫酸二甲脂(DMS)、亚硫酸二乙脂(DES)或冠醚(12-冠-4)中的至少一种。Further, the solvent of the electrolyte includes propylene carbonate (PC), ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), and methyl formate ( MF), methyl acetate (MA), N,N-dimethylacetamide (DMA), fluoroethylene carbonate (FEC), methyl propionate (MP), ethyl propionate (EP), ethyl acetate Ester (EA), γ-butyrolactone (GBL), tetrahydrofuran (THF), 2-methyltetrahydrofuran (2MeTHF), 1,3-dioxolane (DOL), 4-methyl-1,3- Dioxolane (4MeDOL), dimethoxymethane (DMM), 1,2-dimethoxypropane (DMP), triethylene glycol dimethyl ether (DG), dimethyl sulfone (MSM), dimethyl Ether (DME), vinyl sulfite (ES), propylene sulfite (PS), dimethyl sulfite (DMS), diethyl sulfite (DES) or crown ether (12-crown-4) At least one.

上述溶剂典型但非限制性的为碳酸丙烯酯，碳酸乙烯酯，碳酸二乙酯，碳酸二甲酯，碳酸甲乙酯，甲酸甲酯，乙酸甲酯，N,N-二甲基乙酰胺，氟代碳酸乙烯酯，丙酸甲酯，丙酸乙酯，乙酸乙酯，γ-丁内酯，四氢呋喃，2-甲基四氢呋喃，1,3-二氧环戊烷，4-甲基-1,3-二氧环戊烷，二甲氧甲烷，1,2-二甲氧丙烷，三乙二醇二甲醚，二甲基砜，二甲醚，亚硫酸乙烯酯，亚硫酸丙烯脂，亚硫酸二甲脂，亚硫酸二乙脂，冠醚(12-冠-4)，碳酸丙烯酯和碳酸乙烯酯的组合，碳酸二乙酯和碳酸二甲酯的组合，碳酸甲乙酯和甲酸甲酯的组合，乙酸甲酯和N,N-二甲基乙酰胺的组合，氟代碳酸乙烯酯和丙酸甲酯的组合，丙酸乙酯和乙酸乙酯的组合，γ-丁内酯和四氢呋喃的组合，2-甲基四氢呋喃和1,3-二氧环戊烷的组合，4-甲基-1,3-二氧环戊烷和二甲氧甲烷的组合，1,2-二甲氧丙烷和三乙二醇二甲醚的组合，二甲基砜和二甲醚的组合，亚硫酸乙烯酯和亚硫酸丙烯脂的组合，亚硫酸二甲脂和亚硫酸二乙脂的组合，碳酸丙烯酯、碳酸乙烯酯和碳酸二乙酯的组合，碳酸二甲酯、碳酸甲乙酯和甲酸甲酯的组合，乙酸甲酯、N,N-二甲基乙酰胺和氟代碳酸乙烯酯的组合，丙酸甲酯、丙酸乙酯和乙酸乙酯的组合，γ-丁内酯、四氢呋喃和2-甲基四氢呋喃的组合，1,3-二氧环戊烷、4-甲基-1,3-二氧环戊烷和二甲氧甲烷的组合，1,2-二甲氧丙烷、三乙二醇二甲醚和二甲基砜的组合，二甲醚、亚硫酸乙烯酯和亚硫酸丙烯脂的组合，或，亚硫酸二甲脂、亚硫酸二乙脂和冠醚(12-冠-4)的组合等。Typical but non-limiting solvents are propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, methyl formate, methyl acetate, N,N-dimethylacetamide, Fluoroethylene carbonate, methyl propionate, ethyl propionate, ethyl acetate, γ-butyrolactone, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 4-methyl-1 ,3-dioxolane, dimethoxymethane, 1,2-dimethoxypropane, triethylene glycol dimethyl ether, dimethyl sulfone, dimethyl ether, vinyl sulfite, propylene sulfite, Dimethyl sulfite, diethyl sulfite, crown ether (12-crown-4), combination of propylene carbonate and ethylene carbonate, combination of diethyl carbonate and dimethyl carbonate, ethyl methyl carbonate and formic acid Combination of methyl ester, combination of methyl acetate and N,N-dimethylacetamide, combination of fluoroethylene carbonate and methyl propionate, combination of ethyl propionate and ethyl acetate, γ-butyrolactone Combination with tetrahydrofuran, combination of 2-methyltetrahydrofuran and 1,3-dioxolane, combination of 4-methyl-1,3-dioxolane and dimethoxymethane, 1,2-dioxane Combination of methoxypropane and triethylene glycol dimethyl ether, combination of dimethyl sulfone and dimethyl ether, combination of vinyl sulfite and propylene sulfite, combination of dimethyl sulfite and diethyl sulfite , A combination of propylene carbonate, ethylene carbonate and diethyl carbonate, a combination of dimethyl carbonate, ethyl methyl carbonate and methyl formate, methyl acetate, N,N-dimethylacetamide and fluoroethylene carbonate Combination of esters, combination of methyl propionate, ethyl propionate and ethyl acetate, combination of γ-butyrolactone, tetrahydrofuran and 2-methyltetrahydrofuran, 1,3-dioxolane, 4-methyl -1,3-dioxolane and dimethoxymethane combination, 1,2-dimethoxypropane, triethylene glycol dimethyl ether and dimethyl sulfone combination, dimethyl ether, vinyl sulfite Combination with propylene sulfite or dimethyl sulfite, diethyl sulfite and crown ether (12-crown-4), etc.

在一种优选的实施方式中，充电或放电的电流为0.01-1mA/cm ²，充电或放电的时间为100-1小时。 In a preferred embodiment, the current for charging or discharging is 0.01-1 mA/cm ² , and the time for charging or discharging is 100-1 hours.

上述充电或放电的电流典型但非限制性的为0.01mA/cm ²、0.1mA/cm ²、0.2mA/cm ²、 0.3mA/cm ²、0.4mA/cm ²、0.5mA/cm ²、0.6mA/cm ²、0.7mA/cm ²、0.8mA/cm ²、0.9mA/cm ²或1mA/cm ²。通过调节充电或放电的电流大小，可以调控SEI膜的厚度。当充电或放电的电流为0.01-1mA/cm ²时，SEI膜的厚度较为合理，减少负极在首次放电时的不可逆的容量损失，保证负极具有良好的稳定性，同时不会影响负极的电化学性能。 Typical currents of charging or discharging are 0.01 mA/cm ² , 0.1 mA/cm ² , 0.2 mA/cm ² , 0.3 mA/cm ² , 0.4 mA/cm ² , 0.5 mA/cm ² , 0.6 mA/cm ² , 0.7mA/cm ² , 0.8mA/cm ² , 0.9mA/cm ² or 1mA/cm ² . The thickness of the SEI film can be adjusted by adjusting the amount of current charged or discharged. When the charging or discharging current is 0.01-1mA/cm ² , the thickness of the SEI film is more reasonable, reducing the irreversible capacity loss of the negative electrode during the first discharge, ensuring the negative electrode has good stability, and does not affect the negative electrode's electrochemistry performance.

上述充电或放电的时间典型但非限制性的为100小时、95小时、90小时、85小时、80小时、75小时、70小时、65小时、60小时、55小时、50小时、45小时、40小时、35小时、30小时、25小时、20小时、15小时、10小时、5小时或1小时。通过调节充电或放电的时间，可以调控预嵌锂的深度。当充电或放电的时间为100-1小时，金属材料中预嵌锂的深度较为合理，保证负极具有较高的库仑效率，提高储能器件的放电容量。The above charging or discharging time is typically but not limited to 100 hours, 95 hours, 90 hours, 85 hours, 80 hours, 75 hours, 70 hours, 65 hours, 60 hours, 55 hours, 50 hours, 45 hours, 40 Hours, 35 hours, 30 hours, 25 hours, 20 hours, 15 hours, 10 hours, 5 hours or 1 hour. By adjusting the charging or discharging time, the depth of pre-intercalated lithium can be adjusted. When the charging or discharging time is 100-1 hours, the depth of pre-intercalated lithium in the metal material is more reasonable, to ensure that the negative electrode has a higher Coulomb efficiency, and improve the discharge capacity of the energy storage device.

进一步地，所述预嵌锂负极的制备方法包括以下步骤：Further, the preparation method of the pre-intercalated lithium anode includes the following steps:

(a)将所需尺寸的金属箔片作为工作电极备用；(a) Use the metal foil of the required size as the working electrode;

(b)将所需尺寸的金属锂作为对电极备用；(b) The metal lithium of the required size is used as the counter electrode;

(c)配制含有添加剂的电解液备用；(c) Prepare electrolyte containing additives for future use;

(d)将工作电极、对电极和电解液组装成半电池；(d) The working electrode, counter electrode and electrolyte are assembled into a half-cell;

(e)对半电池进行放电，放电完成后得到的预嵌锂的金属箔片即为预嵌锂负极。(e) Discharge the half-cell. The pre-intercalated lithium metal foil obtained after the discharge is the pre-intercalated lithium negative electrode.

进一步地，半电池还包括隔膜，所述隔膜包括但不限于玻璃纤维、聚乙烯隔膜、聚丙烯隔膜、或聚丙烯/聚乙烯/聚丙烯隔膜等。Further, the half-cell also includes a separator, which includes but is not limited to glass fiber, polyethylene separator, polypropylene separator, or polypropylene/polyethylene/polypropylene separator, and the like.

如图1所示为一种半电池的结构示意图，工作电极1和对电极2之间有半电池电解液3和半电池隔膜5，半电池电解液3与工作电极1相接触，半电池隔膜5与对电极2相接触。As shown in FIG. 1, it is a schematic structural diagram of a half-cell. There is a half-cell electrolyte 3 and a half-cell separator 5 between the working electrode 1 and the counter electrode 2. The half-cell electrolyte 3 is in contact with the working electrode 1 and the half-cell separator 5 is in contact with the counter electrode 2.

第二方面，在至少一个实施例中提供了一种采用上述预嵌锂负极的制备方法制备得到的预嵌锂负极。In a second aspect, in at least one embodiment, a pre-lithium-embedded negative electrode prepared by using the above-mentioned method for preparing a pre-embedded lithium anode is provided.

采用上述预嵌锂负极的制备方法得到的预嵌锂负极成本较低，且具有较高的稳定性，其在与锂离子发生合金化/去合金化的过程中而产生的体积膨胀小，不易被粉化，库仑效果高且循环性能好，且该负极具有自重低的优点，能够进一步增加储能器件的能量密度和比容量。The pre-lithium-embedded negative electrode obtained by the above method for preparing a pre-embedded lithium anode has low cost and high stability, and its volume expansion during alloying/dealloying with lithium ions is small, which is not easy After being powdered, the Coulomb effect is high and the cycle performance is good, and the negative electrode has the advantage of low self-weight, which can further increase the energy density and specific capacity of the energy storage device.

第三方面，在至少一个实施例中提供了一种储能器件，包括采用上述预嵌锂负极的制备方法制备而成的预嵌锂负极。该储能器件包括采用上述预嵌锂负极的制备方法制备而成的预嵌锂负极，因而具有器件成本低廉、结构稳定、库仑效率高、放电容量高、能量密度高和循环性能好的优点。In a third aspect, in at least one embodiment, an energy storage device is provided, including a pre-lithium-embedded negative electrode prepared by using the above-mentioned method for preparing a pre-embedded lithium anode. The energy storage device includes the pre-intercalated lithium negative electrode prepared by the above pre-intercalated lithium negative electrode preparation method, and thus has the advantages of low device cost, stable structure, high coulomb efficiency, high discharge capacity, high energy density and good cycle performance.

上述储能器件包括但不限于锂离子电池、双离子电池或锂离子电容器等。The above energy storage devices include but are not limited to lithium ion batteries, dual ion batteries, or lithium ion capacitors.

上述储能器件的核心在于包括采用上述预嵌锂负极的制备方法制备而成的预嵌锂负极，除此之外，该储能器件还包括现有储能器件的其他组件或部件，例如，与预嵌锂负极相匹配的正极、电解液、隔膜和壳体等，本申请对此并不作特别限制；另外，该储能器件的制备方法采用现有的制备方法进行制备即可，本申请对此并不作特别限制。The core of the above energy storage device is to include the pre-intercalated lithium negative electrode prepared by the above-mentioned pre-intercalated lithium negative electrode preparation method. In addition, the energy storage device also includes other components or parts of the existing energy storage device, for example, This application does not specifically limit the positive electrode, electrolyte, separator, and casing that match the pre-embedded lithium negative electrode; in addition, the preparation method of the energy storage device can be prepared by using the existing preparation method, this application There is no particular restriction on this.

优选地，储能器件为锂离子电池，正极材料包括锰酸锂、钴酸锂、磷酸铁锂或三元材料中的至少一种。其中三元材料包括镍钴锰三元材料和/或镍钴铝三元材料。Preferably, the energy storage device is a lithium ion battery, and the positive electrode material includes at least one of lithium manganate, lithium cobaltate, lithium iron phosphate, or a ternary material. The ternary materials include nickel-cobalt-manganese ternary materials and/or nickel-cobalt-aluminum ternary materials.

优选地，储能器件为锂离子电容器，正极材料包括活性炭、碳纳米管、活性碳纤维、石墨烯、介孔碳、碳分子筛或炭泡沫中的至少一种。Preferably, the energy storage device is a lithium ion capacitor, and the positive electrode material includes at least one of activated carbon, carbon nanotubes, activated carbon fiber, graphene, mesoporous carbon, carbon molecular sieve, or carbon foam.

示例性地，正极集流体包括铝、铜、铁、锡、锌、镍、钛或锰中的任意一种或至少含有上述任意一种金属元素的合金，或至少含有上述任意一种金属元素的金属复合材料。Exemplarily, the positive electrode current collector includes any one of aluminum, copper, iron, tin, zinc, nickel, titanium, or manganese, or an alloy containing at least any one of the above metal elements, or an alloy containing at least any one of the above metal elements Metal composite materials.

示例性地，储能器件的制备方法如下：Exemplarily, the manufacturing method of the energy storage device is as follows:

(a)按一定比例称取正极活性材料、导电剂以及粘结剂，之后加入溶剂充分混合形成均匀浆料；其中，浆料中，正极活性材料的质量含量为60％-95％，导电剂的质量含量为5％-30％，粘结剂的质量含量为5％-10％；(a) Weigh the positive electrode active material, conductive agent and binder according to a certain ratio, then add the solvent to mix thoroughly to form a uniform slurry; wherein, in the slurry, the mass content of the positive electrode active material is 60%-95%, the conductive agent The mass content is 5%-30%, and the binder mass content is 5%-10%;

(b)将所述浆料均匀涂覆于正极集流体表面，形成正极活性材料层，待完全干燥后压制并裁切，得到所需尺寸的储能器件正极；(b) The slurry is evenly coated on the surface of the positive electrode current collector to form a positive electrode active material layer, which is pressed and cut after being completely dried to obtain a positive electrode for an energy storage device of a desired size;

(c)配制常规的电解液，加入一定质量分数的添加剂；(c) Formulate conventional electrolytes and add additives with a certain mass fraction;

(d)以采用上述预嵌锂负极的制备方法制备而成的预嵌锂负极作为负极，通过涂片制备的极片作为正极装配储能器件。(d) The pre-intercalated lithium negative electrode prepared by the above-mentioned pre-intercalated lithium negative electrode preparation method is used as the negative electrode, and the pole piece prepared by coating is used as the positive electrode to assemble the energy storage device.

步骤(c)中的添加剂为常规的电解液添加剂，包括酯类、砜类、醚类、腈类以及烯烃类有机溶剂，包括氟代碳酸乙烯酯、碳酸亚乙烯酯、碳酸乙烯亚乙酯、1,3-丙磺酸内酯、1,4-丁磺酸内酯、硫酸乙烯酯、硫酸丙烯酯、硫酸亚乙酯、亚硫酸乙烯酯、亚硫酸丙烯酯、二甲基亚硫酸酯、二乙基亚硫酸酯、亚硫酸亚乙酯、氯代甲酸甲脂或二甲基亚砜中的至少一种。The additives in step (c) are conventional electrolyte additives, including esters, sulfones, ethers, nitriles and olefin organic solvents, including fluoroethylene carbonate, vinylene carbonate, ethylene ethylene carbonate, 1,3-propane sultone, 1,4-butane sultone, vinyl sulfate, propylene sulfate, ethylene sulfate, vinyl sulfite, propylene sulfite, dimethyl sulfite, At least one of diethyl sulfite, ethylene sulfite, methyl chloroformate, or dimethyl sulfoxide.

如图2所示为一种储能器件，包括依次设置的预嵌锂负极6、储能器件隔膜9、储能器件电解液7、正极活性物质10和正极集流体11。As shown in FIG. 2, an energy storage device includes a pre-intercalated lithium negative electrode 6, an energy storage device separator 9, an energy storage device electrolyte 7, a positive electrode active material 10 and a positive electrode current collector 11, which are sequentially arranged.

第四方面，在至少一个实施例中提供了一种储能***，包括上述储能器件。该储能***包括上述储能器件，因而至少具有与上述储能器件相同的优势，具有成本低廉、结构稳定、库仑效率高、比容量高、能量密度高和循环性能好的优点。According to a fourth aspect, in at least one embodiment, an energy storage system is provided, including the foregoing energy storage device. The energy storage system includes the above-mentioned energy storage device, and therefore has at least the same advantages as the above-mentioned energy storage device, and has the advantages of low cost, stable structure, high coulomb efficiency, high specific capacity, high energy density, and good cycle performance.

上述储能***是指主要使用上述储能器件作为电力储存源的电力储存***，包括但不限于家用储能***或分布式储能***等。例如，在家用储能***中，使电力储存在用作电力储存源的上述储能器件中，并且根据需要消耗储存在上述储能器件中的电力以能够使用诸如家用电子产品的各种装置。The above-mentioned energy storage system refers to a power storage system that mainly uses the above-mentioned energy storage device as a power storage source, including but not limited to a home energy storage system or a distributed energy storage system. For example, in a home energy storage system, electric power is stored in the above-mentioned energy storage device used as a power storage source, and the electric power stored in the above-mentioned energy storage device is consumed as necessary to be able to use various devices such as home electronic products.

第五方面，在至少一个实施例中提供了一种用电设备，包括上述储能器件。该用电设备包括上述储能器件，因而至少具有与上述储能器件相同的优势，具有成本低廉、比容量高、能量密度高和循环性能好的优点，该用电设备在相同的充放电电流以及相同环境下使用时，使用寿命更长。According to a fifth aspect, in at least one embodiment, an electrical appliance is provided, including the foregoing energy storage device. The electrical equipment includes the above energy storage device, so it has at least the same advantages as the above energy storage device, has the advantages of low cost, high specific capacity, high energy density and good cycle performance. The electrical equipment has the same charge and discharge current And when used in the same environment, the service life is longer.

上述用电设备包括但不限于电子装置、电动工具或电动车辆等。电子装置是使用上述储能器件作为操作电源执行各种功能(例如，演奏音乐)的电子装置。电动工具是使用上述储能器件作为驱动电源移动部件(例如，钻头)的电动工具。电动车辆是依靠上述储能器件作为驱动电源运行的电动车辆(包括电动自行车和电动汽车)，并且可以是除了上述储能器件之外还装备有其他驱动源的汽车(包括混合动力车)。The above electrical equipment includes, but is not limited to, electronic devices, power tools, or electric vehicles. The electronic device is an electronic device that uses the above energy storage device as an operation power source to perform various functions (for example, playing music). The power tool is a power tool that uses the above energy storage device as a driving power moving part (for example, a drill). The electric vehicle is an electric vehicle (including an electric bicycle and an electric vehicle) that runs on the above energy storage device as a driving power source, and may be an automobile (including a hybrid vehicle) equipped with other driving sources in addition to the above energy storage device.

下面结合实施例和对比例对本申请做进一步详细的说明。The present application will be further described in detail below in conjunction with examples and comparative examples.

实施例1Example 1

一种预嵌锂负极的制备方法，包括以下步骤：A method for preparing a pre-embedded lithium anode includes the following steps:

a)取厚度为50μm的铝箔，裁切成直径为12mm的圆片，用丙酮、乙醇清洗，干燥后置于手套箱中作为工作电极备用；a) Take an aluminum foil with a thickness of 50 μm, cut it into 12 mm diameter wafers, wash with acetone and ethanol, dry it and put it in a glove box as a working electrode;

b)在手套箱中称取一定量的六氟磷酸锂，并加入到碳酸乙烯酯、碳酸二甲酯和碳酸二乙酯(三者体积比为1:1:1)的混合物中，配制成1M的六氟磷酸锂电解液；b) Weigh a certain amount of lithium hexafluorophosphate in the glove box and add it to the mixture of ethylene carbonate, dimethyl carbonate and diethyl carbonate (the volume ratio of the three is 1:1:1) to prepare 1M lithium hexafluorophosphate Electrolyte

c)称取一定量的二氟草酸硼酸锂，搅拌至完全溶解，配制成最后的添加剂含量为10wt.％的电解液；c) Weigh a certain amount of lithium difluorooxalate borate, stir until completely dissolved, and prepare an electrolyte with a final additive content of 10wt.%;

d)将玻璃纤维纸裁切成直径为16mm的圆片，80℃真空干燥12h后置于手套箱中作为隔膜备用；d) Cut the glass fiber paper into 16mm diameter discs, vacuum-dry at 80°C for 12h, then place in a glove box as a diaphragm for use;

e)在氩气气氛的手套箱中，将金属锂、隔膜和金属铝电极依次紧密堆叠，滴加电解液使隔膜完全浸润，然后将上述堆叠部分封装入外壳，然后进行放电预嵌锂，放电的电流大小为0.02mA/cm ²，放电时间为15h，得到预嵌锂的金属铝电极，该电极即为预嵌锂负极。 e) In a glove box under an argon atmosphere, metal lithium, a separator and a metal aluminum electrode are closely stacked in sequence, and the electrolyte is added dropwise to completely infiltrate the separator, and then the above stacked part is encapsulated into the housing, and then the discharge is pre-intercalated with lithium and discharged The current size is 0.02mA/cm ² , the discharge time is 15h, and a metal aluminum electrode pre-intercalated with lithium is obtained, which is a pre-intercalated lithium anode.

实施例2-13Example 2-13

一种预嵌锂负极的制备方法，与实施例1不同的是，实施例2-13中二氟草酸硼酸锂在电解液中的质量分数不同，其他步骤及其参数均与实施例1相同。A method for preparing a pre-intercalated lithium anode is different from that in Example 1. The mass fraction of lithium difluorooxalate borate in Examples 2-13 in the electrolyte is different. The other steps and parameters are the same as those in Example 1.

包括实施例1-13中制备得到的预嵌锂负极的锂离子电容器，制备方法包括以下步骤：The lithium ion capacitor including the pre-intercalated lithium anode prepared in Examples 1-13, the preparation method includes the following steps:

a)在手套箱中称取一定量的六氟磷酸锂，并加入到碳酸乙烯酯、碳酸二甲酯和碳酸二乙酯(三者体积比为1:1:1)的混合物中，配制成1M的六氟磷酸锂电解液；a) Weigh a certain amount of lithium hexafluorophosphate in the glove box and add it to the mixture of ethylene carbonate, dimethyl carbonate and diethyl carbonate (the volume ratio of the three is 1:1:1) to prepare 1M lithium hexafluorophosphate Electrolyte

b)将0.8g活性炭(AC)、0.1g导电碳黑和0.1g聚偏氟乙烯加入到2mL N-甲基吡咯烷酮中，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12小时；对干燥所得电极片裁切成直径为10mm的圆片，用油压机压实(10MPa,10s)，置于手套箱中作为正极备用；b) Add 0.8g activated carbon (AC), 0.1g conductive carbon black and 0.1g polyvinylidene fluoride to 2mL N-methylpyrrolidone, fully grind to obtain a uniform slurry; then apply the slurry evenly on the surface of aluminum foil, Vacuum dry at 80°C for 12 hours; cut the dried electrode pieces into 10mm diameter wafers, compact them with an oil press (10MPa, 10s), and place them in a glove box as a positive electrode;

c)将正极、隔膜和负极依次紧密堆叠，滴加电解液使隔膜完全浸润，然后将上述堆叠部分封装入外壳，完成电容器的组装。c) The positive electrode, the separator, and the negative electrode are closely stacked in sequence, and the electrolyte is dripped to completely infiltrate the separator, and then the above-mentioned stacked portion is packaged into the casing to complete the assembly of the capacitor.

分别对上述锂离子电容器采用0.8A/g的电流密度进行性能测试，测试结果见表1。Respectively, the above-mentioned lithium-ion capacitors were tested with a current density of 0.8A/g.

表1：包括实施例1-13制备得到的预嵌锂负极的锂离子电容器的性能参数表Table 1: Performance parameter table of lithium ion capacitors including pre-embedded lithium anodes prepared in Examples 1-13

实施例14-21Examples 14-21

一种预嵌锂负极的制备方法，与实施例1不同的是，实施例14-21中电解液的添加剂的种类不同，其他步骤及其参数均与实施例1相同。A method for preparing a pre-intercalated lithium negative electrode is different from Example 1 in that the types of additives for the electrolyte in Examples 14-21 are different, and other steps and parameters are the same as those in Example 1.

将实施例14-21制备得到的预嵌锂负极制备成锂离子电容器，制备方法同实施例1，分别对上述锂离子电容器采用0.8A/g的电流密度进行性能测试，测试结果见表2。The pre-intercalated lithium negative electrode prepared in Examples 14-21 was prepared into a lithium ion capacitor in the same manner as in Example 1. Performance tests were conducted on the above lithium ion capacitor with a current density of 0.8 A/g, and the test results are shown in Table 2.

表2：包括实施例14-21制备得到的预嵌锂负极的锂离子电容器的性能参数表Table 2: Performance parameter table of lithium ion capacitors including pre-embedded lithium negative electrodes prepared in Examples 14-21

实施例22-30Examples 22-30

一种预嵌锂负极的制备方法，与实施例1不同的是，实施例22-30中采用的金属材料的种类不同，其他步骤及其参数均与实施例1相同。A method for preparing a pre-intercalated lithium anode is different from that in Example 1. The types of metal materials used in Examples 22-30 are different. The other steps and parameters are the same as those in Example 1.

将实施例22-30制备得到的预嵌锂负极制备成锂离子电容器，制备方法同实施例1，分别对上述锂离子电容器采用0.8A/g的电流密度进行性能测试，测试结果见表3。The pre-intercalated lithium negative electrode prepared in Examples 22-30 was prepared into a lithium ion capacitor. The preparation method was the same as in Example 1. Performance tests were conducted on the above lithium ion capacitor with a current density of 0.8 A/g. The test results are shown in Table 3.

表3：包括实施例22-30制备得到的预嵌锂负极的锂离子电容器的性能参数表Table 3: Performance parameter table of lithium ion capacitors including pre-embedded lithium negative electrodes prepared in Examples 22-30

实施例31Example 31

一种预嵌锂负极的制备方法，与实施例1不同的是，本实施例步骤5)中将碳酸锂电极、隔膜和金属铝电极依次紧密堆叠，进行充电预嵌锂，充电的电流大小为0.02mA/cm ²，充电时间为15h；碳酸锂电极包括电极集流体铝箔和以碳酸锂为活性物质的电极材料；其余步骤及其参数均与实施例1相同。 A method for preparing a pre-embedded lithium anode is different from that in Example 1. In step 5) of this embodiment, a lithium carbonate electrode, a separator, and a metal aluminum electrode are closely stacked in sequence to charge and pre-embed lithium, and the charging current is 0.02mA/cm ² , charging time is 15h; lithium carbonate electrode includes electrode collector aluminum foil and electrode material using lithium carbonate as active material; the remaining steps and parameters are the same as in Example 1.

实施例32-38Examples 32-38

一种预嵌锂负极的制备方法，与实施例31不同的是，将实施例31中的碳酸锂分别替换为硫化锂、氧化锂、硒化锂、氟化锂、草酸锂、钴酸锂和磷酸铁锂，其余步骤及其参数均与实施例32相同。A method for preparing a pre-embedded lithium anode is different from Example 31 in that the lithium carbonate in Example 31 is replaced with lithium sulfide, lithium oxide, lithium selenide, lithium fluoride, lithium oxalate, lithium cobaltate, and Lithium iron phosphate, the remaining steps and parameters are the same as in Example 32.

将实施例31-38制备得到的预嵌锂负极制备成锂离子电容器，制备方法同实施例1，分别对上述锂离子电容器采用0.8A/g的电流密度进行性能测试，测试结果见表4。The pre-intercalated lithium negative electrodes prepared in Examples 31-38 were prepared into lithium ion capacitors. The preparation method was the same as that in Example 1. Performance tests were conducted on the above lithium ion capacitors with a current density of 0.8 A/g. The test results are shown in Table 4.

表4：包括实施例31-38制备得到的预嵌锂负极的锂离子电容器的性能参数表Table 4: Performance parameter table of lithium ion capacitors with pre-embedded lithium anodes prepared in Examples 31-38

包括实施例1-13制备得到的预嵌锂负极的双离子电池，制备方法包括以下步骤：The dual ion battery including the pre-intercalated lithium anode prepared in Examples 1-13, the preparation method includes the following steps:

b)将0.8g天然石墨(NG)、0.1g导电碳黑和0.1g聚偏氟乙烯加入到2mL N-甲基吡咯烷酮中，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12小时；对干燥所得电极片裁切成直径为10mm的圆片，用油压机压实(10MPa,10s)，置于手套箱中作为正极备用；b) Add 0.8g natural graphite (NG), 0.1g conductive carbon black and 0.1g polyvinylidene fluoride to 2mL N-methylpyrrolidone, fully grind to obtain a uniform slurry; then apply the slurry evenly on the surface of aluminum foil , Vacuum drying at 80 ℃ for 12 hours; cut the dried electrode sheet into a 10mm diameter wafer, compact it with a hydraulic press (10MPa, 10s), and place it in the glove box as a positive electrode;

c)将正极、隔膜和负极依次紧密堆叠，滴加电解液使隔膜完全浸润，然后将上述堆叠部分封装入外壳，完成双离子电池的组装。c) The positive electrode, the separator, and the negative electrode are closely stacked in sequence, and the electrolyte is added dropwise to completely infiltrate the separator, and then the above-mentioned stacked part is packaged into the casing to complete the assembly of the dual ion battery.

分别对上述双离子电池采用0.8A/g的电流密度进行性能测试，测试结果见表5。Respectively, the above two-ion batteries were tested with current density of 0.8A/g. The test results are shown in Table 5.

表5：包括实施例1-13制备得到的预嵌锂负极的双离子电池的性能参数表Table 5: Performance parameter table of the dual ion battery including the pre-embedded lithium anode prepared in Examples 1-13

包括实施例1-13制备得到的预嵌锂负极的锂离子电池，制备方法包括以下步骤：The lithium ion battery including the pre-intercalated lithium anode prepared in Examples 1-13, the preparation method includes the following steps:

b)将0.8g磷酸铁锂、0.1g导电碳黑和0.1g聚偏氟乙烯加入到2mL N-甲基吡咯烷酮中，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12小时；对干燥所得电极片裁切成直径为10mm的圆片，用油压机压实(10MPa,10s)，置于手套箱中作为正极备用；b) Add 0.8g lithium iron phosphate, 0.1g conductive carbon black and 0.1g polyvinylidene fluoride to 2mL N-methylpyrrolidone, fully grind to obtain a uniform slurry; then apply the slurry evenly on the surface of aluminum foil, 80 Vacuum dry for 12 hours at ℃; cut the dried electrode pieces into 10mm diameter wafers, compact them with an oil press (10MPa, 10s), and place them in a glove box as a positive electrode;

c)将正极、隔膜和负极依次紧密堆叠，滴加电解液使隔膜完全浸润，然后将上述堆叠部分封装入外壳，完成锂离子电池的组装。c) The positive electrode, the separator, and the negative electrode are closely stacked in sequence, and the electrolyte is dripped to completely infiltrate the separator, and then the above-mentioned stacked part is packaged into the casing to complete the assembly of the lithium ion battery.

分别对上述锂离子电池采用0.8A/g的电流密度进行性能测试，测试结果见表6。Respectively, the above-mentioned lithium-ion batteries were tested with current density of 0.8A/g. The test results are shown in Table 6.

表6：包括实施例1-13制备得到的预嵌锂负极的锂离子电池的性能参数表Table 6: Performance parameter table of the lithium ion battery including the pre-embedded lithium anode prepared in Examples 1-13

对比例1Comparative Example 1

一种预嵌锂负极的制备方法，与实施例1不同的是，本对比例的电解液中不含二氟草酸硼酸锂添加剂。A preparation method of a pre-intercalated lithium negative electrode is different from Example 1 in that the electrolyte of this comparative example does not contain lithium difluorooxalate borate additive.

将对比例1制备得到的预嵌锂负极制备成锂离子电容器，制备方法同实施例1，对上述锂离子电容器采用0.8A/g的电流密度进行性能测试，经测试，电容器循环500次容量保持率为70％、库仑效率为89.2％、能量密度为150Wh/kg以及比电容为115F/g，以上性能均低于实施例1。The pre-intercalated lithium negative electrode prepared in Comparative Example 1 was prepared into a lithium ion capacitor. The preparation method was the same as that in Example 1. The above lithium ion capacitor was tested with a current density of 0.8 A/g. After the test, the capacitor was maintained for 500 cycles. The rate was 70%, the Coulomb efficiency was 89.2%, the energy density was 150 Wh/kg, and the specific capacitance was 115 F/g. The above properties were all lower than those in Example 1.

如图3所示为实施例1和对比例1预嵌锂放电曲线，从曲线中可以看出，实施例1中含有LiODFB，实施例1在放电时存在明显的还原峰，对应于LiODFB的分解，说明铝金属表面钝化膜的形成，而对比例1中不含LiODFB，其在放电时不存在LiODFB分解过程。As shown in Figure 3, the discharge curves of pre-intercalated lithium of Example 1 and Comparative Example 1 can be seen from the curve. Example 1 contains LiODFB, and Example 1 has a significant reduction peak during discharge, which corresponds to the decomposition of LiODFB , Explaining the formation of a passivation film on the surface of aluminum metal, and Comparative Example 1 does not contain LiODFB, which does not have a LiODFB decomposition process during discharge.

图4(a)和图4(b)分别为对比例1和实施例1得到的预嵌锂负极的表面形貌，对比例1和实施例1中负极材料所使用的都是50μm的铝箔，可以看出对比例1中不含LiODFB，负极表面颗粒较大，而实施例1含有LiODFB，负极表面颗粒细小且均匀，说明形成了结构良好的SEI膜。4(a) and 4(b) are the surface morphology of the pre-doped lithium anode obtained in Comparative Example 1 and Example 1, respectively. The negative electrode materials used in Comparative Example 1 and Example 1 are both 50 μm aluminum foil. It can be seen that Comparative Example 1 does not contain LiODFB and the surface particles of the negative electrode are large, while Example 1 contains LiODFB, and the surface particles of the negative electrode are fine and uniform, indicating that a well-structured SEI film is formed.

对比例2Comparative Example 2

一种预嵌锂负极的制备方法，与实施例1不同的是，本对比例的电解液中的添加剂为硝酸锂，硝酸锂无法在金属材料表面形成SEI膜。A preparation method of a pre-embedded lithium negative electrode is different from Example 1 in that the additive in the electrolyte of this comparative example is lithium nitrate, and lithium nitrate cannot form an SEI film on the surface of the metal material.

将对比例2制备得到的预嵌锂负极制备成锂离子电容器，制备方法同实施例1，对上述锂离子电容器采用0.8A/g的电流密度进行性能测试，经测试，电容器循环500次容量保持率为63％、库仑效率为69.1％、能量密度为128Wh/kg以及比电容为97F/g，以上性能均低于实施例1。The pre-intercalated lithium negative electrode prepared in Comparative Example 2 was prepared into a lithium ion capacitor. The preparation method was the same as that in Example 1. The above lithium ion capacitor was tested for performance using a current density of 0.8 A/g. After the test, the capacitor was maintained for 500 cycles. The rate was 63%, the Coulomb efficiency was 69.1%, the energy density was 128 Wh/kg, and the specific capacitance was 97 F/g. The above properties were all lower than those in Example 1.

对比例3Comparative Example 3

a)取厚度为50μm的铝箔，裁切成直径为12mm的圆片，用丙酮、乙醇清洗，干燥后置于手套箱中作为工作电极备用；a) Take an aluminum foil with a thickness of 50 μm, cut it into a 12 mm diameter wafer, wash it with acetone and ethanol, dry it and place it in a glove box as a working electrode;

c)将活性物质碳酸锂和添加剂二氟草酸硼酸锂(二者质量比为9:1)制成浆料后涂覆在集流体铝箔上干燥，作为碳酸锂电极备用；c) The active material lithium carbonate and the additive lithium difluorooxalate borate (the mass ratio of the two are 9:1) are made into a slurry, coated on the aluminum foil of the current collector and dried, and used as a lithium carbonate electrode;

e)在氩气气氛的手套箱中，将碳酸锂电极、隔膜和金属铝电极依次紧密堆叠，滴加电解液使隔膜完全浸润，然后将上述堆叠部分封装入外壳，然后进行充电预嵌锂，充电的电流大小为0.02mA/cm ²，充电时间为15h，得到预嵌锂的金属铝电极，该电极即为预嵌锂负极。 e) In the argon atmosphere glove box, the lithium carbonate electrode, the separator and the metal aluminum electrode are closely stacked in sequence, and the electrolyte is added dropwise to completely infiltrate the separator, and then the above-mentioned stacked part is encapsulated into the casing, and then charged to pre-embed lithium, The charging current is 0.02mA/cm ² and the charging time is 15h. A metal aluminum electrode pre-intercalated with lithium is obtained. This electrode is a pre-intercalated lithium anode.

与实施例31不同的是，本对比例将二氟草酸硼酸锂添加剂添加到了对电极中。Different from Example 31, this comparative example added lithium difluorooxalate borate additive to the counter electrode.

将对比例3制备得到的预嵌锂负极制备成锂离子电容器，制备方法同实施例1，对上述锂离子电容器采用0.8A/g的电流密度进行性能测试，经测试，电容器循环500次容量保持率为60％、库仑效率为61.8％、能量密度为131Wh/kg以及比电容为99F/g，以上性能均低于实施例32。The pre-intercalated lithium negative electrode prepared in Comparative Example 3 was prepared into a lithium ion capacitor. The preparation method was the same as that in Example 1. The above lithium ion capacitor was tested for performance using a current density of 0.8 A/g. After the test, the capacitor was maintained for 500 cycles. The rate was 60%, the coulombic efficiency was 61.8%, the energy density was 131 Wh/kg, and the specific capacitance was 99 F/g. The above properties were all lower than those in Example 32.

尽管已用具体实施例来说明和描述了本申请，然而应意识到，在不背离本申请的精神和范围的情况下可以作出许多其它的更改和修改。因此，这意味着在所附权利要求中包括属于本申请范围内的所有这些变化和修改。Although the application has been illustrated and described with specific embodiments, it should be appreciated that many other changes and modifications can be made without departing from the spirit and scope of the application. Therefore, this means that all such changes and modifications falling within the scope of the present application are included in the appended claims.

Claims

一种预嵌锂负极的制备方法，其特征在于，提供一半电池，对所述半电池进行充电或放电；A method for preparing a pre-embedded lithium negative electrode, characterized in that half a battery is provided and the half battery is charged or discharged;

其中，所述半电池的工作电极为金属材料，对电极为能够提供锂源的材料，电解液为含有添加剂的锂盐溶液；Wherein, the working electrode of the half-cell is a metal material, the counter electrode is a material capable of providing a lithium source, and the electrolyte is a lithium salt solution containing additives;

所述金属材料包括能够与锂离子发生合金化反应的金属、合金或金属复合材料；The metal material includes a metal, alloy or metal composite material capable of alloying reaction with lithium ions;

所述添加剂包括能够分解并在所述金属材料表面形成SEI膜的物质。The additive includes a substance capable of decomposing and forming an SEI film on the surface of the metal material.
根据权利要求1所述的预嵌锂负极的制备方法，其特征在于，所述金属为铝、锡、镁、锌、铜、铁、镍、钛、锰、锑或铋中的任意一种；The method for preparing a pre-intercalated lithium anode according to claim 1, wherein the metal is any one of aluminum, tin, magnesium, zinc, copper, iron, nickel, titanium, manganese, antimony or bismuth;

或，所述合金为至少包括铝、锡、镁、锌、铜、铁、镍、钛、锰、锑或铋中的任意一种的合金；Or, the alloy is an alloy including at least any one of aluminum, tin, magnesium, zinc, copper, iron, nickel, titanium, manganese, antimony or bismuth;

或，所述金属复合材料为至少包括铝、锡、镁、锌、铜、铁、镍、钛、锰、锑或铋中的任意一种的复合材料；Or, the metal composite material is a composite material including at least any one of aluminum, tin, magnesium, zinc, copper, iron, nickel, titanium, manganese, antimony or bismuth;

优选地，所述金属材料的厚度为10-1000μm。Preferably, the thickness of the metal material is 10-1000 μm.
根据权利要求1所述的预嵌锂负极的制备方法，其特征在于，所述能够提供锂源的材料包括金属锂或锂的化合物；The method for preparing a pre-intercalated lithium anode according to claim 1, wherein the material capable of providing a lithium source includes metallic lithium or a lithium compound;

优选地，所述锂的化合物包括硫化锂、氧化锂、硒化锂、氟化锂、草酸锂、钴酸锂、碳酸锂或磷酸铁锂中的至少一种；Preferably, the lithium compound includes at least one of lithium sulfide, lithium oxide, lithium selenide, lithium fluoride, lithium oxalate, lithium cobaltate, lithium carbonate, or lithium iron phosphate;

优选地，所述对电极为金属锂，对以金属锂作为对电极的半电池进行放电；Preferably, the counter electrode is metallic lithium, and the half-cell with metallic lithium as the counter electrode is discharged;

优选地，所述对电极为锂的化合物，对以锂的化合物作为对电极的半电池进行充电。Preferably, the counter electrode is a lithium compound, and a half-cell using the lithium compound as a counter electrode is charged.
根据权利要求1所述的预嵌锂负极的制备方法，其特征在于，所述添加剂包括LiBOB、LiODFB、LiPO ₂F ₂、LiDFOP、LiBMB、LiDFMFMB、LiDFEFMB、LiDFPFMB或LiTFOP中的至少一种； The method for preparing a pre-intercalated lithium anode according to claim 1, wherein the additive comprises at least one of LiBOB, LiODFB, LiPO ₂ F ₂ , LiDFOP, LiBMB, LiDFMFMB, LiDFEFMB, LiDFPFMB, or LiTFOP;

优选地，所述添加剂在电解液中的质量分数为0.1％-30％，优选为8％-15％；Preferably, the mass fraction of the additive in the electrolyte is 0.1%-30%, preferably 8%-15%;

优选地，电解液中的锂盐包括六氟磷酸锂、四氟硼酸锂、氯化锂、碳酸锂、硫酸锂、硝酸锂、氟化锂、三氟甲磺酸锂、双(三氟甲基磺酰基)亚胺锂、双氟磺酰亚胺锂或高氯酸锂中的至少一种；Preferably, the lithium salt in the electrolyte includes lithium hexafluorophosphate, lithium tetrafluoroborate, lithium chloride, lithium carbonate, lithium sulfate, lithium nitrate, lithium fluoride, lithium trifluoromethanesulfonate, bis(trifluoromethylsulfonyl) At least one of lithium imide, lithium difluorosulfonimide, or lithium perchlorate;

优选地，所述电解液中，锂盐的浓度为0.1-10mol/L；Preferably, the concentration of the lithium salt in the electrolyte is 0.1-10mol/L;

优选地，所述电解液的溶剂包括酯类、砜类、醚类、腈类或烯烃类中的至少一种；Preferably, the solvent of the electrolyte includes at least one of esters, sulfones, ethers, nitriles or olefins;

优选地，所述电解液的溶剂包括碳酸丙烯酯(PC)、碳酸乙烯酯(EC)、碳酸二乙酯 (DEC)、碳酸二甲酯(DMC)、碳酸甲乙酯(EMC)、甲酸甲酯(MF)、乙酸甲酯(MA)、N,N-二甲基乙酰胺(DMA)、氟代碳酸乙烯酯(FEC)、丙酸甲酯(MP)、丙酸乙酯(EP)、乙酸乙酯(EA)、γ-丁内酯(GBL)、四氢呋喃(THF)、2-甲基四氢呋喃(2MeTHF)、1,3-二氧环戊烷(DOL)、4-甲基-1,3-二氧环戊烷(4MeDOL)、二甲氧甲烷(DMM)、1,2-二甲氧丙烷(DMP)、三乙二醇二甲醚(DG)、二甲基砜(MSM)、二甲醚(DME)、亚硫酸乙烯酯(ES)、亚硫酸丙烯脂(PS)、亚硫酸二甲脂(DMS)、亚硫酸二乙脂(DES)或冠醚(12-冠-4)中的至少一种。Preferably, the solvent of the electrolyte includes propylene carbonate (PC), ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), methyl formate Ester (MF), methyl acetate (MA), N,N-dimethylacetamide (DMA), fluoroethylene carbonate (FEC), methyl propionate (MP), ethyl propionate (EP), Ethyl acetate (EA), γ-butyrolactone (GBL), tetrahydrofuran (THF), 2-methyltetrahydrofuran (2MeTHF), 1,3-dioxolane (DOL), 4-methyl-1, 3-dioxolane (4MeDOL), dimethoxymethane (DMM), 1,2-dimethoxypropane (DMP), triethylene glycol dimethyl ether (DG), dimethyl sulfone (MSM), Dimethyl ether (DME), vinyl sulfite (ES), propylene sulfite (PS), dimethyl sulfite (DMS), diethyl sulfite (DES) or crown ether (12-crown-4) At least one of them.
根据权利要求1-4任一项所述的预嵌锂负极的制备方法，其特征在于，充电或放电的电流为0.01-1mA/cm ²，充电或放电的时间为100-1小时； The method for preparing a pre-intercalated lithium anode according to any one of claims 1 to 4, wherein the current for charging or discharging is 0.01-1 mA/cm ² , and the time for charging or discharging is 100-1 hours;

优选地，所述半电池还包括隔膜，所述隔膜包括玻璃纤维、聚乙烯隔膜、聚丙烯隔膜、或聚丙烯/聚乙烯/聚丙烯隔膜中的至少一种。Preferably, the half-cell further includes a separator including at least one of glass fiber, polyethylene separator, polypropylene separator, or polypropylene/polyethylene/polypropylene separator.
采用权利要求1-5任一项所述的预嵌锂负极的制备方法制备得到的预嵌锂负极。The pre-intercalated lithium anode prepared by the method for preparing a pre-intercalated lithium anode according to any one of claims 1-5.
一种储能器件，其特征在于，包括采用权利要求1-5任一项所述的预嵌锂负极的制备方法制备而成的预嵌锂负极。An energy storage device is characterized by comprising a pre-lithium-embedded negative electrode prepared by the method for preparing a pre-embedded lithium anode according to any one of claims 1-5.
根据权利要求7所述的储能器件，其特征在于，所述储能器件还包括正极材料；The energy storage device according to claim 7, wherein the energy storage device further comprises a positive electrode material;

优选地，储能器件为锂离子电池，正极材料包括锰酸锂、钴酸锂、磷酸铁锂或三元材料中的至少一种；Preferably, the energy storage device is a lithium ion battery, and the positive electrode material includes at least one of lithium manganate, lithium cobaltate, lithium iron phosphate, or ternary material;

优选地，储能器件为锂离子电容器，正极材料包括活性炭、碳纳米管、活性碳纤维、石墨烯、介孔碳、碳分子筛或炭泡沫中的至少一种；Preferably, the energy storage device is a lithium ion capacitor, and the positive electrode material includes at least one of activated carbon, carbon nanotubes, activated carbon fiber, graphene, mesoporous carbon, carbon molecular sieve, or carbon foam;

优选地，储能器件为双离子电池，正极材料包括天然石墨和/或膨胀石墨。Preferably, the energy storage device is a dual ion battery, and the positive electrode material includes natural graphite and/or expanded graphite.
一种储能***，其特征在于，包括权利要求7或8所述的储能器件。An energy storage system, characterized by comprising the energy storage device according to claim 7 or 8.
一种用电设备，其特征在于，包括权利要求7或8所述的储能器件。An electric appliance, characterized by comprising the energy storage device according to claim 7 or 8.