技术领域technical field
本发明涉及一种锂离子电容器负极单元及其制备方法、锂离子电容器，属于锂离子电容器技术领域。The invention relates to a negative electrode unit of a lithium ion capacitor, a preparation method thereof, and a lithium ion capacitor, belonging to the technical field of lithium ion capacitors.
背景技术Background technique
随着能源利用的不断深入，各种储能器件如铅酸电池、镍氢电池、锂离子电池等都获得了较大的发展。随着近年来电动车市场的迅速发展，对储能器件的能量密度和功率密度的要求也越来越高，传统的二次电池的能量密度较高，但是功率密度低，无法满足电动车辆对动力电源的功率要求，而传统的电容器的能量密度较低，也无法满足电动车辆对动力电源能量密度的要求，在这种情况下，锂离子电容器成为了一种能够均衡上述要求的有效解决方案。With the deepening of energy utilization, various energy storage devices such as lead-acid batteries, nickel-metal hydride batteries, lithium-ion batteries, etc. have achieved great development. With the rapid development of the electric vehicle market in recent years, the requirements for the energy density and power density of energy storage devices are also getting higher and higher. The energy density of traditional secondary batteries is high, but the power density is low, which cannot meet the power requirements of electric vehicles. The power requirements of the power supply, while the energy density of traditional capacitors is low, and it cannot meet the energy density requirements of electric vehicles for power supplies. In this case, lithium-ion capacitors have become an effective solution that can balance the above requirements.
锂离子电容器采用了双电层电容器的原理设计，但是构造上采用锂离子电池负极材料与双电层电容器的正极材料组合，大大提高了电容器的能量密度，同时也具有非常高的功率密度和循环寿命，性能优于传统的锂离子电池和双电层电容器。Lithium-ion capacitors are designed based on the principle of electric double-layer capacitors, but the structure uses a combination of lithium-ion battery negative electrode materials and electric double-layer capacitor positive electrode materials, which greatly improves the energy density of the capacitor, and also has very high power density and cycle. Life, performance is better than traditional lithium-ion batteries and electric double layer capacitors.
锂离子电容器碳质负极需进行预嵌锂，使其电位变低且平坦，并能够提高电容器的能量密度。日本富士重工业株式会社公开了一种锂离子电容器的制造技术，该技术引入了第三极“锂极”，单独的放置在锂离子电容器的外侧或内部，正负极集流体采用了具有贯穿孔特性的铝箔和铜箔；注入电解液时锂极便开始释放锂离子而向负极进行嵌锂，这种结构可以实现嵌锂相对均匀，但是由于正负极集流体采用了具有贯穿孔特性的铝箔和铜箔，不但制作工艺复杂，生产成本较高，而且导电性能较差，且每层负极极片的承载锂量的差异也较大。The carbonaceous negative electrode of lithium-ion capacitors needs to pre-intercalate lithium to make the potential low and flat, and to increase the energy density of the capacitor. Japan's Fuji Heavy Industries Co., Ltd. discloses a manufacturing technology for lithium-ion capacitors. This technology introduces the third pole "lithium pole", which is placed separately on the outside or inside of the lithium-ion capacitor. The positive and negative current collectors have through holes. characteristic aluminum foil and copper foil; when the electrolyte is injected, the lithium electrode starts to release lithium ions and intercalate lithium to the negative electrode. This structure can achieve relatively uniform lithium intercalation, but because the positive and negative current collectors use aluminum foil with through-hole characteristics And copper foil, not only the production process is complicated, the production cost is high, but also the electrical conductivity is poor, and the difference in the amount of lithium carried by each layer of the negative electrode sheet is also large.
授权公告号为CN204360933U(授权公告日为2015年5月27日)公开了一种超级锂离子电容器，包括正极、负极、隔膜和电解液，正极包括第一集流体和设置于第一集流体表面的活性炭层，所述负极包括第二集流体和设置于所述第二集流体表面的硬碳层，所述隔膜设置在所述正极与所述负极之间，以使所述正极与所述负极电绝缘，所述电解液与所述正极和负极物理接触和电接触，以允许离子在所述正极与所述负极间交换，所述超级锂离子电容器还包括锂片层，所述锂片层位于所述硬碳层与所述隔膜之间且设置在所述硬碳层表面。在锂离子电容器注液后，锂片层能够向负极补锂，使负极片有较为充分的锂储备，在一定程度上提高锂离子电容器的能量密度。但是该技术方案中，锂片层与电解液接触不充分，无法高效地使锂与负极充分反应，在提高锂离子电容器的能量密度方面作用非常有限，而且也造成锂片层的浪费。另外，锂离子电容器与锂离子电池一样，在锂离子嵌入负极时会由于SEI膜的形成而产生气体，上述方案中，锂片层覆盖在负极片的硬碳层表面，影响气体的及时排出，负极片和锂片之间的气体集聚较多时，会阻碍锂片与负极片表面的接触，导致锂片从负极片表面脱离开来，造成预嵌锂失败；严重的甚至会导致负极活性物质从集流体表面脱离，在电容器中形成导电性颗粒，导致电容器自放电几率增大。The authorized announcement number is CN204360933U (authorized announcement date is May 27, 2015) discloses a super lithium ion capacitor, including a positive electrode, a negative electrode, a diaphragm and an electrolyte, the positive electrode includes a first current collector and is arranged on the surface of the first current collector activated carbon layer, the negative electrode includes a second current collector and a hard carbon layer arranged on the surface of the second current collector, the separator is arranged between the positive electrode and the negative electrode, so that the positive electrode and the The negative electrode is electrically insulated, and the electrolyte is in physical and electrical contact with the positive electrode and the negative electrode to allow ions to be exchanged between the positive electrode and the negative electrode. The super lithium ion capacitor also includes a lithium sheet layer, and the lithium sheet The layer is located between the hard carbon layer and the separator and is disposed on the surface of the hard carbon layer. After the liquid is injected into the lithium-ion capacitor, the lithium sheet layer can replenish lithium to the negative electrode, so that the negative electrode has a relatively sufficient lithium reserve, which improves the energy density of the lithium-ion capacitor to a certain extent. However, in this technical solution, the contact between the lithium sheet and the electrolyte is insufficient, and the lithium cannot be fully reacted with the negative electrode efficiently, which has a very limited effect on improving the energy density of the lithium ion capacitor, and also causes waste of the lithium sheet. In addition, lithium-ion capacitors are the same as lithium-ion batteries. When lithium ions are inserted into the negative electrode, gas will be generated due to the formation of the SEI film. In the above scheme, the lithium sheet is covered on the surface of the hard carbon layer of the negative electrode, which affects the timely discharge of gas. When there is a lot of gas accumulation between the negative electrode sheet and the lithium sheet, it will hinder the contact between the lithium sheet and the surface of the negative electrode sheet, causing the lithium sheet to detach from the surface of the negative electrode sheet, resulting in the failure of pre-intercalation of lithium; in severe cases, it will even cause the active material of the negative electrode to detach from the surface of the negative electrode sheet. The surface of the current collector is detached, and conductive particles are formed in the capacitor, resulting in an increased probability of self-discharge of the capacitor.
发明内容Contents of the invention
本发明的目的在于提供一种锂离子电容器负极单元，以解决现有技术中的锂离子电容器的负极片上电解液无法与锂片充分接触以及负极片表面的气体无法及时排出的问题。本发明的目的还在于提供一种上述锂离子电容器负极单元的制备方法以及使用上述锂离子电容器负极单元的锂离子电容器。The object of the present invention is to provide a lithium ion capacitor negative electrode unit to solve the problem that the electrolyte on the negative electrode sheet of the lithium ion capacitor in the prior art cannot fully contact the lithium sheet and the gas on the surface of the negative electrode sheet cannot be discharged in time. The object of the present invention is also to provide a preparation method of the negative electrode unit of the lithium ion capacitor and a lithium ion capacitor using the negative electrode unit of the lithium ion capacitor.
为了实现以上目的，本发明的锂离子电容器负极单元的技术方案如下：In order to achieve the above object, the technical scheme of the lithium ion capacitor negative electrode unit of the present invention is as follows:
一种锂离子电容器负极单元，包括负极片，所述负极片包括负极集流体和涂覆在负极集流体表面的负极活性物质层，所述负极活性物质层表面铺设有锂网。A negative electrode unit of a lithium ion capacitor comprises a negative electrode sheet, the negative electrode sheet includes a negative electrode current collector and a negative electrode active material layer coated on the surface of the negative electrode current collector, and a lithium network is laid on the surface of the negative electrode active material layer.
本发明的锂离子电容器负极单元采用在负极片表面设置锂网，通过锂网向负极片嵌锂，既能使电解液与锂网快速浸润，锂网与电解液充分接触，保证负极片充分嵌锂，又能为负极片表面产生的气体提供“逃逸”通道，使气体及时排出，避免气体在负极片表面集聚导致的锂网与负极片脱离，也避免了负极活性物质的脱落，减小了自放电几率。本发明的负极片表面的锂网还能使几乎全部的锂都与负极片实现接触，充分发生电化学反应，提高锂的利用率，便于控制成本，也便于在补锂需求量一定的情况下通过控制锂网的孔隙率来使锂网完全均匀覆盖负极片表面的负极活性物质层，使嵌锂更加均匀。本发明能够有效控制每一层负极极片的锂负载量，并且由于不必使用具有贯穿孔特性的铜箔，能降低成本，同时也可以降低内阻，提高集流体的导电性。The negative electrode unit of the lithium ion capacitor of the present invention adopts the arrangement of a lithium mesh on the surface of the negative electrode sheet, and inserts lithium into the negative electrode sheet through the lithium mesh. Lithium can also provide an "escape" channel for the gas generated on the surface of the negative electrode, so that the gas can be discharged in time, avoiding the detachment of the lithium network from the negative electrode caused by the accumulation of gas on the surface of the negative electrode, and also avoiding the shedding of the negative active material. probability of self-discharge. The lithium network on the surface of the negative electrode sheet of the present invention can also make almost all of the lithium come into contact with the negative electrode sheet, fully electrochemically react, improve the utilization rate of lithium, facilitate cost control, and facilitate lithium supplementation when the demand is constant. By controlling the porosity of the lithium network, the lithium network can completely and evenly cover the negative electrode active material layer on the surface of the negative electrode sheet, so that the lithium intercalation is more uniform. The invention can effectively control the lithium loading capacity of each layer of the negative electrode sheet, and because it is not necessary to use copper foil with through-hole characteristics, the cost can be reduced, and the internal resistance can also be reduced, and the conductivity of the current collector can be improved.
所述锂网的质量与负极活性物质的质量相比，不宜过多，以避免造成成本增加，也不宜过少，以避免嵌锂量不足而导致锂离子电容器容量降低，一般的，所述锂网与所述负极活性物质的质量比为0.05-0.1:1。Compared with the quality of the negative active material, the quality of the lithium network should not be too much, so as to avoid increasing the cost, and should not be too small, so as to avoid the insufficient amount of lithium intercalation and cause the capacity of the lithium ion capacitor to decrease. Generally, the lithium The mass ratio of the mesh to the negative electrode active material is 0.05-0.1:1.
为了增加向负极片表面嵌锂的均匀性，所述锂网的铺设面积大于所述负极活性物质层的面积，锂网的整体面积大于负极活性物质层的面积能够使负极活性物质层被锂网完全覆盖，对负极片进行充分补锂。In order to increase the uniformity of lithium intercalation on the surface of the negative electrode sheet, the laying area of the lithium mesh is larger than the area of the negative electrode active material layer, and the overall area of the lithium mesh is larger than the area of the negative electrode active material layer so that the negative electrode active material layer can be covered by the lithium mesh. Complete coverage, fully supplement lithium to the negative electrode.
锂网的孔隙率可以视需要补锂的量来设置，在所需补锂的量一定时，可以通过调整锂网的孔隙率以使锂网能够完全覆盖负极片表面，一般的，所述锂网的孔隙率为25-75％。The porosity of the lithium mesh can be set according to the amount of lithium supplementation required. When the amount of lithium supplementation required is constant, the porosity of the lithium mesh can be adjusted so that the lithium mesh can completely cover the surface of the negative plate. Generally, the lithium The porosity of the mesh is 25-75%.
负极活性物质层包括负极活性物质，负极活性物质为本领域常用的负极活性物质，如石墨、硬碳、软碳、中间相碳微球中的一种或者几种。The negative electrode active material layer includes negative electrode active materials, which are commonly used negative electrode active materials in the field, such as one or more of graphite, hard carbon, soft carbon, and mesocarbon microspheres.
为了使负极活性物质更好地结合在负极集流体上，所述负极活性物质层还包括粘结剂，该粘结剂为本领域常用的粘结剂，如聚偏氟乙烯(PVDF)、聚四氟乙烯(PTFE)、LA132、丁苯橡胶(SBR)、羧甲基纤维素(CMC)中的一种或几种。其中，丁苯橡胶和羧甲基纤维素同时使用。In order to better combine the negative electrode active material on the negative electrode current collector, the negative electrode active material layer also includes a binder, which is a commonly used binder in the art, such as polyvinylidene fluoride (PVDF), poly One or more of tetrafluoroethylene (PTFE), LA132, styrene-butadiene rubber (SBR), and carboxymethyl cellulose (CMC). Among them, styrene-butadiene rubber and carboxymethyl cellulose are used at the same time.
为了提高负极活性物质层的导电性，所述负极活性物质层还包括导电剂，该导电剂为本领域常用的导电剂，如SuperP、KS-6、石墨烯中的一种。In order to improve the conductivity of the negative electrode active material layer, the negative electrode active material layer further includes a conductive agent, which is a commonly used conductive agent in the field, such as one of SuperP, KS-6, and graphene.
所述负极活性物质层中负极活性物质、导电剂、粘结剂的质量百分比为：负极活性物质85-90％、导电剂3-5％、粘结剂5-10％。The mass percentages of the negative active material, the conductive agent and the binder in the negative active material layer are: 85-90% of the negative active material, 3-5% of the conductive agent, and 5-10% of the binder.
所述负极片的厚度为120-220μm。The thickness of the negative electrode sheet is 120-220 μm.
本发明的锂离子电容器负极单元的制备方法的技术方案如下：The technical scheme of the preparation method of lithium ion capacitor negative electrode unit of the present invention is as follows:
上述锂离子电容器负极单元的制备方法，包括如下步骤：The preparation method of the negative electrode unit of the above-mentioned lithium ion capacitor comprises the following steps:
将锂网与负极片叠放，辊压，即得。Lay the lithium mesh and the negative electrode sheet together, and roll them to get the final product.
本发明的锂离子电容器负极单元的制备方法制得的锂离子电容器负极单元，负极极片嵌锂均匀、产品一致性好、预嵌锂时间短、加工效率高。The negative electrode unit of the lithium ion capacitor prepared by the method for preparing the negative electrode unit of the lithium ion capacitor of the present invention has uniform lithium intercalation in the negative pole piece, good product consistency, short pre-intercalation time for lithium, and high processing efficiency.
所述负极片按照如下方法制得：将负极活性物质、导电剂及粘结剂均匀混合制成负极浆料，涂覆在负极集流体表面，100-150℃烘干，辊压，分条，即得。The negative electrode sheet is prepared according to the following method: uniformly mix the negative electrode active material, the conductive agent and the binder to form the negative electrode slurry, coat it on the surface of the negative electrode current collector, dry it at 100-150°C, roll it, and divide it into strips. Instantly.
辊压压力以能够使锂网牢固贴合在负极片表面为宜，一般的，为了使锂网与负极片接触面积最大化，所述辊压的压力为50-200kg/cm2。The rolling pressure should be such that the lithium mesh can be firmly adhered to the surface of the negative electrode sheet. Generally, in order to maximize the contact area between the lithium mesh and the negative electrode sheet, the rolling pressure is 50-200kg/cm2 .
本发明的锂离子电容器的技术方案如下：The technical scheme of lithium ion capacitor of the present invention is as follows:
一种锂离子电容器，包括正极、负极，所述负极为上述的锂离子电容器负极单元。A lithium ion capacitor includes a positive electrode and a negative electrode, and the negative electrode is the above-mentioned negative electrode unit of the lithium ion capacitor.
所述正极为正极片，正极片包括正极集流体以及涂覆在正极集流体表面的正极活性物质。还包括粘结剂和导电剂。所述正极活性物质、导电剂、粘结剂的质量比为85:7:8。The positive electrode is a positive electrode sheet, and the positive electrode sheet includes a positive electrode collector and a positive electrode active material coated on the surface of the positive electrode collector. Binders and conductive agents are also included. The mass ratio of the positive electrode active material, conductive agent and binder is 85:7:8.
所述正极活性物质为活性炭。所述粘结剂为本领域常用的粘结剂，如聚偏氟乙烯(PVDF)、聚四氟乙烯(PTFE)、LA132、丁苯橡胶(SBR)、羧甲基纤维素(CMC)中的一种或几种。其中，丁苯橡胶和羧甲基纤维素同时使用。该导电剂为本领域常用的导电剂，如SuperP、KS-6、石墨烯中的一种。The positive active material is activated carbon. Described binding agent is the binding agent commonly used in this area, as in polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), LA132, styrene-butadiene rubber (SBR), carboxymethyl cellulose (CMC) one or several. Among them, styrene-butadiene rubber and carboxymethyl cellulose are used at the same time. The conductive agent is a commonly used conductive agent in the field, such as one of SuperP, KS-6, and graphene.
正极片的厚度与负极片的厚度相匹配，保证正极、负极容量匹配，一般的，所述正极片的厚度为200-350μm。The thickness of the positive electrode sheet matches the thickness of the negative electrode sheet to ensure that the capacities of the positive electrode and the negative electrode match. Generally, the thickness of the positive electrode sheet is 200-350 μm.
所述锂离子电容器还包括隔膜和电解液。The lithium ion capacitor also includes a diaphragm and an electrolyte.
所述隔膜为纤维素、聚丙烯、聚乙烯中的一种或者其中的几种复合而成的复合膜。The diaphragm is one of cellulose, polypropylene and polyethylene or a composite film composed of several of them.
所述锂离子电容器还包括电解液，所述电解液包括锂盐和溶剂，所述锂盐为六氟磷酸锂或者四氟硼酸锂，锂盐的浓度为1.0-1.2mol/L，所述溶剂为碳酸丙烯酯、碳酸乙烯酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯中的一种或者几种。The lithium ion capacitor also includes an electrolyte, the electrolyte includes a lithium salt and a solvent, the lithium salt is lithium hexafluorophosphate or lithium tetrafluoroborate, the concentration of the lithium salt is 1.0-1.2mol/L, and the solvent is propylene carbonate One or more of esters, ethylene carbonate, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate.
上述锂离子电容器按照如下方法制得：将正极、隔膜、负极制成卷绕式电芯，入壳，注液，静置4h，并记录最高电压值，用来判断预嵌锂的深度，具体采用如下方法：注入电解液后，金属锂与负极直接短路，金属锂离子化并嵌入负极材料内，相应负极电势电压降低，而锂离子电容器正极活性炭对锂电位会维持在3.0V左右，所以通过测试电容器的电压达到2.8-3.0V即可判断负极预锂化完成，然后在1.5A恒流充电至3.8V，3.8V恒压24h化成，排气，即得。The above-mentioned lithium-ion capacitors were prepared according to the following method: the positive electrode, the separator, and the negative electrode were made into wound-type batteries, put into the shell, injected with liquid, and left to stand for 4 hours, and recorded the highest voltage value to judge the depth of pre-embedded lithium. The following method is adopted: after the electrolyte is injected, the metal lithium and the negative electrode are directly short-circuited, and the metal lithium is ionized and embedded in the negative electrode material, and the corresponding negative electrode potential voltage is reduced, while the positive electrode activated carbon of the lithium ion capacitor maintains the lithium potential at about 3.0V, so by When the voltage of the test capacitor reaches 2.8-3.0V, it can be judged that the pre-lithiation of the negative electrode is completed, and then it is charged at a constant current of 1.5A to 3.8V, formed at a constant voltage of 3.8V for 24 hours, and exhausted.
本发明的锂离子电容器利用锂网进行负极补锂，电解液能够快速的浸润，全部锂金属都能与负极实现电化学短路，每层负极极片都能够均匀的嵌锂，大幅度提高了产品的一致性。The lithium ion capacitor of the present invention utilizes a lithium network to supplement lithium at the negative electrode, the electrolyte can quickly infiltrate, and all lithium metals can electrochemically short circuit with the negative electrode, and each layer of negative electrode sheet can evenly insert lithium, which greatly improves the product quality. consistency.
具体实施方式detailed description
下面结合具体实施例对本发明的技术方案进行进一步的说明。The technical solutions of the present invention will be further described below in conjunction with specific embodiments.
实施例1Example 1
本实施例的锂离子电容器负极单元包括负极片，负极片包括负极集流体铜箔以及涂覆在负极集流体两个表面上的负极活性物质层，负极活性物质层由负极活性物质硬碳、导电剂SuperP、粘结剂聚偏氟乙烯(PVDF)按照质量比90:3:7均匀混合而成，负极片的厚度为200μm，负极片两面的负极活性物质层表面均铺设有锂网，锂网的孔隙率为25％，锂网与负极活性物质的质量比为0.05:1，锂网的整体铺设面积大于负极片表面负极活性物质层的面积以能够将负极活性物质层完全覆盖。The negative electrode unit of the lithium ion capacitor of the present embodiment includes a negative electrode sheet, and the negative electrode sheet includes a negative electrode current collector copper foil and a negative electrode active material layer coated on both surfaces of the negative electrode current collector. The agent SuperP and the binder polyvinylidene fluoride (PVDF) are evenly mixed according to the mass ratio of 90:3:7. The thickness of the negative electrode sheet is 200 μm. The surface of the negative electrode active material layer on both sides of the negative electrode sheet is covered with lithium mesh. The porosity is 25%, the mass ratio of the lithium network to the negative active material is 0.05:1, and the overall laying area of the lithium network is greater than the area of the negative active material layer on the surface of the negative plate to completely cover the negative active material layer.
本实施例的锂离子电容器负极单元的制备方法包括如下步骤：The preparation method of the lithium ion capacitor negative electrode unit of the present embodiment comprises the following steps:
1)将负极活性物质硬碳、导电剂SuperP及粘结剂聚偏氟乙烯加入溶剂NMP均匀混合制成负极浆料，采用涂布机涂覆在负极集流体铜箔的两个表面，120℃烘干，辊压，分条，得负极片；1) Add the negative electrode active material hard carbon, the conductive agent SuperP and the binder polyvinylidene fluoride to the solvent NMP and mix evenly to make the negative electrode slurry, and use a coating machine to coat the two surfaces of the copper foil of the negative electrode current collector at 120°C Drying, rolling, and slitting to obtain the negative electrode sheet;
2)将锂网叠放在步骤1)中制得的负极片表面，在50kg/cm2的压力下辊压，即得。2) Lay the lithium mesh on the surface of the negative electrode sheet prepared in step 1), and roll it under a pressure of 50kg/cm2 to obtain it.
本实施例的锂离子电容器包括正极、负极、隔膜以及电解液，隔膜设置在正极和负极之间，负极使用上述锂离子电容器负极单元。The lithium ion capacitor of this embodiment includes a positive electrode, a negative electrode, a diaphragm and an electrolyte, the diaphragm is arranged between the positive electrode and the negative electrode, and the negative electrode uses the above-mentioned negative electrode unit of the lithium ion capacitor.
上述正极为正极片，正极片包括正极集流体铝箔以及涂覆在正极集流体两个表面的正极活性物质层，正极活性物质层由正极活性物质活性炭、导电剂SuperP、粘结剂聚四氟乙烯(PTFE)按照质量比85:7:8均匀混合而成。该正极片由如下方法制得：将正极活性物质活性炭、导电剂SuperP、粘结剂聚四氟乙烯(PTFE)加入溶剂去离子水均匀混合制成正极浆料，采用涂布机涂覆在正极集流体铝箔上，120℃下烘干，烘干后的涂布厚度为260μm，辊压，辊压后的正极片厚度为120μm，切边、裁片、分条、收卷，制得正极片。The above-mentioned positive electrode is a positive electrode sheet, and the positive electrode sheet includes a positive electrode current collector aluminum foil and a positive electrode active material layer coated on both surfaces of the positive electrode current collector. The positive electrode active material layer is composed of positive electrode active material activated carbon, conductive agent SuperP, binder polytetrafluoroethylene (PTFE) is uniformly mixed according to the mass ratio of 85:7:8. The positive electrode sheet is prepared by the following method: the positive electrode active material activated carbon, the conductive agent SuperP, and the binder polytetrafluoroethylene (PTFE) are added to the solvent deionized water and uniformly mixed to form a positive electrode slurry, which is coated on the positive electrode by a coating machine. On the current collector aluminum foil, dry at 120°C, the coating thickness after drying is 260 μm, roll pressing, the thickness of the positive electrode sheet after rolling is 120 μm, trim, cut into pieces, slitting, and winding to obtain the positive electrode sheet .
隔膜为聚丙烯微孔膜，电解液包括锂盐六氟磷酸锂和溶剂，六氟磷酸锂的浓度为1.0mol/L，溶剂由碳酸乙烯酯、碳酸丙烯酯、碳酸二甲酯按照体积比3：1：4混合而成。The diaphragm is a polypropylene microporous membrane. The electrolyte includes lithium salt lithium hexafluorophosphate and solvent. The concentration of lithium hexafluorophosphate is 1.0mol/L. The solvent is made of ethylene carbonate, propylene carbonate and dimethyl carbonate in a volume ratio of 3:1:4. become.
本实施例的锂离子电容器按照如下方法制得：将正极、隔膜、负极制成卷绕式电芯，入壳，注液，静置4h，并记录最高电压值，用来判断预嵌锂的深度，以2.8-2.9V为合格，然后1.5A恒流充电至3.8V，3.8V恒压24h化成，排气，即得。The lithium-ion capacitor of this embodiment is prepared according to the following method: make the positive electrode, diaphragm, and negative electrode into a wound-type battery cell, put it into the shell, inject liquid, let it stand for 4 hours, and record the highest voltage value, which is used to judge the pre-embedded lithium. Depth, 2.8-2.9V is qualified, then 1.5A constant current charge to 3.8V, 3.8V constant voltage 24h into formation, exhaust, that is.
实施例2Example 2
本实施例的锂离子电容器负极单元包括负极片，负极片包括负极集流体铜箔以及涂覆在负极集流体两个表面上的负极活性物质层，负极活性物质层由负极活性物质硬碳、导电剂SuperP、粘结剂聚四氟乙烯(PTFE)按照质量比86:5:9均匀混合而成，负极片的厚度为200μm，负极片两面的负极活性物质层表面均铺设有锂网，锂网的孔隙率为50％，锂网与负极活性物质的质量比为0.08:1，锂网的整体铺设面积大于负极片表面负极活性物质层的面积以能够将负极活性物质层完全覆盖。The negative electrode unit of the lithium ion capacitor of the present embodiment includes a negative electrode sheet, and the negative electrode sheet includes a negative electrode current collector copper foil and a negative electrode active material layer coated on both surfaces of the negative electrode current collector. The agent SuperP and the binder polytetrafluoroethylene (PTFE) are evenly mixed according to the mass ratio of 86:5:9. The thickness of the negative electrode sheet is 200 μm, and the negative electrode active material layer surface on both sides of the negative electrode sheet is covered with lithium mesh. The porosity is 50%, the mass ratio of the lithium network to the negative active material is 0.08:1, and the overall laying area of the lithium network is greater than the area of the negative active material layer on the surface of the negative plate to completely cover the negative active material layer.
本实施例的锂离子电容器负极单元的制备方法包括如下步骤：The preparation method of the lithium ion capacitor negative electrode unit of the present embodiment comprises the following steps:
1)将负极活性物质硬碳、导电剂SuperP及粘结剂聚偏氟乙烯加入溶剂NMP均匀混合制成负极浆料，采用涂布机涂覆在负极集流体铜箔的两个表面，120℃烘干，辊压，分条，得负极片；1) Add the negative electrode active material hard carbon, the conductive agent SuperP and the binder polyvinylidene fluoride to the solvent NMP and mix evenly to make the negative electrode slurry, and use a coating machine to coat the two surfaces of the copper foil of the negative electrode current collector at 120°C Drying, rolling, and slitting to obtain the negative electrode sheet;
2)将锂网叠放在步骤1)中制得的负极片表面，在100kg/cm2的压力下辊压，即得。2) Lay the lithium mesh on the surface of the negative electrode sheet prepared in step 1), and roll it under a pressure of 100kg/cm2 to obtain it.
本实施例的锂离子电容器包括正极、负极、隔膜以及电解液，隔膜设置在正极和负极之间，负极使用上述锂离子电容器负极单元。The lithium ion capacitor of this embodiment includes a positive electrode, a negative electrode, a diaphragm and an electrolyte, the diaphragm is arranged between the positive electrode and the negative electrode, and the negative electrode uses the above-mentioned negative electrode unit of the lithium ion capacitor.
上述正极为正极片，正极片包括正极集流体铝箔以及涂覆在正极集流体两个表面的正极活性物质层，正极活性物质层由正极活性物质活性炭、导电剂SuperP、粘结剂聚四氟乙烯(PTFE)按照质量比85:7:8均匀混合而成。该正极片由如下方法制得：将正极活性物质活性炭、导电剂SuperP、粘结剂聚四氟乙烯(PTFE)加入溶剂去离子水均匀混合制成正极浆料，采用涂布机涂覆在正极集流体铝箔上，120℃下烘干，烘干后的涂布厚度为260μm，辊压，辊压后的正极片厚度为120μm，切边、裁片、分条、收卷，制得正极片。The above-mentioned positive electrode is a positive electrode sheet, and the positive electrode sheet includes a positive electrode current collector aluminum foil and a positive electrode active material layer coated on both surfaces of the positive electrode current collector. The positive electrode active material layer is composed of positive electrode active material activated carbon, conductive agent SuperP, binder polytetrafluoroethylene (PTFE) is uniformly mixed according to the mass ratio of 85:7:8. The positive electrode sheet is prepared by the following method: the positive electrode active material activated carbon, the conductive agent SuperP, and the binder polytetrafluoroethylene (PTFE) are added to the solvent deionized water and uniformly mixed to form a positive electrode slurry, which is coated on the positive electrode by a coating machine. On the current collector aluminum foil, dry at 120°C, the coating thickness after drying is 260 μm, roll pressing, the thickness of the positive electrode sheet after rolling is 120 μm, trim, cut into pieces, slitting, and winding to obtain the positive electrode sheet .
隔膜为聚乙烯微孔膜，电解液包括锂盐六氟磷酸锂和溶剂，六氟磷酸锂的浓度为1.0mol/L，溶剂由碳酸乙烯酯、碳酸丙烯酯、碳酸二乙酯按照体积比3.5：0.5：4混合而成。The diaphragm is a polyethylene microporous membrane. The electrolyte includes lithium salt lithium hexafluorophosphate and solvent. The concentration of lithium hexafluorophosphate is 1.0mol/L. The solvent is made of ethylene carbonate, propylene carbonate and diethyl carbonate in a volume ratio of 3.5:0.5:4. become.
本实施例的锂离子电容器按照如下方法制得：将正极、隔膜、负极制成叠片式电芯，入壳，注液，静置4h，并记录最高电压值，用来判断预嵌锂的深度，以2.8-2.9V为合格，然后以1.5A恒流充电至3.8V，3.8V恒压24h化成，排气，即得。The lithium ion capacitor of this embodiment is produced according to the following method: make the positive electrode, diaphragm, and negative electrode into laminated batteries, put them into the shell, inject liquid, let stand for 4 hours, and record the highest voltage value, which is used to judge the pre-embedded lithium. Depth, 2.8-2.9V is qualified, then charge to 3.8V with 1.5A constant current, 3.8V constant voltage 24h into formation, exhaust, that is.
实施例3Example 3
本实施例的锂离子电容器负极单元包括负极片，负极片包括负极集流体铜箔以及涂覆在负极集流体两个表面上的负极活性物质层，负极活性物质层由负极活性物质硬碳、导电剂SuperP、混合粘结剂按照质量比90:3:7均匀混合而成，混合粘结剂由丁苯橡胶(SBR)和羧甲基纤维素(CMC)按照质量比5：3混合而成，负极片的厚度为200μm，负极片两面的负极活性物质层表面均铺设有锂网，锂网的孔隙率为70％，锂网与负极活性物质的质量比为0.1:1，锂网的整体铺设面积大于负极片表面负极活性物质层的面积以能够将负极活性物质层完全覆盖。The negative electrode unit of the lithium ion capacitor of the present embodiment includes a negative electrode sheet, and the negative electrode sheet includes a negative electrode current collector copper foil and a negative electrode active material layer coated on both surfaces of the negative electrode current collector. SuperP and mixed binder are evenly mixed according to the mass ratio of 90:3:7. The mixed binder is made of styrene-butadiene rubber (SBR) and carboxymethyl cellulose (CMC) according to the mass ratio of 5:3. The thickness of the negative electrode sheet is 200 μm, and the surface of the negative electrode active material layer on both sides of the negative electrode sheet is covered with a lithium mesh. The porosity of the lithium mesh is 70%, and the mass ratio of the lithium mesh to the negative electrode active material is 0.1:1. The overall laying of the lithium mesh The area is larger than the area of the negative electrode active material layer on the surface of the negative electrode sheet so as to be able to completely cover the negative electrode active material layer.
本实施例的锂离子电容器负极单元的制备方法包括如下步骤：The preparation method of the lithium ion capacitor negative electrode unit of the present embodiment comprises the following steps:
1)将负极活性物质硬碳、导电剂SuperP及粘结剂聚偏氟乙烯加入溶剂NMP均匀混合制成负极浆料，采用涂布机涂覆在负极集流体铜箔的两个表面，150℃烘干，辊压，分条，得负极片；1) Add the negative electrode active material hard carbon, the conductive agent SuperP and the binder polyvinylidene fluoride to the solvent NMP and mix evenly to make the negative electrode slurry, and use a coating machine to coat the two surfaces of the copper foil of the negative electrode current collector at 150°C Drying, rolling, and slitting to obtain the negative electrode sheet;
2)将锂网叠放在步骤1)中制得的负极片表面，在200kg/cm2的压力下辊压，即得。2) Lay the lithium mesh on the surface of the negative electrode sheet prepared in step 1), and roll it under a pressure of 200kg/cm2 to obtain it.
本实施例的锂离子电容器包括正极、负极、隔膜以及电解液，隔膜设置在正极和负极之间，负极片使用上述锂离子电容器负极单元。The lithium ion capacitor of this embodiment includes a positive electrode, a negative electrode, a diaphragm and an electrolyte, the diaphragm is arranged between the positive electrode and the negative electrode, and the negative electrode sheet uses the above-mentioned negative electrode unit of the lithium ion capacitor.
上述正极为正极片，正极片包括正极集流体铝箔以及涂覆在正极集流体两个表面的正极活性物质层，正极活性物质层由正极活性物质活性炭、导电剂SuperP、粘结剂聚四氟乙烯(PTFE)按照质量比85:7:8均匀混合而成。该正极片由如下方法制得：将正极活性物质活性炭、导电剂SuperP、粘结剂聚四氟乙烯(PTFE)加入溶剂去离子水均匀混合制成正极浆料，采用涂布机涂覆在正极集流体铝箔上，120℃下烘干，烘干后的涂布厚度为260μm，辊压，辊压后的正极片厚度为120μm，切边、裁片、分条、收卷，制得正极片。The above-mentioned positive electrode is a positive electrode sheet, and the positive electrode sheet includes a positive electrode current collector aluminum foil and a positive electrode active material layer coated on both surfaces of the positive electrode current collector. The positive electrode active material layer is composed of positive electrode active material activated carbon, conductive agent SuperP, binder polytetrafluoroethylene (PTFE) is uniformly mixed according to the mass ratio of 85:7:8. The positive electrode sheet is prepared by the following method: the positive electrode active material activated carbon, the conductive agent SuperP, and the binder polytetrafluoroethylene (PTFE) are added to the solvent deionized water and uniformly mixed to form a positive electrode slurry, which is coated on the positive electrode by a coating machine. On the current collector aluminum foil, dry at 120°C, the coating thickness after drying is 260 μm, roll pressing, the thickness of the positive electrode sheet after rolling is 120 μm, trim, cut into pieces, slitting, and winding to obtain the positive electrode sheet .
隔膜为聚丙烯微孔膜，电解液包括锂盐六氟磷酸锂和溶剂，六氟磷酸锂的浓度为1.2mol/L，溶剂由碳酸乙烯酯、碳酸丙烯酯、碳酸二甲酯按照体积比3：1：4混合而成。The separator is a polypropylene microporous membrane. The electrolyte includes lithium salt lithium hexafluorophosphate and solvent. The concentration of lithium hexafluorophosphate is 1.2mol/L. The solvent is made of ethylene carbonate, propylene carbonate and dimethyl carbonate in a volume ratio of 3:1:4. become.
本实施例的锂离子电容器按照如下方法制得：将正极、隔膜、负极制成叠片式电芯，入壳，注液，静置4h，并记录最高电压值，用来判断预嵌锂的深度，以2.8-2.9V为合格，然后以1.5A恒流充电至3.8V，3.8V恒压24h化成，排气，即得。The lithium ion capacitor of this embodiment is produced according to the following method: make the positive electrode, diaphragm, and negative electrode into laminated batteries, put them into the shell, inject liquid, let stand for 4 hours, and record the highest voltage value, which is used to judge the pre-embedded lithium. Depth, 2.8-2.9V is qualified, then charge to 3.8V with 1.5A constant current, 3.8V constant voltage 24h into formation, exhaust, that is.
实施例4-9中的负极活性物质种类及锂网与负极活性物质的质量比如表1所示，其他的均与实施例1中的相同。The types of negative electrode active materials and the quality ratios of lithium mesh and negative electrode active materials in Examples 4-9 are shown in Table 1, and the others are the same as those in Example 1.
表1实施例4-9中的负极活性物质种类及锂网与负极活性物质的质量比The mass ratio of negative electrode active material species and lithium network to negative electrode active material in the embodiment 4-9 of table 1
注：Li/Na为锂网与负极活性物质的质量比。Note: Li/Na is the mass ratio of lithium mesh to negative electrode active material.
实验例Experimental example
将实施例1-9中得到的锂离子电容器按照如下方法进行测试：The lithium ion capacitor obtained in embodiment 1-9 is tested according to the following method:
(1)静电容量及能量密度测试。(1) Electrostatic capacity and energy density test.
在20-30℃下，以10A充电至4.0V，搁置15s，然后以10A放电至2.0V，循环5周，取平均值。测试结果如表2所示。At 20-30°C, charge to 4.0V with 10A, leave for 15s, then discharge to 2.0V with 10A, cycle for 5 weeks, and take the average value. The test results are shown in Table 2.
(2)循环寿命测试。(2) Cycle life test.
在20-30℃下，在2.0-4.0V的电压范围内，以15A恒流充放电，循环10万次，并计算最后一次放电容量相对于首次放电容量的保持率。测试结果如表2所示。At 20-30°C, in the voltage range of 2.0-4.0V, charge and discharge at a constant current of 15A, cycle 100,000 times, and calculate the retention rate of the last discharge capacity relative to the first discharge capacity. The test results are shown in Table 2.
(3)DC-Life测试。(3) DC-Life test.
在65℃下，以恒压4.0V持续充电，然后15A恒流放电至2V，再15A恒流充电至4V，循环3周，以第三周放电容量降至初始容量的80％以下或者内阻增至初始值的200％为停止条件，并记录4.0V恒压测试的时间。测试结果如表2所示。At 65°C, charge continuously at a constant voltage of 4.0V, then discharge at a constant current of 15A to 2V, then charge at a constant current of 15A to 4V, cycle for 3 weeks, and the discharge capacity drops below 80% of the initial capacity or the internal resistance in the third week Increase to 200% of the initial value is the stop condition, and record the time of 4.0V constant voltage test. The test results are shown in Table 2.
表2实施例1-9中的锂离子电容器测试结果Lithium ion capacitor test result in table 2 embodiment 1-9
注：Li/Na为锂网与负极活性物质质量比。Note: Li/Na is the mass ratio of lithium mesh to negative electrode active material.
由上表可以看出，本发明的锂离子电容器的能量密度较高，能量密度最大达28.4Wh/kg，循环10万次后容量保持率仍达到81％-89％，4.0V、65℃下DC-Life测试结果最长时间达2100小时。It can be seen from the above table that the lithium ion capacitor of the present invention has a high energy density, the maximum energy density is 28.4Wh/kg, and the capacity retention rate still reaches 81%-89% after 100,000 cycles. DC-Life test results up to 2100 hours.
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| CN201610037631.XACN105655147B (en) | 2016-01-20 | 2016-01-20 | A kind of lithium-ion capacitor negative pole unit and preparation method thereof, lithium-ion capacitor |
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| CN201610037631.XACN105655147B (en) | 2016-01-20 | 2016-01-20 | A kind of lithium-ion capacitor negative pole unit and preparation method thereof, lithium-ion capacitor |
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