WO2016110109A1 - 一种锂离子电容电池的负压阶梯式化成方法 - Google Patents

一种锂离子电容电池的负压阶梯式化成方法 Download PDF

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WO2016110109A1
WO2016110109A1 PCT/CN2015/088106 CN2015088106W WO2016110109A1 WO 2016110109 A1 WO2016110109 A1 WO 2016110109A1 CN 2015088106 W CN2015088106 W CN 2015088106W WO 2016110109 A1 WO2016110109 A1 WO 2016110109A1
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capacitor battery
carbon
lithium ion
active material
voltage
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PCT/CN2015/088106
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English (en)
French (fr)
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阮殿波
袁峻
傅冠生
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宁波南车新能源科技有限公司
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/14—Arrangements or processes for adjusting or protecting hybrid or EDL capacitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Definitions

  • the invention relates to the technical field of lithium ion batteries, and in particular to a method for forming a negative pressure step of a lithium ion capacitor battery.
  • a lithium ion battery is a green secondary battery having a large energy density, a high average output voltage, a small self-discharge, and no toxic substances. After nearly two decades of development, lithium-ion batteries have been able to reach 100Wh/kg to 150Wh/kg, and the working voltage can reach up to 4V.
  • Supercapacitor is an energy storage device based on the principle of double-layer energy storage and high reversibility redox quasi-capacitor. It has the advantages of high power density, short charge and discharge time, long cycle life and wide operating temperature range. The energy density is relatively low and so on.
  • a capacitor battery that has been charged for a long time in a large current tends to cause a small amount of an oxygen-containing functional group in the activated carbon to undergo irreversible redox reaction and decomposition of the electrolyte, resulting in a part of the gas being generated in the battery. If the gas in this part is not removed in time, affecting the performance of the battery, the bulging of the battery may be so severe that the structure of the battery may be damaged.
  • the formation process is a very important step.
  • a passivation layer (SEI film) is formed on the surface of the negative electrode.
  • SEI film passivation layer
  • the degree of formation of the SEI film directly affects the stability and life of the battery. Security and other factors.
  • the traditional long-time small current formation method not only takes a long time, but also causes an increase in the impedance of the SEI film for a capacitor battery with a high operating voltage, which affects the rate performance of the capacitor battery.
  • the object of the present invention is to provide a negative pressure stepwise formation method for a lithium ion capacitor battery, to change the current state of the conventional lithium ion battery formation method, and to find and find an optimum formation method suitable for different system capacitor batteries. Since the redox potentials of the lithium-ion battery used in different types of capacitor batteries are different, and the doping ratios of the positive and negative electrodes of the composite positive and negative electrodes are different, it is necessary to provide different chemical conversion schemes.
  • a step-by-step method for forming a negative pressure of a lithium ion capacitor battery comprises the steps of: sealing a 20 mm long, 5 mm diameter PP pipe for encapsulation of a capacitor battery and connecting it to a vacuum pump
  • the battery capacitor monomer is injected and left to stand for 18 ⁇ 4 hours, and the charge and discharge potential is determined according to the oxidation-reduction potentials of the positive and negative electrodes, and the stepwise type is adopted.
  • the charge and discharge cycle is formed by using different currents.
  • the PP pipe is connected to the vacuum pump to maintain a vacuum of -0.5 MPa.
  • the specific voltage and current of different stages are as follows:
  • the first stage the starting voltage is the initial voltage, the cutoff voltage U1, the current is 0.02-0.05C;
  • the second stage the starting voltage is the lower limit of the working voltage, the cutoff voltage U2, the current is 0.05-0.1C;
  • the third stage the starting voltage is the lower limit of the working voltage, the cutoff voltage U3, the current is 0.1-0.2C;
  • the fourth stage the starting voltage is the lower limit of the working voltage, the cutoff voltage U4, the current is 0.1-0.2C;
  • the fifth stage the starting voltage is the lower limit of the working voltage, the cutoff voltage U5, the current 0.1-0.2C;
  • the U1 ⁇ U2 ⁇ U3 ⁇ U4 ⁇ U5 the upper limit of the operating voltage.
  • the positive electrode material of the capacitor battery comprises two active materials A and B, and the active materials of the class A are LiCoO 2 , LiMn 2 O 4 , LiMnO 2 , LiNiO 2 , LiFePO 4 , LiMnPO 4 , LiNi 0.8 Co 0.2 O 2 , LiNi.
  • the active materials of type B are activated carbon, mesoporous carbon, carbon aerogel, carbon fiber, carbon nanotube, carbon black, hard carbon, One or more mixtures of graphene.
  • the positive electrode material has a distribution ratio of 5% to 85% of the active material of the class A, 5% to 85% of the active material of the type B, 3% to 8% of the conductive agent, and 2% to 7% of the bonding agent. Agent.
  • the B-type active material is used after surface modification treatment, and the surface modification treatment method is: mixing a silane coupling agent anhydrous ethanol solution having a mass concentration of 5-10% with a B-type active substance for 30-50 min. Then, adding a concentration of 8-15% of the aluminate coupling agent in absolute ethanol solution for 30-50min, filtering, drying the filter at 70-80 ° C for 4-5h, and then at 100 ° C -105 ° C The activation is 1-2 h, the amount of the silane coupling agent is 0.5-1% by weight of the B active material, and the amount of the aluminate coupling agent is 1-1.5% by weight of the B active material.
  • the inventors discovered that the first surface treatment of the B-type active substance is first carried out by using a silane coupling agent, and the silane coupling agent can be effectively infiltrated into the B-type active material particles after being mixed with the B-type active material.
  • the gap between the B-type active material particles can be effectively separated, and the dispersibility of the B-type active material can be effectively improved, and then the treated B-type active material is subjected to a second surface treatment by adding an aluminate coupling agent.
  • the oil group is increased, and it is more uniformly mixed with components such as a binder, and the obtained positive electrode material has a uniform distribution of components and stable performance.
  • U1 is 2.7v
  • U2 is 3.2v
  • U3 is 3.4v
  • U4 is 3.6v
  • U5 is 3.8v.
  • the negative electrode active material of the negative electrode material of the capacitor battery is one or more mixtures of activated carbon, natural graphite, artificial graphite, soft carbon, carbon nanotubes, carbon fibers, hard carbon, mesophase carbon microspheres;
  • the distribution ratio is: 90% - 92% of the negative active material, 2% - 5% of the conductive agent, 3% - 5% of the binder.
  • the negative electrode active material is used after the surface modification treatment, and the surface modification treatment method is: mixing a silane coupling agent anhydrous ethanol solution having a mass concentration of 5-10% with the negative electrode active material for 30-50 minutes, and then Adding a solution of aluminate coupling agent in absolute ethanol with a concentration of 8-15% at a concentration of 30-50 min, filtering, and drying the filter at 70-80 ° C for 4-5 h. Further, it is activated at 100 ° C - 105 ° C for 1-2 h, the amount of the silane coupling agent is 0.5-1% by weight of the negative electrode active material, and the amount of the aluminate coupling agent is 1-1.5% by weight of the negative electrode active material.
  • the surface modification treatment method is: mixing a silane coupling agent anhydrous ethanol solution having a mass concentration of 5-10% with the negative electrode active material for 30-50 minutes, and then Adding a solution of aluminate coupling agent in absolute ethanol with a concentration of
  • the inventors discovered that the first surface treatment of the negative electrode active material is carried out by using a silane coupling agent, and the silane coupling agent can be effectively infiltrated into the gap between the negative electrode active material particles after being mixed into the negative electrode active material.
  • the dispersibility of the negative electrode active material can be effectively improved, and then the treated surface active material is subjected to a second surface treatment by adding an aluminate coupling agent, thereby effectively solving the negative electrode activity.
  • the problem of material agglomeration enables the aluminate coupling agent to effectively encapsulate the negative electrode active material, further preventing the agglomeration of the negative electrode active material, and the lipophilic group of the negative electrode active material is increased due to the treatment of the coupling agent, and the binder, etc.
  • the components are more uniformly mixed, and the obtained positive electrode material has a uniform distribution of components and stable performance.
  • the current collector of the capacitor battery is a carbon coated aluminum foil, an aluminum foil, a perforated aluminum foil, a copper foil or a perforated copper foil.
  • the conductive agent is a mixture of one or more of conductive carbon black, graphene, and carbon nanotubes.
  • the conductive agent is a modified carbon nanotube, and the steps of preparing the modified carbon nanotube are as follows:
  • the secondary modified carbon nanotubes and the perchloric acid having a mass concentration of 50-60% are uniformly mixed according to the ratio of material to liquid of 1g: 20-30mL, heated to 60-70 ° C for 24 hours, cooled, filtered, washed with water, The modified carbon nanotubes are obtained after vacuum drying.
  • the more preferred conductive agent of the present invention is a modified carbon nanotube.
  • Typical multi-walled carbon nanotubes generally have a diameter of a few nanometers to several tens of nanometers and a length of several to several tens of micrometers. The prepared samples are mostly disorderly distributed, and the carbon nanotubes are intertwined and difficult to disperse, and the agglomerated carbon nanotubes need to be dispersed into individual carbon nanotubes to exert their special properties.
  • Step (1) mixing the carbon nanotubes with a dimethylformamide solution having a mass concentration of 30-50% and an acid solution, and simultaneously stirring to enlarge the contact surface of the carbon nanotubes with the liquid, so that the carbon nanotubes are uniformly dispersed.
  • the specific solvent combination system of the dimethylformamide solution and the acid solution with a mass concentration of 30-50% can make the carbon nanotubes disperse more uniformly in the system and effectively avoid the agglomeration of the carbon nanotubes.
  • Step (1) first dispersing the carbon nanotubes uniformly, which facilitates the shearing of the step (2), and uniformly disperses the step (1).
  • the hydrothermal reaction of the carbon nanotubes with the specific chemical shear liquid of the present invention can effectively cut the carbon nanotubes to obtain uniform carbon nanotubes having a relatively uniform length (about 100-150 nm in length), and such carbon nanotubes are used.
  • a more excellent electrical and thermal conductivity can be exerted in a smaller amount.
  • Step (3) The homogenized carbon nanotube obtained in the step (2) is hydrothermally reacted in perchloric acid, and the perchloric acid molecule can intercalate and swell the carbon nanotube bundle, so that the carbon nanotubes are separated from each other and the surface thereof is highly reacted.
  • the activated carbonaceous by-products are exposed to achieve selective functionalization of carbonaceous by-products. Similar to surfactants, these functionalized carbon by-products have amphiphilic properties, which can improve the interaction between carbon nanotubes and binders, assist in the dispersion of carbon nanotubes, and greatly improve the preparation of positive and negative materials for carbon nanotubes. Uniform dispersion performance.
  • the acid solution is a mixture of concentrated nitric acid having a mass concentration of 70% and a concentrated sulfuric acid having a mass concentration of 98% in a volume ratio of 1-2:1; the chemical shearing solution is at a concentration of 0.5-0.8 moL/L.
  • the invention has the following beneficial effects:
  • Figure 1 is a graph showing the charge and discharge curves of the formation process.
  • the materials used in the examples of the present invention are all raw materials commonly used in the art, and the methods used in the examples are all conventional methods in the art.
  • Figure 1 shows the charge and discharge curve of the formation process
  • Cathode material LiFePO 4 , activated carbon, conductive agent (graphene), binder (polyvinylidene fluoride), pulping, coating, rolling and pole piece according to the mass ratio of 25:65:5:5 Cut, the pole piece size is 75mm * 56mm.
  • Anode material MCMB, hard carbon, conductive agent (graphene), binder (polyvinylidene fluoride), pulping, coating, rolling and pole piece according to the mass ratio of 50:40:5:5 Cut, the pole piece size is 75mm * 56mm.
  • the performance test was carried out, charging with 1C to 3.8V, 1C discharging to 2.0V, the specific energy of the capacitor battery was 35.6Wh/kg, the specific power was 3800W/kg, and after 15000 charge and discharge cycles of 1C, the capacity was kept at 82.3%.
  • the negative pressure step formation method can greatly improve the metal lithium salt capacity of the lithium ion capacitor battery and the formation of the negative SEI film, and finally obtain the hybrid capacitor battery.
  • the specific energy, specific power and cycle life are significantly improved.
  • Embodiment 1 differs from Embodiment 1 in that:
  • the conductive agents of the positive electrode material and the negative electrode material are modified carbon nanotubes, and the steps for preparing the modified carbon nanotubes are as follows:
  • the chemical shear solution was a mixture of a sodium molybdate solution having a concentration of 0.8 mol/L and a silicomolybdic acid solution having a concentration of 0.5 mol/L in a volume ratio of 1:1.
  • Embodiment 1 differs from Embodiment 1 in that:
  • the conductive agents of the positive electrode material and the negative electrode material are modified carbon nanotubes, and the steps for preparing the modified carbon nanotubes are as follows:
  • Embodiment 1 differs from Embodiment 1 in that:
  • the conductive agents of the positive electrode material and the negative electrode material are modified carbon nanotubes, and the steps for preparing the modified carbon nanotubes are as follows:
  • the chemical shear solution was a mixture of a sodium molybdate solution having a concentration of 0.6 mol/L and a silicomolybdic acid solution having a concentration of 0.4 mol/L in a volume ratio of 1:1.
  • Embodiment 1 differs from Embodiment 1 in that:
  • Activated carbon (B-type active substance) is used after surface modification treatment.
  • the surface modification treatment method is: mixing silane coupling agent anhydrous ethanol solution with mass concentration of 5% with B-type active substance for 30 min, and then adding mass concentration. It is mixed with 8% aluminate coupling agent anhydrous ethanol solution for 30 min, filtered, and the filter is dried at 70 ° C for 5 h and then activated at 100 ° C for 2 h.
  • the amount of silane coupling agent is 0.5 of the weight of the B active substance. %, the amount of aluminate coupling agent is 1% by weight of the B active substance.
  • the surface modification treatment method is: mixing a silane coupling agent anhydrous ethanol solution having a mass concentration of 5% with the negative electrode active material for 30 minutes, and then adding the mass concentration. It is mixed with 8% aluminate coupling agent in anhydrous ethanol for 30 min, filtered, and the filtrate is dried at 70 ° C for 5 h and then activated at 100 ° C for 2 h.
  • the amount of silane coupling agent is 0.5% by weight of the negative active material.
  • the amount of the aluminate coupling agent is 1% by weight of the negative electrode active material.
  • Example 1 Others were the same as in Example 1, and the performance test was slightly improved compared to Example 1.
  • Embodiment 1 differs from Embodiment 1 in that:
  • Activated carbon (B active substance) is used after surface modification treatment.
  • the surface modification treatment method is: mixing silane coupling agent anhydrous ethanol solution with mass concentration of 10% with B active substance for 50 min, and then adding mass concentration. It is a 15% aluminate coupling agent in absolute ethanol solution for 50 min, filtered, and the filtrate is dried at 80 ° C for 4 h and then at 105 ° C for 1 h.
  • the amount of silane coupling agent is 1 of the weight of the B active substance. %, the amount of aluminate coupling agent is 1.5% by weight of the B active substance.
  • the surface modification treatment method is: mixing a silane coupling agent anhydrous ethanol solution having a mass concentration of 10% with the negative electrode active material for 50 minutes, and then adding the mass concentration. It is a 15% aluminate coupling agent in absolute ethanol solution for 50 min, filtered, and the filtrate is dried at 80 ° C for 4 h and then activated at 105 ° C for 1 h.
  • the amount of the silane coupling agent is 1% by weight of the negative electrode active material.
  • the amount of aluminate coupling agent is the weight of the negative active material 1.5%.
  • Example 1 Others were the same as in Example 1, and the performance test was slightly improved compared to Example 1.

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Abstract

一种锂离子电容电池的负压阶梯式化成方法，具体包括以下步骤：在对电容电池的单体进行封装时封上一根20mm长，5mm直径的PP管，用做注液孔并连接真空泵，将电池电容单体注液并且静置18±4小时，根据正极和负极的氧化还原电位确定充放电电位，并采用阶梯式充放电循环使用不同大小的电流进行化成，于此同时将PP管连接上真空泵，保持-0.5MPa的真空度。该方法与现有技术相比，不仅高效且快速，其适用面较广。

Description

一种锂离子电容电池的负压阶梯式化成方法 技术领域
本发明涉及锂离子电池技术领域，具体涉及一种锂离子电容电池的负压阶梯式化成方法。
背景技术
锂离子电池是一种能量密度大，平均输出电压高，自放电小并且不含有毒物质的绿色二次电池。经过了将近二十年的发展，锂离子电池已经能达到100Wh/kg到150Wh/kg，工作电压最大可达4V。超级电容是基于双电层储能原理以及可逆性较高的氧化还原准电容原理的储能器件，具有功率密度高、充放电时间短、循环寿命长、工作温度范围宽等优点，同时也具有能量密度相对较低等劣势。
锂离子电池和超级电容在比能量和比功率上的差异决定了两者充放电速率的差异，而在实际的应用中，由于超级电容和锂离子电池具有各自突出的优点以及局限性，两者结合起来的并联式或者串联式电容电池的应用弥补了这一块的空白。由于锂离子电容电池自身的突出特性，往往将其应用在动力电源等相关领域，在实际使用过程中，动力电源存在的问题就是大电流充电以及反复充放的问题。
长期处于大电流充电的电容电池，往往会导致活性炭中的少量含氧官能团的不可逆氧化还原反应以及电解液的分解，导致产生一部分的气体在电池中。如果该部分的气体未能及时排除，影响电池性能，会导致电池的鼓胀严重得甚至破坏电池的结构。
在电容电池的制作工艺中，化成工艺是非常重要的一个步骤，在化成过程中，负极表面形成一层钝化层(SEI膜),SEI膜形成的程度直接影响到电池的稳定性、寿命、安全性等因素。传统的长时间小电流化成办法不仅耗时较长，而且对于工作电压较高的电容电池来说会导致SEI膜阻抗增大，影响电容电池的倍率性能。
发明内容
本发明的目的是提供一种锂离子电容电池的负压阶梯式化成方法，改变目前沿用传统锂离子电池的化成方法的现状，探索并寻找适合不同体系电容电池最佳的化成方法。由于不同体系的电容电池使用的锂离子电池正负极不同所导致的氧化还原电位不同，以及复合正负极的正负极的掺杂比不同，因此需要提供不同的化成方案。
为了达到上述发明目的，本发明采用以下技术方案：
一种锂离子电容电池的负压阶梯式化成方法，具体包括以下步骤：在对电容电池的单体进行封装时封上一根20mm长，5mm直径的PP管，用做注液孔并连接真空泵，将电池电容单体注液并且静置18±4小时，根据正极和负极的氧化还原电位确定充放电电位，并采用阶梯式 充放电循环使用不同大小的电流进行化成，于此同时将PP管连接上真空泵，保持-0.5MPa的真空度，不同阶段的具体电压和电流大小如下：
第一阶段：起始电压为初始电压，截止电压U1，电流为0.02-0.05C；
第二阶段：起始电压为工作电压下限，截止电压U2，电流0.05-0.1C；
第三阶段：起始电压为工作电压下限，截止电压U3，电流0.1-0.2C；
第四阶段：起始电压为工作电压下限，截止电压U4，电流0.1-0.2C；
第五阶段：起始电压为工作电压下限，截止电压U5，电流0.1-0.2C；
所述U1<U2<U3<U4<U5＝工作电压上限。
作为优选，电容电池的正极材料包括A和B两类活性物质，A类活性物质为LiCoO2、LiMn2O4、LiMnO2、LiNiO2、LiFePO4、LiMnPO4、LiNi0.8Co0.2O2、LiNi1/3Co1/3Mn1/3O2中的一种或多种混合物；B类活性物质为活性炭、介孔碳、碳气凝胶、碳纤维、碳纳米管、炭黑、硬炭、石墨烯中的一种或多种混合物。
作为优选，正极材料的成分配比为：5％-85％的A类活性物质，5％-85％的B类活性物质，3％-8％的导电剂，2％-7％的粘结剂。
作为优选，所述B类活性物质表面改性处理后使用，表面改性处理的方法为：将质量浓度为5-10％的硅烷偶联剂无水乙醇溶液与B类活性物质混合30-50min，然后再加入质量浓度为8-15％的铝酸酯偶联剂无水乙醇溶液在混合30-50min，过滤，过滤物在70-80℃下干燥4-5h，再在100℃-105℃下活化1-2h，硅烷偶联剂用量为B类活性物质重量的0.5-1％，铝酸酯偶联剂用量为B类活性物质重量的1-1.5％。
发明人通过长期的实验研究后发现，先通过使用硅烷偶联剂对B类活性物质进行第一次表面处理，硅烷偶联剂混入B类活性物质后，能有效渗入B类活性物质颗粒之间的间隙，使B类活性物质颗粒间相对隔离，能有效的提高B类活性物质的分散性，然后再通过添加铝酸酯偶联剂对处理过的B类活性物质进行第二次表面处理，这样能有效解决B类活性物质团聚的问题，使铝酸酯偶联剂有效的包裹B类活性物质，进一步的防止了B类活性物质的团聚，由于偶联剂的处理，B类活性物质亲油基团增加，与粘结剂等成分混合的更均匀，所得正极材料成分分布均匀，性能稳定。
作为优选，U1为2.7v，U2为3.2v，U3为3.4v，U4为3.6v，U5为3.8v。
作为优选，电容电池的负极材料的负极活性物质为活性炭、天然石墨、人造石墨、软炭、碳纳米管、炭纤维、硬炭、中间相碳微球中的一种或多种混合物；负极材料的成分配比为：90％-92％的负极活性物质，2％-5％的导电剂，3％-5％的粘结剂。
作为优选，所述负极活性物质表面改性处理后使用，表面改性处理的方法为：将质量浓度为5-10％的硅烷偶联剂无水乙醇溶液与负极活性物质混合30-50min，然后再加入质量浓度为8-15％的铝酸酯偶联剂无水乙醇溶液在混合30-50min，过滤，过滤物在70-80℃下干燥4-5h， 再在100℃-105℃下活化1-2h，硅烷偶联剂用量为负极活性物质重量的0.5-1％，铝酸酯偶联剂用量为负极活性物质重量的1-1.5％。
发明人通过长期的实验研究后发现，先通过使用硅烷偶联剂对负极活性物质进行第一次表面处理，硅烷偶联剂混入负极活性物质后，能有效渗入负极活性物质颗粒之间的间隙，使负极活性物质颗粒间相对隔离，能有效的提高负极活性物质的分散性，然后再通过添加铝酸酯偶联剂对处理过的负极活性物质进行第二次表面处理，这样能有效解决负极活性物质团聚的问题，使铝酸酯偶联剂有效的包裹负极活性物质，进一步的防止了负极活性物质的团聚，由于偶联剂的处理，负极活性物质亲油基团增加，与粘结剂等成分混合的更均匀，所得正极材料成分分布均匀，性能稳定。
作为优选，电容电池的集流体为涂炭铝箔、铝箔、带孔铝箔、铜箔或带孔铜箔。
作为优选，所述导电剂为导电炭黑、石墨烯、碳纳米管中的一种或多种的混合物。
作为优选，所述导电剂为改性碳纳米管，改性碳纳米管的制备方法步骤如下：
(1)将碳纳米管、质量浓度30-50％的二甲基甲酰胺溶液及酸溶液按照1g：10-20mL：5-15mL的料液比混合，控制温度35-45℃下搅拌混合30-50min，过滤，分别用水和无水乙醇洗涤，80-100℃下真空干燥30-60min得初级改性碳纳米管；
(2)将初级改性碳纳米管与化学剪切液按照1g：30-50mL的料液比混合，加热至150-180℃，水热反应40-60h，冷却，水洗，得次级改性碳纳米管；
(3)次级改性碳纳米管与质量浓度50-60％的高氯酸按照1g：20-30mL的料液比混合均匀，加热至60-70℃保持24小时，冷却，过滤，水洗，真空干燥后得改性碳纳米管。
本发明更优选的导电剂为改性碳纳米管，研究表明：在包含碳纳米管的电极中，当碳纳米管的数量大到足以使碳纳米管能够彼此接触时，才能使电极不受碳纳米管自身的电阻影响，而主要受相互之间的接触电阻影响。因此在添加碳纳米管时需要的量就会较大。典型的多壁碳纳米管的直径一般为几纳米至几十纳米，长度为几至几十微米。制备的样品多呈杂乱分布，碳纳米管之间相互缠绕难以分散，成团状的碳纳米管需要被分散成单个的碳纳米管，才能发挥其特殊性能。
步骤(1)将碳纳米管与质量浓度30-50％的二甲基甲酰胺溶液及酸溶液混合，同时辅以搅拌，以扩大碳纳米管与液体的接触面，使得碳纳米管分散均匀，质量浓度30-50％的二甲基甲酰胺溶液及酸溶液的特定溶剂组合体系，能够使得碳纳米管能在体系中分散更均匀，有效避免碳纳米管团聚。
步骤(1)先将碳纳米管分散均匀，这样利于步骤(2)的剪切，将步骤(1)分散均匀的 碳纳米管与本发明特定的化学剪切液水热反应，能有效切断碳纳米管，获得长度较均一(长度大约在100-150nm)左右的均一化碳纳米管，这样的碳纳米管在用于电极材料时，可以用更少的量发挥更优异的导电导热效果。
步骤(3)将步骤(2)得到的均一化碳纳米管在高氯酸中水热反应，高氯酸分子能够插层、溶胀碳纳米管束，使碳纳米管彼此分开并将其表面高反应活性的碳质副产物暴露出来，从而实现选择性功能化碳质副产物。与表面活性剂类似，这些功能化的碳质副产物具有两亲性，可改善碳纳米管与粘结剂的相互作用，协助碳纳米管分散，从而大大提高碳纳米管在制备正负极材料时的均匀分散性能。
作为优选，所述酸溶液为质量浓度70％的浓硝酸与质量浓度98％的浓硫酸按照1-2:1的体积比的混合物；所述化学剪切液为浓度0.5-0.8moL/L的钼酸钠溶液与浓度0.3-0.5moL/L的硅钼酸溶液按照1:1的体积比的混合物。
本发明与现有技术相比，有益效果是：
1本化成方法高效且快速；
2适用面广。
附图说明
图1为化成过程的充放电曲线图。
具体实施方式
下面通过具体实施例对本发明的技术方案作进一步描述说明。
如果无特殊说明，本发明的实施例中所采用的原料均为本领域常用的原料，实施例中所采用的方法，均为本领域的常规方法。
实施例1：
LFP-AC/MCMB软包试样的化成过程，图1为化成过程的充放电曲线图
正极材料：LiFePO4、活性炭、导电剂(石墨烯)、粘结剂(聚偏氟乙烯)按照质量比为25:65:5:5比例进行制浆、涂覆、碾压以及极片的分切，极片大小为75mm*56mm。
负极材料：MCMB、硬炭、导电剂(石墨烯)、粘结剂(聚偏氟乙烯)按照质量比为50:40:5:5比例进行制浆、涂覆、碾压以及极片的分切,极片大小为75mm*56mm。
将正负极各10对进行叠片，使用PP-PE-PP三层聚合隔膜，经过24小时的60℃干燥得到电芯，将电芯进行组装，封装时封上一根20mm长，5mm直径的PP管，用做注液孔及连接真空泵。将电池电容单体注液并且静置18±4小时。
将得到的电容电池的PP注液管连接上真空泵，保持-0.5MPa的真空度，并根据磷酸铁锂和 MCMB的氧化还原电位进行阶段式化成的电流和电压设置，具体情况如下所述：
Figure PCTCN2015088106-appb-000001
经过化成后进行性能测试，用1C充电至3.8V，1C放电至2.0V，电容电池的比能量为35.6Wh/kg,比功率为3800W/kg，经过1C充放电循环15000次后，容量保持在82.3％。
从充放电测试和循环性能可以看出，经过负压阶梯式化成方法能使锂离子电容电池的金属锂盐容量的发挥以及负极SEI膜的形成有了很大的提高，最终得到的混合电容电池的比能量、比功率以及循环寿命均有明显的提高。
实施例2
本实施例与实施例1不同之处在于：
正极材料和负极材料的导电剂均为改性碳纳米管，改性碳纳米管的制备方法步骤如下：
(1)将碳纳米管、质量浓度30％的二甲基甲酰胺溶液及酸溶液按照1g：20mL：5mL的料液比混合，控制温度35℃下搅拌混合50min，过滤，分别用水和无水乙醇洗涤，80℃下真空干燥60min得初级改性碳纳米管；酸溶液为质量浓度70％的浓硝酸与质量浓度98％的浓硫酸按照2:1的体积比的混合物。
(2)将初级改性碳纳米管与化学剪切液按照1g：30mL的料液比混合，加热至150℃，水热反应60h，冷却，水洗，得次级改性碳纳米管；所述化学剪切液为浓度0.8moL/L的钼酸钠溶液与浓度0.5moL/L的硅钼酸溶液按照1:1的体积比的混合物。
(3)次级改性碳纳米管与质量浓度50％的高氯酸按照1g：30mL的料液比混合均匀，加热至60℃保持24小时，冷却，过滤，水洗，真空干燥后得改性碳纳米管。
其它同实施例1，性能测试比实施例1有一定提高。
实施例3
本实施例与实施例1不同之处在于：
正极材料和负极材料的导电剂均为改性碳纳米管，改性碳纳米管的制备方法步骤如下：
(1)将碳纳米管、质量浓度50％的二甲基甲酰胺溶液及酸溶液按照1g：10mL：15mL的料液比混合，控制温度45℃下搅拌混合30min，过滤，分别用水和无水乙醇洗涤，100℃下真空干燥30min得初级改性碳纳米管；酸溶液为质量浓度70％的浓硝酸与质量浓度98％的浓硫酸按照1:1的体积比的混合物。
(2)将初级改性碳纳米管与化学剪切液按照1g：50mL的料液比混合，加热至180℃，水热 反应40h，冷却，水洗，得次级改性碳纳米管；所述化学剪切液为浓度0.5moL/L的钼酸钠溶液与浓度0.3moL/L的硅钼酸溶液按照1:1的体积比的混合物。
(3)次级改性碳纳米管与质量浓度60％的高氯酸按照1g：20mL的料液比混合均匀，加热至70℃保持24小时，冷却，过滤，水洗，真空干燥后得改性碳纳米管。
其它同实施例1，性能测试比实施例1有一定提高。
实施例4
本实施例与实施例1不同之处在于：
正极材料和负极材料的导电剂均为改性碳纳米管，改性碳纳米管的制备方法步骤如下：
(1)将碳纳米管、质量浓度40％的二甲基甲酰胺溶液及酸溶液按照1g：15mL：10mL的料液比混合，控制温度40℃下搅拌混合40min，过滤，分别用水和无水乙醇洗涤，90℃下真空干燥50min得初级改性碳纳米管；酸溶液为质量浓度70％的浓硝酸与质量浓度98％的浓硫酸按照1.5:1的体积比的混合物。
(2)将初级改性碳纳米管与化学剪切液按照1g：40mL的料液比混合，加热至170℃，水热反应50h，冷却，水洗，得次级改性碳纳米管；所述化学剪切液为浓度0.6moL/L的钼酸钠溶液与浓度0.4moL/L的硅钼酸溶液按照1:1的体积比的混合物。
(3)次级改性碳纳米管与质量浓度55％的高氯酸按照1g：25mL的料液比混合均匀，加热至65℃保持24小时，冷却，过滤，水洗，真空干燥后得改性碳纳米管。
其它同实施例1，性能测试比实施例1有一定提高。
实施例5
本实施例与实施例1不同之处在于：
活性炭(B类活性物质)表面改性处理后使用，表面改性处理的方法为：将质量浓度为5％的硅烷偶联剂无水乙醇溶液与B类活性物质混合30min，然后再加入质量浓度为8％的铝酸酯偶联剂无水乙醇溶液在混合30min，过滤，过滤物在70℃下干燥5h，再在100℃下活化2h，硅烷偶联剂用量为B类活性物质重量的0.5％，铝酸酯偶联剂用量为B类活性物质重量的1％。负极活性物质(MCMB+硬炭)表面改性处理后使用，表面改性处理的方法为：将质量浓度为5％的硅烷偶联剂无水乙醇溶液与负极活性物质混合30min，然后再加入质量浓度为8％的铝酸酯偶联剂无水乙醇溶液在混合30min，过滤，过滤物在70℃下干燥5h，再在100℃下活化2h，硅烷偶联剂用量为负极活性物质重量的0.5％，铝酸酯偶联剂用量为负极活性物质重量的1％。
其它同实施例1，性能测试比实施例1有略微提高。
实施例6
本实施例与实施例1不同之处在于：
活性炭(B类活性物质)表面改性处理后使用，表面改性处理的方法为：将质量浓度为10％的硅烷偶联剂无水乙醇溶液与B类活性物质混合50min，然后再加入质量浓度为15％的铝酸酯偶联剂无水乙醇溶液在混合50min，过滤，过滤物在80℃下干燥4h，再在105℃下活化1h，硅烷偶联剂用量为B类活性物质重量的1％，铝酸酯偶联剂用量为B类活性物质重量的1.5％。负极活性物质(MCMB+硬炭)表面改性处理后使用，表面改性处理的方法为：将质量浓度为10％的硅烷偶联剂无水乙醇溶液与负极活性物质混合50min，然后再加入质量浓度为15％的铝酸酯偶联剂无水乙醇溶液在混合50min，过滤，过滤物在80℃下干燥4h，再在105℃下活化1h，硅烷偶联剂用量为负极活性物质重量的1％，铝酸酯偶联剂用量为负极活性物质重量 的1.5％。
其它同实施例1，性能测试比实施例1有略微提高。

Claims (11)

  1. 一种锂离子电容电池的负压阶梯式化成方法，其特征在于，具体包括以下步骤：在对电容电池的单体进行封装时封上一根20mm长，5mm直径的PP管，用做注液孔并连接真空泵，将电池电容单体注液并且静置18±4小时，根据正极和负极的氧化还原电位确定充放电电位，并采用阶梯式充放电循环使用不同大小的电流进行化成，于此同时将PP管连接上真空泵，保持-0.5MPa的真空度，不同阶段的具体电压和电流大小如下：
    第一阶段：起始电压为初始电压，截止电压U1，电流为0.02-0.05C；
    第二阶段：起始电压为工作电压下限，截止电压U2，电流0.05-0.1C；
    第三阶段：起始电压为工作电压下限，截止电压U3，电流0.1-0.2C；
    第四阶段：起始电压为工作电压下限，截止电压U4，电流0.1-0.2C；
    第五阶段：起始电压为工作电压下限，截止电压U5，电流0.1-0.2C；
    所述U1<U2<U3<U4<U5＝工作电压上限。
  2. 根据权利要求1所述的一种锂离子电容电池的负压阶梯式化成方法，其特征在于，电容电池的正极材料包括A和B两类活性物质，A类活性物质为LiCoO2、LiMn2O4、LiMnO2、LiNiO2、LiFePO4、LiMnPO4、LiNi0.8Co0.2O2、LiNi1/3Co1/3Mn1/3O2中的一种或多种混合物；B类活性物质为活性炭、介孔碳、碳气凝胶、碳纤维、碳纳米管、炭黑、硬炭、石墨烯中的一种或多种混合物。
  3. 根据权利要求2所述的一种锂离子电容电池的负压阶梯式化成方法，其特征在于，正极材料的成分配比为：5％-85％的A类活性物质，5％-85％的B类活性物质，3％-8％的导电剂，2％-7％的粘结剂。
  4. 根据权利要求2所述的一种锂离子电容电池的负压阶梯式化成方法，其特征在于：所述B类活性物质表面改性处理后使用，表面改性处理的方法为：将质 量浓度为5-10％的硅烷偶联剂无水乙醇溶液与B类活性物质混合30-50min，然后再加入质量浓度为8-15％的铝酸酯偶联剂无水乙醇溶液在混合30-50min，过滤，过滤物在70-80℃下干燥4-5h，再在100℃-105℃下活化1-2h，硅烷偶联剂用量为B类活性物质重量的0.5-1％，铝酸酯偶联剂用量为B类活性物质重量的1-1.5％。
  5. 根据权利要求1所述的一种锂离子电容电池的负压阶梯式化成方法，其特征在于，U1为2.7v，U2为3.2v，U3为3.4v，U4为3.6v，U5为3.8v。
  6. 根据权利要求1所述的一种锂离子电容电池的负压阶梯式化成方法，其特征在于，电容电池的负极材料的负极活性物质为活性炭、天然石墨、人造石墨、软炭、碳纳米管、炭纤维、硬炭、中间相碳微球中的一种或多种混合物；负极材料的成分配比为：90％-92％的负极活性物质，2％-5％的导电剂，3％-5％的粘结剂。
  7. 根据权利要求6所述的一种锂离子电容电池的负压阶梯式化成方法，其特征在于，所述负极活性物质表面改性处理后使用，表面改性处理的方法为：将质量浓度为5-10％的硅烷偶联剂无水乙醇溶液与负极活性物质混合30-50min，然后再加入质量浓度为8-15％的铝酸酯偶联剂无水乙醇溶液在混合30-50min，过滤，过滤物在70-80℃下干燥4-5h，再在100℃-105℃下活化1-2h，硅烷偶联剂用量为负极活性物质重量的0.5-1％，铝酸酯偶联剂用量为负极活性物质重量的1-1.5％。
  8. 根据权利要求1所述的一种锂离子电容电池的负压阶梯式化成方法，其特征在于，电容电池的集流体为涂炭铝箔、铝箔、带孔铝箔、铜箔或带孔铜箔。
  9. 根据权利要求3或6所述的一种锂离子电容电池的负压阶梯式化成方法，其特征在于，所述导电剂为导电炭黑、石墨烯、碳纳米管中的一种或多种的混合 物。
  10. 根据权利要求3或6所述的一种锂离子电容电池的负压阶梯式化成方法，其特征在于，所述导电剂为改性碳纳米管，改性碳纳米管的制备方法步骤如下：
    (1)将碳纳米管、质量浓度30-50％的二甲基甲酰胺溶液及酸溶液按照1g：10-20mL：5-15mL的料液比混合，控制温度35-45℃下搅拌混合30-50min，过滤，分别用水和无水乙醇洗涤，80-100℃下真空干燥30-60min得初级改性碳纳米管；
    (2)将初级改性碳纳米管与化学剪切液按照1g：30-50mL的料液比混合，加热至150-180℃，水热反应40-60h，冷却，水洗，得次级改性碳纳米管；
    (3)次级改性碳纳米管与质量浓度50-60％的高氯酸按照1g：20-30mL的料液比混合均匀，加热至60-70℃保持24小时，冷却，过滤，水洗，真空干燥后得改性碳纳米管。
  11. 根据权利要求10所述的一种混合型超级电容器，其特征在于：所述酸溶液为质量浓度70％的浓硝酸与质量浓度98％的浓硫酸按照1-2:1的体积比的混合物；所述化学剪切液为浓度0.5-0.8moL/L的钼酸钠溶液与浓度0.3-0.5moL/L的硅钼酸溶液按照1:1的体积比的混合物。
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