WO2021189244A1 - 导电剂及其制备方法、电化学装置和电子装置 - Google Patents

导电剂及其制备方法、电化学装置和电子装置 Download PDF

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WO2021189244A1
WO2021189244A1 PCT/CN2020/080857 CN2020080857W WO2021189244A1 WO 2021189244 A1 WO2021189244 A1 WO 2021189244A1 CN 2020080857 W CN2020080857 W CN 2020080857W WO 2021189244 A1 WO2021189244 A1 WO 2021189244A1
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carbon
conductive agent
active material
positive electrode
electrode active
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PCT/CN2020/080857
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English (en)
French (fr)
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吴剑
邹邦坤
吕婉婉
屈长明
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宁德新能源科技有限公司
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Priority to CN202080009918.6A priority Critical patent/CN113330609B/zh
Priority to PCT/CN2020/080857 priority patent/WO2021189244A1/zh
Publication of WO2021189244A1 publication Critical patent/WO2021189244A1/zh

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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • This application relates to the field of electronic technology, in particular to conductive agents and preparation methods thereof, electrochemical devices and electronic devices.
  • transition metal ions in the positive electrode active material of the positive electrode sheet are easily eluted, which improves the oxidability of the positive electrode active material and degrades the high-temperature storage performance and cycle performance of the electrochemical device.
  • the electrolyte In order to reduce the dissolution of transition metal ions in the positive electrode active material, currently, some nitrile compounds are added to the electrolyte, and the nitrile group of the nitrile compound is complexed with the transition metal atoms on the surface of the positive electrode active material.
  • the free nitrile compounds in the electrolyte have a corrosive effect on the copper foil, thereby deteriorating the storage performance and cycle performance of the electrochemical device.
  • the embodiments of the present application bond the nitrile compound to the carbon-based conductive material to prevent the free nitrile compound from corroding the current collector and deteriorating the storage performance and cycle performance of the electrochemical device.
  • the embodiment of the present application provides a conductive agent including: a compound formed of a carbon-based conductive material and a nitrile compound, wherein the nitrile compound is bonded to the carbon-based conductive material.
  • the curve obtained by the infrared spectrum test of the conductive agent has an absorption peak between 2337 cm -1 and 2351 cm -1.
  • the carbon-based conductive material includes at least one of conductive carbon black, Ketjen black, acetylene black, conductive graphite, carbon nanotubes, or carbon fibers.
  • the nitrile compound includes at least one of a chain organic nitrile, an organic nitrile containing an aromatic ring or a heteroaromatic ring, or a cyano polymer.
  • the nitrile compound includes succinonitrile, adiponitrile, 1,2-benzenediacetonitrile, 1,4-benzenediacetonitrile, 1-naphthaleneacetonitrile, 2-naphthaleneacetonitrile, polypropylene At least one of nitrile or polystyrene acrylonitrile.
  • the embodiment of the present application also provides an electrochemical device, which includes: a positive pole piece, the positive pole piece includes a current collector and a positive electrode active material layer, the positive electrode active material layer is disposed on the current collector; wherein The positive electrode active material layer includes a positive electrode active material and any one of the conductive agents described above.
  • the positive electrode active material includes one or more of lithium cobalt oxide, lithium nickel cobalt manganate, and lithium nickel cobalt aluminate
  • the positive electrode active material is in the positive electrode active material layer.
  • the mass percentage content of the product is 95% to 99.5%.
  • An embodiment of the present application also provides an electronic device, including the electrochemical device described above.
  • the embodiment of the present application also provides a method for preparing a conductive agent, including: mixing a carbon-based conductive material with a nitrile compound to obtain a pretreatment mixture; drying and roasting the pretreatment mixture to obtain the In the conductive agent, wherein the firing treatment includes firing at a temperature of 300°C to 500°C for 1 hour to 3 hours.
  • This application modifies the carbon-containing conductive material and introduces cyano groups on its surface.
  • the positive electrode active material layer the positive electrode active material is protected in situ through the complexation of the cyano group and the transition metal ion to reduce the cycle time.
  • the dissolution of transition metal ions reduces the oxidation of the anode, thereby improving the cycle stability and high-temperature storage performance of the electrochemical device.
  • Fig. 1 shows a flow chart of the preparation method of the conductive agent.
  • Fig. 2 is a schematic diagram of the positive pole piece of the present application.
  • Fig. 3 is a schematic diagram of the electrode assembly of the electrochemical device of the present application.
  • 6 and 7 show scanning electron microscope images of carbon nanotubes of Comparative Example 1 of the present application.
  • FIG. 8 shows the infrared spectrograms of the carbon nanotubes of Example 1 and Comparative Example 1 of the present application.
  • FIG. 9 shows the electron binding energy spectrum of the cobalt ion of Example 1 and Comparative Example 1 of the present application.
  • nitrile compound additives such as succinonitrile and adiponitrile are usually added to the electrolyte, and the nitrile group in the nitrile compound is complexed with the transition metal atom on the surface of the positive electrode active material to reduce the amount of lithium ion batteries.
  • the carbon-based conductive material and the nitrile compound solution are impregnated, dried, high-temperature roasting and other processes, so that the carbon-based conductive material is bonded to the nitrile compound, and the cyano group covers the surface of the carbon-based conductive material without being free to In the electrolyte, the reduction reaction of the cyano group at the negative electrode is avoided, and the protection effect of the positive electrode is improved.
  • the modified conductive agent When used as the positive electrode conductive agent, the cyano group on the surface of the conductive agent can complex with the transition metal atoms of the positive electrode active material, thereby reducing the elution of transition metal ions and reducing the oxidizing property of the positive electrode active material , So that the oxidation consumption of the electrolyte is reduced, and the high-temperature storage performance and cycle performance of the electrochemical device are improved.
  • the conductive agent includes a compound formed of a carbon-based conductive material and a nitrile compound, wherein the nitrile compound is bonded to the carbon-based conductive material.
  • the cyano group of the nitrile compound covers the surface of the carbon-based conductive material without being released into the electrolyte, avoiding the reduction reaction of the cyano group in the negative electrode, and the conductive agent
  • the cyano group on the surface can complex with the transition metal atoms of the positive electrode active material, thereby reducing the dissolution of transition metal ions, reducing the oxidizing property of the positive electrode active material, reducing the oxidation consumption of the electrolyte, and improving the high-temperature storage performance of the electrochemical device And cycle performance.
  • the carbon-based conductive material includes at least one of conductive carbon black, Ketjen black, acetylene black, conductive graphite, carbon nanotubes, or carbon fibers.
  • the nitrile compound includes at least one of a chain organic nitrile, an organic nitrile containing an aromatic ring or a heteroaromatic ring, or a cyano polymer.
  • the nitrile compound includes succinonitrile, adiponitrile, 1,2-benzenediacetonitrile, 1,4-benzenediacetonitrile, 1-naphthaleneacetonitrile, 2-naphthaleneacetonitrile, polyacrylonitrile, or polystyrene At least one of ethylene acrylonitrile.
  • a carbon-carbon bond is formed between the carbon-based conductive material and the nitrile compound.
  • the preparation method includes step 101, mixing a carbon-based conductive material with a nitrile compound, so that the carbon-based conductive material is completely impregnated to obtain a pretreatment mixture.
  • the preparation method of the conductive agent further includes step 102, drying and roasting the pretreatment mixture to obtain the conductive agent.
  • the drying process can remove moisture in the pretreatment mixture slurry.
  • the firing treatment includes firing at a temperature of 300°C to 500°C for 1 hour to 3 hours. In some embodiments, the firing process is performed in an inert atmosphere.
  • the preparation method has simple operation and is easy to realize the modification of the carbon-based conductive material by using a nitrile compound.
  • the electrochemical device includes a positive pole piece, the positive pole piece includes a current collector and a positive electrode active material layer, and the positive electrode active material layer is disposed on the current collector. As shown in FIG. 2, in some embodiments, the positive electrode active material layer 2 is disposed on the current collector 1. It should be understood that although the positive electrode active material layer 2 is shown as being located on one side of the current collector 1 in FIG. 2, this is only exemplary, and the positive electrode active material layer 2 may be located on both sides of the current collector 1. In some embodiments, the positive electrode current collector 1 can be Al foil, of course, other positive electrode current collectors commonly used in the art can also be used. In some embodiments, the positive electrode active material layer may only be coated on a partial area of the positive electrode current collector. In some embodiments, the positive electrode active material layer 2 includes a positive electrode active material and any of the aforementioned conductive agents.
  • the positive electrode active material includes one or more of lithium cobalt oxide, lithium nickel cobalt manganate, and lithium nickel cobalt aluminate, and the content of the positive electrode active material in the positive electrode active material layer is 95% to 95% by mass. 99.5%.
  • the positive active material layer further includes a binder
  • the binder in the positive active material layer may include polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, styrene-acrylate copolymer , Styrene-butadiene copolymer, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, sodium carboxymethyl cellulose, polyvinyl acetate, polyvinylpyrrolidone, polyvinyl ether , At least one of polymethyl methacrylate, polytetrafluoroethylene or polyhexafluoropropylene.
  • the mole percentage of the nitrile group in the conductive agent to the cobalt element in the positive electrode active material is 0.01% to 5%. If the content of the nitrile group in the conductive agent is too small, it cannot sufficiently complex with the cobalt element in the positive electrode active material. If the content of the nitrile group in the conductive agent is too much, the excess nitrile group cannot be complexed with the cobalt element, that is, it cannot prevent the cobalt atom from dissolving out. At the same time, too much nitrile compound bonded with the carbon-based conductive material will reduce The conductivity of the conductive agent affects the cycle performance of the electrochemical device.
  • the electrochemical device further includes a separator and a negative electrode piece. As shown in FIG. 3, the separator 11 is disposed between the positive pole piece 10 and the negative pole piece 12.
  • the negative pole piece includes a negative current collector and a negative active material layer, and the negative active material layer is disposed on the negative current collector. In some embodiments, the negative active material layer is disposed on one or both sides of the negative current collector. In some embodiments, the negative electrode current collector may use at least one of copper foil, aluminum foil, nickel foil, or carbon-based current collector.
  • the negative active material layer may include a negative active material and a binder, and the negative active material includes at least one of a silicon-based material, a carbon material, lithium titanate, or niobium titanate.
  • the silicon-based material includes at least one of silicon, silicon oxide, silicon carbon, or silicon alloy.
  • the carbon material in the negative active material layer includes at least one of artificial graphite, natural graphite, mesocarbon microspheres, soft carbon, or hard carbon.
  • the negative active material layer further includes a conductive agent, and the conductive agent may include at least one of conductive carbon black, sheet graphite, graphene, carbon nanotubes, or carbon fibers.
  • the binder in the negative active material layer may include carboxymethyl cellulose (CMC), polyacrylic acid, polyvinylpyrrolidone, polyaniline, polyimide, polyamideimide, polysilicon At least one of oxane, polystyrene butadiene rubber, epoxy resin, polyester resin, polyurethane resin, or polyfluorene.
  • CMC carboxymethyl cellulose
  • polyacrylic acid polyvinylpyrrolidone
  • polyaniline polyimide
  • polyamideimide polyamideimide
  • polysilicon At least one of oxane, polystyrene butadiene rubber, epoxy resin, polyester resin, polyurethane resin, or polyfluorene.
  • the isolation film 11 includes at least one of polyethylene, polypropylene, polyvinylidene fluoride, polyethylene terephthalate, polyimide, or aramid.
  • polyethylene includes at least one selected from high-density polyethylene, low-density polyethylene, or ultra-high molecular weight polyethylene.
  • polyethylene and polypropylene they have a good effect on preventing short circuits, and can improve the stability of the battery through the shutdown effect.
  • the thickness of the isolation film is in the range of about 5 ⁇ m to 500 ⁇ m.
  • the surface of the isolation membrane may further include a porous layer, the porous layer is disposed on at least one surface of the isolation membrane, the porous layer includes inorganic particles and a binder, and the inorganic particles are selected from alumina (Al 2 O 3 ), Silicon oxide (SiO 2 ), magnesium oxide (MgO), titanium oxide (TiO 2 ), hafnium dioxide (HfO 2 ), tin oxide (SnO 2 ), ceria (CeO 2 ), nickel oxide (NiO), oxide Zinc (ZnO), calcium oxide (CaO), zirconium oxide (ZrO 2 ), yttrium oxide (Y 2 O 3 ), silicon carbide (SiC), boehmite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide or sulfuric acid At least one of barium.
  • alumina Al 2 O 3
  • Silicon oxide SiO 2
  • magnesium oxide MgO
  • titanium oxide TiO 2
  • hafnium dioxide HfO 2
  • the pores of the isolation membrane have a diameter in the range of about 0.01 ⁇ m to 1 ⁇ m.
  • the binder is selected from polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, sodium carboxymethyl cellulose, polyethylene pyrrole At least one of alkanone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene, or polyhexafluoropropylene.
  • the porous layer on the surface of the isolation membrane can improve the heat resistance, oxidation resistance and electrolyte infiltration performance of the isolation membrane, and enhance the adhesion between the isolation membrane and the pole piece.
  • the electrode assembly of the electrochemical device is a wound electrode assembly or a stacked electrode assembly.
  • the electrochemical device includes a lithium ion battery, but the application is not limited thereto.
  • the electrochemical device may further include an electrolyte.
  • the electrolyte includes, but is not limited to, dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), ethylene carbonate (EC), propylene carbonate (PC), At least two of propyl propionate (PP).
  • the electrolyte may additionally include at least one of vinylene carbonate (VC), fluoroethylene carbonate (FEC), or dinitrile compound as an additive to the electrolyte.
  • the electrolyte further includes a lithium salt.
  • the positive pole piece, separator film, and negative pole piece are sequentially wound or stacked into electrode parts, and then packaged in, for example, aluminum-plastic film, and injected into electrolysis.
  • Lithium-ion battery is made by liquid, formed and packaged. Then, perform performance test and cycle test on the prepared lithium-ion battery.
  • the embodiments of the present application also provide an electronic device including the above-mentioned electrochemical device.
  • the electronic device of the embodiment of the present application is not particularly limited, and it can be used in any electronic device known in the prior art.
  • electronic devices may include, but are not limited to, notebook computers, pen-input computers, mobile computers, e-book players, portable phones, portable fax machines, portable copiers, portable printers, headsets, Video recorders, LCD TVs, portable cleaners, portable CD players, mini discs, transceivers, electronic notebooks, calculators, memory cards, portable recorders, radios, backup power supplies, motors, automobiles, motorcycles, assisted bicycles, bicycles, Lighting equipment, toys, game consoles, clocks, power tools, flashlights, cameras, large household storage batteries and lithium-ion capacitors, etc.
  • Preparation of positive electrode conductive agent configure a 20% mass fraction of succinonitrile aqueous solution, and mix 2g battery-grade commercial carbon nanotubes and 6g of the above-mentioned succinonitrile aqueous solution in a beaker evenly to obtain a carbon nanotube conductive agent pretreatment ; Dry the pretreatment material of carbon nanotube conductive agent at 80°C for 12h to remove the moisture in the pretreatment; put the material obtained after drying into a tube furnace, and pass inert protection such as nitrogen or helium It is calcined at 400°C for 2h to obtain nitrile-modified carbon nanotubes.
  • Preparation of positive pole piece Dissolve lithium cobaltate, the prepared nitrile-based modified carbon nanotube conductive agent, and polyvinylidene fluoride in N-methylpyrrolidone (NMP) solution at a weight ratio of 94:3:3 , The formation of positive electrode slurry.
  • the aluminum foil is used as the positive electrode current collector, the positive electrode slurry is coated on the positive electrode current collector, and the positive electrode pieces are obtained after drying, cold pressing, and cutting.
  • the positive electrode compaction density during the cold pressing process is 4.1 g/cm 3 .
  • the preparation of the negative pole piece the artificial graphite, acetylene black, styrene-butadiene rubber and sodium carboxymethyl cellulose are dissolved in deionized water at a weight ratio of 96:1:1.5:1.5 to form a negative electrode slurry.
  • a copper foil with a thickness of 10 ⁇ m is used as the negative electrode current collector, the negative electrode slurry is coated on the negative electrode current collector, and the negative electrode sheet is obtained after drying, cold pressing, and cutting.
  • isolation membrane dissolve polyvinylidene fluoride in water, form a uniform slurry through mechanical stirring, and apply the slurry to both sides of a porous substrate (polyethylene) that has been coated with ceramic coatings on both sides On the surface, an isolation film is formed after drying.
  • a porous substrate polyethylene
  • Lithium-ion battery preparation stack the positive pole piece, separator film, and negative pole piece in sequence, so that the separator film is located between the positive pole piece and the negative pole piece for isolation, and wind to obtain the electrode assembly.
  • the electrode assembly is placed in the outer packaging aluminum plastic film, and after the moisture is removed at 80°C, the above-mentioned electrolyte is injected and packaged, and the lithium ion battery is obtained through the process flow of formation, degassing, and trimming.
  • Examples 2 to 17 and Comparative Examples 1 to 5 are based on the steps of Example 1.
  • the specific changed parameters are shown in Table 1 below.
  • the mole percentage of cobalt atoms in the nitrile group and the positive electrode active material is controlled by The amount of dinitrile aqueous solution added is adjusted.
  • the lithium ion battery Place the lithium ion battery in a thermostat at 45°C ⁇ 2°C for 2 hours, charge it to 4.48V at a rate of 1C, and then charge it to 0.05C at a constant voltage at 4.48V. Subsequently, the cycle performance test was performed by discharging to 3.0V at a 1C rate. When the capacity of the lithium ion battery drops to 80% of the initial capacity, the corresponding cycle number is a parameter for evaluating the cycle performance of the lithium ion battery.
  • High-temperature storage expansion ratio (thickness of lithium-ion battery after high-temperature storage/thickness of lithium-ion battery after formation-1) ⁇ 100%.
  • Table 1 shows the various parameters and evaluation results of the Examples and Comparative Examples.
  • Example 1 and Comparative Example 1, Comparative Example 2 and Comparative Example 4 or Comparative Example 3 and Comparative Example 5 it can be known that by bonding a nitrile compound to a carbon-based conductive material, the cycle performance and storage of lithium ion batteries The expansion rate is improved. This is because the cyano group of the nitrile compound covers the surface of the carbon-based conductive material without being released into the electrolyte, avoiding the reduction reaction of the cyano group on the negative electrode, and the cyano group on the surface of the conductive agent can transition with the positive electrode active material.
  • the metal atoms undergo complexation, thereby reducing the dissolution of transition metal ions, reducing the oxidation of the positive electrode active material, reducing the oxidation consumption of the electrolyte, and improving the high-temperature storage performance and cycle performance of the electrochemical device.
  • FIG. 8 shows the infrared spectra of the carbon nanotubes of Example 1 and Comparative Example 1 of the present application.
  • the carbon nanotubes treated with the nitrile-based compound showed an obvious absorption peak at around 2345 cm-1 , which is a characteristic infrared absorption peak of NH.
  • the carbon nanotubes before the nitrile compound treatment have no absorption peak at this position, and the nitrile compound itself has no NH bond (NC-CC-CN). This shows that the nitrile compounds can effectively bond with the carbon nanotubes, so that the carbon nanotubes are equipped with nitrile functional groups.
  • Other nitrile compounds have the same mechanism of action, and they all can bond with carbon-based conductive materials.
  • FIG. 9 shows the electron binding energy spectrum of the cobalt ion of Example 1 and Comparative Example 1 of the present application.
  • the absorption peaks of Co appeared at 780.07eV and 794.77eV before the nitrile compound treatment (Comparative Example 1), and the Co absorption peaks shifted to 779.73eV and 794.43eV respectively after the nitrile compound treatment (Example 1). It shows that after bonding, the nitrile group in the conductive agent can effectively complex the cobalt ion and reduce the oxidizing property of the cobalt ion.
  • Example 16 and Comparative Example 2 or Comparative Example 17 and Comparative Example 3 it can be seen that when a certain amount of nitrile compound is also contained in the electrolyte, by bonding the nitrile compound to the carbon-based conductive material, the lithium ion battery The cycle performance and storage expansion rate can also be improved.
  • Examples 16 to 17 it can be seen that when the mass content of the nitrile compound in the electrolyte is increased from 5% to 10%, the cycle performance and storage expansion rate of the lithium ion battery can be improved to a certain extent.
  • nitrile compounds to carbon-based conductive materials, it can improve the cobalt elution of positive electrode active materials during cycling and storage under high voltage (>4.2V) systems, and improve the cycle stability and high temperature of electrochemical devices Storage performance.

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Abstract

提供了导电剂及其制备方法、电化学装置和电子装置。导电剂包括：由碳基导电材料与腈类化合物形成的化合物，其中，腈类化合物键合至碳基导电材料。通过使腈类化合物键合至碳基导电材料，使得腈类化合物的氰基覆盖在碳基导电材料的表面而不会游离到电解液中，避免了氰基在负极发生还原反应，同时导电剂表面的氰基可以与正极活性材料的过渡金属原子发生络合作用，从而减少过渡金属离子的溶出，降低正极活性材料的氧化性，使得电解液的氧化消耗减少，改善电化学装置的高温存储性能与循环性能。

Description

导电剂及其制备方法、电化学装置和电子装置 技术领域
本申请涉及电子技术领域，尤其涉及导电剂及其制备方法、电化学装置和电子装置。
背景技术
在诸如锂离子电池的电化学装置的循环过程中，正极极片的正极活性材料中的过渡金属离子容易溶出，提高了正极活性材料的氧化性，劣化电化学装置的高温存储性能和循环性能。
为了减少正极活性材料中的过渡金属离子的溶出，目前通过在电解液中添加一些腈类化合物，利用腈类化合物的腈基基团与正极活性材料表面的过渡金属原子络合来实现。然而，电解液中游离的腈类化合物对铜箔有腐蚀作用，进而劣化电化学装置的存储性能和循环性能。
发明内容
鉴于以上所述现有技术的缺点，本申请的实施例将腈类化合物与碳基导电材料键合，避免游离的腈类化合物对集流体造成腐蚀而劣化电化学装置的存储性能和循环性能。
本申请的实施例提供了一种导电剂，其包括：由碳基导电材料与腈类化合物形成的化合物，其中，所述腈类化合物键合至所述碳基导电材料。
在上述导电剂中，其中，所述碳基导电材料与所述腈类化合物之间形成碳碳键。
在上述导电剂中，其中，所述导电剂通过红外光谱测试得到的曲线在2337cm -1～2351cm -1之间具有吸收峰。
在上述导电剂中，其中，所述碳基导电材料包括导电炭黑、科琴黑、乙炔黑、导电石墨、碳纳米管或碳纤维中的至少一种。
在上述导电剂中，其中，所述腈类化合物包括链状有机腈、含芳环或杂芳环的有机腈或氰基聚合物中的至少一种。
在上述导电剂中，其中，所述腈类化合物包括丁二腈、己二腈、1,2-苯二乙腈、1,4-苯二乙腈、1-萘乙腈、2-萘乙腈、聚丙烯腈或聚苯乙烯丙烯腈中的至少一种。
本申请的实施例还提供了一种电化学装置，其包括：正极极片，所述正极极片包括集流体和正极活性材料层，所述正极活性材料层设置在所述集流体上；其中，所述正极活性材料层包括正极活性材料和上述任一所述的导电剂。
在上述电化学装置中，其中，所述正极活性材料包括钴酸锂、镍钴锰酸锂、镍钴铝酸锂中的一种或多种，所述正极活性材料在所述正极活性材料层的质量百分含量为95％～99.5％。
在上述电化学装置中，其中，所述导电剂中的腈基与所述正极活性材料中的钴元素的摩尔百分比为0.01％～5％。
在上述电化学装置中，其中，所述正极活性材料通过X射线光电子能谱测试获得的钴的吸收峰偏移0.1eV～0.45eV。
本申请的实施例还提供了一种电子装置，包括上述电化学装置。
本申请的实施例还提供了一种制备导电剂的方法，包括：将碳基导电材料与腈类化合物混合，得到预处理混合物；对所述预处理混合物进行烘干处理和焙烧处理，得到所述导电剂，其中，所述焙烧处理包括在300℃～500℃的温度下焙烧1h～3h。
本申请通过对含碳导电材料进行改性，在其表面引入氰基，在正极活性物质层中，通过氰基与过渡金属离子的络合作用对正极活性材料进行原位保护，减少循环过程中过渡金属离子的溶出，降低正极氧化性，进而改善电化学装置的循环稳定性及高温存储性能。
附图说明
图1示出了导电剂的制备方法的流程图。
图2是本申请的正极极片的示意图。
图3是本申请的电化学装置的电极组件的示意图。
图4和图5示出了本申请的实施例1的碳纳米管的扫描电镜图像。
图6和图7示出了本申请的对比例1的碳纳米管的扫描电镜图像。
图8示出了本申请的实施例1和对比例1的碳纳米管的红外光谱图。
图9示出了本申请的实施例1和对比例1的钴离子的电子结合能图谱。
具体实施方式
下面的实施例可以使本领域技术人员更全面地理解本申请，但不以任何方式限制本申请。
目前，通常在电解液中添加丁二腈、己二腈等腈类化合物添加剂，通过腈类化合物中的腈基基团与正极活性材料表面的过渡金属原子的络合来减少诸如锂离子电池的电化学装置的正极活性材料中的过渡金属离子的溶出。然而，电解液中游离的腈类化合物对铜箔有腐蚀作用，先后发生如下反应：LiPF 6+H 2O→POF 3+LiF+2HF，2H ++CuO X→H 2O+Cu 2+，Cu n++2CN-R+nPF 6 -→Cu(CN-R) 2PF 6/Cu(CN-R) 2(PF 6) 2，Cu n++n F -→CuF n(微溶)，Cu n++n PF 6 -→Cu(PF 6) n↓，Cu n++ne -→Cu↓(负极表面还原析出)。铜在负极的析出会导致负极界面产生黑斑，而黑斑位置无法嵌锂，使电化学装置的存储性能及循环性能变差。
本申请通过碳基导电材料与腈类化合物溶液的浸渍、烘干、高温焙烧等工序，使得碳基导电材料键合至腈类化合物，氰基覆盖在碳基导电材料的表面而不会游离到电解液中，进而避免了氰基在负极发生还原反应，改善正极保护效果。当将改性后的导电剂用作正极导电剂时，导电剂表面的氰基可以与正极活性材料的过渡金属原子发生络合作用，从而减少过渡金属离子的溶出，降低正极活性材料的氧化性，使得电解液的氧化消耗减少，改善电化学装置的高温存储性能与循环性能。
本申请的一些实施例提供了一种导电剂，导电剂包括由碳基导电材料与腈类化合物形成的化合物，其中，腈类化合物键合至碳基导电材料。通过使腈类化合物键合至碳基导电材料，使得腈类化合物的氰基覆盖在碳基导电材料的表面而不会游离到电解液中，避免了氰基在负极发生还原反应，同时导电剂表面的氰基可以与正极活性材料的过渡金属原子发生络合作用，从 而减少过渡金属离子的溶出，降低正极活性材料的氧化性，使得电解液的氧化消耗减少，改善电化学装置的高温存储性能与循环性能。
在一些实施例中，碳基导电材料包括导电炭黑、科琴黑、乙炔黑、导电石墨、碳纳米管或碳纤维中的至少一种。在一些实施例中，腈类化合物包括链状有机腈、含芳环或杂芳环的有机腈或氰基聚合物中的至少一种。在一些实施例中，腈类化合物包括丁二腈、己二腈、1,2-苯二乙腈、1,4-苯二乙腈、1-萘乙腈、2-萘乙腈、聚丙烯腈或聚苯乙烯丙烯腈中的至少一种。在一些实施例中，碳基导电材料与腈类化合物之间形成碳碳键。
如图1所示，示出了导电剂的制备方法的流程图。该制备方法包括步骤101，将碳基导电材料与腈类化合物混合，使碳基导电材料被完全浸渍，得到预处理混合物。在一些实施例中，导电剂的制备方法还包括步骤102，对预处理混合物进行烘干处理和焙烧处理，得到导电剂。在一些实施例中，烘干处理可以去除预处理混合物浆料中的水分。在一些实施例中，焙烧处理包括在300℃～500℃的温度下焙烧1h～3h。在一些实施例中，焙烧处理在惰性气氛中进行。该制备方法操作简单，容易实现利用腈类化合物对碳基导电材料进行改性。
本申请的一些实施例提供了一种电化学装置，电化学装置包括正极极片，正极极片包括集流体和正极活性材料层，正极活性材料层设置在集流体上。如图2所示，在一些实施例中，正极活性材料层2设置在集流体1上。应该理解，虽然图2中将正极活性材料层2示出为位于集流体1的一侧上，但是这仅是示例性的，正极活性材料层2可以位于集流体1的两侧上。在一些实施例中，正极集流体1可以采用Al箔，当然，也可以采用本领域常用的其他正极集流体。在一些实施例中，正极活性材料层可以仅涂覆在正极集流体的部分区域上。在一些实施例中，正极活性材料层2包括正极活性材料和上述任一导电剂。
在一些实施例中，正极活性材料包括钴酸锂、镍钴锰酸锂、镍钴铝酸锂中的一种或多种，正极活性材料在正极活性材料层的质量百分含量为95％～99.5％。在一些实施例中，正极活性材料层还包括粘结剂，正极活性材料层中的粘结剂可以包括聚偏氟乙烯、偏氟乙烯-六氟丙烯的共聚物、苯乙烯-丙烯酸酯共聚物、苯乙烯-丁二烯共聚物、聚酰胺、聚丙烯腈、聚丙烯酸酯、 聚丙烯酸、聚丙烯酸盐、羧甲基纤维素纳、聚醋酸乙烯酯、聚乙烯呲咯烷酮、聚乙烯醚、聚甲基丙烯酸甲酯、聚四氟乙烯或聚六氟丙烯中的至少一种。
在一些实施例中，导电剂中的腈基与正极活性材料中的钴元素的摩尔百分比为0.01％～5％。如果导电剂中的腈基含量太少，则不能充分地与正极活性材料中的钴元素络合。如果导电剂中的腈基含量太多，则多余的腈基不能与钴元素络合，即不能起到防止钴原子溶出的作用，同时与碳基导电材料键合的过多腈类化合物会降低导电剂的导电性，从而影响电化学装置的循环性能。
在一些实施例中，电化学装置还包括隔离膜和负极极片。如图3所示，隔离膜11设置于正极极片10和负极极片12之间。在一些实施例中，负极极片包括负极集流体和负极活性材料层，负极活性材料层设置在负极集流体上。在一些实施例中，负极活性材料层设置在负极集流体的一侧或两侧上。在一些实施例中，负极集流体可以采用铜箔、铝箔、镍箔或碳基集流体中的至少一种。在一些实施例中，负极活性材料层可以包括负极活性材料和粘结剂，负极活性材料包括硅基材料、碳材料、钛酸锂或钛酸铌中的至少一种。在一些实施例中，硅基材料包括硅、硅氧、硅碳或硅合金中的至少一种。在一些实施例中，负极活性材料层中的碳材料包括人造石墨、天然石墨、中间相碳微球、软碳或硬碳中的至少一种。在一些实施例中，负极活性材料层中还包括导电剂，导电剂可以包括导电炭黑、片层石墨、石墨烯、碳纳米管或碳纤维中的至少一种。在一些实施例中，负极活性材料层中的粘结剂可以包括羧甲基纤维素(CMC)、聚丙烯酸、聚乙烯基吡咯烷酮、聚苯胺、聚酰亚胺、聚酰胺酰亚胺、聚硅氧烷、聚丁苯橡胶、环氧树脂、聚酯树脂、聚氨酯树脂或聚芴中的至少一种。应该理解，以上公开的材料仅是示例性，负极活性材料层可以采用任何合适的材料。
在一些实施例中，隔离膜11包括聚乙烯、聚丙烯、聚偏氟乙烯、聚对苯二甲酸乙二醇酯、聚酰亚胺或芳纶中的至少一种。例如，聚乙烯包括选自高密度聚乙烯、低密度聚乙烯或超高分子量聚乙烯中的至少一种。尤其是聚乙烯和聚丙烯，它们对防止短路具有良好的作用，并可以通过关断效应改善电池的稳定性。在一些实施例中，隔离膜的厚度在约5μm～500μm 的范围内。
在一些实施例中，隔离膜表面还可以包括多孔层，多孔层设置在隔离膜的至少一个表面上，多孔层包括无机颗粒和粘结剂，无机颗粒选自氧化铝(Al 2O 3)、氧化硅(SiO 2)、氧化镁(MgO)、氧化钛(TiO 2)、二氧化铪(HfO 2)、氧化锡(SnO 2)、二氧化铈(CeO 2)、氧化镍(NiO)、氧化锌(ZnO)、氧化钙(CaO)、氧化锆(ZrO 2)、氧化钇(Y 2O 3)、碳化硅(SiC)、勃姆石、氢氧化铝、氢氧化镁、氢氧化钙或硫酸钡中的至少一种。在一些实施例中，隔离膜的孔具有在约0.01μm～1μm的范围的直径。粘结剂选自聚偏氟乙烯、偏氟乙烯-六氟丙烯的共聚物、聚酰胺、聚丙烯腈、聚丙烯酸酯、聚丙烯酸、聚丙烯酸盐、羧甲基纤维素纳、聚乙烯呲咯烷酮、聚乙烯醚、聚甲基丙烯酸甲酯、聚四氟乙烯或聚六氟丙烯中的至少一种。隔离膜表面的多孔层可以提升隔离膜的耐热性能、抗氧化性能和电解质浸润性能，增强隔离膜与极片之间的粘接性。
在本申请的一些实施例中，电化学装置的电极组件为卷绕式电极组件或堆叠式电极组件。
在一些实施例中，电化学装置包括锂离子电池，但是本申请不限于此。在一些实施例中，电化学装置还可以包括电解液。在一些实施例中，电解液包括但不限于碳酸二甲酯(DMC)、碳酸甲乙酯(EMC)、碳酸二乙酯(DEC)、碳酸乙烯酯(EC)、碳酸丙烯酯(PC)、丙酸丙酯(PP)中的至少两种。此外，电解液还可以额外地包括作为电解液添加剂的碳酸亚乙烯酯(VC)、氟代碳酸乙烯酯(FEC)或二腈化合物中的至少一种。在一些实施例中，电解液还包括锂盐。
在本申请的一些实施例中，以锂离子电池为例，将正极极片、隔离膜、负极极片按顺序卷绕或堆叠成电极件，之后装入例如铝塑膜中进行封装，注入电解液，化成、封装，即制成锂离子电池。然后，对制备的锂离子电池进行性能测试及循环测试。
本领域的技术人员将理解，以上描述的电化学装置(例如，锂离子电池)的制备方法仅是实施例。在不背离本申请公开的内容的基础上，可以采用本领域常用的其他方法。
本申请的实施例还提供了包括上述电化学装置的电子装置。本申请实施例的电子装置没有特别限定，其可以是用于现有技术中已知的任何电子装置。在一些实施例中，电子装置可以包括，但不限于，笔记本电脑、笔输入型计算机、移动电脑、电子书播放器、便携式电话、便携式传真机、便携式复印机、便携式打印机、头戴式立体声耳机、录像机、液晶电视、手提式清洁器、便携CD机、迷你光盘、收发机、电子记事本、计算器、存储卡、便携式录音机、收音机、备用电源、电机、汽车、摩托车、助力自行车、自行车、照明器具、玩具、游戏机、钟表、电动工具、闪光灯、照相机、家庭用大型蓄电池和锂离子电容器等。
下面列举了一些具体实施例和对比例以更好地对本申请进行说明，其中，采用锂离子电池作为示例。
实施例1
正极导电剂的制备：配置质量分数为20％的丁二腈水溶液，将2g电池级商用碳纳米管与6g上述丁二腈水溶液在烧杯中进行均匀搅拌混合，得到碳纳米管导电剂预处理物；将碳纳米管导电剂预处理物在80℃下烘干处理12h，以除去预处理物中的水分；将烘干后所得材料放入管式炉中，通入氮气或氦气等惰性保护性气体，在400℃下焙烧2h，获得腈基改性碳纳米管。
正极极片的制备：将钴酸锂与制备的腈基改性碳纳米管导电剂、聚偏二氟乙烯按重量比94：3：3的比例溶于N-甲基吡咯烷酮(NMP)溶液中，形成正极浆料。采用铝箔作为正极集流体，将正极浆料涂覆于正极集流体上，经过干燥、冷压、裁切后得到正极极片，冷压过程的正极压实密度为4.1g/cm 3。
负极极片的制备：将人造石墨、乙炔黑、丁苯橡胶及羧甲基纤维素钠按重量比96：1：1.5：1.5的比例溶于去离子水中，形成负极浆料。采用10μm厚度铜箔作为负极集流体，将负极浆料涂覆于负极集流体上，经过干燥、冷压、裁切后得到负极极片。
隔离膜的制备：将聚偏二氟乙烯溶于水，通过机械搅拌形成均匀浆料，将浆料涂布到已经涂布好两面均为陶瓷涂层的多孔基材(聚乙烯)的两侧表面上，烘干后形成隔离膜。
电解液的制备：在含水量小于10ppm的环境下，将六氟磷酸锂与非水有机溶剂(碳酸乙烯酯(EC)：碳酸二乙酯(DEC)：碳酸亚丙酯(PC)：丙酸丙酯(PP)：碳酸亚乙烯酯(VC)＝20；30；20；28；2，重量比)按重量比8：92配制以形成电解液。
锂离子电池的制备：将正极极片、隔离膜、负极极片按顺序依次叠好，使隔离膜处于正极极片和负极极片中间起到隔离的作用，并卷绕得到电极组件。将电极组件置于外包装铝塑膜中，在80℃下脱去水分后，注入上述电解液并封装，经过化成，脱气，切边等工艺流程得到锂离子电池。
实施例2～17和对比例1～5是在实施例1步骤的基础上进行参数变更，具体变更的参数如下表1所示，其中腈基与正极活性材料中钴原子的摩尔百分比通过控制丁二腈水溶液的加入量来调节。
下面描述本申请的循环性能和存储膨胀率测试方法。
循环性能测试：
将锂离子电池置于45℃±2℃的恒温箱中静置2小时，以1C倍率进行充电至4.48V，然后在4.48V下恒压充电至0.05C。随后以1C倍率放电至3.0V进行循环性能测试，当锂离子电池的容量下降到初始容量的80％时对应的循环次数为评价锂离子电池的循环性能的参数。
存储膨胀率测试：
将锂离子电池置于25℃±2℃的恒温箱中静置2小时，以1C倍率恒流充电至4.48V，然后在4.48V恒压充电至0.05C，随后将锂离子电池存放在80℃±2℃的恒温箱中7小时。待高温存储后，使用测厚装置对高温存储锂离子电池的厚度进行测试后，记录高温存储后的厚度变化。每组取4块锂离子电池，取平均值，计算锂离子电池的高温存储膨胀率。
高温存储膨胀率＝(高温存储后锂离子电池的厚度/化成后的锂离子电池的厚度-1)×100％。
表1示出了实施例和对比例的各个参数和评估结果。
表1
Figure PCTCN2020080857-appb-000001
Figure PCTCN2020080857-appb-000002
Figure PCTCN2020080857-appb-000003
通过比较实施例1和对比例1、比较实施例2和对比例4或比较实施例3和对比例5可知，通过在碳基导电材料上键合腈类化合物，锂离子电池的循环性能和存储膨胀率均得到改善。这是由于腈类化合物的氰基覆盖在碳基导电材料的表面而不会游离到电解液中，避免了氰基在负极发生还原反应，同时导电剂表面的氰基可以与正极活性材料的过渡金属原子发生络合作用，从而减少过渡金属离子的溶出，降低正极活性材料的氧化性，使得电解液的氧化消耗减少，改善了电化学装置的高温存储性能与循环性能。
图4和图5示出了本申请的实施例1的碳纳米管的扫描电镜图像。图6和图7示出了本申请的对比例1的碳纳米管的扫描电镜图像。从图4至图7可知，腈基化合物处理对碳纳米管的形貌无明显影响。
图8示出了本申请的实施例1和对比例1的碳纳米管的红外光谱图。如图8所示，腈基化合物处理后的碳纳米管在2345cm -1处左右出现明显的吸收峰，为N-H的特征红外吸收峰。而腈基化合物处理前的碳纳米管在该位置则无吸收峰，且腈类化合物本身无N-H键(NC-C-C-CN)。由此说明腈类化合物可以有效地与碳纳米管发生键合作用，使碳纳米管带上腈基官能团。其他腈类化合物的作用机理相同，均可与碳基导电材料发生键合作用。
图9示出了本申请的实施例1和对比例1的钴离子的电子结合能图谱。如图9所示，腈类化合物处理前(对比例1)Co在780.07eV及794.77eV出 现吸收峰，腈类化合物处理后(实施例1)Co吸收峰分别偏移至779.73eV及794.43eV，说明发生键合后，导电剂中的腈基可以有效络合钴离子，降低钴离子的氧化性。
通过比较实施例1和4～7可知，碳基导电材料的种类对锂离子电池的循环性能和存储膨胀率具有一定的影响，但是区别不大。
通过比较实施例1和8～11可知，腈类化合物的种类对锂离子电池的循环性能和存储膨胀率具有一定的影响，但是区别不大。
通过比较实施例1和12～15可知，在导电剂中的腈基与正极活性材料中的钴元素的摩尔百分比为0.01％～5％时，随着该摩尔百分比的增大，锂离子电池的循环性能先增强后降低，锂离子电池的存储膨胀率先减小后增大。
通过比较实施例16和对比例2或比较实施例17和对比例3可知，在电解液中也含有一定量的腈类化合物时，通过在碳基导电材料上键合腈类化合物，锂离子电池的循环性能和存储膨胀率也能得到改善。通过比较实施例16～17可知，电解液中的腈类化合物的质量含量从5％增加到10％时，锂离子电池的循环性能和存储膨胀率能够得到一定程度的改善。
本申请通过在碳基导电材料上键合腈类化合物，可以改善高电压(>4.2V)体系下正极活性材料在循环及存储过程中的钴元素溶出，提高电化学装置的循环稳定性及高温存储性能。
以上描述仅为本申请的较佳实施例以及对所运用技术原理的说明。本领域技术人员应当理解，本申请中所涉及的公开范围，并不限于上述技术特征的特定组合而成的技术方案，同时也应涵盖在不脱离上述公开构思的情况下，由上述技术特征或其等同特征进行任意组合而形成的其它技术方案。例如上述特征与本申请中公开的具有类似功能的技术特征进行互相替换而形成的技术方案。

Claims (12)

  1. 一种导电剂，其包括：
    由碳基导电材料与腈类化合物形成的化合物，其中，所述腈类化合物键合至所述碳基导电材料。
  2. 根据权利要求1所述的导电剂，其中，所述碳基导电材料与所述腈类化合物之间形成碳碳键。
  3. 根据权利要求1所述的导电剂，其中，所述导电剂通过红外光谱测试得到的曲线在2337cm -1～2351cm -1之间具有吸收峰。
  4. 根据权利要求1所述的导电剂，其中，所述碳基导电材料包括导电炭黑、科琴黑、乙炔黑、导电石墨、碳纳米管或碳纤维中的至少一种。
  5. 根据权利要求1所述的导电剂，其中，所述腈类化合物包括链状有机腈、含芳环或杂芳环的有机腈或氰基聚合物中的至少一种。
  6. 根据权利要求1所述的导电剂，其中，所述腈类化合物包括丁二腈、己二腈、1,2-苯二乙腈、1,4-苯二乙腈、1-萘乙腈、2-萘乙腈、聚丙烯腈或聚苯乙烯丙烯腈中的至少一种。
  7. 一种电化学装置，其包括：
    正极极片，所述正极极片包括集流体和正极活性材料层，所述正极活性材料层设置在所述集流体上；
    其中，所述正极活性材料层包括正极活性材料和根据权利要求1至6中任一项所述的导电剂。
  8. 根据权利要求7所述的电化学装置，其中，所述正极活性材料包括钴酸锂、镍钴锰酸锂、镍钴铝酸锂中的一种或多种，所述正极活性材料在所述正极活性材料层的质量百分含量为95％～99.5％。
  9. 根据权利要求7所述的电化学装置，其中，所述导电剂中的腈基与所述正极活性材料中的钴元素的摩尔百分比为0.01％～5％。
  10. 根据权利要求8所述的电化学装置，其中，所述正极活性材料通过X射线光电子能谱测试获得的钴的吸收峰偏移0.1eV～0.45eV。
  11. 一种电子装置，包括根据权利要求7至10中任一项所述的电化学装置。
  12. 一种制备导电剂的方法，包括：
    将碳基导电材料与腈类化合物混合，得到预处理混合物；
    对所述预处理混合物进行烘干处理和焙烧处理，得到所述导电剂，
    其中，所述焙烧处理包括在300℃～500℃的温度下焙烧1h～3h。
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