WO2021119983A1 - 一种正极极片的制备方法及制得的正极极片和锂氟化碳电池 - Google Patents

一种正极极片的制备方法及制得的正极极片和锂氟化碳电池 Download PDF

Info

Publication number
WO2021119983A1
WO2021119983A1 PCT/CN2019/125892 CN2019125892W WO2021119983A1 WO 2021119983 A1 WO2021119983 A1 WO 2021119983A1 CN 2019125892 W CN2019125892 W CN 2019125892W WO 2021119983 A1 WO2021119983 A1 WO 2021119983A1
Authority
WO
WIPO (PCT)
Prior art keywords
pole piece
positive pole
binder
particles
collecting net
Prior art date
Application number
PCT/CN2019/125892
Other languages
English (en)
French (fr)
Inventor
李琦旸
袁中直
张海波
刘子文
赖江洪
林锦芳
刘金成
Original Assignee
惠州亿纬锂能股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 惠州亿纬锂能股份有限公司 filed Critical 惠州亿纬锂能股份有限公司
Priority to PCT/CN2019/125892 priority Critical patent/WO2021119983A1/zh
Publication of WO2021119983A1 publication Critical patent/WO2021119983A1/zh

Links

Classifications

    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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

Definitions

  • the present disclosure belongs to the technical field of battery preparation, and in particular relates to a method for preparing a positive pole piece and a prepared positive pole piece and a lithium carbon fluoride battery.
  • lithium-ion batteries With the continuous innovation and development of electronic communication technology, secondary batteries have received increasing attention. With the advantages of high specific capacity and good cycle stability, lithium-ion batteries are considered to be the most promising and promising secondary batteries. With the continuous improvement of people’s requirements for energy density, lithium-ion batteries have been difficult to meet in specific applications. The increasing demand for specific energy in the field.
  • the lithium carbon fluoride battery uses carbon fluoride CF x as the positive electrode active material and metal lithium as the negative electrode. It is currently the primary battery with the highest theoretical specific energy (2180Wh/kg). In addition, due to the use of CF x as the active material, the lithium carbon fluoride battery has the advantages of stable working voltage, extremely high safety and environmental protection. Therefore, lithium fluorocarbon batteries have great application prospects in military industry, precision equipment, aerospace and other fields, and have been used in the United States, Japan and other countries for a long time. However, fluorinated carbon CF x has very poor conductivity and often needs to be mixed with a large amount of conductive agent during use. This not only causes the battery energy density to decrease in practical applications, but also increases the difficulty in the production process.
  • CN109786842A discloses a method for preparing a high-safety and high-specific energy lithium/carbon fluoride battery, which uses lithium salt to be dissolved in an organic solvent or compounded with a solid polymer to obtain a high lithium salt concentration electrolyte or a high lithium salt concentration solid polymer electrolyte.
  • the lithium/carbon fluoride battery is assembled by using the high lithium salt concentration electrolyte or the high lithium salt concentration solid polymer electrolyte.
  • the method can increase the specific energy of a lithium/carbon fluoride battery, but the anode adopts a conventional manufacturing process, and thicker pole pieces cannot be obtained to further increase the specific energy of the battery, and the voltage platform is low.
  • CN107895794A discloses a high specific energy lithium carbon fluoride battery.
  • the composition and weight percentage of the positive electrode material of the battery are: elemental sulfur modified carbon fluoride 80% to 90%, conductive agent 5% to 10%, viscous 5% to 10% binder; in the electrolyte of the battery, the solute is 1.0mol/L lithium bistrifluoromethanesulfonimide and 0.5 to 1.5wt% lithium nitrate, and the solvent is 1,3-dioxolane and ethyl acetate. Glycol dimethyl ether.
  • the purpose of the present disclosure is to provide a method for preparing a positive pole piece and the prepared positive pole piece and a lithium carbon fluoride battery.
  • the present disclosure adopts the "particle-one-step forming" method to prepare the positive pole piece, the weight and size of the prepared positive pole piece are controllable, the battery has high electrical performance consistency, and the preparation process is simple, which is easy to realize large-scale production.
  • the lithium carbon fluoride battery obtained by the method of the present disclosure can have a working life of more than 2 years.
  • the present disclosure adopts the following technical solutions.
  • One of the objectives of the present disclosure is to provide a method for preparing a positive pole piece, the method includes the following steps:
  • the present disclosure adopts the "particle-one-step molding" method to prepare positive electrode pieces, that is, the technology of composite compression molding of small positive electrode particles and metal current collectors, which improves the contact between the positive electrode active material and the current collector, thereby reducing the battery internal
  • the output capacity of the battery is improved, and the positive pole piece prepared by the method of the present disclosure has a porous structure as a whole, which is easier to infiltrate the electrolyte;
  • the slurry mass is made into particles, and then compressed, to directly produce the positive pole piece, eliminating the need for coating and other processes in the process of preparing the pole piece, the preparation process is simpler, and the present disclosure uses a mold in one step
  • the forming can realize the controllability of the weight, thickness and size of the positive pole piece, which is suitable for the preparation of different types of batteries.
  • the method for forming the slurry mass into particles in step (2) includes: extruding the slurry mass into particles.
  • the diameter of the particles is 0.5-10mm, for example, 1mm, 2mm, 3mm, 4mm, 5mm, 6mm, 7mm, 8mm or 9mm.
  • the pole piece pores formed are too large, resulting in uneven local reactions and insufficient battery capacity; if the diameter of the particles is too small, it is difficult to form in the subsequent pressing process .
  • the thermal fibrillation process in step (2) includes: forming the slurry mass into pellets for heat treatment.
  • the temperature of the heat treatment is 150°C to 300°C, for example, 160°C, 180°C, 200°C, 220°C, 250°C, 260°C, or 280°C.
  • the heat treatment time is 1min-60min, such as 5min, 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min or 55min, etc.
  • the thermal fiberization process described in the present disclosure facilitates the dispersion of the binder in the positive electrode, thereby improving the binding property of the positive electrode.
  • the pressing pressure in step (3) is 0.1-20 MPa, such as 0.5 MPa, 1 MPa, 2 MPa, 5 MPa, 8 MPa, 10 MPa, 12 MPa, 15 MPa or 18 MPa.
  • the pressing pressure is too low, the active material in the positive electrode and the conductive agent have poor contact, resulting in poor overall battery electrical performance; if the pressing pressure is too large, the overall porosity of the positive electrode is low, which is not conducive to subsequent Electrolyte infiltration.
  • the pressing time is 5s-10min, such as 10s, 20s, 30s, 40s, 50s, 1min, 2min, 3min, 4min, 5min, 6min, 7min, 8min or 9min.
  • step (3) and after step (2) the process of step (2') is further included: the precursor particles are immersed in a solvent.
  • the solvent includes any one or a combination of at least two of ethanol, isopropanol, butanol and propylene glycol.
  • the thickness of the precursor particles pressed on the metal collecting net in step (3) is 0.2mm-50mm, preferably 0.2mm-20mm, such as 1mm, 2mm, 3mm, 5mm, 6mm, 8mm, 10mm, 12mm, 15mm, 16mm, 18mm, 20mm, 22mm, 25mm, 30mm, 35mm, 40mm, 45mm or 48mm, etc.
  • the precursor particles in step (3) are compressed on both sides of the metal current collecting net.
  • the thickness of the precursor particles pressed on both sides of the metal collecting net in step (3) is independently selected from 0.2mm-50mm, preferably 0.2mm-20mm, such as 1mm, 2mm, 3mm, 5mm, 6mm , 8mm, 10mm, 12mm, 15mm, 16mm, 18mm, 20mm, 22mm, 25mm, 30mm, 35mm, 40mm, 45mm or 48mm, etc.
  • the drying temperature is 40-100°C, such as 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 80°C, 85°C, 90°C, or 95°C.
  • the metal current collecting mesh in step (3) includes any one or a combination of at least two of nickel mesh, aluminum mesh, Ti mesh and stainless steel mesh.
  • the metal current collecting net selected in the present disclosure is a current collecting net designed integrally with the metal current collecting net of the lug, that is, the lug is a part of the metal current collecting net to prevent the welding lug from falling off during the pressing and forming process of the positive electrode.
  • the thickness of the metal collecting net in step (3) is 0.01mm-2mm, for example, 0.05mm, 0.08mm, 0.1mm, 0.2mm, 0.5mm, 0.6mm, 0.8mm, 1mm, 1.2mm, 1.5mm , 1.6mm or 1.8mm, etc.
  • the present disclosure does not specifically limit the hole shape of the metal collector net in step (3), and those skilled in the art can choose according to actual needs.
  • Exemplary shapes are circle, square, rectangle, rhombus and special shape (except for the above regular shapes).
  • Outer shape any one or a combination of at least two.
  • the aperture of the metal collecting net in step (3) is 0.5mm-5mm, such as 1mm, 1.5mm, 2mm, 2.5mm, 3mm, 3.5mm, 4mm or 4.5mm.
  • the surface of the metal current collecting net in step (3) contains conductive glue.
  • the conductive adhesive includes any one or a combination of at least two of conductive carbon black, conductive graphite, carbon nanotubes and graphene.
  • the conductive agent in step (1) includes any one or a combination of at least two of conductive carbon black Super P, acetylene black, Ketjen black, conductive graphite, carbon nanotubes and graphene.
  • the binder in step (1) includes any one or a combination of at least two of polytetrafluoroethylene, polyvinylidene fluoride, and sodium carboxymethyl cellulose.
  • the total mass ratio of carbon fluoride, conductive agent and binder in the slurry mass is calculated as 100%, and the content of carbon fluoride is 50% to 99.9%, such as 52%, 55%, 58%. %, 60%, 65%, 70%, 72%, 75%, 78%, 80%, 85%, 88%, 90%, 92%, 95%, 98%, 99%, etc.
  • the total mass ratio of carbon fluoride, conductive agent and binder in the slurry mass is calculated as 100%, and the binder content is 0.05%-25%, such as 0.1%, 0.2%, 0.5%. %, 0.8%, 1%, 2%, 5%, 8%, 10%, 12%, 15%, 16%, 18%, 20% or 22%, etc.
  • the content of the conductive agent is 0.05%-25%, such as 0.1%, 0.2%, 0.5% , 0.8%, 1%, 2%, 5%, 8%, 10%, 12%, 15%, 16%, 18%, 20% or 22%, etc.
  • the preparation process of the binder solution in step (1) includes: adding a mixed solution of water and ethanol to the binder emulsion for demulsification.
  • the added amount of the mixed solution is 5% to 60% of the weight of the mixed powder in step (1), such as 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, or 55%, etc.
  • the mass content of water in the mixed solution is 0.1%-50%, such as 0.5%, 1%, 5%, 15%, 20%, 25%, 30%, 35%, 40% or 45%, etc. .
  • the mass content of ethanol in the mixed solution is 50% to 99.9%, such as 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% or 95%.
  • the method for preparing a positive pole piece described in the present disclosure includes the following steps:
  • the mass ratio of carbon fluoride, conductive agent and binder in the slurry mass is calculated as 100 %, the content of the carbon fluoride is 50% to 99.9%, the content of the binder is 0.05% to 25%, and the content of the conductive agent is 0.05% to 25%;
  • the precursor particles are immersed in a solvent, and then the precursor particles are pressed on both sides of a metal collecting net with a thickness of 0.01 mm to 2 mm and a hole diameter of 0.5 mm to 5 mm, and the pressing pressure is 0.1 ⁇ 20MPa, the time is 5s ⁇ 10min, the thickness of the precursor particles pressed on both sides of the metal current collecting net is independently selected from 0.2mm ⁇ 50mm, and dried at 40 ⁇ 100°C to obtain the positive pole piece.
  • the second objective of the present disclosure is to provide a positive pole piece prepared by the method described in one of the objectives.
  • the positive pole piece includes a metal current collecting net and a porous active material layer distributed on both sides of the metal current collecting net.
  • the active material in the porous active material layer includes fluorinated carbon.
  • the porosity of the porous active material layer is 20% to 70%, such as 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60% or 65%.
  • the thickness of the positive pole piece is 0.1-45mm, such as 0.5mm, 1mm, 5mm, 10mm, 15mm, 20mm, 25mm, 30mm, 35mm, 40mm or 42mm.
  • the third object of the present disclosure is to provide a lithium carbon fluoride battery, in which the positive electrode piece in the lithium carbon fluoride battery is the positive electrode piece described in the second object.
  • the present disclosure adopts the "particle-one-step molding" method to prepare positive pole pieces, that is, the technology of composite compression molding of small positive particles and metal current collectors, which improves the contact between the positive electrode active material and the current collector, thereby reducing
  • the internal resistance of the battery improves the output capacity of the battery
  • the positive pole piece prepared by the method of the present disclosure has a porous structure as a whole, which is easier to infiltrate the electrolyte.
  • the slurry mass is made into particles, and then compressed, to directly produce the positive pole piece, eliminating the need for coating and other processes in the process of preparing the pole piece, the preparation process is simpler, and the present disclosure uses a mold One-step forming can realize the controllability of the weight, thickness and size of the positive pole piece, which is suitable for the preparation of different types of batteries, and is easier to realize mass production.
  • a method for preparing a positive pole piece includes the following steps:
  • the precursor particles are soaked in ethanol, and a layer of the precursor particles with a thickness of 1mm is laid on the mold as the bottom layer, and then a metal collector with a thickness of 0.03mm and a circular diameter of 2mm is added.
  • a mesh nickel mesh
  • a layer of the precursor particles with a thickness of 1 mm as the top layer pressed at 15 MPa for 1 min, and dried at 80° C. to obtain a positive electrode piece.
  • Example 1 The difference from Example 1 is that the slurry mass described in step (3) is extruded into particles with a diameter of 0.5 mm.
  • Example 1 The difference from Example 1 is that the slurry mass described in step (3) is extruded into particles with a diameter of 10 mm.
  • Example 1 The difference from Example 1 is that the slurry mass in step (3) is extruded into particles with a diameter of 0.3 mm.
  • Example 1 The difference from Example 1 is that the slurry mass described in step (3) is extruded into particles with a diameter of 12 mm.
  • Example 1 The difference from Example 1 is that the pressing pressure in step (4) is 0.1 MPa, and the time is 10 min.
  • Example 1 The difference from Example 1 is that the pressing pressure in step (4) is 20 MPa, and the time is 1 min.
  • Example 1 The difference from Example 1 is that the pressing pressure in step (4) is 0.05 MPa, and the time is 20 min.
  • Example 1 The difference from Example 1 is that the pressing pressure in step (4) is 22 MPa, and the time is 5 s.
  • a method for preparing a positive pole piece includes the following steps:
  • the precursor particles are soaked in ethanol, and a layer of the precursor particles with a thickness of 1.2mm is laid on the mold as the bottom layer, and then the thickness is 0.03mm, and the hole diameter (distance to the farthest point) is A 3mm diamond-shaped metal current collecting net (aluminum net), and then a layer of the precursor particles with a thickness of 1.2 mm as the top layer, pressed at 15 MPa for 1 min, and dried at 40° C. to obtain a positive pole piece.
  • a method for preparing a positive pole piece includes the following steps:
  • the precursor particles are soaked in ethanol, and a layer of the precursor particles with a thickness of 1.5mm is laid on the mold as the bottom layer, and then the thickness is 0.03mm, and the hole diameter (distance to the farthest point) is A 2mm rectangular metal current collecting net (Ti net) was laid with a layer of the precursor particles with a thickness of 0.8mm as the top layer, pressed at 5MPa for 1 min, and dried at 100°C to obtain a positive pole piece.
  • Ti net 2mm rectangular metal current collecting net
  • Steps (3) and (4) are replaced with: two sheet-shaped pole pieces are made by rolling the slurry mass (the thickness is the same as the bottom layer and the top layer in Example 1) , Sandwich a metal current collecting net (nickel mesh) the same as in Example 1 between the two sheet-shaped pole pieces, and adopt the same pressing method as in Example 1 to obtain a positive pole piece.
  • two sheet-shaped pole pieces are made by rolling the slurry mass (the thickness is the same as the bottom layer and the top layer in Example 1) , Sandwich a metal current collecting net (nickel mesh) the same as in Example 1 between the two sheet-shaped pole pieces, and adopt the same pressing method as in Example 1 to obtain a positive pole piece.
  • Pole piece test the thickness of the caliper is measured, and the pole piece resistance is measured by the four-probe method;
  • Example 4 of the present disclosure has obvious powder loss. This is because the particle size of the extruded particles in Example 4 is smaller, and the small particles are likely to form burrs during the pressing process. As a result, it falls off and makes it difficult to form the pole piece. Therefore, although the electrical performance of Embodiment 4 is equivalent to that of Embodiment 1, it will cause the problem of large battery self-discharge; Embodiment 5 of the present disclosure has doubled the pole piece resistance compared to Embodiment 1. Because the particle size of the extruded particles in Example 5 is relatively large, and the gap between the particles is large during the pressing process, the electronic conductivity of the pole piece decreases. Therefore, the overall electrical performance of Example 5 is poorer than that of Example 1.
  • Example 1 It can be seen from Table 1 that compared with Example 1, the pole piece resistance of Embodiment 8 of the present disclosure is increased and the hysteresis voltage and working voltage are significantly reduced. Because the pressing pressure in Embodiment 8 is relatively small, it is difficult to realize the positive electrode interparticle in the positive pole piece. Under this pressure, even for a long time, the technical effect of Example 1 cannot be achieved. Therefore, the electrical performance of Example 8 is poorer than that of Example 1.
  • the overall thickness of the positive electrode of Example 9 of the present disclosure is relative to that of Example 1. Decrease, but the pole piece resistance and the working voltage after assembled into the battery drop.
  • Example 9 This is because the pressing pressure in Example 9 is relatively large, which reduces the porosity between the pole pieces, which affects the wettability of the electrolyte and causes ion migration. However, under this pressure, even if the time is short, the technical effect of Embodiment 1 cannot be achieved. Therefore, the performance of Embodiment 9 is inferior to that of Embodiment 1.
  • the pole piece resistance of Comparative Example 1 of the present disclosure is increased by an order of magnitude relative to that of Example 1, because in Comparative Example 1, the sheet-shaped pole piece is prepared and then pressed with a metal current collecting net.
  • the obtained pole piece has a low porosity, so that the pole piece cannot have good electrolyte wettability, and a positive pole piece with a pore structure cannot be obtained. Therefore, the electrical performance of Comparative Example 1 is poorer than that of Example 1, and the method prepared It is difficult for the pole piece to reach a thickness of 1mm under high pressure, resulting in a large thickness of the pole piece.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

一种正极极片的制备方法及制得的正极极片和锂氟化碳电池。所述正极极片的制备方法包括如下步骤：(1)将含有氟化碳和导电剂的混合粉料与粘结剂溶液混合，得到浆料团；(2)将所述浆料团制成颗粒，并进行热起纤，得到前驱体颗粒；(3)将所述前驱体颗粒压制在金属集流网上，得到正极极片。采用"颗粒-一步成型"法制备正极极片，改善了正极活性材料和集流体间的接触性，从而通过降低电极电阻和极片的电解液浸润性，降低了电池的内阻，提高了电池的输出能力；采用上述方法制备的正极极片整体为多孔的结构，更易于电解液的浸润；可以实现正极极片重量、厚度、及尺寸可控。

Description

一种正极极片的制备方法及制得的正极极片和锂氟化碳电池 技术领域
本公开属于电池制备技术领域，具体涉及一种正极极片的制备方法及制得的正极极片和锂氟化碳电池。
背景技术
随着电子通信技术的不断革新和发展，二次电池日益受到人们的关注。锂离子电池凭借比容量高、循环稳定性好等优势，被认为是最具发展潜力和前景的二次电池，随着人们对能量密度要求的不断提高，锂离子电池已经很难满足在特定应用领域日益提高的比能量的需求。
锂氟化碳电池以氟化碳CF x作为正极活性材料，金属锂作为负极，是目前理论比能量(2180Wh/kg)最高的一次电池。除此之外，由于使用CF x作为活性物质，锂氟化碳电池具有工作电压平稳、极高的安全性和环保的优点。因此，锂氟化碳电池在军工、精密设备和航空航天等领域有极大的应用前景，已在美国、日本等国家长期使用。然而，氟化碳CF x的导电性极差，使用时往往需要与大量的导电剂进行混合，这不仅造成了实际应用情况中电池能量密度下降，也增加了生产过程中的难度。
CN109786842A公开了一种高安全高比能量锂/氟化碳电池制备方法，利用锂盐溶于有机溶剂或与固体聚合物复合制备得到高锂盐浓度电解液或高锂盐浓度固体聚合物电解质，采用该高锂盐浓度电解液或高锂盐浓度固体聚合物电解质组装得到锂/氟化碳电池。所述方法可以提升锂/氟化碳电池的比能量，但是其正极选用常规的制作工艺，无法获得较厚极片从而进一步提高电池的比能量，且电压平台较低。
CN107895794A公开了一种高比能锂氟化碳电池，所述电池的正极材料的组成及重量百分比为：单质硫改性的氟化碳80％～90％，导电剂5％～10％，粘结剂5％～10％；电池的电解液中，溶质为1.0mol/L双三氟甲烷磺酰亚胺锂和0.5～1.5wt％硝酸锂，溶剂为1,3-二氧戊环和乙二醇二甲醚。所述电池对于氟化碳改性后，提高了电池整体的能量密度，但其正极工艺采用常规的涂布工艺，并不适宜进一步提高正极活性物质载量。
因此，本领域亟需一种新型锂氟化碳电池，所述电池可以在简单易行的正极制备前提下，保证电池具有高比容量和高能量密度。
发明内容
以下是对本公开详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。
本公开的目的在于提供一种正极极片的制备方法及制得的正极极片和锂氟化碳电池。本公开采用“颗粒-一步成型”法制备正极极片，制备的正极极片重量、尺寸可控，电池的电性能一致性高，且制备过程简单，易于实现规模化生产。通过本公开的方法得到的锂氟化碳电池可以具有长达2年以上的工作寿命。
为达此目的，本公开采用以下技术方案。
本公开的目的之一在于提供一种正极极片的制备方法，所述方法包括如下步骤：
(1)将含有氟化碳和导电剂的混合粉料与粘结剂溶液混合，得到浆料团；
(2)将所述浆料团制成颗粒，并进行热起纤，得到前驱体颗粒；
(3)将所述前驱体颗粒压制在金属集流网上，得到正极极片。
本公开采用“颗粒-一步成型”法制备正极极片，即正极小颗粒和金属集 流网复合压制成型的技术，改善了正极活性材料和集流体间的接触性，从而降低了电池的内阻，提高了电池的输出能力，并且采用本公开的方法制备的正极极片整体为多孔的结构，更易于电解液的浸润；
同时，本公开将浆料团制成颗粒，然后进行压制，可直接制得正极极片，省去了在制备极片过程中需要涂布等过程，制备过程更加简单，且本公开采用模具一步成型可以实现正极极片重量、厚度、及尺寸可控，可适用于不同种类电池的制备。
优选地，步骤(2)所述浆料团制成颗粒的方法包括：将所述浆料团挤出制成颗粒。
优选地，所述颗粒的直径为0.5～10mm，例如1mm、2mm、3mm、4mm、5mm、6mm、7mm、8mm或9mm等。
本公开中，若所述颗粒的直径过大，形成的极片孔隙过大，造成局部反应不均匀，使电池容量发挥不充分；若所述颗粒的直径过小，在后续压制过程中难以成型。
优选地，步骤(2)所述热起纤的过程包括：将所述浆料团制成颗粒进行热处理。
优选地，所述热处理的温度为150℃～300℃，例如160℃、180℃、200℃、220℃、250℃、260℃或280℃等。
优选地，所述热处理的时间为1min～60min，例如5min、10min、15min、20min、25min、30min、35min、40min、45min、50min或55min等。
本公开所述热起纤过程有助于粘结剂在正极中的分散，从而提高正极的粘结性。
优选地，步骤(3)所述压制的压力为0.1～20MPa，例如0.5MPa、1MPa、 2MPa、5MPa、8MPa、10MPa、12MPa、15MPa或18MPa等。
本公开中，若所述压制的压力过小，正极中活性物质和导电剂接触性差，从而使电池整体电性能差；若所述压制的压力过大，造成正极整体孔隙率低，不利于后续电解液浸润。
优选地，所述压制的时间为5s～10min，例如10s、20s、30s、40s、50s、1min、2min、3min、4min、5min、6min、7min、8min或9min等。
优选地，步骤(3)之前，步骤(2)之后还包括步骤(2’)的过程：将前驱体颗粒采用溶剂进行浸泡。
优选地，所述溶剂包括乙醇、异丙醇、丁醇和丙二醇中的任意一种或至少两种的组合。
优选地，步骤(3)所述前体颗粒压制在金属集流网上的厚度为0.2mm～50mm，优选为0.2mm～20mm，例如1mm、2mm、3mm、5mm、6mm、8mm、10mm、12mm、15mm、16mm、18mm、20mm、22mm、25mm、30mm、35mm、40mm、45mm或48mm等。
优选地，步骤(3)所述前体颗粒压制在金属集流网的两侧。
优选地，步骤(3)中所述前体颗粒压制在金属集流网两侧的厚度各自独立地选自0.2mm～50mm，优选为0.2mm～20mm，例如1mm、2mm、3mm、5mm、6mm、8mm、10mm、12mm、15mm、16mm、18mm、20mm、22mm、25mm、30mm、35mm、40mm、45mm或48mm等。
优选地，步骤(2)所述热起纤之前和步骤(3)所述压制之后，各自独立地包括烘干的过程。
优选地，所述烘干的温度为40～100℃，例如45℃、50℃、55℃、60℃、65℃、70℃、80℃、85℃、90℃或95℃等。
优选地，步骤(3)所述金属集流网包括镍网、铝网、Ti网和不锈钢网中的任意一种或至少两种的组合。
本公开选取的金属集流网为极耳金属集流网一体式设计的集流网，即极耳为金属集流网的一部分，避免焊接的极耳在正极压制成型过程中的脱落。
优选地，步骤(3)所述金属集流网的厚度为0.01mm～2mm，例如0.05mm、0.08mm、0.1mm、0.2mm、0.5mm、0.6mm、0.8mm、1mm、1.2mm、1.5mm、1.6mm或1.8mm等。
本公开对步骤(3)所述金属集流网的孔形状不作具体限定，本领域技术人员可根据实际需要进行选择，示例性的为圆形、正方形、长方形、菱形和异形(除以上规则形状外的形状)中的任意一种或至少两种的组合。
优选地，步骤(3)所述金属集流网的孔径为0.5mm～5mm，例如1mm、1.5mm、2mm、2.5mm、3mm、3.5mm、4mm或4.5mm等。
优选地，步骤(3)所述金属集流网的表面含有导电胶。
优选地，所述导电胶包括导电炭黑、导电石墨、碳纳米管和石墨烯中的任意一种或至少两种的组合。
优选地，步骤(1)所述导电剂包括导电炭黑Super P、乙炔黑、科琴黑、导电石墨、碳纳米管和石墨烯中的任意一种或至少两种的组合。
优选地，步骤(1)所述粘结剂包括聚四氟乙烯、聚偏氟乙烯、羧甲基纤维素钠中的任意一种或至少两种的组合。
优选地，以浆料团中氟化碳、导电剂和粘结剂的质量之比和计为100％，所述氟化碳的含量为50％～99.9％，例如52％、55％、58％、60％、65％、70％、72％、75％、78％、80％、85％、88％、90％、92％、95％、98％或99％等。
优选地，以浆料团中氟化碳、导电剂和粘结剂的质量之比和计为100％， 所述粘结剂的含量为0.05％～25％，例如0.1％、0.2％、0.5％、0.8％、1％、2％、5％、8％、10％、12％、15％、16％、18％、20％或22％等。
优选地，以浆料团中氟化碳、导电剂和粘结剂的质量之比和计为100％，所述导电剂的含量为0.05％～25％，例如0.1％、0.2％、0.5％、0.8％、1％、2％、5％、8％、10％、12％、15％、16％、18％、20％或22％等。
优选地，步骤(1)所述粘结剂溶液的制备过程包括：在粘结剂的乳液中加入水和乙醇的混合溶液进行破乳。
优选地，所述混合溶液的加入量为步骤(1)中的混合粉料重量的5％～60％，例如10％、15％、20％、25％、30％、35％、40％、45％、50％或55％等。
优选地，所述混合溶液中水的质量含量为0.1％～50％，例如0.5％、1％、5％、15％、20％、25％、30％、35％、40％或45％等。
优选地，所述混合溶液中乙醇的质量含量为50％～99.9％，例如55％、60％、65％、70％、75％、80％、85％、90％或95％等。
作为优选技术方案，本公开所述一种正极极片的制备方法包括如下步骤：
(1)将含有氟化碳和导电剂的混合粉料与粘结剂溶液混合，得到浆料团，以浆料团中氟化碳、导电剂和粘结剂的质量之比和计为100％，所述氟化碳的含量为50％～99.9％，粘结剂的含量为0.05％～25％，导电剂的含量为0.05％～25％；
(2)将所述浆料团挤出制成直径为0.5～10mm的颗粒，40～100℃烘干，并进行温度为150～300℃的热起纤1min～60min，得到前驱体颗粒；
(3)将前驱体颗粒采用溶剂进行浸泡，然后将所述前驱体颗粒压制在厚度为0.01mm～2mm，且孔径为0.5mm～5mm的金属集流网两侧，所述压制的压力为0.1～20MPa，时间为5s～10min，所述前体颗粒压制在金属集流网两侧的厚度 各自独立地选自0.2mm～50mm，在40～100℃烘干，得到正极极片。
本公开的目的之二在于提供一种正极极片，所述正极极片通过目的之一所述的方法制备得到。
优选地，所述正极极片包括金属集流网和分布于所述金属集流网两侧的多孔活性材料层。
优选地，所述多孔活性材料层中的活性材料包括氟化碳。
优选地，所述多孔活性材料层的孔隙率为20％～70％，例如25％、30％、35％、40％、45％、50％、55％、60％或65％等。
优选地，所述正极极片的厚度为0.1～45mm，例如0.5mm、1mm、5mm、10mm、15mm、20mm、25mm、30mm、35mm、40mm或42mm等。
本公开的目的之三在于提供一种锂氟化碳电池，所述锂氟化碳电池中的正极极片为目的之二所述的正极极片。
相对于现有技术，本公开具有以下有益效果：
(1)本公开采用“颗粒-一步成型”法制备正极极片，即正极小颗粒和金属集流网复合压制成型的技术，改善了正极活性材料和集流体间的接触性，从而降低了电池的内阻，提高了电池的输出能力，并且采用本公开的方法制备的正极极片整体为多孔的结构，更易于电解液的浸润。
(2)本公开将浆料团制成颗粒，然后进行压制，可直接制得正极极片，省去了在制备极片过程中需要涂布等过程，制备过程更加简单，且本公开采用模具一步成型可以实现正极极片重量、厚度、及尺寸可控，可适用于不同种类电池的制备，更易于实现大规模生产。
具体实施方式
下面通过具体实施方式来进一步说明本公开的技术方案。本领域技术人员 应该明了，所述实施例仅仅是帮助理解本公开，不应视为对本公开的具体限制。
实施例1
一种正极极片的制备方法包括如下步骤：
(1)在粘结剂(聚四氟乙烯)的乳液中加入水和乙醇进行破乳(水和乙醇的质量比为1:1)，并搅拌均匀，得到粘结剂溶液；
(2)将含有氟化碳和导电剂(科琴黑)的混合粉料与粘结剂溶液混合，得到浆料团，以浆料团中氟化碳、导电剂和粘结剂的质量比之和计为100％，所述氟化碳的质量含量为85％，粘结剂的质量含量为5％，导电剂的质量含量为10％；
(3)将所述浆料团挤出制成直径为3mm的颗粒，80℃烘干，并在250℃下热起纤30min，得到前驱体颗粒；
(4)将所述前驱体颗粒采用乙醇进行浸泡，在模具上铺一层厚度为1mm的所述前驱体颗粒，作为底层，然后加入厚度为0.03mm，且孔径为2mm圆形的金属集流网(镍网)，再铺一层厚度为1mm的所述前驱体颗粒作为顶层，在15MPa压制1min，80℃烘干，得到正极极片。
实施例2
与实施例1的区别在于，步骤(3)所述浆料团挤出制成直径为0.5mm的颗粒。
实施例3
与实施例1的区别在于，步骤(3)所述浆料团挤出制成直径为10mm的颗粒。
实施例4
与实施例1的区别在于，步骤(3)所述浆料团挤出制成直径为0.3mm的颗粒。
实施例5
与实施例1的区别在于，步骤(3)所述浆料团挤出制成直径为12mm的颗粒。
实施例6
与实施例1的区别在于，步骤(4)所述压制的压力为0.1MPa，时间为10min。
实施例7
与实施例1的区别在于，步骤(4)所述压制的压力为20MPa，时间为1min。
实施例8
与实施例1的区别在于，步骤(4)所述压制的压力为0.05MPa，时间为20min。
实施例9
与实施例1的区别在于，步骤(4)所述压制的压力为22MPa，时间为5s。
实施例10
一种正极极片的制备方法包括如下步骤：
(1)在粘结剂(聚偏氟乙烯)的乳液中加入水和乙醇进行破乳(水和乙醇的质量比为1:2)，并搅拌均匀，得到粘结剂溶液；
(2)将含有氟化碳和导电剂(导电炭黑Super P)的混合粉料与粘结剂溶液混合，得到浆料团，以浆料团中氟化碳、导电剂和粘结剂的质量之比和计为100％，所述氟化碳的含量为55％，粘结剂的含量为15％，导电剂的含量为 30％；
(3)将所述浆料团挤出制成直径为3mm的颗粒，40℃烘干，并进行温度为150℃的热起纤1min时间，得到前驱体颗粒；
(4)将所述前驱体颗粒采用乙醇进行浸泡，在模具上铺一层厚度为1.2mm的所述前驱体颗粒，作为底层，然后加入厚度为0.03mm，且孔径(最远点距离)为3mm菱形的金属集流网(铝网)，再铺一层厚度为1.2mm的所述前驱体颗粒作为顶层，在15MPa压制1min，40℃烘干，得到正极极片。
实施例11
一种正极极片的制备方法包括如下步骤：
(1)在粘结剂(羧甲基纤维素钠)的乳液中加入水和乙醇进行破乳(水和乙醇的质量比为1:5)，并搅拌均匀，得到粘结剂溶液；
(2)将含有氟化碳和导电剂(碳纳米管)的混合溶液与粘结剂溶液混合，得到浆料团，以浆料团中氟化碳、导电剂和粘结剂的质量之和计为100％，所述氟化碳的含量为95％，粘结剂的含量为2.5％，导电剂的含量为2.5％；
(3)将所述浆料团挤出制成直径为8mm的颗粒，100℃烘干，并进行温度为250℃的热起纤30min，得到前驱体颗粒；
(4)将所述前驱体颗粒采用乙醇进行浸泡，在模具上铺一层厚度为1.5mm的所述前驱体颗粒，作为底层，然后加入厚度为0.03mm，且孔径(最远点距离)为2mm长方形的金属集流网(Ti网)，再铺一层厚度为0.8mm的所述前驱体颗粒作为顶层，在5MPa压制1min，100℃烘干，得到正极极片。
对比例1
与实施例1的区别在于：步骤(3)和(4)替换为：将所述浆料团通过碾压制得两个片状极片(厚度分别与实施例1中的底层和顶层相同)，在两个片 状极片中夹一个与实施例1相同的金属集流网(镍网)，采用与实施例1相同的压制方式，得到正极极片。
性能测试：
(1)极片测试：卡尺测试厚度，使用四探针法测试极片电阻；
(2)电池性能测试：
将得到的正极极片、锂片、隔膜和电解液(1mol/L LiPF 6/PC:DME，PC和DME的体积比为1:1)组装成2032型扣式电池，进行电性能测试；
(a)开路电压和内阻测试：采用日置内阻仪测试电池开路电压和内阻；
(b)工作电压和滞后电压测试：采用蓝电电池测试仪测试电池的电化学性能，放电电压区间为3.4～2.0V，测试电池在0.1C下进行恒流放电时工作电压；并读取开始放电时，电压下降的最低点为滞后电压。
表1
Figure PCTCN2019125892-appb-000001
Figure PCTCN2019125892-appb-000002
通过表1可以看出，本公开实施例4相对于实施例1正极出现明显掉粉的现象，这是因为实施例4中挤出颗粒的粒径较小，小颗粒容易在压制过程中形成毛边从而脱落，造成极片成型困难，因此实施例4相对于实施例1虽然电性能相当，但会造成电池自放电大的问题；本公开实施例5相对于实施例1极片电阻成倍增加，因为实施例5中挤出颗粒的粒径较大，进而压制过程中颗粒间隙较大造成极片电子导电性下降，因此实施例5相对于实施例1整体电性能较差。
通过表1可以看出，本公开实施例8相对于实施例1极片电阻增加且滞后电压和工作电压明显降低，因为实施例8中压制的压力较小，正极极片中难以实现正极颗粒间的良好接触，在此压力下即使时间较长也达不到实施例1的技术效果，因此实施例8相对于实施例1电性能较差；本公开实施例9相对于实施例1正极整体厚度下降，但是极片电阻以及组装成电池后的工作电压下降，这是因为实施例9中压制的压力较大，使极片间孔隙率降低，进而影响了电解液的浸润性，造成了离子迁移受限，在此压力下即使时间较短其也达不到实施例1的技术效果，因此实施例9相对于实施例1性能较差。
通过表1可以看出，本公开对比例1相对于实施例1极片电阻成数量级增加，因为对比例1中为制备成片状极片后再与金属集流网进行压制，通过此方法制得的极片孔隙率低，使极片无法具有良好的电解液浸润性，无法得到带有孔隙结构的正极极片，因此对比例1相对于实施例1电性能较差，且该方法制 备的极片难以在较大压力下达到1mm的厚度，造成极片厚度较大。
本公开通过上述实施例来说明本发明的详细方法，但本发明并不局限于上述详细方法，即不意味着本发明必须依赖上述详细方法才能实施。所属技术领域的技术人员应该明了，对本公开的任何改进，对本公开产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。

Claims (11)

  1. 一种正极极片的制备方法，其中所述方法包括如下步骤：
    (1)将含有氟化碳和导电剂的混合粉料与粘结剂溶液混合，得到浆料团；
    (2)将所述浆料团制成颗粒，并进行热起纤，得到前驱体颗粒；
    (3)将所述前驱体颗粒压制在金属集流网上，得到正极极片。
  2. 如权利要求1所述的制备方法，其中，步骤(2)所述浆料团制成颗粒的方法包括：将所述浆料团挤出制成颗粒。
  3. 如权利要求1或2所述的制备方法，其中，所述颗粒的直径为0.5～10mm。
  4. 如权利要求1-3之一所述的制备方法，其中，步骤(2)所述热起纤的过程包括：将所述浆料团制成颗粒进行热处理；
    优选地，所述热处理的温度为150℃～300℃；
    优选地，所述热处理的时间为1min～60min。
  5. 如权利要求1-4之一所述的制备方法，其中，步骤(3)所述压制的压力为0.1～20MPa；
    优选地，所述压制的时间为5s～10min；
    优选地，步骤(3)之前，步骤(2)之后还包括步骤(2’)的过程：将前驱体颗粒采用溶剂进行浸泡；
    优选地，所述溶剂包括乙醇、异丙醇、丁醇和丙二醇中的任意一种或至少两种的组合；
    优选地，步骤(3)所述前体颗粒压制在金属集流网上的厚度为0.2mm～50mm，优选为0.2mm～20mm；
    优选地，步骤(3)所述前体颗粒压制在金属集流网的两侧；
    优选地，步骤(3)中所述前体颗粒压制在金属集流网两侧的厚度各自独立 地选自0.2mm～50mm，优选为0.2mm～20mm；
    优选地，步骤(2)所述热起纤之前和步骤(3)所述压制之后，各自独立地包括烘干的过程；
    优选地，所述烘干的温度为40～100℃。
  6. 如权利要求1-5之一所述的制备方法，其中，步骤(3)所述金属集流网包括镍网、铝网、Ti网和不锈钢网中的任意一种或至少两种的组合；
    优选地，步骤(3)所述金属集流网的厚度为0.01mm～2mm；
    优选地，步骤(3)所述金属集流网的孔径为0.5mm～5mm；
    优选地，步骤(3)所述金属集流网的表面含有导电胶；
    优选地，所述导电胶包括导电炭黑、导电石墨、碳纳米管和石墨烯中的任意一种或至少两种的组合。
  7. 如权利要求1-6之一所述的制备方法，其中，步骤(1)所述导电剂包括导电炭黑Super P、乙炔黑、科琴黑、导电石墨、碳纳米管和石墨烯中的任意一种或至少两种的组合；
    优选地，步骤(1)所述粘结剂包括聚四氟乙烯、聚偏氟乙烯、羧甲基纤维素钠中的任意一种或至少两种的组合；
    优选地，以浆料团中氟化碳、导电剂和粘结剂的质量之比和计为100％，所述氟化碳的含量为50％～99.9％；
    优选地，以浆料团中氟化碳、导电剂和粘结剂的质量之比和计为100％，所述粘结剂的含量为0.05％～25％；
    优选地，以浆料团中氟化碳、导电剂和粘结剂的质量之比和计为100％，所述导电剂的含量为0.05％～25％；
    优选地，步骤(1)所述粘结剂溶液的制备过程包括：在粘结剂的乳液中加 入水和乙醇的混合溶液进行破乳；
    优选地，所述混合溶液的加入量为步骤(1)中的混合粉料重量的5％～60％；
    优选地，所述混合溶液中水的质量含量为0.1％～50％；
    优选地，所述混合溶液中乙醇的质量含量为50％～99.9％。
  8. 如权利要求1-7之一所述的制备方法，其中，所述方法包括如下步骤：
    (1)将含有氟化碳和导电剂的混合粉料与粘结剂溶液混合，得到浆料团，以浆料团中氟化碳、导电剂和粘结剂的质量之比和计为100％，所述氟化碳的含量为50％～99.9％，粘结剂的含量为0.05％～25％，导电剂的含量为0.05％～25％；
    (2)将所述浆料团挤出制成直径为0.5～10mm的颗粒，40～100℃烘干，并进行温度为150～300℃的热起纤1min～60min，得到前驱体颗粒；
    (3)将前驱体颗粒采用溶剂进行浸泡，然后将所述前驱体颗粒压制在厚度为0.01mm～2mm，且孔径为0.5mm～5mm的金属集流网两侧，所述压制的压力为0.1～20MPa，时间为5s～10min，所述前体颗粒压制在金属集流网两侧的厚度各自独立地选自0.2mm～50mm，在40～100℃烘干，得到正极极片。
  9. 一种正极极片，其通过权利要求1～8之一所述的方法制备得到。
  10. 如权利要求9所述的正极极片，其中，所述正极极片包括金属集流网和分布于所述金属集流网一侧或两侧的多孔活性材料层；
    优选地，所述多孔活性材料层中的活性材料包括氟化碳；
    优选地，所述多孔活性材料层的孔隙率为20％～70％；
    优选地，所述正极极片的厚度为0.1～45mm。
  11. 一种锂氟化碳电池，其中所述锂氟化碳电池中的正极极片为权利要求9或10所述的正极极片。
PCT/CN2019/125892 2019-12-17 2019-12-17 一种正极极片的制备方法及制得的正极极片和锂氟化碳电池 WO2021119983A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/CN2019/125892 WO2021119983A1 (zh) 2019-12-17 2019-12-17 一种正极极片的制备方法及制得的正极极片和锂氟化碳电池

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2019/125892 WO2021119983A1 (zh) 2019-12-17 2019-12-17 一种正极极片的制备方法及制得的正极极片和锂氟化碳电池

Publications (1)

Publication Number Publication Date
WO2021119983A1 true WO2021119983A1 (zh) 2021-06-24

Family

ID=76478236

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/125892 WO2021119983A1 (zh) 2019-12-17 2019-12-17 一种正极极片的制备方法及制得的正极极片和锂氟化碳电池

Country Status (1)

Country Link
WO (1) WO2021119983A1 (zh)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114203969A (zh) * 2021-11-29 2022-03-18 湖南立方新能源科技有限责任公司 一种电极极片的制备方法及电极极片和二次电池
CN114267890A (zh) * 2021-12-28 2022-04-01 广东国光电子有限公司 一种正极极片及其制备方法与应用
CN114284462A (zh) * 2021-12-22 2022-04-05 珠海冠宇动力电池有限公司 一种正极片、电池及正极片的制备方法
CN116612934A (zh) * 2023-07-18 2023-08-18 江苏新视界先进功能纤维创新中心有限公司 一种弹性导电薄膜和高导电纤维的制备方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1649194A (zh) * 2004-12-13 2005-08-03 武汉孚特电子科技有限公司 一种锂亚硫酰氯电池的阴极载体
CN101800316A (zh) * 2010-02-23 2010-08-11 惠州亿纬锂能股份有限公司 一种多孔碳阴极材料的制备方法以及使用这种材料的锂原电池
CN102569735A (zh) * 2010-12-17 2012-07-11 中国电力科学研究院 锂亚硫酰氯电池正极的制备方法
CN103236516A (zh) * 2013-04-03 2013-08-07 河南迈奇能源技术有限公司 一种高温电池正极的制备方法
CN104538631A (zh) * 2014-12-31 2015-04-22 广州市里亚电池有限公司 一种电池正极材料及其制备方法
US20160133932A1 (en) * 2014-11-06 2016-05-12 Schlumberger Technology Corporation Lithium carbon fluoride primary battery
CN109786842A (zh) * 2018-12-26 2019-05-21 中国电子科技集团公司第十八研究所 一种高安全高比能量锂/氟化碳电池制备方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1649194A (zh) * 2004-12-13 2005-08-03 武汉孚特电子科技有限公司 一种锂亚硫酰氯电池的阴极载体
CN101800316A (zh) * 2010-02-23 2010-08-11 惠州亿纬锂能股份有限公司 一种多孔碳阴极材料的制备方法以及使用这种材料的锂原电池
CN102569735A (zh) * 2010-12-17 2012-07-11 中国电力科学研究院 锂亚硫酰氯电池正极的制备方法
CN103236516A (zh) * 2013-04-03 2013-08-07 河南迈奇能源技术有限公司 一种高温电池正极的制备方法
US20160133932A1 (en) * 2014-11-06 2016-05-12 Schlumberger Technology Corporation Lithium carbon fluoride primary battery
CN104538631A (zh) * 2014-12-31 2015-04-22 广州市里亚电池有限公司 一种电池正极材料及其制备方法
CN109786842A (zh) * 2018-12-26 2019-05-21 中国电子科技集团公司第十八研究所 一种高安全高比能量锂/氟化碳电池制备方法

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114203969A (zh) * 2021-11-29 2022-03-18 湖南立方新能源科技有限责任公司 一种电极极片的制备方法及电极极片和二次电池
CN114284462A (zh) * 2021-12-22 2022-04-05 珠海冠宇动力电池有限公司 一种正极片、电池及正极片的制备方法
CN114267890A (zh) * 2021-12-28 2022-04-01 广东国光电子有限公司 一种正极极片及其制备方法与应用
CN116612934A (zh) * 2023-07-18 2023-08-18 江苏新视界先进功能纤维创新中心有限公司 一种弹性导电薄膜和高导电纤维的制备方法
CN116612934B (zh) * 2023-07-18 2023-11-17 江苏新视界先进功能纤维创新中心有限公司 一种弹性导电薄膜和高导电纤维的制备方法

Similar Documents

Publication Publication Date Title
WO2021119983A1 (zh) 一种正极极片的制备方法及制得的正极极片和锂氟化碳电池
CN109167020B (zh) 一种具有高能量密度的多孔锂离子极片及其制备方法及锂离子电池
US20230115744A1 (en) Lithium iron phosphate positive electrode sheet, preparation method therefor, and lithium iron phosphate lithium-ion battery
CN113764644B (zh) 一种快充复合石墨材料及其制备方法
WO2016206548A1 (zh) 一种锂电池高电压改性负极材料的制备方法
JP2020503232A (ja) グラフェンフラワーの製造方法及びリチウム硫電池へのその使用
CN108288699A (zh) 一种复合磷酸铁锂材料及其制备方法、正极极片、锂离子电池
CN114613974B (zh) 一种长寿命快充型锂离子电池负极材料及其制备方法
CN115566170B (zh) 一种高能量密度快充锂离子电池负极材料的制备方法
CN109755498B (zh) 一种碱性二次电池铁基负极添加剂，制备方法和使用该添加剂的铁基负极板及其应用
CN112234202A (zh) 一种高性能锂氟化碳电池及其制备方法
WO2018059180A1 (zh) 一种高功率高能量化学电源及其制备方法
CN104659333A (zh) 锂离子二次电池Mg2Si/SiOx/C复合负极材料膜电极的制备方法
CN111900362A (zh) 一种快充型高比容量的负极片及包括该负极片的锂离子电池
CN110649226B (zh) 一种锰基锂氧化物正极及其制备方法
Ma et al. Lithium cobaltate: a novel host material enables high-rate and stable lithium–sulfur batteries
CN109300698A (zh) 一种锂离子电容器及其制备方法
CN114497508A (zh) 一种功率型人造石墨复合材料及其制备方法
EP4145476A1 (en) Positive electrode of hybrid capacitor and manufacturing method therefor and use thereof
CN108899211B (zh) 一种兼备高能量密度与高功率密度的钠离子电容器及其制备方法
CN101752546A (zh) 一种磷酸铁锂电极的制备方法
KR20230148406A (ko) 리튬 이온 배터리의 음극재의 제조방법
CN110311134B (zh) 一种铝离子电池极片及制作方法
CN105702962A (zh) 一种锂硫电池正极极片及其制备方法
CN104916834A (zh) 一种高电压锂离子负极材料的制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19956238

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19956238

Country of ref document: EP

Kind code of ref document: A1