WO2023173412A1 - 电化学装置和电子装置 - Google Patents

电化学装置和电子装置 Download PDF

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WO2023173412A1
WO2023173412A1 PCT/CN2022/081723 CN2022081723W WO2023173412A1 WO 2023173412 A1 WO2023173412 A1 WO 2023173412A1 CN 2022081723 W CN2022081723 W CN 2022081723W WO 2023173412 A1 WO2023173412 A1 WO 2023173412A1
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layer
graphite
crystallinity
electrochemical device
negative electrode
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PCT/CN2022/081723
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English (en)
French (fr)
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黄雅雯
陶威
刘奥
李磊
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宁德新能源科技有限公司
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Priority to PCT/CN2022/081723 priority Critical patent/WO2023173412A1/zh
Priority to CN202280004958.0A priority patent/CN115735283A/zh
Publication of WO2023173412A1 publication Critical patent/WO2023173412A1/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
    • 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
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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 application relates to the field of electrochemical energy storage, and in particular to electrochemical devices and electronic devices.
  • electrochemical energy storage technology With the development of electrochemical energy storage technology, higher and higher requirements have been placed on the energy density and kinetic performance of electrochemical devices (e.g., lithium-ion batteries), and further improvements in this area are expected.
  • electrochemical devices e.g., lithium-ion batteries
  • Embodiments of the present application provide an electrochemical device.
  • the electrochemical device includes a negative electrode piece.
  • the negative electrode piece includes a negative electrode current collector, a first layer and a second layer, wherein the first layer is disposed between the negative electrode current collector and the second layer. Between two layers; wherein both the first layer and the second layer include graphite, and the ratio of the crystallinity of the graphite in the second layer to the crystallinity of the graphite in the first layer is 0.4 to 0.8.
  • the graphite in the second layer has a crystallinity of 20 nm to 28 nm. In some embodiments, the graphite in the first layer has a crystallinity of 30 nm to 50 nm. In some embodiments, the ratio of the thickness of the first layer to the second layer is 3 to 5. In some embodiments, the mass percentage of graphite in the first layer ranges from 70% to 98%. In some embodiments, the mass percentage of graphite in the second layer ranges from 70% to 98%. In some embodiments, the first layer further includes a first binder and a first dispersant, and the second layer includes a second binder and a second dispersant.
  • the first binder and the second binder each independently include polyacrylic acid, polyvinylpyrrolidone, polyaniline, polyimide, polyamideimide, polysiloxane, styrene-butadiene At least one of rubber, epoxy resin, polyester resin, polyurethane resin or polyfluorene.
  • the first dispersant and the second dispersant each independently include at least one of carboxymethylcellulose or a carboxymethylcellulose salt.
  • An embodiment of the present application also provides an electronic device, including the above electrochemical device.
  • this application can exert a higher capacity and improve the energy density of the electrochemical device.
  • using graphite with a lower crystallinity in the second layer can avoid the high temperature of the lower layer.
  • the problem of lithium precipitation on the surface of crystalline graphite improves the kinetic performance of electrochemical devices.
  • Figure 1 shows a cross-sectional view of a negative electrode plate according to some embodiments of the present application.
  • Graphite with high crystallinity has low defect density, high capacity and first-time efficiency, but poor kinetic properties, which can easily lead to lithium precipitation on the surface of the negative electrode sheet.
  • Embodiments of the present application provide an electrochemical device, which includes a negative electrode piece.
  • FIG. 1 shows a cross-sectional view of the cross-section along the width direction and thickness direction of the negative electrode plate according to some embodiments.
  • the negative electrode sheet includes a negative electrode current collector 101 , a first layer 102 and a second layer 103 , wherein the first layer 102 is disposed between the negative electrode current collector 101 and the second layer 103 .
  • both the first layer 102 and the second layer 103 include graphite, and the ratio of the crystallinity of the graphite in the second layer 103 to the crystallinity of the graphite in the first layer 102 is 0.4 to 0.8.
  • the crystallinity of graphite can be defined by Lc, which is the thickness of graphite sheets stacked along the c-axis direction perpendicular to the sheet plane.
  • the crystallinity (Lc) of graphite can be tested by the following method, but this is only exemplary and other suitable testing methods can also be used: Use an X-ray diffractometer (XRD, Bruker D8 Advance, Germany) to test the X-ray of graphite powder Diffraction pattern, scanning range is 5° ⁇ 80°.
  • XRD X-ray diffractometer
  • the diffraction peaks in the range of 20° to 30° correspond to the (002) crystal plane, and the half-maximum width ⁇ 002 corresponding to the (002) peak can be obtained, that is, the full width of the spectrum band when the maximum height of the (002) peak is half the height.
  • Testing the XRD of the surface layer of the negative electrode plate can obtain the crystallinity information of the graphite in the second layer. After scraping off the surface graphite with a scraper, and then performing an XRD test, the crystallinity information of the graphite in the first layer can be obtained. The boundary between the first layer and the second layer can be identified by SEM of the negative electrode plate cross-section.
  • the first layer close to the negative electrode current collector is made of graphite with higher crystallinity
  • the second layer far away from the negative electrode current collector is made of graphite with smaller crystallinity.
  • the second layer of low crystallinity graphite has many active sites, which is beneficial to lithium ions.
  • the intercalation and deintercalation of graphite makes it difficult for lithium to precipitate, and enables fuller contact between the electrolyte and the negative electrode sheet; the first layer of graphite has a small defect density and high crystallinity, and can exert a relatively high capacity.
  • the ratio of the crystallinity of the graphite in the second layer 103 to the crystallinity of the graphite in the first layer 102 is too small, usually the defect density of the graphite in the second layer 103 is too high, which is not conducive to the stability of the structure. ; If the ratio of the crystallinity of the graphite in the second layer 103 to the crystallinity of the graphite in the first layer 102 is too large, usually the crystallinity of the graphite in the first layer 102 is too low, which is not conducive to fully improving the electricity. Capacity of chemical plant.
  • the graphite in second layer 103 has a crystallinity of 20 nm to 28 nm. If the crystallinity of the graphite in the second layer 103 is too small, the defect density of the graphite in the second layer 103 is too high, which is not conducive to the stability of the graphite structure; if the crystallinity of the graphite in the second layer 103 is too large, Therefore, the effect of improving lithium precipitation on the surface of the negative electrode piece is relatively limited.
  • the graphite in first layer 102 has a crystallinity of 30 nm to 50 nm.
  • the crystallinity of the graphite in the first layer 102 is too small, the capacity of the electrochemical device cannot be fully increased; if the crystallinity of the graphite in the first layer 102 is too large, the requirements for graphite materials will be higher and the cost will be higher. higher.
  • the ratio of the thicknesses of first layer 102 to second layer 103 is 3 to 5. If the ratio of the thickness of the first layer 102 to the second layer 103 is too small, the thickness of the second layer 103 is too thick, which is not conducive to the full use of the capacity of the high crystallinity graphite in the electrochemical device. If the ratio of the thickness of the first layer 102 to the second layer 103 is too large, the thickness of the second layer 103 is too small, and the effect of the second layer 103 on improving lithium deposition on the surface of the negative electrode plate is relatively limited.
  • the mass percentage of graphite in the first layer 102 is 70% to 98%. If the mass percentage of graphite in the first layer 102 is too small, it is not conducive to fully increasing the energy density of the electrochemical device; if the mass percentage of graphite in the first layer 102 is too large, the first layer 102 The content of other components (eg, binder) in is too small, which is not conducive to the overall structural stability of the first layer 102 . In some embodiments, the mass percentage of graphite in the second layer 103 is 70% to 98%.
  • the mass percentage of graphite in the second layer 103 is too small, it is not conducive to fully increasing the energy density of the electrochemical device; if the mass percentage of graphite in the second layer 103 is too large, the second layer 103 The content of other components (eg, binder) in is too small, which is not conducive to the overall structural stability of the second layer 103.
  • other components eg, binder
  • the first layer 102 further includes a first binder and a first dispersant
  • the second layer 103 includes a second binder and a second dispersant.
  • the first binder and the second binder each independently include polyacrylic acid, polyvinylpyrrolidone, polyaniline, polyimide, polyamideimide, polysiloxane, styrene-butadiene At least one of rubber, epoxy resin, polyester resin, polyurethane resin or polyfluorene.
  • the first dispersant and the second dispersant each independently include at least one of carboxymethylcellulose or a carboxymethylcellulose salt.
  • the first layer 102 and the second layer 103 may each independently include at least one of silicon, silicon alloy, silicon-oxygen material, silicon-carbon material, hard carbon, or tin-based material.
  • the negative electrode current collector may use at least one of copper foil, nickel foil, or carbon-based current collector. Of course, other negative electrode current collectors commonly used in the art may also be used. In some embodiments, the thickness of the negative electrode current collector may be 1 ⁇ m to 200 ⁇ m.
  • the electrochemical device may include an electrode assembly, and the electrode assembly may include a separator, a positive electrode piece, and the above-mentioned negative electrode piece, wherein the isolation film is disposed between the positive electrode piece and the negative electrode piece.
  • the positive electrode sheet may include a positive current collector and a positive active material layer located on one or both sides of the positive current collector.
  • the positive electrode current collector may be an aluminum (Al) foil. Of course, other positive electrode current collectors commonly used in the art may also be used.
  • the thickness of the cathode current collector may be 1 ⁇ m to 200 ⁇ m.
  • the cathode active material layer may include a cathode active material, and the cathode active material may include lithium cobalt oxide, lithium manganate, lithium iron phosphate, lithium nickel cobalt manganate, lithium nickel cobalt aluminate, or lithium nickel manganate. of at least one.
  • the positive active material layer further includes a binder and a conductive agent.
  • 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 carboxymethylcellulose, polyvinyl acetate, polyvinylpyrrolidone, polyvinyl ether, polymethylmethacrylate, polytetrafluoroethylene At least one of vinyl fluoride or polyhexafluoropropylene.
  • the conductive agent in the cathode active material layer may include at least one of conductive carbon black, Ketjen black, flake graphite, graphene, carbon nanotubes or carbon fibers.
  • the mass ratio of the cathode active material, the conductive agent and the binder in the cathode active material layer may be 91 ⁇ 99:0.5 ⁇ 3:0.5 ⁇ 6. It should be understood that the above is only an example, and the positive active material layer may adopt any other suitable materials, thicknesses and mass ratios.
  • the release film 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.
  • the thickness of the isolation film ranges from about 5 ⁇ m to 20 ⁇ m.
  • the surface of the isolation membrane may also 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.
  • the inorganic particles are selected from aluminum oxide (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.
  • the pores of the isolation film have a diameter in the range of about 0.01 ⁇ m to 1 ⁇ m.
  • the binder of the porous layer is selected from polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, sodium carboxymethylcellulose, poly At least one of vinylpyrrolidone, polyvinyl ether, polymethylmethacrylate, polytetrafluoroethylene or polyhexafluoropropylene.
  • the porous layer on the surface of the isolation membrane can improve the heat resistance, oxidation resistance and electrolyte wetting 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, although the application is not limited thereto.
  • the electrochemical device may also include an electrolyte.
  • the electrolyte may be one or more of a gel electrolyte, a solid electrolyte, and an electrolyte solution, and the electrolyte solution includes a lithium salt and a non-aqueous solvent.
  • the lithium salt is selected from LiPF 6 , LiBF 4 , LiAsF 6 , LiClO 4 , LiB(C 6 H 5 ) 4 , LiCH 3 SO 3 , LiCF 3 SO 3 , LiN(SO 2 CF 3 ) 2 , LiC(SO 2 CF 3 ) 3 , one or more of LiSiF 6 , LiBOB or lithium difluoroborate.
  • LiPF 6 was chosen for the lithium salt because it gives high ionic conductivity and improves cycle characteristics.
  • the non-aqueous solvent may be selected from carbonate compounds, carboxylate compounds, ether compounds, other organic solvents, or combinations thereof.
  • the carbonate compound may be selected from chain carbonate compounds, cyclic carbonate compounds, fluorocarbonate compounds, or combinations thereof.
  • the chain carbonate compound may be selected from diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), methyl carbonate Ethyl ester (MEC) and its combinations.
  • the cyclic carbonate compound may be selected from ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), vinyl ethylene carbonate (VEC) or combinations thereof.
  • the fluorocarbonate compound may be selected from the group consisting of fluoroethylene carbonate (FEC), 1,2-difluoroethylene carbonate, 1,1-difluoroethylene carbonate, and 1,1,2-trifluoroethylene carbonate.
  • the carboxylate compound may be selected from the group consisting of methyl acetate, ethyl acetate, n-propyl acetate, tert-butyl acetate, methyl propionate, ethyl propionate, propyl propionate, ⁇ -butyrolactone, decanolactone, Valerolactone, mevalonolactone, caprolactone, methyl formate or combinations thereof.
  • the ether compound may be selected from dibutyl ether, tetraglyme, diglyme, 1,2-dimethoxyethane, 1,2-diethoxyethane, ethoxymethoxy ethane, 2-methyltetrahydrofuran, tetrahydrofuran or combinations thereof.
  • organic solvents may be selected from dimethyl sulfoxide, 1,2-dioxolane, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone, methane Amides, dimethylformamide, acetonitrile, trimethyl phosphate, triethyl phosphate, trioctyl phosphate, and phosphate esters or combinations thereof.
  • the positive electrode sheet, the separator film, and the negative electrode sheet are wound or stacked in order to form an electrode piece, and are then packaged in, for example, an aluminum plastic film, and electrolyte is injected liquid, formed, and packaged to make a lithium-ion battery. Then, the prepared lithium-ion battery was tested for performance.
  • electrochemical devices eg, lithium-ion batteries
  • electrochemical devices eg, lithium-ion batteries
  • Other methods commonly used in the art can be used without departing from the content disclosed in this application.
  • Embodiments of the present application also provide an electronic device including the above electrochemical device.
  • the electronic device in the embodiment of the present application is not particularly limited and may be used in any electronic device known in the prior art.
  • electronic devices may include, but are not limited to, laptop computers, pen computers, mobile computers, e-book players, portable telephones, portable fax machines, portable copiers, portable printers, stereo headsets, Video recorders, LCD TVs, portable cleaners, portable CD players, mini discs, transceivers, electronic notepads, calculators, memory cards, portable recorders, radios, backup power supplies, motors, cars, motorcycles, power-assisted bicycles, bicycles, Lighting appliances, toys, game consoles, clocks, power tools, flashlights, cameras, large household batteries and lithium-ion capacitors, etc.
  • Preparation of the positive electrode sheet Dissolve the positive active material lithium cobalt oxide, conductive agent conductive carbon black, and binder polyvinylidene fluoride in N-methylpyrrolidone (NMP) solution in a weight ratio of 97.6:1.3:1.1. Form positive electrode slurry. Aluminum foil is used as the positive electrode current collector, and the positive electrode slurry is coated on the positive electrode current collector with a coating thickness of 80 ⁇ m. After drying, cold pressing, and cutting, the positive electrode pieces are obtained.
  • NMP N-methylpyrrolidone
  • isolation film The base material of the isolation film is 8 ⁇ m thick polyethylene (PE). A 2 ⁇ m alumina ceramic layer is coated on both sides of the isolation film base material. Finally, 2.5 ⁇ m alumina ceramic layer is coated on both sides of the ceramic layer. mg of the binder polyvinylidene fluoride (PVDF), dried.
  • PE polyethylene
  • PVDF binder polyvinylidene fluoride
  • Preparation of lithium-ion battery Stack the positive electrode sheet, isolation film, and negative electrode sheet in order, so that the isolation film is between the positive electrode sheet and the negative electrode sheet for isolation, and wind it to obtain the electrode assembly.
  • the electrode assembly is placed in the outer packaging aluminum plastic film. After removing the moisture at 80°C, the above-mentioned electrolyte is injected and packaged. After formation, degassing, trimming and other processes, the thickness is 4mm, the width is 35mm, and the length is 80mm lithium-ion battery.
  • the preparation of the negative electrode piece of Example 1 is as follows:
  • Copper foil was used as the negative electrode current collector, and the first slurry was coated on the negative electrode current collector with a coating weight of 30 mg/1540 cm 2 to obtain the first layer.
  • the second slurry is applied on the first layer to a thickness of 120 mg/1540 cm to obtain the second layer.
  • the negative electrode piece After drying, cold pressing, and cutting, the negative electrode piece is obtained.
  • the thickness of the cold-pressed electrode piece is about 23 ⁇ m for the second layer and about 92 ⁇ m for the first layer.
  • Examples 2 to 6 differ in the crystallinity Lc of the graphite in the first layer and/or the second layer. Specific parameter differences are shown in Table 1 below.
  • the test environment temperature is 25°C.
  • the same charging process is used to cycle charge and discharge 10 times.
  • the lithium-ion battery is then disassembled to compare and observe the negative electrode plate to obtain the lithium precipitation interface. Charging process:
  • Step 1 Charge the lithium-ion battery to 4.5V with a constant current of 2C;
  • Step 2 Charge the lithium-ion battery to 0.05C with a constant voltage of 4.5V;
  • Step 3 Let the lithium-ion battery sit for 5 minutes
  • Step 4 Discharge the lithium-ion battery to 3.0V at a constant current of 0.5C;
  • Step 5 Let the lithium-ion battery sit for 5 minutes
  • Step 6 Repeat steps 1 to 5 above for a total of 10 times.
  • the test environment temperature is 25°C.
  • the same charging process is used to cycle charge and discharge 600 times.
  • the discharge capacity of the battery after 600 cycles of charge and discharge is divided by the discharge capacity of the first cycle to obtain the capacity retention rate.
  • Step 1 Charge the lithium-ion battery to 4.5V with a constant current of 2C;
  • Step 2 Charge the lithium-ion battery to 0.05C with a constant voltage of 4.5V;
  • Step 3 Let the lithium-ion battery sit for 5 minutes
  • Step 4 Discharge the lithium-ion battery to 3.0V at a constant current of 0.5C;
  • Step 5 Let the lithium-ion battery sit for 5 minutes
  • Step 6 Repeat steps 1 to 5 above for a total of 600 times.
  • Table 1 shows various parameters and evaluation results of Examples 1 to 6 and Comparative Examples 1 to 3.
  • Table 2 shows the respective parameters and evaluation results of Examples 7 to 12. Among them, the thickness of the first layer and the second layer in Examples 7 to 12 is different from that in Example 3, and the other aspects are the same as Example 3.

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Abstract

本申请提供了电化学装置和电子装置。电化学装置包括负极极片，负极极片包括负极集流体、第一层和第二层，其中，第一层设置在负极集流体和第二层之间；其中，第一层和第二层均包括石墨，并且第二层中的石墨的结晶度与第一层中的石墨的结晶度的比率为0.4至0.8。通过在第一层中采用结晶度较高的石墨，能够发挥较高的容量，提升电化学装置的能量密度，同时在第二层中采用结晶度较低的石墨，可以避免下层的高结晶度石墨的表层析锂问题，改善电化学装置的动力学性能。

Description

电化学装置和电子装置 技术领域
本申请涉及电化学储能领域，具体地，涉及电化学装置和电子装置。
背景技术
伴随电化学储能技术的发展，对电化学装置(例如，锂离子电池)的能量密度和动力学性能提出了越来越高的要求，期望这方面的进一步改进。
发明内容
本申请的实施例提供了一种电化学装置，该电化学装置包括负极极片，负极极片包括负极集流体、第一层和第二层，其中，第一层设置在负极集流体和第二层之间；其中，第一层和第二层均包括石墨，并且第二层中的石墨的结晶度与第一层中的石墨的结晶度的比率为0.4至0.8。
在一些实施例中，第二层中的石墨的结晶度为20nm至28nm。在一些实施例中，第一层中的石墨的结晶度为30nm至50nm。在一些实施例中，第一层与第二层的厚度的比率为3至5。在一些实施例中，第一层中的石墨的质量百分含量为70％至98％。在一些实施例中，第二层中的石墨的质量百分含量为70％至98％。在一些实施例中，第一层还包括第一粘结剂和第一分散剂，第二层包括第二粘结剂和第二分散剂。在一些实施例中，第一粘结剂和第二粘结剂各自独立地包括聚丙烯酸、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、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。在一些实施例中，第一分散剂和第二分散剂各自独立地包括羧甲基纤维素或羧甲基纤维素盐中的至少一种。
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。
本申请通过在第一层中采用结晶度较高的石墨，能够发挥较高的容量，提升电化学装置的能量密度，同时在第二层中采用结晶度较低的石墨，可以避免下层的高结晶度石墨的表层析锂问题，改善电化学装置的动力学性能。
附图说明
图1示出了本申请的一些实施例的负极极片的截面图。
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。
结晶度高的石墨缺陷密度低，容量和首次效率高，但动力学性能差，容易导致负极极片的表层析锂。
本申请的实施例提供了一种电化学装置，该电化学装置包括负极极片。图1示出了根据一些实施例的负极极片的宽度方向和厚度方向所在的截面的截面图。如图1所示，负极极片包括负极集流体101、第一层102和第二层103，其中，第一层102设置在负极集流体101和第二层103之间。
在一些实施例中，第一层102和第二层103均包括石墨，并且第二层103中的石墨的结晶度与第一层102中的石墨的结晶度的比率为0.4至0.8。在一些实施例中，石墨的结晶度可以用Lc来定义，Lc是石墨片沿着与片平面垂直的c轴方向进行堆积的厚度。石墨的结晶度(Lc)可以通过以下方法进行测试，但是这仅是示例性的，还可以采用其他合适的测试方法：使用X射线衍射仪(XRD，德国Bruker D8 Advance)测试石墨粉末的X射线衍射图谱，扫描范围为5°～80°。在20°～30°范围内的衍射峰对应(002)晶面，可得(002)峰对应的半高宽β 002，即(002)峰高度最大处高度一半时谱带的全宽。Lc＝K*λ/β 002*COSθ 002，其中，K＝0.089，
Figure PCTCN2022081723-appb-000001
θ 002为(002)峰对应的θ值，β 002为(002)峰的半高宽。测试负极极片表层的XRD能够得到第二层中的石墨的结晶度信息，用刮刀刮掉表层石墨后，再做XRD测试能够得到第一层中的石墨的结晶度信息。第一层和第二层的分界可以通过负极极片截面的SEM辨别。
靠近负极集流体的第一层采用结晶度更高的石墨，远离负极集流体的第二层采用结晶度更小的石墨，第二层的低结晶度石墨的活性位点多，有利于锂离子的嵌入和脱嵌，不易析锂，并且使得电解液与负极极片的接触更充分；第一层的石墨的缺陷密度小，结晶度较高，能够发挥相对较高的容量。因此，在不损失容量的情况下，可有效避免第一层作为负极极片的表层时由高结晶 度石墨引起的表层析锂问题，能够有效改善电化学装置的动力学性能并且能够减缓循环衰减，提升电化学装置的循环性能。
另外，如果第二层103中的石墨的结晶度与第一层102中的石墨的结晶度的比率太小，则通常地第二层103中的石墨的缺陷密度太高，不利于结构的稳定；如果第二层103中的石墨的结晶度与第一层102中的石墨的结晶度的比率太大，则通常地第一层102中的石墨的结晶度太低，不利于充分地提升电化学装置的容量。
在一些实施例中，第二层103中的石墨的结晶度为20nm至28nm。如果第二层103中的石墨的结晶度太小，则第二层103中的石墨的缺陷密度太高，不利于石墨的结构的稳定；如果第二层103中的石墨的结晶度太大，则改善负极极片的表面析锂的作用相对受限。在一些实施例中，第一层102中的石墨的结晶度为30nm至50nm。如果第一层102中的石墨的结晶度太小，则不能充分地提升电化学装置的容量；如果第一层102中的石墨的结晶度太大，则对石墨材料的要求较高，成本也较高。
在一些实施例中，第一层102与第二层103的厚度的比率为3至5。如果第一层102与第二层103的厚度的比率太小，则第二层103的厚度太厚，不利于电化学装置中的高结晶度石墨的容量的充分发挥。如果第一层102与第二层103的厚度的比率太大，则第二层103的厚度太小，第二层103改善负极极片的表面析锂的作用相对受限。
在一些实施例中，第一层102中的石墨的质量百分含量为70％至98％。如果第一层102中的石墨的质量百分含量太小，则不利于充分地提升电化学装置的能量密度；如果第一层102中的石墨的质量百分含量太大，则第一层102中的其他组分(例如，粘结剂)的含量太少，不利于第一层102整体的结构稳定。在一些实施例中，第二层103中的石墨的质量百分含量为70％至98％。如果第二层103中的石墨的质量百分含量太小，则不利于充分地提升电化学装置的能量密度；如果第二层103中的石墨的质量百分含量太大，则第二层103中的其他组分(例如，粘结剂)的含量太少，不利于第二层103整体的结构稳定。
在一些实施例中，第一层102还包括第一粘结剂和第一分散剂，第二层103包括第二粘结剂和第二分散剂。在一些实施例中，第一粘结剂和第二粘 结剂各自独立地包括聚丙烯酸、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、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。在一些实施例中，第一分散剂和第二分散剂各自独立地包括羧甲基纤维素或羧甲基纤维素盐中的至少一种。在一些实施例中，第一层102和第二层103还可以各自独立地包括硅、硅合金、硅氧材料、硅碳材料、硬碳或锡基材料中的至少一种。
在一些实施例中，负极集流体可以采用铜箔、镍箔或碳基集流体中的至少一种，当然，也可以采用本领域常用的其他负极集流体。在一些实施例中，负极集流体的厚度可以为1μm至200μm。
在一些实施例中，电化学装置可以包括电极组件，电极组件可以包括隔离膜、正极极片和上述负极极片，其中隔离膜设置在正极极片和负极极片之间。在一些实施例中，正极极片可以包括正极集流体和正极活性材料层，正极活性材料层位于正极集流体的一侧或两侧上。在一些实施例中，正极集流体可以采用铝(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，正极集流体的厚度可以为1μm至200μm。
在一些实施例中，正极活性材料层可以包括正极活性材料，正极活性材料可以包括钴酸锂、锰酸锂、磷酸铁锂、镍钴锰酸锂、镍钴铝酸锂或镍锰酸锂中的至少一种。在一些实施例中，正极活性材料层还包括粘结剂和导电剂。在一些实施例中，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、羧甲基纤维素钠、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，正极活性材料层中的导电剂可以包括导电炭黑、科琴黑、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，正极活性材料层中的正极活性材料、导电剂和粘结剂的质量比可以为91～99：0.5～3：0.5～6。应该理解，以上所述仅是示例，正极活性物质层可以采用任何其他合适的材料、厚度和质量比。
在一些实施例中，隔离膜包括聚乙烯、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至20μm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至1μm的范围的直径。多孔层的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、羧甲基纤维素钠、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质。电解质可以是凝胶电解质、固态电解质和电解液中的一种或多种，电解液包括锂盐和非水溶剂。锂盐选自LiPF 6、LiBF 4、LiAsF 6、LiClO 4、LiB(C 6H 5) 4、LiCH 3SO 3、LiCF 3SO 3、LiN(SO 2CF 3) 2、LiC(SO 2CF 3) 3、LiSiF 6、LiBOB或者二氟硼酸锂中的一种或多种。例如，锂盐选用LiPF 6，因为它可以给出高的离子导电率并改善循环特性。
非水溶剂可选自碳酸酯化合物、羧酸酯化合物、醚化合物、其它有机溶剂或它们的组合。
碳酸酯化合物可选自链状碳酸酯化合物、环状碳酸酯化合物、氟代碳酸酯化合物或其组合。
链状碳酸酯化合物可选自碳酸二乙酯(DEC)、碳酸二甲酯(DMC)、 碳酸二丙酯(DPC)、碳酸甲丙酯(MPC)、碳酸乙丙酯(EPC)、碳酸甲乙酯(MEC)及其组合。所述环状碳酸酯化合物可选自碳酸亚乙酯(EC)、碳酸亚丙酯(PC)、碳酸亚丁酯(BC)、碳酸乙烯基亚乙酯(VEC)或者其组合。所述氟代碳酸酯化合物可选自碳酸氟代亚乙酯(FEC)、碳酸1,2-二氟亚乙酯、碳酸1,1-二氟亚乙酯、碳酸1,1,2-三氟亚乙酯、碳酸1,1,2,2-四氟亚乙酯、碳酸1-氟-2-甲基亚乙酯、碳酸1-氟-1-甲基亚乙酯、碳酸1,2-二氟-1-甲基亚乙酯、碳酸1,1,2-三氟-2-甲基亚乙酯、碳酸三氟甲基亚乙酯或者其组合。
羧酸酯化合物可选自乙酸甲酯、乙酸乙酯、乙酸正丙酯、乙酸叔丁酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、γ-丁内酯、癸内酯、戊内酯、甲瓦龙酸内酯、己内酯、甲酸甲酯或者其组合。
醚化合物可选自二丁醚、四甘醇二甲醚、二甘醇二甲醚、1,2-二甲氧基乙烷、1,2-二乙氧基乙烷、乙氧基甲氧基乙烷、2-甲基四氢呋喃、四氢呋喃或者其组合。
其它有机溶剂可选自二甲亚砜、1,2-二氧戊环、环丁砜、甲基环丁砜、1,3-二甲基-2-咪唑烷酮、N-甲基-2-吡咯烷酮、甲酰胺、二甲基甲酰胺、乙腈、磷酸三甲酯、磷酸三乙酯、磷酸三辛酯、和磷酸酯或者其组合。
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。
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。
对比例1
正极极片的制备：将正极活性材料钴酸锂、导电剂导电炭黑、粘结剂聚偏氟乙烯按重量比97.6：1.3：1.1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，涂布厚度为80μm，经过干燥、冷压、分切后得到正极极片。
负极极片的制备：将负极活性材料石墨(结晶度Lc＝20nm)、粘结剂丁苯橡胶和分散剂羧甲基纤维素钠按重量比98：1：1的比例溶于去离子水中，形成负极浆料。采用铜箔作为负极集流体，将负极浆料涂覆于负极集流体上，涂布厚度为115μm，经过干燥、冷压、裁切得到负极极片。
隔离膜的制备：隔离膜基材为8μm厚的聚乙烯(PE)，在隔离膜基材的两侧各涂覆2μm氧化铝陶瓷层，最后在涂布了陶瓷层的两侧各涂覆2.5mg的粘结剂聚偏二氟乙烯(PVDF)，烘干。
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厚度为4mm、宽度为35mm、长度为80mm的锂离子电池。
其他对比例和实施例是在对比例1步骤的基础上进行参数变更，仅是负极极片的制备与对比例1不同。其中，对比例2的石墨的结晶度Lc＝25nm，对比例3的石墨的结晶度Lc＝35nm。
实施例1的负极极片的制备如下：
将负极活性材料石墨(结晶度Lc＝32nm)、粘结剂丁苯橡胶和分散剂羧甲基纤维素钠按重量比98：1：1的比例溶于去离子水中，形成第一浆料。采用铜箔作为负极集流体，将第一浆料涂覆于负极集流体上，涂布重量为30mg/1540cm 2得到第一层。将负极活性材料石墨(结晶度Lc＝25nm)、粘结剂丁苯橡胶和分散剂羧甲基纤维素钠按重量比98：1：1的比例溶于去离子水中，形成第二浆料，将第二浆料涂覆于第一层上，涂布厚度为120mg/1540cm 2得到第二层。经过干燥、冷压、裁切得到负极极片，冷压后的极片厚度为第二层约23μm，第一层约92μm。
实施例2至实施例6是第一层和/或第二层中的石墨的结晶度Lc不同。具体的参数差异示出于下表1中。
下面描述本申请的各个参数的测试方法。
1)析锂界面比较：
测试环境温度为25℃，使用相同的充电流程循环充放电10次，再拆解锂离子电池对比观察负极极片得到析锂界面。充电流程：
步骤1：以2C恒流将锂离子电池充电至4.5V；
步骤2：以4.5V恒压将锂离子电池充电至0.05C；
步骤3：将锂离子电池静置5分钟；
步骤4：以0.5C恒流将锂离子电池放电至3.0V；
步骤5：将锂离子电池静置5分钟；
步骤6：循环上述步骤1至步骤5，总共循环10次。
2)容量保持率：
测试环境温度为25℃，使用相同的充电流程循环充放电600次，再将电池循环充放电600次后的放电容量除以其循环第一次时的放电容量以得到该容量保持率。充电流程：
步骤1：以2C恒流将锂离子电池充电至4.5V；
步骤2：以4.5V恒压将锂离子电池充电至0.05C；
步骤3：将锂离子电池静置5分钟；
步骤4：以0.5C恒流将锂离子电池放电至3.0V；
步骤5：将锂离子电池静置5分钟；
步骤6：循环上述步骤1至步骤5，总共循环600次。
表1示出了实施例1至6和对比例1至3的各个参数和评估结果。
表1
Figure PCTCN2022081723-appb-000002
通过比较对比例1、对比例3、对比例4和实施例3可知，通过采用双层涂布设计，第一层中的石墨的结晶度较高，第二层中的石墨的结晶度较低，在改善析锂的同时，也能够提升锂离子电池的容量保持率。同样地，通过比较对比例2和实施例1也能够得到同样的结论。这主要是由于远离负极集流体的第二层采用低结晶度石墨，有利于锂离子的嵌入和脱嵌，不易析锂；而 靠近负极集流体的第一层采用高结晶度石墨，能够发挥相对较高的容量，如此，在不损失容量的情况下，改善了锂离子电池的动力学性能和循环性能。
另外，通过比较实施例1至实施例6可知，在第二层中的石墨的结晶度与第一层中的石墨的结晶度的比率为0.4至0.8时，随着该比率的增大，容量保持率有先增大后减小的趋势。
表2示出了实施例7至12的各个参数和评估结果。其中，实施例7至12中的第一层和第二层的厚度与实施例3不同，其他方面与实施例3相同。
表2
Figure PCTCN2022081723-appb-000003
通过比较实施例7至12可知，随着第一层与第二层的厚度的比率的减小，容量保持率先增大后减小，并且在第一层与第二层的厚度的比率为3至5的范围内时，容量保持率可以维持在90％以上。
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 (10)

  1. 一种电化学装置，其包括：
    负极极片，所述负极极片包括负极集流体、第一层和第二层，所述第一层位于所述负极集流体和所述第二层之间；
    其中，所述第一层和所述第二层均包括石墨，并且所述第二层中的石墨的结晶度与所述第一层中的石墨的结晶度的比率为0.4至0.8。
  2. 根据权利要求1所述的电化学装置，其中，所述第二层中的石墨的结晶度为20nm至28nm。
  3. 根据权利要求1所述的电化学装置，其中，所述第一层中的石墨的结晶度为30nm至50nm。
  4. 根据权利要求1所述的电化学装置，其中，所述第一层与所述第二层的厚度的比率为3至5。
  5. 根据权利要求1所述的电化学装置，其中，所述第一层中的石墨的质量百分含量为70％至98％。
  6. 根据权利要求1所述的电化学装置，其中，所述第二层中的石墨的质量百分含量为70％至98％。
  7. 根据权利要求1所述的电化学装置，其中，所述第一层还包括第一粘结剂和第一分散剂，所述第二层包括第二粘结剂和第二分散剂。
  8. 根据权利要求7所述的电化学装置，其中，所述第一粘结剂和所述第二粘结剂各自独立地包括聚丙烯酸、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、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。
  9. 根据权利要求7所述的电化学装置，其中，所述第一分散剂和所述第二分散剂各自独立地包括羧甲基纤维素或羧甲基纤维素盐中的至少一种。
  10. 一种电子装置，包括根据权利要求1至9中任一项所述的电化学装置。
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CN101202338A (zh) * 2006-09-01 2008-06-18 索尼株式会社 负极和使用该负极的非水电解质二次电池
JP2019175851A (ja) * 2018-03-29 2019-10-10 大阪ガスケミカル株式会社 リチウムイオン二次電池用負極活物質及びその製造方法
CN110534701A (zh) * 2019-08-06 2019-12-03 荣盛盟固利新能源科技有限公司 一种电极极片,电极极片制造方法及电化学装置
CN110885083A (zh) * 2018-09-07 2020-03-17 三星Sdi株式会社 负极活性物质及其制备方法、负电极和可再充电锂电池
CN111584825A (zh) * 2020-06-01 2020-08-25 湖北亿纬动力有限公司 一种负极片及其制备方法和用途

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101202338A (zh) * 2006-09-01 2008-06-18 索尼株式会社 负极和使用该负极的非水电解质二次电池
JP2019175851A (ja) * 2018-03-29 2019-10-10 大阪ガスケミカル株式会社 リチウムイオン二次電池用負極活物質及びその製造方法
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