CN114556629A - Negative electrode material, electrochemical device, and electronic device - Google Patents

Negative electrode material, electrochemical device, and electronic device Download PDF

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CN114556629A
CN114556629A CN202180005831.6A CN202180005831A CN114556629A CN 114556629 A CN114556629 A CN 114556629A CN 202180005831 A CN202180005831 A CN 202180005831A CN 114556629 A CN114556629 A CN 114556629A
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negative electrode
anode
electrode material
range
peak
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刘茜
郑席
杜鹏
谢远森
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Ningde Amperex Technology Ltd
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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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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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Abstract

Provided are an anode material, an electrochemical device, and an electronic device, wherein particles of the anode material include a core and a shell; the number of pores having a pore diameter in the range of 0.4nm to 5nm in the range of 20nm × 20nm of the cross section of the core body is 5 to 100, thereby ensuring the dynamic performance while ensuring a high capacity of the anode material.

Description

Negative electrode material, electrochemical device, and electronic device
Technical Field
The present application relates to the field of electrochemical energy storage, and in particular, to an anode material, an electrochemical device, and an electronic device.
Background
As electrochemical devices (e.g., lithium ion batteries) are developed and advanced, higher and higher requirements are placed on their capacity and the dynamic performance of the electrochemical devices. At present, in order to improve the capacity and the dynamic performance of an electrochemical device, some measures have been taken to achieve some improvements, but the improvements are not satisfactory, and further improvements are expected.
Disclosure of Invention
The embodiment of the application provides a negative electrode material, and a particle of the negative electrode material comprises a core body and a shell layer; the number of pores having a pore diameter in the range of 0.4nm to 5nm is 5 to 100 in the range of 20nm x 20nm of the cross section of the core body. The core-shell structure is beneficial to improving the stability of the cathode material, reduces the contact between the inner hole of the core body and electrolyte and reduces the consumption of the electrolyte.
In some embodiments, the number of pores having a pore diameter in the range of 2nm to 5nm is 5 to 50 in the 20nm x 20nm range of the cross section of the core body. In some embodiments, the number of pores having a pore diameter in the range of 2nm to 5nm is 12 to 50 in the 20nm x 20nm range of the cross section of the core body. The dynamic performance is ensured while the high capacity of the cathode material is ensured.
In some embodiments, the negative electrode material comprises a carbon material. In some embodiments, the shell layer is located on the surface of the core body. In some embodiments, the shell is analyzed using transmission electron microscopy at any 400nm of the shell2In the range of (1), the number of pores having a pore diameter in the range of 2nm to 5nm is less than or equal to 5. Not only can improve the ion conduction, but also can give consideration to gram capacity.
In some embodiments, the anode material satisfies at least one of the following (a) to (c): (a) the thickness of the shell layer is 10nm to 200 nm; (b) the crystal face spacing of the microchip layer of the shell layer is 0.36nm to 0.4 nm; (c) the shell layer includes amorphous carbon. Ensure ion transmission and improve the dynamic performance.
In some embodiments, the anode material satisfies at least one of (d) to (h) shown below: (d) in the photoelectron spectrum of the anode material, at 285.4 + -0.3 eV, 287.8 + -0.3 eV and 288.9 + -0.3 eVA position having at least one peak; (e) the specific surface area of the negative electrode material is 2m2G to 10m2(ii)/g; (f) the powder conductivity of the negative electrode material was 1X 10-06Mu S/cm to 9X 10-08Mu S/cm; (g) in an X-ray diffraction pattern of the negative electrode material, a diffraction peak is formed between 18 degrees and 30 degrees, and the half-peak width of the diffraction peak is 4 degrees to 10 degrees; (h) the peak intensity ratio I of the G peak and the D peak in the Raman spectrum of the anode materialG/IDIs 0.6 to 1.
In some embodiments, the anode material satisfies at least one of (i) to (k) shown below: (i) the Dv10 of the negative electrode material is 1 μm to 5 μm; (g) the Dv50 of the negative electrode material is 4 μm to 15 μm; (k) the Dv90 of the negative electrode material was 13 μm to 30 μm. In some embodiments, the anode material has a Dv50 of 5 μm to 10 μm. The Dv10, the Dv50 and the Dv90 are in a proper range, so that the diffusion of ions in the negative electrode active material layer is effectively improved, and the rate capability and the lithium fast-releasing capacity of the negative electrode material are improved.
In some embodiments, the negative electrode material comprises a carbon material. The carbon material can reduce the contact between the inner hole of the core body and the electrolyte and reduce the consumption of the electrolyte.
An embodiment of the present application further provides an electrochemical device, including: a positive electrode, a negative electrode, an electrolyte and a separator; the negative electrode includes a negative electrode current collector and a negative electrode active material layer on the negative electrode current collector, the negative electrode active material layer including the negative electrode material of any one of the above.
In some embodiments, the electrochemical device satisfies at least one of the following (l) to (n): (l) The resistance of the cathode is 10m Ω to 60m Ω, and optionally 20m Ω to 40m Ω. (m) the electrochemical device includes an electrolyte including at least one of fluoroether, fluoroethylene carbonate, or ether nitrile. (n) the electrochemical device includes an electrolyte including a lithium salt including lithium bis (fluorosulfonyl) imide and lithium hexafluorophosphate, the lithium salt having a concentration of 1 to 2mol/L, and a mass ratio of the lithium bis (fluorosulfonyl) imide to the lithium hexafluorophosphate being 0.06 to 5. In some embodiments, the mass ratio of lithium bis (fluorosulfonyl) imide to lithium hexafluorophosphate is from 0.062 to 4.105. The lithium bis (fluorosulfonyl) imide can act on a porous negative electrode material, and can effectively improve the cycle and expansion performance of the lithium ion battery.
The present application also provides an electronic device comprising the electrochemical device of any one of the above.
The embodiment of the application provides a negative electrode material, and a particle of the negative electrode material comprises a core body and a shell layer; the number of pores having a pore diameter in the range of 0.4nm to 5nm in the range of 20nm × 20nm of the cross section of the core body is 5 to 100, thereby ensuring the dynamic performance while ensuring a high capacity of the anode material.
Drawings
Fig. 1 is a cross-sectional view of one anode material of the present disclosure.
Detailed Description
The following examples are presented to enable those skilled in the art to more fully understand the present application and are not intended to limit the present application in any way.
Electrochemical devices, such as lithium ion batteries, are widely used in various fields, and users' demands for electrochemical devices are also increasing. For the negative electrode material of electrochemical devices, ion storage capacity, i.e., capacity and kinetics, is currently the main performance enhancement. The negative electrode materials used at present are mainly graphite and silicon materials. The theoretical gram capacity of the graphite is 372mAh/g, and the capacity of the graphite applied at present is close to the limit level. The capacity of the graphite material is improved mainly by changing the methods of a precursor, granulation, sintering process and the like, but the bottleneck for improving the capacity is very large, and the improving space is small. The graphite material can also be coated with a material with high dynamics on the surface of the graphite in a coating mode, so that the quick charging and discharging capacity is improved, but the method usually causes the loss of first effect and capacity, and cannot completely achieve better effect on the performance. The theoretical gram capacity of silicon is 3400mAh/g, the silicon belongs to a high-gram-capacity material, the effect of improving the energy density is very obvious, however, the silicon material expands very greatly in the charging and discharging processes, particles are broken, at present, a very effective method is difficult to find for solving the problem, the requirements on quick charging and quick discharging cannot be met, and the factors limit the application of the silicon material.
The embodiment of the application provides a negative electrode material, and a particle of the negative electrode material comprises a core body and a shell layer; the number of pores having a pore diameter in the range of 0.4nm to 5nm is 5 to 100 in the range of 20nm x 20nm of the cross section of the core body. In some embodiments of the present application, the negative electrode material may be photographed by using a Transmission Electron Microscope (TEM), a 20nm × 20nm region may be selected on the photographed TEM, the number and the aperture of the holes may be counted, and the maximum diameter of the holes may be selected as the aperture when the aperture of the holes is counted. For the anode material, when it has a pore structure with a pore diameter of not less than 0.4nm, it can have an ion storage capacity (ions are, for example, lithium ions) to increase the capacity, and when the pore diameter is too large, it has a small contribution to the ion storage capacity and may cause a decrease in the volumetric energy density, so that in some embodiments of the present application, the pore diameter is not more than 5nm to ensure the volumetric energy density of the anode material. In addition, when the number of pores is less than 5, the ion storage capacity of the anode material may not be significantly increased, and when the number of pores is greater than 100, the volume energy density is reduced, and on the other hand, the number of pores is too large, resulting in lack of ion diffusion channels. Therefore, the particles of the negative electrode material in some examples of the present application have a pore number of 5 to 100 in a range of 0.4nm to 5nm in a cross section of 20nm × 20nm of the core body, thereby ensuring dynamic performance while ensuring a high capacity of the negative electrode material.
In some embodiments of the application, the number of pores present in the pore diameter range of 2nm to 5nm is 5 to 50 in the 20nm x 20nm range of the cross section of the core body. In some embodiments, a pore size in the range of 2nm to 5nm can have both a better ion storage capacity and better guarantee ion transport. In some embodiments, the anode material includes a core having microcrystalline graphite with pores formed by a combination of microcrystalline graphite, the number of pores having a pore diameter in the range of 2nm to 5nm in the range of 20nm x 20nm of the cross section of the core body cannot be excessively low to secure the capacity of the anode material, the ratio of the graphite microcrystalline area to the pore area is expected to be at least 4:1, the maximum number of pores is 100, but an excessively large number of pores results in a lack of ion diffusion channels, and thus the upper limit of the number of pores having a pore diameter in the range of 2nm to 5nm in the range of 20nm x 20nm of the cross section of the core body is 50.
Some embodimentsThe negative electrode material includes a carbon material, which in some embodiments may be hard carbon, and the negative electrode material may be composed of hard carbon. In some embodiments of the disclosure, the shell layer is located on a surface of the core body. In some embodiments, the particles of the negative electrode material provided by the present disclosure have a core-shell structure, which is beneficial to improving the stability of the negative electrode material, and reducing the contact between the internal pores of the core body and the electrolyte, and reducing the consumption of the electrolyte. In some embodiments of the present application, the shell layer is analyzed using transmission electron microscopy at any 400nm of the shell layer2In the range of (1), the number of pores having a pore diameter in the range of 2nm to 5nm is less than 5. In some embodiments, the shell is made of a denser material, so that the core body can be protected well, the permeation of electrolyte into the core body is reduced, and the consumption of the electrolyte is reduced. In some embodiments, the core and shell may be hard carbon.
In some embodiments of the present application, the shell layer of the anode material has a thickness of 10nm to 200 nm. In some embodiments, an excessively small shell thickness may result in reduced protection of the nucleus, and an excessively large shell thickness may affect ion conduction and may result in a loss of gram capacity.
In some embodiments of the present application, the interplanar spacing of the microchip layer of the shell layer of the anode material is 0.36nm to 0.4 nm. In some embodiments, when the interplanar spacing of the microchip layer of the shell layer of the negative electrode material is too small, ion transport may be hindered, kinetic performance may be affected, and rate performance may be not favorable, and when the interplanar spacing of the microchip layer is too large, the volumetric energy density may be affected, and optionally, the interplanar spacing of the microchip layer is 0.36nm to 0.39 nm. In some embodiments, the negative electrode material may be photographed using a transmission electron microscope, and the photographed photographs may be analyzed to determine the interplanar spacing of the microchip layer.
In some embodiments of the present application, the shell layer comprises amorphous carbon. In some embodiments, the shell layer may comprise a carbon material. The amorphous carbon structure of the shell layer is beneficial to improving ion transmission, so that the dynamic performance of the negative electrode material is enhanced.
In some embodiments of the present disclosure, the anode material has at least one peak in the photoelectron spectrum at the positions of 285.4 ± 0.3eV, 287.8 ± 0.3eV, and 288.9 ± 0.3 eV. In some embodiments, the 285.4 ± 0.3eV peak is a C-O peak, the 287.8 ± 0.3eV peak is a C ═ O peak, and the 288.9 ± 0.3eV peak is a COO peak. In some embodiments, the negative electrode material is prepared by sintering, in order to ensure the kinetic performance of the shell layer, the sintering temperature is not too high and is not affected by the coating source functional group, and the sintered negative electrode material has an oxygen-containing functional group on the surface and can be obtained by a photoelectron spectroscopy test.
In some embodiments of the present disclosure, the anode material has a specific surface area of 2m2G to 10m2(ii) in terms of/g. In some embodiments, the specific surface area is not less than 2m, influenced by the negative electrode material itself2In some embodiments, when the specific surface area of the negative electrode material is not less than 2m, the number of contact sites between the surface of the negative electrode material and the electrolyte is large, and side reactions between the negative electrode material and the electrolyte are increased, which may reduce the first efficiency of the material2A ratio of the total amount of the carbon atoms to the total amount of the carbon atoms is not more than 7m2At the time of per gram, the first effect of the negative electrode material is kept at a level of more than 70%, and when the specific surface area of the negative electrode material is continuously increased, the first effect is continuously reduced, so that the application requirement is difficult to meet. In some embodiments, the specific surface area of the anode material was tested as follows: a sample of 1.5g to 3.5g of the negative electrode material was weighed into a test sample tube of TriStar II 3020, degassed at 200 ℃ for 120min, and then tested. And (3) at constant temperature and low temperature, measuring the adsorption quantity of gas on the surface of the negative electrode material under different relative pressures, and then calculating the adsorption quantity of the monomolecular layer of the sample based on the Bronuore-Eltt-Taylor adsorption theory and the formula thereof, thereby calculating the specific surface area of the negative electrode material.
In some embodiments of the present disclosure, the negative electrode material has a powder conductivity of 1 × 10-06Mu S/cm to 9X 10-08μ S/cm. In some embodiments, the powder conductivity of the negative electrode material is not higher than 9 × 10 due to the property of the negative electrode material itself-08μ S/cm, on the other hand, the powder conductivity of the negative electrode material is not less than 1X 10 to ensure the dynamic performance of the negative electrode material-06μ S/cm. In some embodiments, the powder of the negative electrode materialThe conductivity was measured as follows: putting the powder of the cathode material into a tabletting mould, leading out leads at two sides of the mould, and pressurizing while measuring the resistance until the resistance is unchanged. The pressed piece is then removed and subjected to conductivity testing using a four-probe method or ac impedance.
In some embodiments of the present application, in an X-ray diffraction pattern of the anode material, there is one diffraction peak between 18 ° and 30 °, and a half-peak width of the diffraction peak is 4 ° to 10 °. In some embodiments, having a diffraction peak between 18 ° and 30 ° with a half-peak width of 4 ° to 10 ° indicates that the negative electrode material is not a graphite material, which may be a material including hard carbon. In some embodiments, the anode material has a peak intensity ratio I of the G peak and the D peak in the raman spectrumG/IDIs 0.6 to 1. In some embodiments, the peak intensity ratio I of the G peak to the D peakG/IDShowing the defect ratio inside the anode material, IG/IDThe larger the ratio of (A) is, the less defects are in the negative electrode material, the higher the crystallinity is, and in some embodiments of the present application, the negative electrode material contains a certain number of pores, therefore IG/IDShould be 0.6 to 1.
In some embodiments of the present application, the Dv10 of the anode material is 1 μm to 5 μm. In some embodiments, the anode material has a Dv50 of 4 μm to 15 μm. In some embodiments, the anode material has a Dv90 of 13 μm to 30 μm. In some embodiments, too small a particle size of the negative electrode material may result in increased consumption of the electrolyte and adversely affect cycle performance, and too large a particle size of the negative electrode material may result in poor dynamic performance and affect rate performance. By limiting the particle size of the negative electrode material, the rapid conduction of electrons in the negative electrode material can be ensured. In some embodiments, Dv10, Dv50, and Dv99 were obtained by analyzing the particle size of samples using a Mastersizer 3000 laser particle size distribution tester. Dv10, Dv50 and Dv90 respectively indicate particle diameters of 10%, 50% and 90% in volume accumulation from the small particle diameter side in the volume-based particle size distribution. During the test, the sample injection system is Hydro2000SM wet dispersion, the measuring range is 0.01 μm to 3500 μm, the light source is Red light, Helium neon laser/blue light, Solid state light source, and the detection angle is 0-144 degrees. The sample test time was 6s, the background test time was 6s, the snap number of the sample test was 6000 times, the test cycle was 3 times of averaging, the rotation speed of the stirring pump was 3000rpm, and the analysis mode was set to General purpose.
In some embodiments of the present application, the negative electrode material comprises a carbon material. In some embodiments, the anode material may be synthesized using the following method: mixing sodium carbonate and a phenol material in a first solvent to obtain a first mixture, wherein the phenol can be phenol, resorcinol, hydroquinone, catechol and the like, and the first solvent is formaldehyde, acetal, furfural and the like; dissolving a copolymer material in a mixed solution of ethanol and water to obtain a second mixed material, wherein the copolymer material can be F127 (poloxamer, polyoxyethylene polyoxypropylene ether block copolymer), P123 (polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer), SBS (styrene-butadiene-styrene block copolymer) and the like; and mixing the first mixture and the second mixture, and adding hydrochloric acid to obtain a third mixture. And solidifying and crushing the third mixture, adding a fourth mixture, solidifying and sintering, and crushing to obtain the anode material, wherein the fourth mixture can be a solution containing phenolic resin, a solution containing epoxy resin, a solution containing cane sugar, a solution containing glucose and the like.
The negative electrode material provided in some embodiments of the present disclosure is a carbon material having a core-shell structure, as shown in fig. 1, the core body has a porous structure, and the shell layer has a relatively dense amorphous carbon structure, which has a high capacity, a fast ion transport capability, and a relatively small specific surface area, and has a high capacity and a high dynamic performance.
An embodiment of the present application further provides an electrochemical device, including: a positive electrode, a negative electrode, an electrolyte and a separator; the negative electrode includes a negative electrode current collector and a negative electrode active material layer on the negative electrode current collector, the negative electrode active material layer including the negative electrode material of any one of the above. In some embodiments of the present application, the resistance of the negative electrode is 10m Ω to 60m Ω. In some embodiments, the resistance of the negative electrode is affected by the material property, and is not less than 10m Ω, and in order to ensure the dynamic property of the negative electrode, the resistance of the negative electrode is optionally 20m Ω to 40m Ω.
In some embodiments of the present application, the electrochemical device includes an electrolyte including at least one of fluoroether, fluoroether carbonate, or ether nitrile. In some embodiments, the electrolyte includes a lithium salt including lithium bis (fluorosulfonyl) imide and lithium hexafluorophosphate, the lithium salt having a concentration of 1 to 2mol/L, and a mass ratio of the lithium bis (fluorosulfonyl) imide to the lithium hexafluorophosphate being 0.06 to 5.
In some embodiments, a conductive agent and a binder may also be included in the anode active material layer. In some embodiments, the conductive agent in the negative active material layer may include at least one of conductive carbon black, ketjen black, flake graphite, graphene, carbon nanotubes, or carbon fibers. In some embodiments, the binder in the negative electrode active material layer may include at least one of carboxymethyl cellulose (CMC), polyacrylic acid, polyvinyl pyrrolidone, polyaniline, polyimide, polyamideimide, polysiloxane, styrene-butadiene rubber, epoxy resin, polyester resin, polyurethane resin, or polyfluorene. In some embodiments, the mass ratio of the anode material, the conductive agent, and the binder in the anode active material layer may be (78 to 98.5): (0.1 to 10): (0.1 to 10). The negative electrode material may be a mixture of a silicon-based material and other materials. It will be appreciated that the above description is merely exemplary and that any other suitable materials and mass ratios may be employed. In some embodiments, the negative electrode current collector may employ at least one of a copper foil, a nickel foil, or a carbon-based current collector.
In some embodiments, the electrochemical device comprises a separator disposed between the positive electrode and the negative electrode. The isolation film comprises at least one of polyethylene, polypropylene, polyvinylidene fluoride, polyethylene terephthalate, polyimide or aramid. For example, the polyethylene includes at least one selected from high density polyethylene, low density polyethylene, or ultra high molecular weight polyethylene. Particularly polyethylene and polypropylene, which have a good effect on preventing short circuits and can improve the stability of the battery through a shutdown effect. In some embodiments, the thickness of the isolation film is in the range of about 5 μm to 50 μm.
In some embodiments, the surface of the separator may further include a porous layer disposed on at least one surface of the separator, the porous layer including inorganic particles selected from alumina (Al) and a binder2O3) Silicon oxide (SiO)2) Magnesium oxide (MgO), titanium oxide (TiO)2) Hafnium oxide (HfO)2) Tin oxide (SnO)2) Cerium oxide (CeO)2) Nickel oxide (NiO), zinc oxide (ZnO), calcium oxide (CaO), zirconium oxide (ZrO)2) Yttrium oxide (Y)2O3) At least one of silicon carbide (SiC), boehmite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, or barium sulfate. In some embodiments, the pores of the separator film have a diameter in the range of about 0.01 μm to 1 μm. The binder of the porous layer is at least one selected from polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, sodium carboxymethylcellulose, polyvinylpyrrolidone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene and polyhexafluoropropylene. The porous layer on the surface of the isolating membrane can improve the heat resistance, the oxidation resistance and the electrolyte infiltration performance of the isolating membrane and enhance the adhesion between the isolating membrane and the pole piece.
In some embodiments of the present application, the electrochemical device is of a rolled, stacked or folded type.
In some embodiments, the positive electrode and/or the negative electrode of the electrochemical device may be a multilayer structure formed by winding or stacking, or may be a single-layer structure in which a single-layer positive electrode, a single-layer negative electrode, and a separator are stacked.
In some embodiments, the electrochemical device comprises a lithium ion battery, but the application is not so limited. In some embodiments, the electrochemical device may further include an electrolyte. The electrolyte may be one or more of a gel electrolyte, a solid electrolyte, and an electrolytic solution including a lithium salt and a non-aqueous solvent. The lithium salt is selected from LiPF6、LiBF4、LiAsF6、LiClO4、LiB(C6H5)4、LiCH3SO3、LiCF3SO3、LiN(SO2CF3)2、LiC(SO2CF3)3、LiSiF6One or more of LiBOB or lithium difluoroborate. For example, LiPF is selected as lithium salt6. The non-aqueous solvent may be a carbonate compound, an ester-based compound, an ether-based compound, a ketone-based compound, an alcohol-based compound, an aprotic solvent, or a combination thereof. The carbonate compound may be a chain carbonate compound, a cyclic carbonate compound, a fluoro carbonate compound, or a combination thereof.
Examples of the chain carbonate compound are diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), Methyl Propyl Carbonate (MPC), Ethyl Propyl Carbonate (EPC), Methyl Ethyl Carbonate (MEC), and combinations thereof. Examples of the cyclic carbonate compound are Ethylene Carbonate (EC), Propylene Carbonate (PC), Butylene Carbonate (BC), Vinyl Ethylene Carbonate (VEC), or a combination thereof. Examples of the fluoro carbonate compound are fluoroethylene carbonate (FEC), 1, 2-difluoroethylene carbonate, 1, 2-trifluoroethylene carbonate, 1,2, 2-tetrafluoroethylene carbonate, 1-fluoro-2-methylethylene carbonate, 1-fluoro-1-methylethylene carbonate, 1, 2-difluoro-1-methylethylene carbonate, 1, 2-trifluoro-2-methylethylene carbonate, trifluoromethylethylene carbonate, or a combination thereof.
Examples of carboxylate compounds are methyl acetate, ethyl acetate, n-propyl acetate, t-butyl acetate, methyl propionate, ethyl propionate, propyl propionate, gamma-butyrolactone, decalactone, valerolactone, mevalonic lactone, caprolactone, methyl formate, or combinations thereof.
Examples of the ether compound are dibutyl ether, tetraglyme, diglyme, 1, 2-dimethoxyethane, 1, 2-diethoxyethane, ethoxymethoxyethane, 2-methyltetrahydrofuran, tetrahydrofuran, or a combination thereof.
Examples of other organic solvents are dimethylsulfoxide, 1, 2-dioxolane, sulfolane, methyl sulfolane, 1, 3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone, formamide, dimethylformamide, acetonitrile, trimethyl phosphate, triethyl phosphate, trioctyl phosphate, and phosphate esters or combinations thereof.
In some embodiments of the present application, taking a lithium ion battery as an example, a positive electrode, a separator, and a negative electrode are sequentially wound or stacked to form an electrode member, and then the electrode member is placed in, for example, an aluminum plastic film for packaging, and an electrolyte is injected into the electrode member for formation and packaging, so as to form the lithium ion battery. And then, performing performance test on the prepared lithium ion battery.
Those skilled in the art will appreciate that the above-described methods of making electrochemical devices (e.g., lithium ion batteries) are merely examples. Other methods commonly used in the art may be employed without departing from the disclosure herein.
Embodiments of the present application also provide an electronic device including the electrochemical device described above. The electronic device of the embodiment of the present application is not particularly limited, and may be any electronic device known in the art. In some embodiments, the electronic device may include, but is not limited to, a notebook computer, a pen-input computer, a mobile computer, an electronic book player, a portable phone, a portable facsimile machine, a portable copier, a portable printer, a headphone, a video recorder, a liquid crystal television, a handheld cleaner, a portable CD player, a mini-disc, a transceiver, an electronic notebook, a calculator, a memory card, a portable recorder, a radio, a backup power source, an electric motor, an automobile, a motorcycle, a power-assisted bicycle, a bicycle, an unmanned aerial vehicle, a lighting fixture, a toy, a game machine, a clock, an electric tool, a flashlight, a camera, a large household battery, a lithium ion capacitor, and the like.
The following is a list of specific examples and comparative examples to better illustrate the application, wherein button cells and lithium ion batteries are used as examples.
Assembly of button cell (as shown in tables 1 to 3):
mixing a negative electrode material, a conductive agent carbon black (Super P) and sodium carboxymethyl cellulose (CMC) according to a certain proportion of 96: 0.5: and 3.5, preparing slurry with a certain solid content (50%), uniformly coating the slurry on the surface of the copper foil by using a scraper, drying the pole piece (85 ℃, 4 hours), and punching the dried pole piece into a small wafer with the diameter of 14 mm. The obtained small round piece, foamed nickel, a separation film (7 mu m, PP polypropylene substrate), a lithium piece (0.066g) and a steel shell (diameter is 24mm) are added with electrolyte to assemble the button cell.
Preparing an electrolyte: in a dry argon atmosphere glove box, Ethylene Carbonate (EC), diethyl carbonate (DEC) were mixed in a mass ratio of EC: PC: DEC ═ 3: 7, then 2 wt% of fluoroethylene carbonate is added to dissolve and fully stir, and then lithium salt LiPF is added6Mixing uniformly to obtain electrolyte, wherein LiPF6The concentration of (2) is 1 mol/L.
Lithium ion battery preparation (as shown in table 4):
preparation of the positive electrode: mixing a positive electrode active material lithium cobaltate, conductive carbon black (Super P) and polyvinylidene fluoride (PVDF) according to a weight ratio of 97: 1.4: 1.6, adding N-methyl pyrrolidone (NMP) as a solvent, and uniformly stirring. And uniformly coating the slurry (with the solid content of 72 wt%) on an aluminum foil of a current collector of the positive electrode, wherein the coating thickness is 80 mu m, drying at 85 ℃, then carrying out cold pressing, cutting into pieces, slitting, and drying for 4 hours at 85 ℃ under a vacuum condition to obtain the positive electrode.
Preparation of a negative electrode: the negative electrode material, binder styrene butadiene rubber and sodium carboxymethyl cellulose (CMC) adopted in example 3 are mixed according to the weight ratio of 97: 1.5: the ratio of 1.5 was dissolved in deionized water to form a negative electrode slurry (40 wt% solids). And (2) adopting copper foil with the thickness of 10 microns as a negative current collector, coating the negative slurry on the current collector of the negative electrode, drying at 85 ℃, then carrying out cold pressing, cutting into pieces, slitting, and drying for 12 hours at 120 ℃ under a vacuum condition to obtain the negative electrode.
Preparing an isolating membrane: the separator was 7 μm thick Polyethylene (PE).
Preparing a lithium ion battery: and sequentially stacking the anode, the isolating membrane and the cathode in sequence to enable the isolating membrane to be positioned between the anode and the cathode to play an isolating role, and winding to obtain the electrode assembly. And (3) placing the electrode assembly in an outer packaging aluminum-plastic film, dehydrating at 80 ℃, injecting the electrolyte, packaging, and performing technological processes such as formation, degassing, edge cutting and the like to obtain the lithium ion battery.
Testing the cycle performance of the lithium ion battery:
the average value of 5 lithium ion batteries prepared in examples 20 to 23 was obtained. The lithium ion battery was repeatedly charged and discharged through the following steps, and the discharge capacity retention rate and the thickness expansion of the lithium ion battery were calculated.
Firstly, carrying out first charging and discharging in an environment of 25 ℃, carrying out constant current charging under a charging current of 0.7 ℃ until the upper limit voltage reaches 4.48V, then converting into constant voltage charging, then carrying out constant current discharging under a discharging current of 1.0 ℃ until the final voltage is 3V, and recording the first-cycle discharging capacity and the thickness of a fully-charged lithium ion battery; and then, 400 times of charging and discharging cycles are carried out, and the discharging capacity and the thickness of the fully charged lithium ion battery at the 400 th cycle are recorded.
The cycle capacity retention rate ═ (discharge capacity at 400 th cycle/discharge capacity at first cycle) × 100%;
cycle thickness expansion (thickness of fully charged lithium ion battery at 400 th cycle/thickness of fully charged lithium ion battery at first cycle) x 100%.
Testing of the number of holes in a Material
1) Sample preparation
The method comprises the following steps: fully grinding the material, grinding the sample by using a mortar as far as possible to ensure that the size of the sample is between 50nm and 70nm, then dissolving the powder sample in absolute ethyl alcohol, dispersing the sample as far as possible by using an ultrasonic dispersion method, and then fishing up the sample by using a supporting net to prepare the sample.
The method 2 comprises the following steps: embedding and curing the material with epoxy resin, and cutting the material into 50-70 nm size by an ultrathin section method to prepare a sample.
2) Test procedure
1. In the image field, a micro-area is selected, the magnification (exciting current of the projection lens) is not too large (about 2000 x), and an area with good light transmission is found. 2. The intensity (intensity) of the converging beam is adjusted to focus the converging electron beam to the center. 3. Press the diffration button to turn to the diffraction field. If the focusing is not good at this time, the electron beams cannot be converged, and the focus button is adjusted to focus. 4. The objective grating is modulated to the 4 th gear (from the original neutral position), namely exactly one spot is selected, and the transmitted beam passes through the center. 5. Pressing the diffration button switches back to the image field. 6. Finding a grain to be observed in the image field, the darker the area color, the better. 7. And adjusting an intensity button of the electron convergent beam to converge the electron beam at the center. 8. Pressing the diffration button returns the diffraction field. 9. The diffraction field can see the chrysanthemum pool zone and the chrysanthemum pool pole, and then the central point is adjusted to the chrysanthemum pool point. 10. Zooming back to the image field by differentiation, zooming in by intensity, and if the sample stage is tilted double, adjusting the alpha and beta values, and paying attention to the image, ensuring that the center remains in the grain. 11. Adjust the intensity button of the electron convergence beam to converge the electron beam at the center, press the diffraction button, go back to the diffraction field, see if adjust to the Juju Po pole. 12. Repeat 10 to 11 until the chrysanthemum pool is adjusted. 13. And opening the grating of the selected area according to the diffration to return to the image field, selecting the area in the 2 nd gear, and returning to the diffraction field according to the diffration to see the electron diffraction spot diagram.
3) Determination of holes
At 20X 20nm or 400nm2In the range of (1), the judgment of the well by observing the sample is: within a defined region of 2nm to 5nm, without any microchip layer, this region is in a blank state, surrounded by microchip layers.
Method for testing gram capacity of material
And (3) electrically standing the obtained button cell for 4 hours, and testing according to the following flow to obtain the material capacity: 0.05C to 0V, 50 μ A to 0V, 20 μ A to 0V, rest for 5min, 0.01C to 2.5V, the gram capacity charged is recorded as the gram capacity of the material.
First effect: method for testing first effect of material
Standing the obtained button cell for 4 hours, and testing according to the following procedures to obtain the material capacity: discharging to 0V at 0.05C, discharging to 0V at 50 muA, discharging to 0V at 20 muA, standing for 5min, charging to 2.5V at 0.1C, and taking the ratio of gram capacity charged to gram capacity discharged as the first effect of the material.
Method for testing rate capability of material
Fast lithium intercalation property:
and (3) standing the obtained button cell for 4 hours, and testing according to the following procedures to obtain the quick charge performance of the material: discharging to 0V at 0.05C, discharging to 0.005C at constant voltage, standing for 5min, charging to 2.5V at 0.01C, and recording the gram discharge capacity as D; discharging to 0V at 0.01C, 0.02C, 0.05C, 0.1C, 0.2C, 0.5C and 1C respectively, discharging to 0.005C at constant voltage, standing for 5min, charging to 2.5V at 0.01C, and recording the discharge capacities as D1, D2, D3, D4, D5, D6 and D7 respectively.
Fast delithiation performance:
standing the obtained button cell for 4 hours, and testing according to the following procedures to obtain the quick charge performance of the material: 0.05C to 0V, 50 muA to 0V, 20 muA to 0V, standing for 5min, 0.01C to 2.5V, gram charge capacity is recorded as C, 0.05C to 0V, 50 muA to 0V, 20 muA to 0V, standing for 5min, 0.01C, 0.02C, 0.05C, 0.1C, 0.2C, 0.5C, 1C to 2.5V, and discharge capacity is recorded as C1, C2, C3, C4, C5, C6, C7, respectively.
The number of core pores in table 1 was controlled by adjusting the amount of the template F127 (polyoxyethylene polyoxypropylene ether block copolymer) in the experiment, and the effects in table 1 could be achieved by certain adjustment. To adjust the number of pores, the F127: the ratio of phenols to aldehydes is in the range of (0.3 to 0.6) to (0.8 to 1.2).
Table 1 shows the parameters and evaluation results of each of the anode materials of examples 1 to 10.
Figure BDA0003589591660000131
Note: the core-pore number is the number of pores in the range of 20nm x 20nm and the pore diameter in the range of 2nm to 5nm of the cross section of the core. Shell-pore number 400nm of shell2In the range of (1), the number of pores having a pore diameter in the range of 2nm to 5 nm.
Referring to table 1, examples 1 to 6 show the effect of the number of pores of 2nm to 5nm in the range of 20nm × 20nm in the cross section of the core body of the anode material on the performance. As can be seen from table 1, when the core-pore number is more than 100 (comparative example 2), the values of C7/C1 and D7/D1 are small, which indicates that the negative electrode material has poor performance of rapid lithium intercalation and rapid lithium deintercalation, and when the core-pore number is less than 5 (comparative example 1), the negative electrode material has a large difference in gram capacity compared to the examples, although C7/C1 and D7/D1 are not greatly different and the overall electrochemical performance is low, and therefore, when the core-pore number is 5 to 100, the performance is good.
Since the pores in the core body have a lithium storage function, the gram capacity of the anode material is lower in the case where the number of the core body-pores is 5 than in the case where the number of the core body-pores is 50, and the influence of the number of the pores in the core body of the anode material on the gram capacity of the anode material is reflected here, that is, the higher the number of the pores is, the higher the gram capacity is, and examples 5 and 6 show that the number of the pores continues to increase, which is advantageous for the capacity.
Comparative example 1 shows that the core has a small pore structure, the material capacity is low, and comparative example 2 has a core body with too many pores to a certain extent to form a supercapacitor-like negative electrode structure, so that the overall first effect of the material is reduced, and the lithium removal voltage platform is high, which is not beneficial to application. And the porosity performance is degraded.
Table 2 shows the parameters and evaluation results of each of the anode materials of examples 7 to 10.
Figure BDA0003589591660000141
As shown in examples 7 to 10 in table 2, the first effect decreases with the increase in the number of shell-pores, the number of shell-pores increases, the specific surface area of the shell of the negative electrode material increases, the electrolyte easily enters the core body to react with the core body, the side reaction between the negative electrode material and the electrolyte increases, and the first effect and the gram volume are affected. The number of the shell layers is controlled mainly by controlling a temperature rise program, so that the component volatilization process in the material combustion process is controlled, and the number of the shell layer holes with different materials is obtained.
In Table 3, the shell variation is obtained by adjusting the concentration of the fourth mixed material, the higher the concentration is, the thicker the shell is, wherein the concentration is controlled to be in the range of 0.1mol/L to 20 mol/L.
Table 3 shows the parameters and evaluation results of each of the anode materials of examples 11 to 20.
Figure BDA0003589591660000142
Referring to table 3, as shown in examples 11 to 15, under the condition that the shell thicknesses of the negative electrode materials are different, the first effect of the negative electrode material is affected, and under the condition that the shell of the negative electrode material is thin, part of the core layer pore structure is exposed due to the fact that the shell is difficult to be uniformly coated, the specific surface area of the negative electrode material is increased, the first effect of the negative electrode material is low, and the first effect of the negative electrode material is improved as the shell thickness of the negative electrode material is increased, but the shell thickness of the negative electrode material is increased, the core layer lithium storage space is reduced, and the capacity is weakened to a certain extent, so that the capacity and the first effect need to be combined, and the shell thickness needs to be in an appropriate range.
From examples 15 to 19, it can be seen that when the particle size Dv50 of the negative electrode material is small, the specific surface area is increased, which affects the overall first effect of the negative electrode material, while when the particle size Dv50 of the negative electrode material is too large, the specific surface area is reduced, the lithium intercalation channel is reduced, and the particle size is too large, which affects the diffusion of ions in the negative electrode active material layer to a certain extent, thereby reducing the rate capability of the negative electrode material and affecting the capability of rapid lithium deintercalation.
Table 4 shows the results of different evaluations of the electrolyte compositions of the lithium ion batteries of examples 20 to 23.
Figure BDA0003589591660000151
Note: LiFSI molar mass of 187.07g/mol, LiPF6The molar mass was 151.91 g/mol.
In table 4, the anode materials used in examples 20 to 23 were the anode materials used in example 3. By comparing example 20 with examples 21 to 23, it is known that the cycle and expansion performance of the lithium ion battery can be effectively improved by adding LiFSI (lithium bis (fluorosulfonyl) imide) to the electrolyte, which can act as the porous negative electrode material of the present invention.
The above description is only a preferred embodiment of the application and is illustrative of the principles of the technology employed. It will be appreciated by those skilled in the art that the scope of the disclosure herein is not limited to the particular combination of features described above, but also encompasses other combinations of features described above or equivalents thereof. For example, the above features and the technical features having similar functions disclosed in the present application are mutually replaced to form the technical solution.

Claims (10)

1. A negative electrode material, characterized in that,
the particles of the negative electrode material comprise a core body and a shell layer;
the number of pores having a pore diameter in the range of 0.4nm to 5nm is 5 to 100 in the range of 20nm x 20nm of the cross section of the core body.
2. The anode material according to claim 1, wherein the number of pores having a pore diameter in a range of 2nm to 5nm is 5 to 50 in a range of 20nm x 20nm of a cross section of the core body.
3. The anode material according to claim 1, wherein the anode material comprises a carbon material.
4. The anode material of claim 1, wherein the shell layer is on the surface of the core body, and wherein the shell layer is analyzed by transmission electron microscopy at 400nm2The number of pores with a pore diameter in the range of 2nm to 5nm is less than 5 in the range of area.
5. The anode material according to claim 1, wherein at least one of the following (a) to (c) is satisfied:
(a) the thickness of the shell layer is 10nm to 200 nm;
(b) the interplanar spacing of the microchip layer of the shell layer is 0.36nm to 0.4 nm;
(c) the shell layer includes amorphous carbon.
6. The anode material according to claim 1, wherein at least one of (d) to (h) shown below is satisfied:
(d) at least one peak is provided at positions of 285.4 +/-0.3 eV, 287.8 +/-0.3 eV and 288.9 +/-0.3 eV in a photoelectron spectrum of the anode material;
(e) the specific surface area of the negative electrode material is 2m2G to 10m2/g；
(f) The powder conductivity of the negative electrode material is 1 x 10-06Mu S/cm to 9X 10-08μS/cm；
(g) In an X-ray diffraction pattern of the negative electrode material, a diffraction peak is arranged between 18 degrees and 30 degrees, and the half-peak width of the diffraction peak is 4 degrees to 10 degrees;
(h) the ratio I of the peak intensity of the G peak to the peak intensity of the D peak in the Raman spectrum of the anode materialG/IDIs 0.6 to 1.
7. The anode material according to claim 1, wherein at least one of (i) to (k) shown below is satisfied:
(i) the Dv10 of the negative electrode material is 1 μm to 5 μm;
(g) the Dv50 of the negative electrode material is 4 μm to 15 μm;
(k) the Dv90 of the negative electrode material is 13 μm to 30 μm.
8. An electrochemical device, comprising:
a positive electrode, a negative electrode, an electrolyte and a separator;
the anode includes an anode current collector and an anode active material layer on the anode current collector, the anode active material layer including the anode material according to any one of claims 1 to 7.
9. The electrochemical device according to claim 8, wherein at least one of the following (l) to (n) is satisfied:
(l) The resistance of the negative electrode is 10m omega to 60m omega;
(m) the electrolyte comprises at least one of fluoroether, fluoroethylene carbonate or ether nitrile;
(n) the electrolyte includes a lithium salt including lithium bis (fluorosulfonyl) imide and lithium hexafluorophosphate, the lithium salt having a concentration of 1 to 2mol/L, and a mass ratio of lithium bis (fluorosulfonyl) imide to lithium hexafluorophosphate being 0.06 to 5.
10. An electronic device comprising the electrochemical device according to claim 8 or 9.
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