WO2024239691A1 - 负极材料、负极极片及制备方法、储能装置和用电装置 - Google Patents

负极材料、负极极片及制备方法、储能装置和用电装置 Download PDF

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WO2024239691A1
WO2024239691A1 PCT/CN2024/073414 CN2024073414W WO2024239691A1 WO 2024239691 A1 WO2024239691 A1 WO 2024239691A1 CN 2024073414 W CN2024073414 W CN 2024073414W WO 2024239691 A1 WO2024239691 A1 WO 2024239691A1
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negative electrode
hard carbon
present application
porous
electrode material
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French (fr)
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林颖鑫
王铈汶
谌庆春
朱开达
张敏
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Xiamen Hithium Energy Storage Technology Co Ltd
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Xiamen Hithium Energy Storage Technology Co Ltd
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Priority to EP24809941.8A priority Critical patent/EP4712170A1/en
Publication of WO2024239691A1 publication Critical patent/WO2024239691A1/zh
Priority to US19/393,603 priority patent/US20260070790A1/en
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • 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
    • H01M4/04—Processes of manufacture in general
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/14—Pore volume
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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

Definitions

  • the present application belongs to the field of batteries, and specifically, relates to negative electrode materials, negative electrode plates and preparation methods, energy storage devices and power consumption devices.
  • hard carbon Compared with graphite negative electrode, hard carbon has a rich disordered structure and a large interlayer spacing, which can accelerate ion diffusion and is considered to be a very promising battery negative electrode material.
  • hard carbon materials have low first-week charge and discharge efficiency, low capacity and poor rate characteristics, which hinder the development of hard carbon materials in the battery field.
  • hard carbon is coated with soft carbon to cover the micropores on the surface of the hard carbon, thereby reducing its specific surface area and reducing the side reactions between the hard carbon and the electrolyte, thereby improving the first-week charge and discharge efficiency of the battery.
  • the method of coating hard carbon with soft carbon will reduce the active sites of ions (such as sodium ions), resulting in a decrease in battery capacity.
  • ions such as sodium ions
  • atoms such as phosphorus, nitrogen, and sulfur are doped into hard carbon materials to improve the capacity and rate performance of hard carbon materials, but this method will reduce the first-week charge and discharge efficiency of the battery.
  • the present application aims to solve at least one of the technical problems in the related art to a certain extent.
  • one purpose of the present application is to propose a negative electrode material, a negative electrode sheet and a preparation method, an energy storage device and an electric device, wherein the negative electrode material has a high capacity and first-cycle charge and discharge efficiency, and has good kinetic performance, which is conducive to taking into account the energy density, rate performance and cycle performance of the battery.
  • the present application provides a negative electrode material.
  • the negative electrode material includes hard carbon, the hard carbon has a porous structure, and the hard carbon satisfies: 0.32 ⁇ Dv50/1000V ⁇ 2.40, wherein the unit of Dv50 of the hard carbon is ⁇ m, and the total volume of pores in the hard carbon is V, and the unit is cm 3 /g.
  • the hard carbon having a porous structure is included, and the ratio of the Dv50 of the hard carbon particles to the total volume of the porous hard carbon is controlled within the above range to achieve matching between the particle size of the hard carbon material and the porous structure. It is not only beneficial to the storage of ions (such as sodium ions, etc.), and improves the capacity of hard carbon materials, but also beneficial to the transmission of ions (such as sodium ions, etc.), and accelerates the kinetics of ion diffusion.
  • ions such as sodium ions, etc.
  • the present application proposes a negative electrode plate.
  • the negative electrode plate includes a negative electrode active material layer, and the negative electrode active material layer includes the above-mentioned negative electrode material.
  • the present application proposes a method for preparing the above-mentioned negative electrode material. According to an embodiment of the present application, the method comprises:
  • this method can be used to prepare the above-mentioned negative electrode material with high capacity and first-cycle charge and discharge efficiency and good kinetic performance, which is beneficial to taking into account the energy density, rate performance and cycle performance of the battery.
  • the present application proposes a method for preparing the above-mentioned negative electrode sheet.
  • a negative electrode active slurry is applied to at least one side of a current collector to obtain a negative electrode sheet, wherein the negative electrode active slurry includes the above-mentioned negative electrode material or the negative electrode material obtained by the above-mentioned method.
  • This method not only has a simple preparation process and is conducive to industrial production, but also can obtain a negative electrode sheet with higher capacity, first-cycle charge and discharge efficiency and better kinetic performance.
  • the present application proposes an energy storage device.
  • the energy storage device includes the above-mentioned negative electrode plate. Compared with the prior art, the energy storage device has better comprehensive performance and can have higher energy density, better rate performance and cycle performance.
  • the present application proposes an electric device.
  • the electric device includes the above energy storage device, and compared with the prior art, the electric device has a longer battery life and battery life, and has a higher market satisfaction.
  • FIG. 1 is a flow chart of a method for preparing a negative electrode material according to one embodiment of the present application.
  • a negative electrode material in a first aspect of the present application, includes hard carbon, the hard carbon has a porous structure, and the hard carbon satisfies: 0.32 ⁇ Dv50/1000V ⁇ 2.40, wherein the unit of Dv50 of the hard carbon is ⁇ m, and the total volume of pores in the hard carbon is V, and the unit is cm 3 /g.
  • the negative electrode material of the above-mentioned embodiment of the present application includes hard carbon with a porous structure, and at the same time, the ratio of Dv50 of the hard carbon particles to the total volume of the pores in the hard carbon is controlled within the above-mentioned range to achieve matching between the particle size and the porous structure of the hard carbon material.
  • This is not only beneficial to the storage of ions (such as sodium ions, etc.) and improving the capacity of the hard carbon material, but also beneficial to the transmission of ions (such as sodium ions, etc.) and accelerating the ion diffusion dynamics.
  • the particle size and porous volume of the hard carbon do not match, for example, when the total porous volume corresponding to the hard carbon material with large particle size is small, it is not conducive to the diffusion and transmission of ions, affecting the kinetic properties of the porous hard carbon, and causing the rate performance of the battery to decrease; when the total porous volume corresponding to the hard carbon material with small particle size is large, the contact area between the porous hard carbon and the electrolyte will be increased, causing the side reactions between the hard carbon and the electrolyte to increase, affecting the first-week charge and discharge efficiency and cycle performance of the battery.
  • the present application controls the Dv50 of the hard carbon and the total porous volume V to satisfy the above relationship, so that the negative electrode material can have a higher capacity and first-week charge and discharge efficiency, and at the same time have better kinetic performance, which is beneficial to taking into account the energy density, rate performance and cycle performance of the battery.
  • the negative electrode material in the present application may include only the above-mentioned hard carbon, or may include other negative electrode materials, such as graphite, etc., wherein, based on the total mass of the negative electrode material, the mass proportion of hard carbon in the negative electrode material may be not less than 50wt%, for example, not less than 60wt%, not less than 70wt%, not less than 80wt%, not less than 85wt%, not less than 90wt% or not less than 95wt%, etc.
  • the Dv50 of the hard carbon and the total volume V of the porous hard carbon can satisfy 0.42 ⁇ Dv50/1000V ⁇ 1.44, for example, Dv50/1000V can be 0.6, 0.8, 1.0, 1.2, 1.4, etc., which is more conducive to ensuring that the negative electrode material has both high capacity, first cycle charge and discharge efficiency and good kinetic performance, and can be further improved. Improve the energy density, rate performance and cycle performance of the battery in one step.
  • the Dv50 of the hard carbon can be 5 ⁇ m-18 ⁇ m, for example, it can be 6 ⁇ m, 8 ⁇ m, 10 ⁇ m, 13 ⁇ m, 15 ⁇ m or 17 ⁇ m, etc. If the Dv50 of the hard carbon is too small, it is easy to make its specific surface area too large, resulting in an increase in the side reactions between the negative electrode material and the electrolyte, which may increase the irreversible capacity of the battery and affect the first week charge and discharge efficiency and cycle performance of the battery; if the Dv50 of the hard carbon is too large, it is not only easy to slow down the solid phase diffusion of ions (such as sodium ions, etc.) in the hard carbon, increase the internal resistance of the battery, and affect the rate performance of the battery, but also is not conducive to improving the compaction density of the negative electrode active material layer, affecting the energy density of the battery.
  • ions such as sodium ions, etc.
  • the present application controls the Dv50 of the hard carbon within the above range, which is conducive to taking into account the energy density, rate performance and cycle performance of the battery. Furthermore, the Dv50 of the hard carbon can be 5 ⁇ m-14 ⁇ m, which is conducive to further improving the energy density of the battery. It should be noted that Dv50 herein refers to the particle size corresponding to when the cumulative volume distribution number of hard carbon reaches 50%.
  • the total volume V of the porous structure in the hard carbon can be 0.005 cm 3 /g-0.022 cm 3 /g, for example, it can be 0.006 cm 3 /g, 0.01 cm 3 /g, 0.015 cm 3 /g, 0.018 cm 3 /g or 0.02 cm 3 /g, etc.
  • the total volume of the porous structure in the hard carbon is too large, it is easy to increase the side reactions between the negative electrode material and the electrolyte, thereby reducing the first-week charge and discharge efficiency and cycle performance of the negative electrode sheet; if the total volume of the porous structure in the hard carbon is too small, it may reduce the number of ion active sites in the negative electrode material, affecting the capacity of the negative electrode sheet.
  • the present application controls the total volume V of the porous structure in the hard carbon within the above range, which is beneficial to taking into account the energy density, first-week charge and discharge efficiency and cycle performance of the battery.
  • the total volume V of the porous hard carbon can be 0.008 cm 3 /g-0.016 cm 3 /g, thereby further ensuring that the battery has a high energy density, first-cycle charge and discharge efficiency, and good cycle performance. It should be noted that the total volume V of the porous hard carbon can be obtained by nitrogen adsorption and desorption testing, and the isothermal adsorption and desorption curve is obtained to obtain the total adsorption pore volume when the relative pressure P/P 0 is 0.99, which is the total volume V of the porous hard carbon.
  • the average pore size of the hard carbon can be 3nm-10nm, for example, 3nm, 5nm, 7nm or 9nm, etc. If the average pore size of the hard carbon is too small, it will affect the transmission of ions, reduce the kinetic performance of the hard carbon, and affect the rate performance of the battery; if the average pore size of the hard carbon is too large, it will lead to the metallic property of the deposited sodium to be enhanced, bringing the risk of short circuit to the battery, and the excessive pore size will reduce the specific surface area of the material, resulting in a reduction in the sodium storage capacity.
  • the present application controls the average pore size of the porous in the hard carbon within the above range, which is conducive to taking into account the energy density and rate performance of the battery. It should be noted that the average pore size of the hard carbon can be tested by the nitrogen adsorption and desorption method, and the isothermal adsorption and desorption curve is obtained to obtain the adsorption average pore size, which is the average pore size of the porous in the hard carbon.
  • the present application proposes a method for preparing the above-mentioned negative electrode material.
  • the method includes:
  • a hard carbon precursor is mixed with a pore former so that a uniformly distributed porous structure is introduced into the hard carbon through the decomposition of the pore former during the subsequent carbonization process.
  • the mixing ratio of the hard carbon precursor and the pore former can be 1: (0.02-0.2), for example, it can be 1/0.05, 1/0.1 or 1/0.15, etc.
  • the amount of the pore former is too much, the number of pores formed is too large and the total volume of the pores is too large, which will lead to the enhancement of the metallic properties of the deposited sodium and bring the risk of short circuit to the battery; if the amount of the pore former is too little, the number of pores formed is small and the total volume of the pores is too small, which is not conducive to ion transport and reduces the kinetic properties of the hard carbon. It should be noted that there is no particular restriction on the specific types of hard carbon precursors and pore formers in the present application, and those skilled in the art can flexibly choose according to actual conditions.
  • the hard carbon precursor may include but is not limited to phenolic resin, biomass, etc.
  • the pore former may include but is not limited to inorganic salts, such as at least one of sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, and calcium bicarbonate.
  • the dispersion of the hard carbon precursor is dried and then carbonized, so that the hard carbon precursor is pyrolyzed to obtain hard carbon, and the pore-forming agent is also thermally decomposed to form a porous structure inside the hard carbon.
  • the carbonization treatment can be carried out under a protective atmosphere, and the temperature of the carbonization treatment can be 900°C-1100°C, for example, 920°C, 960°C, 1000°C, 1050°C, etc.
  • the heating rate can be 0.5°C/min-10°C/min, for example, 1°C/min, 3°C/min, 5°C/min, 7°C/min or 8°C/min, etc., thereby facilitating the acquisition of a porous structure having the above-mentioned particle size matching the hard carbon.
  • the carbonization treatment can be carried out under nitrogen and/or an inert atmosphere.
  • the hard carbon material obtained after carbonization treatment is washed, crushed and sieved in sequence to achieve matching of the particle size and porous structure of the hard carbon material, so that the Dv50 of the hard carbon and the total porous volume V of the hard carbon satisfy 0.32 ⁇ Dv50/1000V ⁇ 2.40, so that the hard carbon meets a higher capacity and first-cycle charge and discharge efficiency, and at the same time has better kinetic performance, which is beneficial to taking into account the energy density, rate performance and cycle performance of the battery.
  • this method not only has a simple preparation process and is conducive to industrial production, but also can obtain negative electrode materials with higher capacity, first-cycle charge and discharge efficiency and better kinetic performance.
  • the present application proposes a negative electrode plate.
  • the negative electrode plate includes a negative electrode active material layer, and the negative electrode active material layer includes the above-mentioned negative electrode material or the negative electrode material obtained by the above-mentioned method.
  • the battery loaded with the negative electrode plate has good energy density, rate performance and first-cycle charge and discharge efficiency.
  • the porosity of the negative electrode active material layer can be 28%-40%, for example, 30%, 32%, 34%, 36% or 38%, etc.
  • the porosity of the negative electrode active material layer will affect the infiltration of the electrolyte into the negative electrode sheet.
  • the wetting and liquid retention capacity of the negative electrode active material layer will affect the transmission of ions.
  • the porosity of the negative electrode active material layer is too large, the side reactions during the formation and circulation process will be aggravated, affecting the long-cycle performance of the battery; if the porosity of the negative electrode active material layer is too small, it will affect the wetting effect of the electrolyte in the negative electrode plate, and at the same time, the liquid retention amount will decrease, which will easily increase the resistance to ion transmission and affect the battery's cycle performance and kinetic performance.
  • the present application helps to improve the wetting effect of the electrolyte in the negative electrode plate and reduce the transmission resistance of sodium ions by controlling the porosity of the negative electrode active material layer within the above range, thereby helping to improve the battery's cycle performance and kinetic performance.
  • the porosity of the negative electrode active material layer can be obtained by mercury intrusion (also known as “mercury intrusion") testing, and the specific reference standard is GB/T 21650.1-2008 Mercury intrusion and gas adsorption method for determination of pore size distribution and porosity of solid materials Part 1: Mercury intrusion.
  • the negative electrode active material layer may further include: a binder and/or a conductive agent.
  • the amount of the negative electrode material may be 90 parts by weight to 98 parts by weight, for example, 95.5 parts by weight, etc.
  • the amount of the binder may be 0.5 parts by weight to 5 parts by weight, for example, 1.5 parts by weight, etc.
  • the amount of the conductive agent may be 1 part by weight to 5 parts by weight, for example, 3 parts by weight, etc. It should be noted that there is no particular restriction on the specific types of the binder and the conductive agent in the present application, and those skilled in the art may flexibly select them according to actual conditions.
  • the binder may include at least one of styrene-butadiene rubber, polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, polyacrylonitrile, polyacrylic acid, polyacrylate, carboxymethyl cellulose, and sodium alginate;
  • the conductive agent may include at least one of acetylene black, Super-P, carbon nanotubes, carbon fibers, and graphene.
  • the present application proposes a method for preparing the above-mentioned negative electrode sheet.
  • a negative electrode active slurry is applied to at least one side of the current collector to obtain a negative electrode sheet, wherein the negative electrode active slurry includes the above-mentioned negative electrode material.
  • This method not only has a simple preparation process and is conducive to industrial production, but also can obtain a negative electrode sheet with high capacity, first-week charge and discharge efficiency and good kinetic performance.
  • the current collector may include at least one of copper foil, stainless steel foil, copper alloy foil, carbon-coated copper foil, aluminum foil, and carbon-coated aluminum foil.
  • the present application proposes an energy storage device.
  • the energy storage device includes the above-mentioned negative electrode plate.
  • the energy storage device has better comprehensive performance and can have higher energy density, better rate performance and cycle performance.
  • the energy storage device can be a battery
  • the battery can include a positive electrode plate, a separator and an electrolyte, wherein the positive electrode plate includes a positive electrode active material layer, and the positive electrode active material layer can include a positive electrode active material, a binder and a conductive agent.
  • the positive electrode active material, the binder and the conductive agent in the positive electrode active material layer are there is no particular restriction on the specific types of, for example, for sodium ion batteries, the positive electrode active material may include at least one of transition metal oxides, polyanionic compounds, organic polymers, and Prussian blue materials; the present application has no particular restriction on the specific composition of the diaphragm, for example, the diaphragm may include at least one of polypropylene (PP), polyethylene (PE), and ceramic diaphragms; the electrolyte may include electrolyte salts and organic solvents, wherein the specific types and compositions of the electrolyte salts and organic solvents are not particularly limited, and those skilled in the art may select according to actual needs.
  • the positive electrode active material may include at least one of transition metal oxides, polyanionic compounds, organic polymers, and Prussian blue materials
  • the present application has no particular restriction on the specific composition of the diaphragm, for example, the diaphragm may include at least one
  • the present application proposes an electric device.
  • the electric device includes the above energy storage device, and compared with the prior art, the electric device has a longer battery life and battery life, and has a higher market satisfaction.
  • Porous hard carbon, conductive carbon black, sodium hydroxymethyl cellulose and styrene-butadiene rubber are mixed in a mass ratio of 95.5:1.5:1:2, the mixed powder is placed in a vacuum mixer, deionized water is added and stirred to obtain a negative electrode active slurry; the negative electrode slurry is evenly coated on the opposite sides of the negative electrode current collector to form a negative electrode active material layer, the negative electrode current collector coated with the negative electrode active slurry is transferred to an oven for drying, and then rolled and cut to obtain a negative electrode sheet, wherein the porosity of the negative electrode active material layer is 32%;
  • Ethylene carbonate (EC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) are mixed in a volume ratio of 1:1:1 to obtain a mixed solution, and dry sodium salt NaPF 6 is added to the mixed solution to prepare an electrolyte with a concentration of 1 mol/L. adding 2 wt % of fluoroethylene carbonate (FEC) additive to obtain an electrolyte;
  • the positive electrode sheet, negative electrode sheet and polypropylene separator are stacked in order so that the separator is between the positive and negative electrode sheets, and then wound to obtain a bare cell.
  • the bare cell is placed in an aluminum-plastic film soft package, and the electrolyte is injected after drying. After vacuum packaging, standing, forming, shaping and other processes, a secondary battery is obtained.
  • step (1) the coconut shell powder treated before crushing is mixed with potassium bicarbonate solution, wherein the mass ratio of coconut shell powder to potassium bicarbonate is 1:0.09, to obtain a dispersion of hard carbon precursor; the dispersion of hard carbon precursor is placed in a vacuum oven and dried for 20 hours, and then heated to 1100°C at a heating rate of 4°C/min under nitrogen protection for carbonization treatment to obtain a carbonized product; the carbonized product is crushed, washed with hydrochloric acid and deionized water in turn, dried, and then sieved and demagnetized to obtain porous hard carbon, wherein the Dv50 of the porous hard carbon is 7 ⁇ m, the pore size of a single pore in the porous hard carbon is 7.3nm, the total porous volume V is 0.010cm3 /g, and the Dv50/1000V is 0.7.
  • step (1) the coconut shell powder treated before crushing is mixed with potassium bicarbonate solution, wherein the mass ratio of coconut shell powder to potassium bicarbonate is 1:0.15, to obtain a dispersion of hard carbon precursor; the dispersion of hard carbon precursor is placed in a vacuum oven and dried for 20 hours, and then heated to 1100°C at a heating rate of 2°C/min under nitrogen protection for carbonization treatment to obtain a carbonized product; the carbonized product is crushed, washed with hydrochloric acid and deionized water in turn, dried, and then sieved and demagnetized to obtain porous hard carbon, wherein the Dv50 of the porous hard carbon is 7 ⁇ m, the pore size of a single pore in the porous hard carbon is 3.8nm, the total porous volume V is 0.022cm3 /g, and the Dv50/1000V is 0.32.
  • step (1) the coconut shell powder treated before crushing is mixed with potassium bicarbonate solution, wherein the mass ratio of coconut shell powder to potassium bicarbonate is 1:0.10, to obtain a dispersion of hard carbon precursor; the dispersion of hard carbon precursor is placed in a vacuum oven and dried for 20 hours, and then heated to 1100°C at a heating rate of 3°C/min under nitrogen protection for carbonization treatment to obtain a carbonized product; the carbonized product is crushed, washed with hydrochloric acid and deionized water in turn, dried, and then sieved and demagnetized to obtain porous hard carbon, wherein the Dv50 of the porous hard carbon is 5 ⁇ m, the pore size of a single pore in the porous hard carbon is 6.4nm, the total porous volume V is 0.012cm3 /g, and the Dv50/1000V is 0.42.
  • step (1) the coconut shell powder treated before crushing is mixed with a potassium bicarbonate solution, wherein the mass ratio of the coconut shell powder to the potassium bicarbonate is 1:0.08, to obtain a dispersion of a hard carbon precursor; the dispersion of the hard carbon precursor is placed in a vacuum oven and dried for 20 hours, and then heated to 1100°C at a heating rate of 4°C/min under nitrogen protection to obtain a carbonized product; the carbonized product is crushed, washed with hydrochloric acid and deionized water, and dried in turn.
  • a potassium bicarbonate solution wherein the mass ratio of the coconut shell powder to the potassium bicarbonate is 1:0.08, to obtain a dispersion of a hard carbon precursor
  • the dispersion of the hard carbon precursor is placed in a vacuum oven and dried for 20 hours, and then heated to 1100°C at a heating rate of 4°C/min under nitrogen protection to obtain a carbonized product
  • the carbonized product is crushed, washed with hydrochloric acid and deionized
  • the porous hard carbon was obtained through screening and demagnetization, wherein the Dv50 of the porous hard carbon was 9 ⁇ m, the pore size of a single pore in the porous hard carbon was 7.6 nm, the total porous volume V was 0.009 cm 3 /g, and the Dv50/1000V was 1.0.
  • step (1) the coconut shell powder treated before crushing is mixed with potassium bicarbonate solution, wherein the mass ratio of coconut shell powder to potassium bicarbonate is 1:0.08, to obtain a dispersion of hard carbon precursor; the dispersion of hard carbon precursor is placed in a vacuum oven and dried for 20 hours, and then heated to 1100°C at a heating rate of 5°C/min under nitrogen protection for carbonization treatment to obtain a carbonized product; the carbonized product is crushed, washed with hydrochloric acid and deionized water in turn, dried, and then sieved and demagnetized to obtain porous hard carbon, wherein the Dv50 of the porous hard carbon is 13 ⁇ m, the pore size of a single pore in the porous hard carbon is 8.1nm, the total porous volume V is 0.009cm3 /g, and the Dv50/1000V is 1.44.
  • step (1) the coconut shell powder treated before crushing is mixed with potassium bicarbonate solution, wherein the mass ratio of coconut shell powder to potassium bicarbonate is 1:0.06, to obtain a dispersion of hard carbon precursor; the dispersion of hard carbon precursor is placed in a vacuum oven and dried for 20 hours, and then heated to 1100°C at a heating rate of 5°C/min under nitrogen protection for carbonization treatment to obtain a carbonized product; the carbonized product is crushed, washed with hydrochloric acid and deionized water in turn, dried, and then sieved and demagnetized to obtain porous hard carbon, wherein the Dv50 of the porous hard carbon is 14 ⁇ m, the pore size of a single pore in the porous hard carbon is 8.3nm, the total porous volume V is 0.006cm3 /g, and the Dv50/1000V is 2.33.
  • step (2) commercially available hard carbon is used as the negative electrode active material, and the Dv50 of the hard carbon is 8 ⁇ m.
  • step (1) the coconut shell powder treated before crushing is mixed with potassium bicarbonate solution, wherein the mass ratio of coconut shell powder to potassium bicarbonate is 1:0.24, to obtain a dispersion of hard carbon precursor; the dispersion of hard carbon precursor is placed in a vacuum oven and dried for 20 hours, and then heated to 1100°C at a heating rate of 2°C/min under nitrogen protection for carbonization treatment to obtain a carbonized product; the carbonized product is crushed, washed with hydrochloric acid and deionized water in turn, dried, and then sieved and demagnetized to obtain porous hard carbon, wherein the Dv50 of the porous hard carbon is 6 ⁇ m, the pore size of a single pore in the porous hard carbon is 3.2nm, the total porous volume V is 0.021cm3 /g, and the Dv50/1000V is 0.29.
  • step (1) the coconut shell powder treated before crushing is mixed with a potassium bicarbonate solution, wherein the mass ratio of the coconut shell powder to the potassium bicarbonate is 1:0.05, to obtain a dispersion of a hard carbon precursor; the dispersion of the hard carbon precursor is placed in a vacuum oven and dried for 20 hours, and then heated to 1100° C. at a heating rate of 5° C./min under nitrogen protection.
  • the carbonized product was carbonized and crushed, washed with hydrochloric acid and deionized water, dried, sieved and demagnetized to obtain porous hard carbon, wherein the Dv50 of the porous hard carbon was 16 ⁇ m, the pore size of a single pore in the porous hard carbon was 9.2 nm, the total porous volume V was 0.006 cm 3 /g, and the Dv50/1000V was 2.67.
  • step (1) the coconut shell powder treated before crushing is mixed with potassium bicarbonate solution, wherein the mass ratio of coconut shell powder to potassium bicarbonate is 1:0.16, to obtain a dispersion of hard carbon precursor; the dispersion of hard carbon precursor is placed in a vacuum oven and dried for 20 hours, and then heated to 1100°C at a heating rate of 3°C/min under nitrogen protection for carbonization treatment to obtain a carbonized product; the carbonized product is crushed, washed with hydrochloric acid and deionized water in turn, dried, and then sieved and demagnetized to obtain porous hard carbon, wherein the Dv50 of the porous hard carbon is 4 ⁇ m, the pore size of a single pore in the porous hard carbon is 4.5nm, the total porous volume V is 0.016cm3 /g, and the Dv50/1000V is 0.25.
  • step (1) the coconut shell powder treated before crushing is mixed with a potassium bicarbonate solution, wherein the mass ratio of coconut shell powder to potassium bicarbonate is 1:0.09, to obtain a dispersion of a hard carbon precursor; the dispersion of the hard carbon precursor is placed in a vacuum oven and dried for 20 hours, and then heated to 1100°C at a heating rate of 5°C/min under nitrogen protection for carbonization treatment to obtain a carbonized product; the carbonized product is crushed, washed with hydrochloric acid and deionized water in turn, dried, and then sieved and demagnetized to obtain porous hard carbon, wherein the Dv50 of the porous hard carbon is 20 ⁇ m, the pore size of a single pore in the porous hard carbon is 8.3nm, the total porous volume V is 0.007cm3 /g, and the Dv50/1000V is 2.86.
  • step (1) the coconut shell powder treated before crushing is mixed with potassium bicarbonate solution, wherein the mass ratio of coconut shell powder to potassium bicarbonate is 1:0.30, to obtain a dispersion of hard carbon precursor; the dispersion of hard carbon precursor is placed in a vacuum oven and dried for 20 hours, and then heated to 1100°C at a heating rate of 2°C/min under nitrogen protection for carbonization treatment to obtain a carbonized product; the carbonized product is crushed, washed with hydrochloric acid and deionized water in turn, dried, and then sieved and demagnetized to obtain porous hard carbon, wherein the Dv50 of the porous hard carbon is 7 ⁇ m, the pore size of a single pore in the porous hard carbon is 2.4nm, the total porous volume V is 0.027cm3 /g, and the Dv50/1000V is 0.26.
  • step (1) the coconut shell powder treated before crushing is mixed with a potassium bicarbonate solution, wherein the mass ratio of coconut shell powder to potassium bicarbonate is 1:0.03, to obtain a dispersion of a hard carbon precursor; the dispersion of the hard carbon precursor is placed in a vacuum oven and dried for 20 hours, and then heated to 1100°C at a heating rate of 6°C/min under nitrogen protection for carbonization treatment to obtain a carbonized product; the carbonized product is crushed, washed with hydrochloric acid and deionized water in turn, dried, and then sieved and demagnetized to obtain a porous hard carbon, wherein the Dv50 of the porous hard carbon is 15 ⁇ m, and the single pore in the porous hard carbon is The pore diameter is 11.7 nm, the total porous volume V is 0.004 cm 3 /g, and the Dv50/1000V is 3.75.
  • Energy density Weigh the battery using an electronic balance at 25°C. Charge and discharge the battery at a rate of 1.5C at 25°C, and record the actual discharge energy. The ratio of the actual discharge energy of the battery to the battery weight is the energy density of the battery.
  • Cycle performance The battery is charged at a 2C rate and discharged at a 1C rate, and a full charge and discharge cycle test is performed. The battery capacity retention rate after 1,000 cycles is recorded to characterize the battery's cycle performance.
  • Kinetic performance At 25°C, the battery is fully charged at nC and fully discharged at 1C. After repeating the charge and discharge cycle 10 times, the battery is charged to a full state at nC rate (n>0), and then the negative electrode is disassembled and the sodium precipitation on the surface of the negative electrode is observed. Among them, the area of sodium precipitation on the surface of the negative electrode is less than 2%, which is considered to be no sodium precipitation.
  • the sodium precipitation rate means that if there is no sodium precipitation on the surface of the negative electrode, the charging rate is increased from nC by a gradient of 0.1C, and the test is performed again until sodium is precipitated on the surface of the negative electrode. At this time, the charging rate nC minus 0.1C is the maximum charging rate of the battery without sodium precipitation.

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Abstract

负极材料、负极极片及制备方法、储能装置和用电装置。该负极材料包括硬碳，硬碳具有多孔结构，硬碳满足：0.32≤Dv50/1000V≤2.40，其中，硬碳的Dv50的单位为μm，硬碳中多孔的总体积为V，单位为cm 3/g。

Description

负极材料、负极极片及制备方法、储能装置和用电装置 技术领域
本申请属于电池领域，具体而言，涉及负极材料、负极极片及制备方法、储能装置和用电装置。
背景技术
与石墨负极相比，硬碳具有丰富的无序结构，且层间距较大，可加快离子扩散，被认为是十分有前景的电池负极材料，然而硬碳材料的首周充放电效率较低，容量较低和倍率特性不佳，阻碍了硬碳材料在电池领域的发展。
公开内容
本申请主要是基于以下问题和发现提出的：
为了改善硬碳负极活性材料首周充放电效率低，容量低和倍率特性不佳等问题，人们尝试多种方法对硬碳结构进行调整，例如，有通过对硬碳进行软碳包覆，覆盖硬碳表面的微孔，从而降低其比表面积，减少硬碳与电解液的副反应，进而提高电池的首周充放电效率，但软碳包覆硬碳的方式会减少离子(如钠离子等)的活性位点，导致电池容量下降；再例如，有在硬碳材料中掺杂磷、氮、硫等原子，以提高硬碳材料的容量和倍率性能，但该方法会降低电池首周充放电效率。
本申请旨在至少在一定程度上解决相关技术中的技术问题之一。为此，本申请的一个目的在于提出负极材料、负极极片及制备方法、储能装置和用电装置，该负极材料具有较高的容量和首周充放电效率，同时具有较好的动力学性能，有利于兼顾电池的能量密度、倍率性能和循环性能。
在本申请的第一个方面，本申请提出了一种负极材料。根据本申请的实施例，所述负极材料包括硬碳，所述硬碳具有多孔结构，所述硬碳满足：0.32≤Dv50/1000V≤2.40，其中，所述硬碳的Dv50的单位为μm，所述硬碳中多孔的总体积为V，单位为cm3/g。
根据本申请上述实施例的负极材料，包括具有多孔结构的硬碳，同时控制硬碳颗粒的Dv50与硬碳中多孔的总体积之比在上述范围，以实现硬碳材料的粒径和多孔结构相匹配， 不仅有利于离子(如钠离子等)的存储，提高硬碳材料的容量，还有利于实现离子(如钠离子等)的传输，加快离子扩散动力学。当硬碳的粒径和多孔体积不匹配时，如大粒径的硬碳材料对应的多孔总体积较小时，不利于离子的扩散与传输，影响多孔硬碳的动力学性能，导致电池的倍率性能下降；如小粒径的硬碳材料对应的多孔总体积较大时，则会增大多孔硬碳与电解液的接触面积，使得硬碳与电解液的副反应增多，影响电池的首周充放电效率和循环性能，本申请通过控制硬碳的Dv50与多孔的总体积V满足上述关系，可以使负极材料具有较高的容量和首周充放电效率，同时具有较好的动力学性能，有利于兼顾电池的能量密度、倍率性能和循环性能。
在本申请的第二个方面，本申请提出了一种负极极片。根据本申请的实施例，该负极极片包括负极活性物质层，所述负极活性物质层包括上述负极材料。由此，装载该负极极片的电池具有较好的能量密度、倍率性能和库伦效率。
在本申请的第三个方面，本申请提出了一种制备上述所述负极材料的方法。根据本申请的实施例，该方法包括：
(1)将硬碳前驱体与造孔剂混合，得到所述硬碳前驱体的分散液；
(2)将所述硬碳前驱体的分散液干燥后进行碳化处理，洗涤、粉碎、筛分得到所述负极材料。
由此，采用该方法可以制备得到上述具有较高的容量和首周充放电效率，同时具有较好的动力学性能的负极材料，有利于兼顾电池的能量密度、倍率性能和循环性能。
在本申请的第四个方面，本申请提出了一种制备上述负极极片的方法。根据本申请的实施例，将负极活性浆料施加在集流体的至少一侧，以便得到负极极片，其中，所述负极活性浆料包括上述的负极材料或采用上述方法得到的负极材料。该方法不仅制备工艺简单，有利于工业化生产，而且可以得到具有较高的电容量、首周充放电效率和较好的动力学性能的负极极片。
在本申请的第五个方面，本申请提出了一种储能装置。根据本申请的实施例，该储能装置包括上述负极极片，与现有技术相比，该储能装置综合性能较好，能够兼具较高的能量密度、较好的倍率性能和循环性能。
在本申请的第六个方面，本申请提出了一种用电装置。根据本申请的实施例，该用电装置包括上述储能装置，与现有技术相比，该用电装置的续航时间和电池使用寿命较长，市场满意度较高。
本申请的附加方面和优点将在下面的描述中部分给出，部分将从下面的描述中变得明 显，或通过本申请的实践了解到。
附图说明
本申请的上述和/或附加的方面和优点从结合下面附图对实施例的描述中将变得明显和容易理解，其中：
图1是根据本申请一个实施例的制备负极材料的方法流程图。
具体实施方式
下面详细描述本申请的实施例，所述实施例的示例在附图中示出，其中自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。下面描述的实施例是示例性的，旨在用于解释本申请，而不能理解为对本申请的限制。
在本申请的第一个方面，本申请提出了一种负极材料。根据本申请的实施例，负极材料包括硬碳，硬碳具有多孔结构，硬碳满足：0.32≤Dv50/1000V≤2.40，其中，硬碳的Dv50的单位为μm，硬碳中多孔的总体积为V，单位为cm3/g。
根据本申请上述实施例的负极材料，包括具有多孔结构的硬碳，同时控制硬碳颗粒的Dv50与硬碳中多孔的总体积之比在上述范围，以实现硬碳材料的粒径和多孔结构相匹配，不仅有利于离子(如钠离子等)的存储，提高硬碳材料的容量，还有利于实现离子(如钠离子等)的传输，加快离子扩散动力学。当硬碳的粒径和多孔体积不匹配时，如大粒径的硬碳材料对应的多孔总体积较小时，不利于离子的扩散与传输，影响多孔硬碳的动力学性能，导致电池的倍率性能下降；如小粒径的硬碳材料对应的多孔总体积较大时，则会增大多孔硬碳与电解液的接触面积，使得硬碳与电解液的副反应增多，影响电池的首周充放电效率和循环性能，本申请通过控制硬碳的Dv50与多孔的总体积V满足上述关系，可以使负极材料具有较高的容量和首周充放电效率，同时具有较好的动力学性能，有利于兼顾电池的能量密度、倍率性能和循环性能。需要说明的是，本申请中负极材料可以仅包括上述硬碳，也可以包括其它负极材料，如石墨等，其中，以负极材料的总质量为基准，负极材料中，硬碳的质量占比可以不小于50wt％，例如可以不小于60wt％、不小于70wt％、不小于80wt％、不小于85wt％、不小于90wt％或不小于95wt％等。
根据本申请的实施例，在负极材料中，硬碳的Dv50与硬碳中多孔的总体积V可以满足0.42≤Dv50/1000V≤1.44，例如，Dv50/1000V可以为0.6、0.8、1.0、1.2、1.4等，由此更有利于保证该负极材料兼具较高的容量、首周充放电效率和较好的动力学性能，可以进 一步提高电池的能量密度、倍率性能和循环性能。
根据本申请的实施例，硬碳的Dv50可以为5μm-18μm，例如可以为6μm、8μm、10μm、13μm、15μm或17μm等，若硬碳的Dv50过小，容易使其比表面积过大，导致负极材料与电解液发生的副反应增多，可能使电池的不可逆容量增加，影响电池的首周充放电效率和循环性能；若硬碳的Dv50过大，不仅容易使离子(如钠离子等)在硬碳内部固相扩散的速度减慢，增大电池内阻，影响电池的倍率性能，还不利于提高负极活性物质层的压实密度，影响电池的能量密度。本申请通过控制硬碳的Dv50在上述范围，有利于兼顾电池的能量密度、倍率性能和循环性能。进一步地，硬碳的Dv50可以为5μm-14μm，由此有利于进一步提高电池的能量密度。需要说明的是，在此Dv50是指硬碳的累计体积分布数达到50％时所对应的粒径大小。
根据本申请的实施例，硬碳中多孔的总体积V可以为0.005cm3/g-0.022cm3/g，例如可以为0.006cm3/g、0.01cm3/g、0.015cm3/g、0.018cm3/g或0.02cm3/g等，若硬碳中孔结构的总体积过大，容易使负极材料与电解液的副反应增多，降低负极极片的首周充放电效率和循环性能；若硬碳中孔结构的总体积过小，可能使得负极材料中离子活性位点的数量减少，影响负极极片的容量。本申请通过控制硬碳中多孔的总体积V在上述范围，有利于兼顾电池的能量密度、首周充放电效率和循环性能。进一步地，硬碳上多孔的总体积V可以为0.008cm3/g-0.016cm3/g，由此，可以进一步保证电池同时具有较高的能量密度、首周充放电效率和较好的循环性能。需要说明的是，硬碳中多孔的总体积V可以通过氮气吸脱附法测试得到，获取等温吸脱附曲线，得到相对压力P/P0为0.99时的吸附总孔体积，即为硬碳中多孔的总体积V。
根据本申请的实施例，硬碳的平均孔径可以为3nm-10nm，例如可以为3nm、5nm、7nm或9nm等，若硬碳的平均孔径过小，会影响离子的传输，使硬碳动力学性能降低，影响电池的倍率性能；若硬碳的平均孔径过大，会导致沉积钠的金属性增强，为电池带来短路的风险，且过大的孔径会使材料的比表面积降低，导致储钠容量减少，本申请通过控制硬碳中多孔的平均孔径在上述范围，有利于兼顾电池的能量密度和倍率性能。需要说明的是，硬碳的平均孔径可以通过氮气吸脱附法进行测试，获取等温吸脱附曲线，得到吸附平均孔径，即为硬碳中多孔的平均孔径。
在本申请的第二个方面，本申请提出了一种制备上述负极材料的方法。根据本申请的实施例，结合图1理解，该方法包括：
S100：将硬碳前驱体与造孔剂混合，得到硬碳前驱体的分散液
根据本申请的实施例，通过将硬碳前驱体与造孔剂混合，以便在后续碳化处理过程中通过造孔剂的分解在硬碳中引入均匀分布的多孔结构。根据本申请的一些具体示例，硬碳前驱体与造孔剂的混合比例可以为1：(0.02-0.2)，例如可以为1/0.05、1/0.1或1/0.15等，若造孔剂的用量过多，则形成的孔数量过多、多孔的总体积过大，会导致沉积钠的金属性增强，为电池带来短路的风险；若造孔剂的用量过少，则形成的多孔数量较少且多孔的总体积过小，不利于离子传输，降低硬碳的动力学性能。需要说明的是，本申请中对于硬碳前驱体和造孔剂的具体类型没有特别限制，本领域技术人员可以根据实际情况灵活选择，例如硬碳前驱体可以包括但不限于酚醛树脂、生物质等，造孔剂可以包括但不限于无机盐，如具体可以包括碳酸钠、碳酸氢钠、碳酸钾、碳酸氢钾、碳酸氢钙中的至少之一。
S200：将硬碳前驱体的分散液干燥后进行碳化处理，洗涤、粉碎、筛分得到负极材料
根据本申请的实施例，将硬碳前驱体的分散液干燥后进行碳化处理，使得硬碳前驱体热解得到硬碳，同时造孔剂也发生热分解，在硬碳内部形成多孔结构。根据本申请的一些具体示例，碳化处理可以在保护气氛下进行，碳化处理的温度可以为900℃-1100℃，例如可以为920℃、960℃、1000℃、1050℃等，升温速率可以为0.5℃/min-10℃/min，例如可以为1℃/min、3℃/min、5℃/min、7℃/min或8℃/min等，由此，有利于得到具有上述与硬碳粒径相匹配的多孔结构。需要说明的是，本申请中对于保护气氛的具体类型没有特别限制，本领域技术人员可以根据实际情况灵活选择，例如可以在氮气和/或惰性气氛下进行碳化处理。
根据本申请的实施例，将碳化处理后得到的硬碳材料依次进行洗涤、粉碎、筛分，以实现硬碳材料的粒径和多孔结构相匹配，使得硬碳的Dv50和硬碳中多孔的总体积V满足0.32≤Dv50/1000V≤2.40，从而硬碳满足较高的电容量和首周充放电效率，同时具有较好的动力学性能，有利于兼顾电池的能量密度、倍率性能和循环性能。
总的来说，该方法不仅制备工艺简单，有利于工业化生产，而且可以得到具有较高的容量、首周充放电效率和较好的动力学性能的负极材料。
在本申请的第三个方面，本申请提出了一种负极极片。根据本申请的实施例，该负极极片包括负极活性物质层，所述负极活性物质层包括上述负极材料或采用上述方法得到的负极材料。由此，装载该负极极片的电池具有较好的能量密度、倍率性能和首周充放电效率。
根据本申请的实施例，负极活性物质层的孔隙率可以为28％-40％，例如可以为30％、32％、34％、36％或38％等，负极活性物质层的孔隙率大小会影响电解液在负极极片中的浸 润和保液能力，从而影响离子的传输，具体地，若负极活性物质层的孔隙率过大，会导致化成及循环过程中的副反应加剧，影响电池的长循环性能；若负极活性物质层的孔隙率过小，会影响电解液在负极极片中的浸润效果，同时保液量下降，容易加大离子传输的阻力，影响电池的循环性能和动力学性能。本申请通过控制负极活性物质层的孔隙率在上述范围，有助于提升电解液在负极极片中的浸润效果，降低钠离子的传输阻力，进而有利于提高电池的循环性能和动力学性能。需要说明的是，负极活性物质层的孔隙率可以通过压汞法(又称“水银压入法”)测试得到，具体参考标准为GB/T 21650.1-2008压汞法和气体吸附法测定固体材料孔径分布和孔隙度第1部分：压汞法。
根据本申请的实施例，负极活性物质层还可以包括：粘结剂和/或导电剂，在负极活性物质层中，负极材料的用量可以为90重量份-98重量份，例如可以为95.5重量份等，粘结剂的用量可以为0.5重量份-5重量份，例如可以为1.5重量份等，导电剂的用量可以为1重量份-5重量份，例如可以为3重量份等。需要说明的是，本申请中对于粘结剂和导电剂的具体类型没有特别限制，本领域技术人员可以根据实际情况灵活选择，例如，粘结剂可以包括丁苯橡胶、聚偏氟乙烯、聚四氟乙烯、聚乙烯醇、聚丙烯腈、聚丙烯酸、聚丙烯酸酯、羧甲基纤维素、海藻酸钠中的至少之一；导电剂可以包括乙炔黑、Super-P、碳纳米管、碳纤维、石墨烯中的至少之一。
在本申请的第四个方面，本申请提出了一种制备上述负极极片的方法。根据本申请的实施例，将负极活性浆料施加在集流体的至少一侧，以便得到负极极片，其中，所述负极活性浆料包括上述负极材料。该方法不仅制备工艺简单，有利于工业化生产，而且可以得到具有较高的容量、首周充放电效率和较好的动力学性能的负极极片。需要说明的是，本申请中对于集流体的具体类型没有特别限制，本领域技术人员可以根据实际情况灵活选择，例如集流体可以包括铜箔、不锈钢箔、铜合金箔、涂炭铜箔、铝箔、涂碳铝箔中的至少之一。
在本申请的第五个方面，本申请提出了一种储能装置。根据本申请的实施例，该储能包括上述负极极片，与现有技术相比，该储能装置综合性能较好，能够兼具较高的能量密度、较好的倍率性能和循环性能。
根据本申请的实施例，本申请中对于储能装置的具体类型没有特别限制，本领域技术人员可以根据实际情况灵活选择，例如储能装置可以为电池，电池可以包括正极极片、隔膜和电解液，其中，正极极片包括正极活性物质层，正极活性物质层可以包括正极活性材料、粘结剂和导电剂，本申请中对于正极活性物质层中的正极活性材料、粘结剂和导电剂 的具体类型均没有特别限制，例如，对于钠离子电池而言，正极活性材料可以包括过渡金属氧化物、聚阴离子型化合物、有机聚合物、普鲁士蓝类材料中的至少之一；本申请对于隔膜的具体组成也没有特别限制，例如隔膜可以包括聚丙烯(PP)、聚乙烯(PE)、陶瓷隔膜中的至少之一；电解液可以包括电解质盐及有机溶剂，其中电解质盐和有机溶剂的具体种类及组成也没有特别限制，本领域技术人员可根据实际需求进行选择。
在本申请的第六个方面，本申请提出了一种用电装置。根据本申请的实施例，该用电装置包括上述储能装置，与现有技术相比，该用电装置的续航时间和电池使用寿命较长，市场满意度较高。
下面详细描述本申请的实施例。下面描述的实施例是示例性的，仅用于解释本申请，而不能理解为对本申请的限制。实施例中未注明具体技术或条件的，按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规产品。
实施例1
(1)将粉碎前处理好的椰壳粉末与碳酸氢钾溶液混合，其中椰壳粉末与碳酸氢钾的质量比为1：0.07，得到硬碳前驱体的分散液；将该硬碳前驱体的分散液放入真空烘箱中干燥20h后在氮气保护下以5℃/min的升温速率升温至1100℃进行碳化处理得到碳化产物；将该碳化产物进行粉碎，依次用盐酸和去离子水洗涤、干燥后再通过筛分、除磁，得到多孔硬碳，其中，多孔硬碳的Dv50为15μm，多孔硬碳中单孔的孔径为8.8nm、多孔的总体积V为0.007cm3/g、Dv50/1000V为2.14；
(2)将多孔硬碳、导电炭黑、羟甲基纤维素钠、丁苯橡胶按照95.5:1.5:1:2的质量比混合，将混合后的粉料置于真空搅拌机中，加入去离子水搅拌，得到负极活性浆料；将该负极浆料均匀涂覆在负极集流体的相对两侧表面上形成负极活性材料层，将涂有负极活性浆料的负极集流体转移至烘箱内干燥，然后经过辊压、分切后得到负极极片，其中，负极活性物质层的孔隙率为32％；
(3)将Na3V2(PO4)3、导电剂Super-P、粘结剂PVDF按照95:2.5:2.5的质量比混合，将混合后的粉料置于真空搅拌机中，加入N-甲基吡咯烷酮，搅拌均匀得到正极活性浆料；将正极活性浆料均匀涂覆于正极集流体铝箔的相对两侧表面上形成正极活性材料层，将涂有正极浆料的正极集流体转移至烘箱内干燥，然后经过辊压、分切后得到正极极片；
(4)将碳酸乙烯酯(EC)、碳酸甲乙酯(EMC)、碳酸二乙酯(DEC)按体积比1:1:1混合得到混合溶液，向混合溶液中加入干燥的钠盐NaPF6，配成浓度为1mol/L的电解液， 加入2wt％氟代碳酸乙烯酯(FEC)添加剂，得到电解液；
(5)将上述的正极极片、负极极片和聚丙烯隔膜按顺序叠好，使隔膜处于正负极极片之间，然后卷绕得到裸电芯，将裸电芯装入铝塑膜软包中，干燥后注入电解液，经过真空封装、静置、化成、整形等工序后得到二次电池。
实施例2
与实施例1的区别在于，步骤(1)中：将粉碎前处理好的椰壳粉末与碳酸氢钾溶液混合，其中椰壳粉末与碳酸氢钾的质量比为1：0.09，得到硬碳前驱体的分散液；将该硬碳前驱体的分散液放入真空烘箱中干燥20h后在氮气保护下以4℃/min的升温速率升温至1100℃进行碳化处理得到碳化产物；将该碳化产物进行粉碎，依次用盐酸和去离子水洗涤、干燥后再通过筛分、除磁，得到多孔硬碳，其中，多孔硬碳的Dv50为7μm，多孔硬碳中单孔的孔径为7.3nm、多孔的总体积V为0.010cm3/g、Dv50/1000V为0.7。
实施例3
与实施例1的区别在于，步骤(1)中：将粉碎前处理好的椰壳粉末与碳酸氢钾溶液混合，其中椰壳粉末与碳酸氢钾的质量比为1：0.15，得到硬碳前驱体的分散液；将该硬碳前驱体的分散液放入真空烘箱中干燥20h后在氮气保护下以2℃/min的升温速率升温至1100℃进行碳化处理得到碳化产物；将该碳化产物进行粉碎，依次用盐酸和去离子水洗涤、干燥后再通过筛分、除磁，得到多孔硬碳，其中，多孔硬碳的Dv50为7μm，多孔硬碳中单孔的孔径为3.8nm、多孔的总体积V为0.022cm3/g、Dv50/1000V为0.32。
实施例4
与实施例1的区别在于，步骤(1)中：将粉碎前处理好的椰壳粉末与碳酸氢钾溶液混合，其中椰壳粉末与碳酸氢钾的质量比为1：0.10，得到硬碳前驱体的分散液；将该硬碳前驱体的分散液放入真空烘箱中干燥20h后在氮气保护下以3℃/min的升温速率升温至1100℃进行碳化处理得到碳化产物；将该碳化产物进行粉碎，依次用盐酸和去离子水洗涤、干燥后再通过筛分、除磁，得到多孔硬碳，其中，多孔硬碳的Dv50为5μm，多孔硬碳中单孔的孔径为6.4nm、多孔的总体积V为0.012cm3/g、Dv50/1000V为0.42。
实施例5
与实施例1的区别在于，步骤(1)中：将粉碎前处理好的椰壳粉末与碳酸氢钾溶液混合，其中椰壳粉末与碳酸氢钾的质量比为1：0.08，得到硬碳前驱体的分散液；将该硬碳前驱体的分散液放入真空烘箱中干燥20h后在氮气保护下以4℃/min的升温速率升温至1100℃进行碳化处理得到碳化产物；将该碳化产物进行粉碎，依次用盐酸和去离子水洗涤、干燥 后再通过筛分、除磁，得到多孔硬碳，其中，多孔硬碳的Dv50为9μm，多孔硬碳中单孔的孔径为7.6nm、多孔的总体积V为0.009cm3/g、Dv50/1000V为1.0。
实施例6
与实施例1的区别在于，步骤(1)中：将粉碎前处理好的椰壳粉末与碳酸氢钾溶液混合，其中椰壳粉末与碳酸氢钾的质量比为1：0.08，得到硬碳前驱体的分散液；将该硬碳前驱体的分散液放入真空烘箱中干燥20h后在氮气保护下以5℃/min的升温速率升温至1100℃进行碳化处理得到碳化产物；将该碳化产物进行粉碎，依次用盐酸和去离子水洗涤、干燥后再通过筛分、除磁，得到多孔硬碳，其中，多孔硬碳的Dv50为13μm，多孔硬碳中单孔的孔径为8.1nm、多孔的总体积V为0.009cm3/g、Dv50/1000V为1.44。
实施例7
与实施例1的区别在于，步骤(1)中：将粉碎前处理好的椰壳粉末与碳酸氢钾溶液混合，其中椰壳粉末与碳酸氢钾的质量比为1：0.06，得到硬碳前驱体的分散液；将该硬碳前驱体的分散液放入真空烘箱中干燥20h后在氮气保护下以5℃/min的升温速率升温至1100℃进行碳化处理得到碳化产物；将该碳化产物进行粉碎，依次用盐酸和去离子水洗涤、干燥后再通过筛分、除磁，得到多孔硬碳，其中，多孔硬碳的Dv50为14μm，多孔硬碳中单孔的孔径为8.3nm、多孔的总体积V为0.006cm3/g、Dv50/1000V为2.33。
对比例1
与实施例1的区别在于，步骤(2)中采用市售硬碳作为负极活性材料，硬碳的Dv50为8μm。
对比例2
与实施例1的区别在于，步骤(1)中：将粉碎前处理好的椰壳粉末与碳酸氢钾溶液混合，其中椰壳粉末与碳酸氢钾的质量比为1:0.24，得到硬碳前驱体的分散液；将该硬碳前驱体的分散液放入真空烘箱中干燥20h后在氮气保护下以2℃/min的升温速率升温至1100℃进行碳化处理得到炭化产物；将该碳化产物进行粉碎，依次用盐酸和去离子水洗涤、干燥后再通过筛分、除磁，得到多孔硬碳，其中，多孔硬碳的Dv50为6μm，多孔硬碳中单孔的孔径为3.2nm、多孔的总体积V为0.021cm3/g、Dv50/1000V为0.29。
对比例3
与实施例1的区别在于，步骤(1)中：将粉碎前处理好的椰壳粉末与碳酸氢钾溶液混合，其中椰壳粉末与碳酸氢钾的质量比为1：0.05，得到硬碳前驱体的分散液；将该硬碳前驱体的分散液放入真空烘箱中干燥20h后在氮气保护下以5℃/min的升温速率升温至1100℃ 进行碳化处理得到炭化产物；将该碳化产物进行粉碎，依次用盐酸和去离子水洗涤、干燥后再通过筛分、除磁，得到多孔硬碳，其中，多孔硬碳的Dv50为16μm，多孔硬碳中单孔的孔径为9.2nm、多孔的总体积V为0.006cm3/g、Dv50/1000V为2.67。
对比例4
与实施例1的区别在于，步骤(1)中：将粉碎前处理好的椰壳粉末与碳酸氢钾溶液混合，其中椰壳粉末与碳酸氢钾的质量比为1：0.16，得到硬碳前驱体的分散液；将该硬碳前驱体的分散液放入真空烘箱中干燥20h后在氮气保护下以3℃/min的升温速率升温至1100℃进行炭化处理得到碳化产物；将该碳化产物进行粉碎，依次用盐酸和去离子水洗涤、干燥后再通过筛分、除磁，得到多孔硬碳，其中，多孔硬碳的Dv50为4μm，多孔硬碳中单孔的孔径为4.5nm、多孔的总体积V为0.016cm3/g、Dv50/1000V为0.25。
对比例5
与实施例1的区别在于，步骤(1)中：将粉碎前处理好的椰壳粉末与碳酸氢钾溶液混合，其中椰壳粉末与碳酸氢钾的质量比为1：0.09，得到硬碳前驱体的分散液；将该硬碳前驱体的分散液放入真空烘箱中干燥20h后在氮气保护下以5℃/min的升温速率升温至1100℃进行碳化处理得到碳化产物；将该碳化产物进行粉碎，依次用盐酸和去离子水洗涤、干燥后再通过筛分、除磁，得到多孔硬碳，其中，多孔硬碳的Dv50为20μm，多孔硬碳中单孔的孔径为8.3nm、多孔的总体积V为0.007cm3/g、Dv50/1000V为2.86。
对比例6
与实施例1的区别在于，步骤(1)中：将粉碎前处理好的椰壳粉末与碳酸氢钾溶液混合，其中椰壳粉末与碳酸氢钾的质量比为1：0.30，得到硬碳前驱体的分散液；将该硬碳前驱体的分散液放入真空烘箱中干燥20h后在氮气保护下以2℃/min的升温速率升温至1100℃进行碳化处理得到碳化产物；将该碳化产物进行粉碎，依次用盐酸和去离子水洗涤、干燥后再通过筛分、除磁，得到多孔硬碳，其中，多孔硬碳的Dv50为7μm，多孔硬碳中单孔的孔径为2.4nm、多孔的总体积V为0.027cm3/g、Dv50/1000V为0.26。
对比例7
与实施例1的区别在于，步骤(1)中：将粉碎前处理好的椰壳粉末与碳酸氢钾溶液混合，其中椰壳粉末与碳酸氢钾的质量比为1：0.03，得到硬碳前驱体的分散液；将该硬碳前驱体的分散液放入真空烘箱中干燥20h后在氮气保护下以6℃/min的升温速率升温至1100℃进行碳化处理得到碳化产物；将该碳化产物进行粉碎，依次用盐酸和去离子水洗涤、干燥后再通过筛分、除磁，得到多孔硬碳，其中，多孔硬碳的Dv50为15μm，多孔硬碳中单孔 的孔径为11.7nm、多孔的总体积V为0.004cm3/g、Dv50/1000V为3.75。
上述实施例1～7和对比例1～7的区别如表1所示。
表1实施例1～7和对比例1～7实验参数
测试与分析
在相同条件下，对上述实施例1～7和对比例1～7制备得到的电池进行能量密度、循环性能、动力学性能的测试，具体测试方法如下：
能量密度：在25℃下，使用电子天平对电池进行称重；在25℃下，将电池以1.5C倍率充电和放电，记录此时的实际放电能量；电池的实际放电能量与电池重量的比值即为电池的能量密度。
循环性能：将电池以2C倍率充电、以1C倍率放电，进行满充满放循环测试，记录循环1000圈后的电池容量保持率，用来表征电池的循环性能。
动力学性能：在25℃下，将电池以nC满充，以1C满放，重复充放电循环10次后，再将该电池以nC倍率(n＞0)充电至满电态，然后拆解出负极极片，并观察负极极片表面析钠情况。其中，负极极片表面析钠区域面积小于2％认为是不析钠。析钠倍率指的是，如果负极极片表面未析钠，则将充电倍率从nC以0.1C的梯度递增，再次进行测试，直至负极表面析钠，此时的充电倍率nC减去0.1C则为电池在不析钠条件下的最大充电倍率。
测试结果如表2所示。
表2实施例1～7和对比例1～7的测试结果
结果与讨论
由表1～2可知，与对比例1～7相比，本申请上述实施例1～7制备得到的钠离子电池兼具较高的首周充放电效率、能量密度以及较好的倍率性能和循环性能，表明通过采用本申请上述实施例的多孔硬碳，控制硬碳颗粒的粒径与硬碳中多孔的总体积之比在上述范围，可以实现硬碳材料的粒径和多孔结构相匹配，使多孔硬碳具有较高的容量和首周充放电效率，同时具有较好的动力学性能，进而兼顾电池的能量密度、倍率性能和循环性能。
在本说明书的描述中，参考术语“一个实施例”、“一些实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本申请的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不必须针对的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任一个或多个实施例或示例中以合适的方式结合。此外，在不相互矛盾的情况下，本领域的技术人员可以将本说明书中描述的不同实施例或示例以及不同实施例或示例的特征进行结合和组合。
尽管上面已经示出和描述了本申请的实施例，可以理解的是，上述实施例是示例性的，不能理解为对本申请的限制，本领域的普通技术人员在本申请的范围内可以对上述实施例进行变化、修改、替换和变型。

Claims (12)

  1. 一种负极材料，其中，所述负极材料包括硬碳，所述硬碳具有多孔结构，所述硬碳满足：0.32≤Dv50/1000V≤2.40，其中，所述硬碳的Dv50的单位为μm，所述硬碳中多孔的总体积为V，单位为cm3/g。
  2. 根据权利要求1所述的负极材料，其中，所述硬碳满足：0.42≤Dv50/1000V≤1.44。
  3. 根据权利要求1或2所述的负极材料，其中，满足下列条件中的至少之一：所述硬碳的Dv50为5μm-18μm；
    所述硬碳中多孔的总体积V为0.005cm3/g-0.022cm3/g；
    所述硬碳中多孔的平均孔径为3nm-10nm。
  4. 根据权利要求1～3中任一项所述的负极材料，其中，满足下列条件中的至少之一：
    所述硬碳的Dv50为5μm-14μm；
    所述硬碳中多孔的总体积V为0.008cm3/g-0.016cm3/g。
  5. 一种负极极片，其中，所述负极极片包括负极活性物质层，所述负极活性物质层包括权利要求1～4中任一项所述的负极材料。
  6. 根据权利要求5所述的负极极片，其中，所述负极活性物质层的孔隙率为28％-40％。
  7. 根据权利要求5或6所述的负极极片，其中，所述负极活性物质层还包括：粘结剂和/或导电剂，在所述负极活性物质层中，所述负极材料的用量为90重量份-98重量份，所述粘结剂的用量为0.5重量份-5重量份，所述导电剂的用量为1重量份-5重量份。
  8. 一种制备权利要求1～4中任一项所述的负极材料的方法，其中，包括：
    (1)将硬碳前驱体与造孔剂混合，得到所述硬碳前驱体的分散液；
    (2)将所述硬碳前驱体的分散液干燥后进行碳化处理，洗涤、粉碎、筛分得到所述负极材料。
  9. 根据权利要求8所述的方法，其中，步骤(1)中，所述硬碳前驱体与所述造孔剂的质量比为1：(0.02-0.3)。
  10. 一种制备权利要求5～7中任一项所述的负极极片的方法，其中，将负极活性浆料施加在集流体的至少一侧，以便得到负极极片，其中，所述负极活性浆料包括权利要求1～4中任一项所述的负极材料或采用权利要求8或9所述的方法得到的所述负极材料。
  11. 一种储能装置，其中，包括权利要求5～7中任一项所述的负极极片。
  12. 一种用电装置，其中，包括权利要求11所述的储能装置。
PCT/CN2024/073414 2023-05-19 2024-01-22 负极材料、负极极片及制备方法、储能装置和用电装置 Ceased WO2024239691A1 (zh)

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CN117658106B (zh) * 2023-12-22 2025-12-19 厦门海辰储能科技股份有限公司 硬碳材料、硬碳负极材料、电池及硬碳材料的制备方法
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