CN116741991A - Secondary battery and method for manufacturing the same - Google Patents
Secondary battery and method for manufacturing the same Download PDFInfo
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- CN116741991A CN116741991A CN202310473844.7A CN202310473844A CN116741991A CN 116741991 A CN116741991 A CN 116741991A CN 202310473844 A CN202310473844 A CN 202310473844A CN 116741991 A CN116741991 A CN 116741991A
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- Prior art keywords
- active material
- secondary battery
- negative electrode
- battery according
- anode active
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- 238000000034 method Methods 0.000 title description 17
- 239000007773 negative electrode material Substances 0.000 claims abstract description 27
- 239000011148 porous material Substances 0.000 claims abstract description 26
- 229910021385 hard carbon Inorganic materials 0.000 claims abstract description 25
- 239000011734 sodium Substances 0.000 claims abstract description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 8
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- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
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- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- ITOJEBDYSWRTML-UHFFFAOYSA-N carbon tetroxide Chemical compound O=C1OOO1 ITOJEBDYSWRTML-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
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- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
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- 239000011888 foil Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
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- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
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- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M10/058—Construction or manufacture
-
- 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
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application relates to the field of sodium ion batteries, in particular to a secondary battery and a preparation method thereof. The secondary battery includes a negative electrode sheet including a negative electrode active material including a porous material including hard carbon; the pore volume of the negative electrode active material is 0.008-0.025 cm 3 /g; the porosity of the negative plate is 20-40%. Is remarkable inThe sodium ion transmission channel is improved, the sodium storage capacity is improved, the long-cycle performance and the first discharge specific capacity of the secondary battery are improved, and the preparation cost of the hard carbon negative electrode active material of the secondary battery is reduced.
Description
Technical Field
The application relates to the field of secondary batteries, in particular to a secondary battery and a preparation method thereof.
Background
The porosity of the negative electrode plate directly influences the cycle performance and the first charge-discharge specific capacity of the sodium ion battery, and the regulation and control of the porosity of the negative electrode plate of the sodium ion battery can be started from a negative electrode active material.
The hard carbon has the advantages of low raw material cost, wide source, simple synthesis and the like, and becomes a cathode active material of a sodium ion battery with great prospect. It is widely accepted that hard carbon can effectively store sodium ions in its pores. Thus, suitable pore volume is more efficient for sodium ion storage, which is beneficial to significantly improving the capacity performance of hard carbon materials.
Disclosure of Invention
In view of the above, an object of the present application is to provide a secondary battery and a method for manufacturing the same, which further improve the long cycle performance and the first discharge specific capacity of the secondary battery.
In order to achieve the above object, as a first aspect of the present application, there is provided a secondary battery including a negative electrode sheet including a negative electrode active material including a porous material including hard carbon; the pore volume of the negative electrode active material is 0.008-0.025 cm 3 /g; the porosity of the negative plate is 20-40%.
Further, the specific surface area of the negative electrode active material is 4-10 m 2 /g。
Further, the negative electrode active material has a particle size D50 of 3.5 to 6 μm.
Further, the pore diameter of the negative electrode active material is 2 to 10nm.
Further, the negative electrode active material has a compacted density of 0.9 to 1.3g/cm 3 。
Further, the negative electrode active material contains a metal element, and the metal element contains at least one of Li, na, K, mg, ca, fe, co, cu, zn, al.
Further, in the negative electrode active material, the mass percentage of the metal element is lower than 0.2%.
Further, the secondary battery includes a positive electrode sheet including a positive electrode active material including a sodium-containing compound.
In a second aspect of the present application, there is provided a method for manufacturing the above secondary battery, comprising:
uniformly mixing plastic particles with a metal compound, and calcining at a high temperature of 1000-1800 ℃ for 2-6 hours to obtain a hard carbon precursor;
washing the hard carbon precursor with water and/or acid to remove metal compounds, thereby obtaining the anode active material;
and mixing the hard carbon porous material, the conductive agent and the binder to form slurry, coating the slurry on a current collector, and rolling, drying and cutting to obtain the negative plate.
Further, the mass ratio of the plastic particles to the metal compound is (90-99): (1-10).
The anode active material of the application improves the pore structure of hard carbon to ensure that the pore volume of the anode active material reaches 0.008cm to 0.025cm 3 And/g. The negative electrode active material is used for preparing a negative electrode plate, and the porosity of the negative electrode plate is 20-40%. The negative plate provided by the application obviously improves a sodium ion transmission channel and improves the sodium storage capacity. Not only improves the long cycle performance and the first discharge specific capacity of the secondary battery, but also reduces the preparation cost of the hard carbon anode active material of the secondary battery.
Detailed Description
The application discloses a secondary battery and a preparation method thereof, and a person skilled in the art can refer to the content of the secondary battery and properly improve the technological parameters. It is expressly noted that all such similar substitutions and modifications will be apparent to those skilled in the art, and are deemed to be included in the present application. While the method of the present application has been described in terms of preferred embodiments, it will be apparent to those skilled in the relevant art that the application can be practiced and practiced with modification and alteration and combination of the methods described herein without departing from the spirit and scope of the application. It will be apparent that the described embodiments are some, but not all, embodiments of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
It should be noted that, in this document, relational terms such as "first" and "second," "step 1" and "step 2," and "(1)" and "(2)" and the like, if any, are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element. Meanwhile, the embodiments of the present application and features in the embodiments may be combined with each other without collision.
In a first aspect thereof, the present application provides a secondary battery including a negative electrode sheet including a negative electrode active material including a porous material including hard carbon; the pore volume of the negative electrode active material is 0.008-0.025 cm 3 /g; the porosity of the negative plate is 20-40%.
In some embodiments of the present application, the pore volume of the anode active material may be 0.008cm 3 /g、0.010cm 3 /g、0.012cm 3 /g、0.015cm 3 /g、0.018cm 3 /g、0.020cm 3 /g、0.022cm 3 /g、0.025cm 3 G or any two values thereof. The pore volume of the anode active material is in the range of the application, which is beneficial to improving the sodium storage capacity of the anode active material, thereby improving the long-cycle capacity and the first discharge specific capacity of the battery. Furthermore, in electricityWhen the cell is filled with liquid, the porosity of the anode active material is in the range of the application, which is beneficial to regulating and controlling the contact area of the electrolyte and the material, improving the circulation capacity of the cell and reducing the risk of leakage of the electrolyte. The porosity of the negative electrode sheet may be 20%, 22%, 24%, 26%, 28%, 30%, 32%, 34%, 36%, 38%, 40% or a range of any two of these. The cathode plate is prepared from the cathode active material, the porosity of the cathode plate can be controlled to be 20-40%, and the first charge and discharge capacity and the cycle performance of the battery are improved.
In some embodiments of the present application, the specific surface area of the anode active material is 4 to 10m 2 /g, e.g. 4m 2 /g、5m 2 /g、6m 2 /g、7m 2 /g、8m 2 /g、9m 2 /g、10m 2 G or any two values thereof. The specific surface area of the negative electrode active material is within the range of the application, which is beneficial to improving the first effect of the battery and balancing the first effect and the specific capacity.
In certain embodiments of the present application, the particle size distribution D50 of the anode active material is 3.5 to 6 μm, for example, 3.5 μm, 4.0 μm, 4.5 μm, 5.0 μm, 5.5 μm, 6.0 μm, or a range formed by any two values thereof.
In certain embodiments of the application, the pore size of the anode active material is in the range of 2 to 10nm, such as 2nm, 3nm, 4nm, 5nm, 6nm, 7nm, 8nm, 9nm, 10nm, or any two values therein. The pore size affects the specific surface area of the material, and pore diameters within the scope of the present application are advantageous for ensuring that the specific surface area is within the scope of the present application.
In some embodiments of the present application, the negative electrode active material has a compacted density of 0.9 to 1.3g/cm 3 For example 0.9g/cm 3 、1.0g/cm 3 、1.1g/cm 3 、1.2g/cm 3 、1.3g/cm 3 Or a range in which any two values form.
In some embodiments of the present application, the negative electrode active material includes a metal element therein, and the metal element includes at least one of Li, na, K, mg, ca, fe, co, cu, zn, al.
In some embodiments of the present application, the negative electrode active material includes less than 0.2% by mass of metal elements. For example, 0.01%, 0.05%, 0.08%, 0.1%, 0.12%, 0.14%, 0.16%, 0.18%, 0.2% or a range of any two of these. The content of the metal element is within the above range, which is advantageous for improving the specific capacity of the anode active material.
In some embodiments of the present application, the negative electrode active material includes 0.05 to 0.2% by mass of metal element
In certain embodiments of the present application, the secondary battery comprises a positive electrode sheet comprising a positive electrode active material comprising a sodium-containing compound.
In a second aspect of the present application, there is provided a method for manufacturing the secondary battery, comprising:
uniformly mixing plastic particles with a metal compound, and calcining at a high temperature of 1000-1800 ℃ for 2-6 hours to obtain a hard carbon precursor;
washing the hard carbon precursor with water and/or acid to remove metal compounds, thereby obtaining the anode active material;
and mixing the anode active material, the conductive agent and the binder to form slurry, coating the slurry on a current collector, and rolling, drying and cutting to obtain the anode sheet.
Wherein the carbon source of the hard carbon comprises plastic particles. The plastic is widely applied to the packaging bags, the used plastic can only be used as garbage for landfill treatment, and the plastic garbage still has the problem of difficult degradation after being subjected to a plurality of years, so that the plastic garbage causes great pollution to the environment. The plastic is applied to a carbon source of hard carbon, so that the effects of effectively saving resources and cost are achieved.
In certain embodiments of the present application, the metal compound comprises at least one of a metal oxide, a metal chloride, a metal nitrate, a metal sulfate, wherein the metal comprises one of Li, na, K, mg, ca, fe, co, cu, zn, al. More specifically, the metal ion includes Li + 、Na + 、K + 、Mg 2+ 、Ca 2+ 、Fe 3+ 、Co 2+ 、Cu 2+ 、Zn 2+ 、Al 3+ One of the following; in still other embodiments of the present application, the metal compound comprises at least one of sodium chloride, calcium oxide, magnesium oxide, cobalt chloride.
In still other embodiments of the present application, the plastic particles comprise at least one of polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyisobutylene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, polymethacrylate, ethylene-vinyl acetate copolymer, polyethylene terephthalate, polyvinyl alcohol, polybutyl terephthalate, polyamide, polycarbonate, polyoxymethylene ester, polyphenylene ether, polyphenylene sulfide, polyurethane plastic particles; wherein the polymerization degree of the polymer adopts the polymerization degree in the range of the conventional industrial grade products, and in other embodiments of the application, the molecular weight of the polyethylene is 1 ten thousand to 10 ten thousand, the molecular weight of the polyvinyl chloride is 5 ten thousand to 11 ten thousand, the molecular weight of the polyisobutene is 3 ten thousand to 10 ten thousand, the molecular weight of the ethylene-vinyl acetate copolymer is 1000 to 4000, the molecular weight of the polyethylene terephthalate is 1 ten thousand to 4 ten thousand, the molecular weight of the polyvinyl alcohol is 2 ten thousand to 15 ten thousand, the molecular weight of the polyamide is 17000 to 23000, and the molecular weight of the polycarbonate is 1 ten thousand to 5 ten thousand.
In certain embodiments of the present application, the mixing of the plastic particles with the metal compound comprises mixing the plastic particles with the metal compound using an organic solvent as a medium; in still other embodiments of the present application, the organic solvent comprises at least one of para-xylene, trichlorobenzene, nitrobenzene, isoamyl acetate, ethyl acetate, hexane, chloroform, carbon tetroxide, tetrahydrofuran, cyclohexanone, ketone, dimethylformamide, dimethyl sulfoxide, m-cresol, o-chlorophenol, trichloroacetic acid. In still other embodiments of the present application, the plastic particles, the metal compound, and the organic solvent are mixed and contacted sufficiently and then dried, the drying temperature being 100 to 200 ℃.
In certain embodiments of the application, the homogeneously mixing further comprises milling.
In certain embodiments of the application, the mass ratio of plastic particles to metal compound is (90-99): (1-10). The mass ratio of the plastic particles to the metal compound is controlled within the range of the application, so that the pore structure of the anode active material can be regulated and controlled.
In certain embodiments of the application, the organic solvent is added in an amount of 5% to 15% of the total mass of the plastic particles and the metal compound.
In certain embodiments of the application, the high temperature calcination temperature is 1000 ℃, 1100 ℃, 1200 ℃, 1300 ℃, 1400 ℃, 1500 ℃, 1600 ℃, 1700 ℃, 1800 ℃, or a range formed of any two values; in other embodiments of the application, the high temperature calcination has a ramp rate of 2 to 20 ℃/min.
In some embodiments of the present application, during the water washing and/or acid washing to remove the metal compound, the water washing mainly removes the metal compound which is easily soluble in water, such as sodium chloride, the acid washing removes the metal compound which is insoluble in water or reduced metal, and the negative electrode active material contains almost no metal compound of the original additive after washing. The metal compound mainly has pore-forming effect on the anode active material to form a porous anode active material with pore volume of 0.008-0.025 cm 3 Negative electrode active material per gram. In still other embodiments of the present application, the acid comprises at least one of sulfuric acid, nitric acid, hydrochloric acid, and hydrofluoric acid, and the concentration of the acid is not required, and a concentration of 1 to 3M may be selected.
In certain embodiments of the application, the water and/or acid wash to remove metal compounds further comprises drying, said drying temperature being in the range of 100 to 200 ℃.
In a third aspect of the present application, a sodium ion battery is provided, which includes a positive electrode sheet, a separator, an electrolyte and a negative electrode sheet according to the present application, where the sodium ion battery may be a full battery, a half battery or a symmetrical battery, and may also be a button battery, a soft pack battery, etc.
In certain embodiments of the present application, the positive electrode material may be a transition metal layered oxide, a polyanion compound, a prussian blue analog, or the like; the diaphragm can be made of polyethylene, polypropylene and the like; the electrolyte may be, for example, an electrolyte containing 1 to 1.5M sodium hexafluorophosphate, in which ethylene carbonate EC, dimethyl carbonate DMC and ethylmethyl carbonate EMC are mixed in a volume ratio of 1:1:1.
In still other embodiments of the present application, conventional materials may be used when the positive electrode material and the negative electrode active material of the present application are referred to using a conductive agent and a binder, for example, the conductive agent may include carbon black, conductive graphite, VGCF (vapor grown carbon fiber), carbon nanotube, graphene, etc., and the binder may include polyvinylidene fluoride (PVDF), carboxymethyl cellulose (CMC), styrene-butadiene rubber (SBR), polyacrylic acid (PAA) and salts thereof, polytetrafluoroethylene (PTFE), polyvinyl alcohol (PVA), etc.
In each of the comparative experiments provided by the present application, unless otherwise specified, other experimental conditions, materials, etc. were kept consistent to allow for comparability, except for the differences noted in each group. In addition, the materials used in the present application are all commercially available.
The secondary battery and the method for manufacturing the same according to the present application are further described below.
Example 1:
polyethylene (molecular weight: 2 ten thousand) and sodium chloride powder were mixed in a mass ratio of 93:7, p-xylene was added in an amount of 10% of the total amount of the mixture, and sufficiently ground to obtain a mixed slurry. And drying the mixed slurry at 150 ℃, calcining the dried mixed slurry at 1200 ℃ for 2 hours at a heating rate of 5 ℃/min, and preparing the hard carbon material precursor. And washing, filtering and drying the obtained precursor in water, and removing sodium chloride to obtain the anode active material. Uniformly mixing the anode active material, the conductive agent acetylene black (Super P) and the binder (SBR) according to the mass ratio of 80:10:10, coating the mixed slurry on a copper foil with the diameter of 12mm, and carrying out vacuum baking to obtain the anode sheet. And then the negative plate is placed in a 2023 button cell shell, and the half cell is assembled by taking sodium foil as a counter electrode.
Remaining examples and comparative examples:
the preparation methods of the remaining examples and comparative examples negative electrode active materials refer to example 1, with the differences shown in table 1;
TABLE 1
The results of the performance test are shown in Table 2
The performance test method comprises the following steps:
the method for testing the specific capacity of the first discharge comprises the following steps: and (3) carrying out charge and discharge test under the condition of 0.1C multiplying power, wherein the voltage range is 2.0V-4.0V. Firstly, performing a charging test to obtain a specific charging capacity Q c Then, discharge test is carried out to obtain the discharge specific capacity Q d ，Q d The specific capacity of the first discharge.
The method for calculating the capacity retention rate comprises the following steps: the ratio of the first discharge voltage to the first charge voltage, i.e. Q d /Q c Is the capacity retention rate.
TABLE 2
As can be seen from the data of tables 1 and 2, examples 1 to 13 and comparative example 1, compared with the case where the anode active material was prepared by pore-forming using a metal compound during the preparation, the anode active material prepared had a pore volume of 0.008 to 0.025cm 3 In the range of/g, a more suitable active site is provided for sodium storage of the hard carbon anode active material, and meanwhile, the porosity of the prepared anode sheet is controlled between 20 and 40 percent, so that the initial discharge specific capacity and the cycle life of the examples 1 to 13 are promotedHigher than the hard carbon anode active material which is not subjected to pore formation by adopting a metal compound.
Comparison between examples 2, 7 and comparative example 3 shows that when the mass ratio of plastic particles to metal compound is controlled to be (90 to 99): in the range of (1-10), the pore volume of the hard carbon anode active material is advantageously maintained at 0.008-0.025 cm 3 The porosity of the negative plate and the negative plate is 20-40% in the range of/g, thereby promoting the performance of the battery to be improved. In the application, the metal compound mainly plays a role of creating holes for the hard carbon anode active material, so that the mass ratio of the plastic particles to the metal compound has a larger influence on the pore volume of the hard carbon anode active material.
The foregoing is only a specific embodiment of the application to enable those skilled in the art to understand or practice the application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A secondary battery comprising a negative electrode sheet comprising a negative electrode active material comprising a porous material comprising hard carbon;
the pore volume of the negative electrode active material is 0.008-0.025 cm 3 /g；
The porosity of the negative plate is 20-40%.
2. The secondary battery according to claim 1, wherein the specific surface area of the anode active material is 4 to 10m 2 /g。
3. The secondary battery according to claim 1, wherein the particle size D50 of the anode active material is 3.5 to 6 μm.
4. The secondary battery according to claim 1, wherein the pore diameter of the anode active material is 2 to 10nm.
5. The secondary battery according to claim 1, wherein the negative electrode active material has a compacted density of 0.9 to 1.3g/cm 3 。
6. The secondary battery according to claim 1, wherein the anode active material contains a metal element, and wherein the metal element contains at least one of Li, na, K, mg, ca, fe, co, cu, zn, al.
7. The secondary battery according to claim 1, wherein the content of the metal element in the anode active material is less than 0.2% by mass.
8. The secondary battery according to any one of claims 1 to 7, wherein the secondary battery comprises a positive electrode sheet comprising a positive electrode active material comprising a sodium-containing compound.
9. The method of manufacturing a secondary battery according to claim 1, comprising the steps of:
uniformly mixing plastic particles with a metal compound, and calcining at a high temperature of 1000-1800 ℃ for 2-6 hours to obtain a hard carbon precursor;
washing the hard carbon precursor with water and/or acid to remove metal compounds, thereby obtaining the anode active material;
and mixing the anode active material, the conductive agent and the binder to form slurry, coating the slurry on a current collector, and rolling, drying and cutting to obtain the anode sheet.
10. The method of manufacturing a secondary battery according to claim 9, wherein the mass ratio of the plastic particles to the metal compound is (90 to 99): (1-10).
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