CN115621464A - Sodium ion battery negative electrode slurry and preparation method thereof, battery negative electrode sheet and preparation method thereof, and battery and preparation method thereof - Google Patents

Sodium ion battery negative electrode slurry and preparation method thereof, battery negative electrode sheet and preparation method thereof, and battery and preparation method thereof Download PDF

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CN115621464A
CN115621464A CN202211327343.XA CN202211327343A CN115621464A CN 115621464 A CN115621464 A CN 115621464A CN 202211327343 A CN202211327343 A CN 202211327343A CN 115621464 A CN115621464 A CN 115621464A
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sodium
ion battery
negative electrode
lubricant
preparation
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李顺利
卢林
柏丽
李庆玲
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Trina Energy Storage Solutions Jiangsu Co Ltd
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Trina Energy Storage Solutions Jiangsu Co 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • 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

Abstract

The invention relates to a negative electrode slurry of a sodium-ion battery and a preparation method thereof, a negative electrode sheet of the battery and a preparation method thereof, and the battery and the preparation method thereof, wherein the negative electrode slurry of the sodium-ion battery comprises the following components: hard carbon, lubricant, conductive agent, thickener, binder and water; the lubricant is selected from one or more of graphene, black phosphorus, moS2, ti3C2, snS, C3N4, tungsten carbide and hexagonal boron nitride; the mass ratio of the lubricant in the hard carbon, the lubricant, the conductive agent, the thickener, and the binder is 0.1 to 8%. The sodium ion battery cathode slurry takes the two-dimensional material as the lubricant, and the lubricant coats the hard carbon material in the pole piece, or is arranged in the gap between the hard carbons, or is inserted between the hard carbon layers, so that the hard carbon material is easier to slide, and the energy density of the battery and the cycle performance of the battery are further improved.

Description

Sodium ion battery negative electrode slurry and preparation method thereof, battery negative electrode sheet and preparation method thereof, and battery and preparation method thereof
Technical Field
The invention relates to the technical field of batteries, in particular to a sodium ion battery negative electrode slurry and a preparation method thereof, a battery negative electrode sheet and a preparation method thereof, and a battery and a preparation method thereof.
Background
Energy is a material basis on which society lives and develops, and with the continuous progress of the society and the continuous improvement of the living standard, the demand of human beings on energy is increasing day by day. Until now, fossil fuels still play a major role in energy structure, and more than 90% of global energy consumption depends on fossil energy such as coal and petroleum. But not only is the chemical energy source limited, but its large combustion also aggravates the greenhouse effect.
With the development of new energy industry, the technology of lithium ion batteries is also rapidly advancing, however, the shortage of lithium resources causes the cost of lithium batteries to increase continuously, which hinders the application of lithium batteries in the field of energy storage, and therefore, it is necessary to develop and design a novel energy storage device to realize partial replacement of lithium ion batteries; the sodium element and the lithium element are located in the same main group, have similar chemical properties, have excellent energy storage mechanism as electrode materials, and meanwhile, the sodium metal resource is abundant on the earth and far larger than the lithium metal, so that great advantages are provided for research, development and application of sodium ion battery energy storage devices. In order to meet huge market demands, the energy storage material is used as an evaluation standard according to electrochemical properties such as energy density, charge-discharge rate, cost, circulation and the like, and compared with a lithium ion battery, the theoretical energy density of the sodium ion battery is lower due to the fact that the relative atomic mass of sodium element is higher than that of lithium.
The hard carbon material is generally used as a negative electrode active substance of the sodium ion battery, and due to the characteristics of the hard carbon material, the pole piece design of the sodium ion battery cannot be completely consistent with that of the lithium ion battery.
Patent CN201010258975.6 proposes a liquid lubricant, which is added into a negative electrode slurry to shorten the stirring time and improve the uniformity and stability of the slurry, however, the addition of alcohol, ketone or a mixture of alcohol and ketone may introduce new impurities, which may have a certain effect on the capacity of a battery cell. CN113437252A discloses a negative electrode, an electrochemical device and an electronic device including the negative electrode, in this scheme, graphene is used as one of the composite conductive pastes, and the improvement of graphene on the process performance is not clarified. CN114204125A discloses a preparation method of an integrated solid lithium iron phosphate battery, which proposes a novel black phosphorus-graphene composite conductive agent with high conductivity, and also proposes only the influence on the conductivity and cycle life of a pole piece.
In the prior art, graphene is generally added as a conductive agent, and the content of graphene in a pole piece is extremely low. The sodium ion battery has the problem of low energy density, and most of the solutions for solving the problem in the prior patents have the problems of adding substances with certain side effects or having difficulty in commercialization and the like. The technical problem to be solved at present is how to improve the energy density and the cycle performance aiming at the characteristics of low energy density, poor cycle performance and low compaction degree of a hard carbon negative electrode of a sodium ion battery cell.
Disclosure of Invention
The invention aims to provide a negative electrode slurry of a sodium-ion battery and a preparation method thereof, a negative electrode sheet of the battery and a preparation method thereof, and the battery and the preparation method thereof, so that the negative electrode slurry of the sodium-ion battery is improved to improve the compactness of the negative electrode sheet, and further improve the performance of the sodium-ion battery.
In a first aspect, the present invention relates to a sodium ion battery negative electrode slurry, which comprises the following components: hard carbon, lubricant, conductive agent, thickener, binder and water; the lubricant is selected from graphene, black phosphorus and MoS 2 、Ti 3 C 2 、SnS、C 3 N 4 One or more combinations of tungsten carbide and hexagonal boron nitride; the mass ratio of the lubricant in the hard carbon, the lubricant, the conductive agent, the thickener, and the binder is 0.1 to 8%.
Optionally, the mass ratio of the lubricant in the hard carbon, the lubricant, the conductive agent, the thickener, and the binder is 1.5 to 4.5%.
Optionally, a mass ratio of a total mass of the hard carbon, the lubricant, the conductive agent, the thickener, and the binder to water is 100: (95-120); the mass ratio of the hard carbon, the conductive agent, the thickener, the binder, and the lubricant is (80-99): (0.1-3): (0.1-3): (0.1-3): (0.1-8).
Optionally, the conductive agent is conductive carbon black, the thickener is selected from carboxymethyl cellulose or hydroxypropyl cellulose, and the binder is selected from one or more of styrene butadiene rubber, PVDF, sodium alginate, polyvinyl alcohol, polymethyl methacrylate, hydrogenated nitrile butadiene rubber, polytetrafluoroethylene and polyacrylic acid.
In a second aspect, the present invention relates to a preparation method of the negative electrode slurry for the sodium-ion battery, the preparation method comprising: mixing hard carbon, a thickening agent, a conductive agent, a lubricant and water to obtain first slurry, and dispersing a binder into the first slurry to obtain the negative electrode slurry of the sodium-ion battery.
Optionally, the mixing of the hard carbon, the thickener, the conductive agent, the lubricant, and the water is performed at a first stirring speed, and the dispersing of the binder into the first slurry is performed at a second stirring speed, the first stirring speed being greater than the second stirring speed.
In a third aspect, the invention relates to a sodium-ion battery negative plate, which comprises a negative current collector and a membrane layer, wherein the membrane layer is made of the sodium-ion battery negative electrode slurry or the sodium-ion battery negative electrode slurry prepared by the preparation method.
In a fourth aspect, the invention relates to a preparation method of a sodium-ion battery negative electrode sheet, which comprises the following steps: and rolling the coating of the negative electrode slurry of the sodium-ion battery prepared by the preparation method on the surface of a negative electrode current collector.
In a fifth aspect, the invention relates to a sodium-ion battery, which comprises a positive plate and a negative plate, wherein the negative plate is the negative plate of the sodium-ion battery or is prepared by the preparation method.
In a sixth aspect, the present invention relates to a method for preparing a sodium ion battery, the method comprising: assembling the positive plate, the negative plate and the diaphragm into a battery cell in a winding mode, and then sequentially carrying out top sealing, liquid injection, standing, formation, shaping and degassing; the negative plate is the sodium ion battery negative plate or is prepared by the preparation method.
Has the advantages that:
the sodium ion battery cathode slurry takes the two-dimensional material as the lubricant, and the lubricant plays a role in coating the hard carbon material in the pole piece, or is arranged in the gap between the hard carbons, or is inserted between the hard carbon layers, so that the hard carbon material is easier to slide, and the energy density of the battery and the cycle performance of the battery are further improved.
Drawings
Fig. 1 is a schematic diagram of an embodiment of a membrane layer in a sodium-ion battery negative electrode sheet according to the invention.
Description of the reference numerals
1, hard carbon; 2, lubricant.
Detailed Description
The present application is described in further detail below with reference to the figures and examples. The features and advantages of the present application will become more apparent from the description.
The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments. While the various aspects of the embodiments are presented in drawings, the drawings are not necessarily drawn to scale unless specifically indicated.
In addition, the technical features described below in the different embodiments of the present application may be combined with each other as long as they do not conflict with each other.
In a first aspect, the present invention relates to a sodium ion battery negative electrode slurry, which comprises the following components: hard carbon, lubricant, conductive agent, thickener, binder and water; the lubricant is selected from graphene, black phosphorus and MoS 2 、Ti 3 C 2 、SnS、C 3 N 4 One or more combinations of tungsten carbide and hexagonal boron nitride; the lubricant isThe mass ratio among the hard carbon, the lubricant, the conductive agent, the thickener, and the binder is 0.1 to 8%.
In addition, two-dimensional materials such as graphene, black phosphorus and MoS are added into the negative electrode slurry of the sodium-ion battery 2 、Ti 3 C 2 、SnS、C 3 N 4 Tungsten carbide and hexagonal boron nitride as lubricants. The two-dimensional material is a nano material with 1-100 molecular layers and large specific surface area, such as graphene, black phosphorus and Ti 3 C 2 The two-dimensional materials can play a role in lubricating when being subjected to rolling pressure, so that the compactness of the negative pole piece is improved, meanwhile, the two-dimensional materials of the type have good conductivity, can provide a multidirectional ion diffusion path and contribute to increasing the multiplying power performance of a negative pole, and the two-dimensional materials such as graphene and black phosphorus also have certain capacity, so that the introduction of the lubricant does not influence the capacity of an electric core.
Specifically, as shown in fig. 1, hard carbon 1 material is hard and hard to move under the condition of external pressure, after the two-dimensional material in sheet form, namely lubricant 2, is added, the two-dimensional material plays a role in coating the hard carbon material in the pole piece, or in the gap between the hard carbons, or is inserted between the hard carbon layers, so that the effect of enabling the hard carbon material to slide more easily can be achieved, and under the condition of the same external pressure, the pole piece compaction density is higher, thereby improving the energy density of the battery. Meanwhile, the two-dimensional materials such as black phosphorus, graphene and the like have high conductivity and high ion conductivity, the existence of sodium dendrite can be reduced, the multiplying power performance and the cycle performance of the material are further improved, certain sodium ions can be adsorbed and embedded, and the influence on the capacity of the battery cell is further slowed down. In conclusion, the sodium-ion battery negative electrode slurry disclosed by the invention has the advantages that a small amount of two-dimensional material is added to be used as a lubricant, so that the compaction performance of a pole piece is improved, and the energy density of a sodium-ion battery cell is further increased.
In the sodium ion battery negative electrode slurry of the present invention, the lubricant is not limited to the above-described ones, and may be any other two-dimensional nitride, two-dimensional metal carbide, or the like having the above-described two-dimensional structure.
According to a particular embodiment of the first aspect of the present invention, the lubricant is present in a mass proportion of 1.5 to 4.5% in the hard carbon, the lubricant, the conductive agent, the thickener and the binder.
In addition, as a preferred embodiment, the mass ratio of the lubricant in the hard carbon, the lubricant, the conductive agent, the thickener and the binder is controlled to be 1.5-4.5%, so that the compaction density of the pole piece, the cell capacity and the cycle performance of the battery can be further remarkably improved.
According to a particular embodiment of the first aspect of the invention, the mass ratio of the total mass of the hard carbon, the lubricant, the conductive agent, the thickener and the binder to water is 100: (95-120); the mass ratio of the hard carbon, the conductive agent, the thickener, the binder and the lubricant is (80-99): (0.1-3): (0.1-3): (0.1-3): (0.1-8).
In the sodium-ion battery negative electrode slurry of the present invention, the mass ratio of the lubricant to the hard carbon, the lubricant, the conductive agent, the thickener, and the binder is controlled such that the mass ratio of the total mass of the hard carbon, the lubricant, the conductive agent, the thickener, and the binder to water is 100: (95-120), while controlling the mass ratio of the hard carbon, the conductive agent, the thickener, the binder, and the lubricant within the above range, can further improve the compacted density of the pole piece, the cell capacity, and the cycle performance of the battery.
According to a specific embodiment of the first aspect of the present invention, the conductive agent is conductive carbon black, the thickener is selected from carboxymethyl cellulose or hydroxypropyl cellulose, and the binder is selected from one or more of styrene-butadiene rubber, PVDF, sodium alginate, polyvinyl alcohol, polymethyl methacrylate, hydrogenated nitrile-butadiene rubber, polytetrafluoroethylene and polyacrylic acid.
It should be noted that the conductive carbon black may be represented as SP, the carboxymethyl cellulose may be represented as CMC, the hydroxypropyl cellulose may be represented as HPC, the styrene-butadiene rubber may be represented as SBR, the PVDF may be represented as polyvinylidene fluoride, the sodium alginate may be represented as SA, the polyvinyl alcohol may be represented as PVA, the polymethyl methacrylate may be represented as PMMA, the hydrogenated nitrile-butadiene rubber may be represented as HNBR, the polytetrafluoroethylene may be represented as PTFE, and the polyacrylic acid may be represented as PAA.
It should be noted that in the negative electrode slurry for the sodium-ion battery of the present invention, the conductive agent, the thickening agent, and the binder are selected to be the above-mentioned materials, so that various materials can be well compounded to obtain the negative electrode slurry capable of significantly improving the battery performance.
In a second aspect, the invention relates to a preparation method of the negative electrode slurry of the sodium-ion battery, which comprises the following steps: mixing hard carbon, a thickening agent, a conductive agent, a lubricant and water to obtain first slurry, and dispersing a binder into the first slurry to obtain the negative electrode slurry of the sodium-ion battery.
It should be noted that, in the preparation method of the present invention, the hard carbon, the thickener, the conductive agent, the lubricant and the water are first mixed to obtain the first slurry, so that the hard carbon, the conductive agent and the lubricant can be well mixed and dispersed, and then mixed with the binder, so that the hard carbon, the conductive agent and the lubricant are in a very good dispersion state in the obtained cathode slurry.
According to a specific embodiment of the second aspect of the present invention, the mixing of the hard carbon, the thickener, the conductive agent, the lubricant, and the water is performed at a first stirring speed, and the dispersing of the binder into the first slurry is performed at a second stirring speed, the first stirring speed being greater than the second stirring speed.
The first stirring speed is controlled to be higher than the second stirring speed, so that the uniformity of the prepared negative electrode slurry is good, and the performance of the battery can be better improved.
In a third aspect, the invention relates to a sodium-ion battery negative plate, which comprises a negative current collector and a membrane layer, wherein the membrane layer is made of the sodium-ion battery negative electrode slurry or the sodium-ion battery negative electrode slurry prepared by the preparation method.
In the sodium-ion battery negative electrode sheet of the present invention, as shown in fig. 1, the lubricant can perform a lubricating function in the sheet layer, so that gaps between hard carbons can be filled better, and thus the degree of compaction of the negative electrode sheet is higher.
In a fourth aspect, the invention relates to a preparation method of a sodium-ion battery negative electrode sheet, which comprises the following steps: and rolling the coating of the negative electrode slurry of the sodium-ion battery prepared by the preparation method on the surface of a negative electrode current collector.
The preparation method of the sodium ion battery cathode piece is simple, and the sodium ion battery cathode slurry prepared by the method can be prepared only by rolling the slurry on the surface of the cathode current collector.
In a fifth aspect, the invention relates to a sodium-ion battery, which comprises a positive plate and a negative plate, wherein the negative plate is the negative plate of the sodium-ion battery or is prepared by the preparation method.
It should be noted that the membrane layer of the negative electrode sheet in the sodium ion battery is made of the negative electrode slurry prepared by the invention, wherein the hard carbon obtains greater compactness due to the existence of the lubricant, and further the cycle performance of the battery is better.
In a sixth aspect, the present invention relates to a method for preparing a sodium ion battery, the method comprising: assembling the positive plate, the negative plate and the diaphragm into a battery cell in a winding mode, and then sequentially carrying out top sealing, liquid injection, standing, formation, shaping and degassing; the negative plate is the sodium ion battery negative plate or is prepared by the preparation method.
In the preparation method of the sodium ion battery of the present invention, conventional processes in the art may be adopted for processes of cell assembly, top sealing, liquid injection, standing, formation, shaping, degassing, and the like.
In summary, the compaction of the negative electrode plate is increased by adding the two-dimensional material into the negative electrode plate as the lubricant of the sodium-ion battery, so as to improve the energy density of the sodium-ion battery cell. The two-dimensional material with excellent conductivity and ion conducting performance can also improve the multiplying power performance of the negative plate, reduce the dendrite of sodium ions, and meanwhile, part of the two-dimensional material also has a certain effect of storing sodium ions, so that the capacity of the sodium ion battery cell cannot be reduced. The two-dimensional material can be coated on the surface of the active substance or inserted between the active substance layers, so that the active substance material can move more easily in the rolling process, and the compaction of the pole piece is increased, thereby improving the energy density of the battery.
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited thereto. The reagents used in the following examples are all commercially available reagents.
The separator used in the following examples was a commercial PE single-coated ceramic separator. The procedures of cell assembling, top sealing, liquid injection, standing, formation, shaping, degassing and the like in the following examples are all performed by adopting conventional methods in the field.
In the following examples, CMC means carboxymethyl cellulose, SBR means styrene-butadiene rubber, and SP means conductive carbon black; the SBR glue solution is an aqueous solution with the SBR mass concentration of 3.5 percent, and the adding amount of the SBR glue solution in the subsequent embodiment is the mass/mass concentration of the SBR.
The positive electrode sheet used in the following examples was prepared by the following method:
the preparation method comprises the steps of uniformly stirring and dispersing a commercially available layered sodium-ion battery positive electrode material, a conductive agent (SP or CNT), a binder (PVDF) and NMP (solvent), coating, and rolling to prepare the positive electrode piece. The mass ratio of the layered sodium-ion battery positive electrode material to the conductive agent to the binder is 95.5. SP represents conductive carbon black, CNT represents carbon nanotube, PVDF represents polyvinylidene fluoride, and NMP represents N-methylpyrrolidone.
Example 1
And (3) stirring and mixing the hard carbon, the conductive agent SP, the CMC, the graphene and the deionized water at a high speed, adding the SBR glue solution after dispersing uniformly, and stirring at a low speed to obtain the negative electrode slurry. Hard carbon, SP, CMC, SBR, graphene and water, the mass ratio is 90.0:3.0:3.0:2.5:1.5:120. and (3) pressing the obtained negative electrode slurry on a negative electrode current collector through a coating roll to obtain a negative electrode plate, assembling the negative electrode plate, a diaphragm and a positive electrode plate into a battery cell (with the nominal capacity of 2 Ah) in a winding mode, and performing top sealing, liquid injection (with the sodium salt concentration of 1 mol/L), standing, formation, shaping, degassing and other processes to prepare the sodium ion battery.
Example 2
And (3) stirring and mixing the hard carbon, the CMC, the conductive agent SP, the black phosphorus and the deionized water at a high speed, adding the SBR glue solution after uniformly dispersing, and stirring at a low speed to obtain the cathode slurry. Hard carbon, SP, CMC, SBR, black phosphorus and water, wherein the mass ratio is 90.0:3.0:3.0:2.5:1.5:120. and (3) pressing the obtained negative electrode slurry on a negative electrode current collector through a coating roll to obtain a negative electrode plate, assembling the negative electrode plate, a diaphragm and a positive electrode plate into a battery cell (with the nominal capacity of 2 Ah) in a winding mode, and performing top sealing, liquid injection (with the sodium salt concentration of 1 mol/L), standing, formation, shaping, degassing and other processes to prepare the sodium ion battery.
Example 3
Mixing hard carbon, CMC, conductive agent SP, moS 2 And stirring and mixing the mixture and deionized water at a high speed, adding SBR glue solution after the mixture is uniformly dispersed, and stirring at a low speed to obtain the cathode slurry. Hard carbon, SP, CMC, SBR, moS 2 And water, the mass ratio is 90.0:3.0:3.0:2.5:1.5:120. and (3) pressing the obtained negative electrode slurry on a negative electrode current collector through a coating roll to obtain a negative electrode plate, assembling the negative electrode plate, a diaphragm and a positive electrode plate into a battery cell (with the nominal capacity of 2 Ah) in a winding mode, and performing top sealing, liquid injection (with the sodium salt concentration of 1 mol/L), standing, formation, shaping, degassing and other processes to prepare the sodium ion battery.
Example 4
Negative electrode slurry, cells and sodium ion batteries were prepared as in example 1. The difference from the embodiment 1 is that the hard carbon, SP, CMC, SBR, graphene and water are mixed according to the mass ratio of 90.0:3.0:2.5:1.5:3:120.
example 5
Negative electrode slurry, cells and sodium ion batteries were prepared as in example 1. The difference from the example 1 is that the mass ratio of hard carbon, SP, CMC, SBR, graphene and water is 88.5: 1.5:2.5:4.5:120.
example 6
Negative electrode pastes, cells and sodium ion batteries were prepared as in example 1. The difference from the example 1 is that the hard carbon, the SP, the CMC, the SBR, the graphene and the water are mixed according to the mass ratio of 91.4:3.0:3.0:2.5:0.1:120.
example 7
Negative electrode slurry, cells and sodium ion batteries were prepared as in example 1. The difference from the example 1 is that the mass ratio of hard carbon, SP, CMC, SBR, graphene and water is 83.5:3.0:3.0:2.5:8:120.
comparative example 1
Uniformly stirring and dispersing hard carbon, SBR, SP, CMC and deionized water to obtain negative electrode slurry, wherein the ratio is 90.0:4.0:4.5:1.5: and 120, pressing the obtained negative electrode slurry on a negative electrode current collector through a coating roll to obtain a negative electrode plate, assembling the negative electrode plate, a diaphragm and a positive electrode plate into a battery cell (with the nominal capacity of 2 Ah) in a winding mode, and performing top sealing, liquid injection (with the sodium salt concentration of 1 mol/L), standing, formation, shaping, degassing and other processes to prepare the sodium ion battery.
Comparative example 2
Negative electrode slurry, cells and sodium ion batteries were prepared as in example 1. The difference from the embodiment 1 is that the hard carbon, SP, CMC, SBR, graphene and water are mixed according to the mass ratio of 90.0:3.0:3.0:2.5:0.05:120.
comparative example 3
Negative electrode slurry, cells and sodium ion batteries were prepared as in example 1. The difference from the embodiment 1 is that the hard carbon, SP, CMC, SBR, graphene and water are mixed according to the mass ratio of 90.0:3.0:3.0:2.5:10:120.
test example 1
The compacted densities of the negative electrode pole pieces prepared in the above examples and comparative examples were tested and calculated, wherein the test method of the compacted densities of the pole pieces was as follows:
cutting the pole piece with a fixed area size, wherein the area is s, weighing the mass of the cut pole piece and the current collector, namely m1 and m2, measuring the thickness of the pole piece and the current collector by adopting a thickness meter, namely h1 and h2, and calculating the compaction density according to the following formula:
compacted density = (m 1-m 2) ÷ s ÷ (h 1-h 2).
The values of the compacted densities of the negative electrode sheets in the obtained examples and comparative examples are shown in Table 1.
Test example 2
The cell capacities of the cells prepared in the above examples and comparative examples were measured by the charge/discharge method of 0.33C/0.33C, and the measured values are shown in table 1. The discharge rate (5C) of the sodium ion batteries prepared in the above examples and comparative example 1 was measured by the method of 0.33C charging and 5C discharging, and the measured values are shown in table 1. The sodium ion batteries prepared in the above examples and comparative examples were tested for cycle performance by the 1C/1C method, and the cycle performance (100 cyc) refers to the retention capacity after 100 cycles of charge and discharge.
TABLE 1
Figure BDA0003912392810000101
In conclusion, compared with the method of adding no lubricating additive in comparative example 1, the method has the advantage that the compaction performance, the circulation performance and the rate performance are obviously improved after the lubricating additive is added. Examples 1, 4 and 5 changed the content of the added lubricant (1.5%, 3%, 4.5%), both the compaction performance and the cycle performance were increased, the reason for the increase in compaction performance may be that the two-dimensional graphene plays a role in lubrication, and then under external pressure conditions, hard carbon moves, improving the compaction performance of the bulk material, the increase in rate performance may be related to the rapid conduction and ion conduction channels of graphene, and the reason for the increase in cycle performance may be that the growth of sodium dendrites is alleviated. Examples 1, 6 and 7 change the content of the added lubricant, wherein in example 6, the lower limit of the added amount of the lubricant is 0.1%, the performance is slightly improved, but the performance is not remarkable enough, and it is proved that a sufficient amount of the lubricant is needed to achieve the corresponding effect, and in example 7, the upper limit of the added amount of the lubricant is 8%, so that the capacity is obviously lost, possibly because the added amount is too much, and the capacity is prevented from being exerted. Examples 2 and 3 were exchanged for different two-dimensional materials, demonstrating a certain versatility of this type of material.
In the description of the present application, it should be noted that the terms "upper", "lower", "inner", "outer", "front", "rear", "left", "right", and the like indicate orientations or positional relationships based on operational states of the present application, and are only used for convenience in describing and simplifying the present application, but do not indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present application.
In the description of the present application, it is to be noted that the terms "mounted," "connected," and "connected" are to be construed broadly unless otherwise explicitly stated or limited. The specific meaning of the above terms in this application will be understood to be a specific case for those of ordinary skill in the art.
The present application has been described above with reference to preferred embodiments, but these embodiments are merely exemplary and merely illustrative. On the basis of the above, the present application can be subjected to various substitutions and improvements, and the substitutions and the improvements are all within the protection scope of the present application.

Claims (10)

1. The negative electrode slurry for the sodium-ion battery is characterized by comprising the following components:
hard carbon, lubricant, conductive agent, thickener, binder and water; the lubricant is selected from graphene, black phosphorus and MoS 2 、Ti 3 C 2 、SnS、C 3 N 4 One or more combinations of tungsten carbide and hexagonal boron nitride;
the mass ratio of the lubricant in the hard carbon, the lubricant, the conductive agent, the thickener, and the binder is 0.1 to 8%.
2. The sodium-ion battery anode slurry according to claim 1, wherein the lubricant is present in the hard carbon, the lubricant, the conductive agent, the thickener, and the binder in a ratio of 1.5 to 4.5% by mass.
3. The sodium-ion battery anode slurry according to claim 1, wherein a mass ratio of a total mass of the hard carbon, the lubricant, the conductive agent, the thickener, and the binder to water is 100: (95-120);
the mass ratio of the hard carbon, the conductive agent, the thickener, the binder, and the lubricant is (80-99): (0.1-3): (0.1-3): (0.1-3): (0.1-8).
4. The negative electrode slurry for the sodium-ion battery according to any one of claims 1 to 3, wherein the conductive agent is conductive carbon black, the thickening agent is selected from carboxymethyl cellulose or hydroxypropyl cellulose, and the binder is selected from one or more of styrene-butadiene rubber, PVDF, sodium alginate, polyvinyl alcohol, polymethyl methacrylate, hydrogenated nitrile-butadiene rubber, polytetrafluoroethylene and polyacrylic acid.
5. A preparation method of the negative electrode slurry of the sodium-ion battery as claimed in any one of claims 1 to 4, characterized in that the preparation method comprises the following steps:
mixing hard carbon, a thickening agent, a conductive agent, a lubricant and water to obtain first slurry, and dispersing a binder into the first slurry to obtain the negative electrode slurry of the sodium-ion battery.
6. The production method according to claim 5, wherein the mixing of the hard carbon, the thickener, the conductive agent, the lubricant, and the water is performed at a first stirring speed, and the dispersing of the binder into the first slurry is performed at a second stirring speed, the first stirring speed being greater than the second stirring speed.
7. A negative plate of a sodium-ion battery is characterized by comprising a negative current collector and a diaphragm layer, wherein the diaphragm layer is made of the negative electrode slurry of the sodium-ion battery in any one of claims 1 to 4 or the negative electrode slurry of the sodium-ion battery prepared by the preparation method in claim 5 or 6.
8. A preparation method of a sodium ion battery negative plate is characterized by comprising the following steps:
and (3) coating and rolling the negative electrode slurry of the sodium-ion battery prepared by the preparation method of claim 5 or 6 on the surface of a negative electrode current collector.
9. A sodium-ion battery, characterized in that, the sodium-ion battery comprises a positive plate and a negative plate, the negative plate is the sodium-ion battery negative plate of claim 7 or is prepared by the preparation method of claim 8.
10. A method for preparing a sodium-ion battery, the method comprising: assembling the positive plate, the negative plate and the diaphragm into a battery cell in a winding mode, and then sequentially carrying out top sealing, liquid injection, standing, formation, shaping and degassing;
the negative plate is the sodium-ion battery negative plate of claim 7 or is prepared by the preparation method of claim 8.
CN202211327343.XA 2022-10-27 2022-10-27 Sodium ion battery negative electrode slurry and preparation method thereof, battery negative electrode sheet and preparation method thereof, and battery and preparation method thereof Pending CN115621464A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116130808A (en) * 2023-02-09 2023-05-16 宁夏宝丰昱能科技有限公司 Composite pole piece, preparation method thereof and secondary battery
CN116207257A (en) * 2023-03-10 2023-06-02 东莞格林德能源有限公司 Sodium ion battery water-based negative electrode slurry, sodium ion battery and preparation method

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116130808A (en) * 2023-02-09 2023-05-16 宁夏宝丰昱能科技有限公司 Composite pole piece, preparation method thereof and secondary battery
CN116207257A (en) * 2023-03-10 2023-06-02 东莞格林德能源有限公司 Sodium ion battery water-based negative electrode slurry, sodium ion battery and preparation method

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