CN116825962A - Sodium ion battery composite negative electrode, battery and preparation method of negative electrode - Google Patents

Sodium ion battery composite negative electrode, battery and preparation method of negative electrode Download PDF

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CN116825962A
CN116825962A CN202310783459.2A CN202310783459A CN116825962A CN 116825962 A CN116825962 A CN 116825962A CN 202310783459 A CN202310783459 A CN 202310783459A CN 116825962 A CN116825962 A CN 116825962A
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sodium
philic
negative electrode
ion battery
active material
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吴秋杰
卢林
蒋治亿
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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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    • 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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
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    • 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
    • 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
    • H—ELECTRICITY
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    • 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
    • H01M4/626—Metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10—Energy storage using batteries

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Abstract

The application relates to a composite negative electrode of a sodium ion battery, which comprises a current collector, wherein a sodium-philic layer is coated on the current collector, and the sodium-philic layer contains sodium-philic substances. The sodium ion battery comprises a positive plate, an isolating film and electrolyte, wherein the sodium ion battery is a composite negative electrode. And a preparation method of the sodium ion battery composite anode, comprising the following steps: dispersing a sodium-philic substance, a conductive agent and a binder in N-methyl pyrrolidone to form sodium-philic layer slurry, coating the sodium-philic layer slurry on two sides of a current collector, and heating and drying to form a sodium-philic layer to obtain the sodium-philic current collector; dispersing an active material, a conductive agent and a binder in deionized water to form a negative electrode active material slurry, coating the negative electrode active material slurry on two surfaces of a sodium-philic current collector, and heating and drying to form a negative electrode active material layer. According to the application, the current collector of the composite negative electrode of the sodium ion battery is coated with the sodium-philic layer, so that the conductivity of the negative electrode plate is improved, and the circulation and safety performance are improved.

Description

Sodium ion battery composite negative electrode, battery and preparation method of negative electrode
Technical Field
The application belongs to the technical field of batteries, relates to a sodium ion battery, and in particular relates to a composite negative electrode of the sodium ion battery, a battery and a preparation method of the negative electrode.
Background
The lithium ion battery has great attention in the field of electrochemical energy storage because of the advantages of high energy density, long cycle life, small self-discharge effect and the like, and is widely used in the scenes of two-wheel electric vehicles, four-wheel automobiles, outdoor power supplies, energy storage power stations and the like. However, lithium resources are scarce and unevenly distributed, so that the price of lithium carbonate is stricken all the way, and the price of the battery cell is continuously increased.
The sodium element is used as a sixth abundant element in the crust, the reserve of the sodium element is 400 times that of the lithium element, and the distribution of the sodium element is more uniform than that of the lithium element. Sodium ion batteries have been widely studied in academia and industry because of their lower theoretical price, and a number of sodium ion battery companies have now put forward corresponding products. In sodium ion battery systems, graphite anode materials commonly used in lithium ion batteries fail to form stable NaC6 compounds with sodium for thermodynamic reasons, resulting in graphite materials that fail to provide adequate capacity. The hard carbon material can contain more sodium ions due to larger interlayer spacing and rich holes, and becomes a first choice of the negative electrode material of the sodium ion battery. However, the hard carbon has a disordered microcrystalline structure, the conductivity of the hard carbon is far smaller than that of graphite, the electron transmission rate is low, and the phenomenon of sodium precipitation on the surface of a pole piece is easy to occur. The precipitated sodium is continuously dissolved and precipitated in the circulating process, and a large amount of electrolyte is consumed for film formation, so that the problems of poor circulating life, serious gas production and the like are caused. In addition, the sodium in the form of dendrites runs the risk of puncturing the separator and causing the cell to short circuit.
At present, the conductivity of the grade sheet is enhanced by changing the formula of the cathode slurry to improve the proportion of conductive carbon. However, using an increased conductive carbon duty ratio reduces the first coulombic efficiency of the battery, deteriorating the storage performance, while increasing the cost.
The electrolyte formulation is also optimized by varying the hard carbon ramp region to plateau region capacity contribution ratio.
For example, chinese patent application publication No. CN115692827a discloses a sodium ion battery, by regulating and controlling the ratio of the capacity of the platform region and the capacity of the slope region of the anode active material, the sufficient capacity of the anode is ensured to be exerted, the capacity release ratio of the anode and the cathode is stabilized, so that na+ released from the anode can be fully embedded into the anode, na+ is prevented from being precipitated in the anode, the occurrence of sodium precipitation is effectively inhibited, meanwhile, the electrolyte uses NaFSI and the content range is controlled, the conductivity of the electrolyte is improved, meanwhile, the film forming stability of the anode and the cathode side of the battery is good, the current collector is not corroded, and the rate performance and the cycle stability of the battery are effectively improved.
However, the regulation of the capacity ratio of each part of the hard carbon requires custom development of each material, so that the material has no universality, and the cost is increased by changing sodium salt in the electrolyte to NaFSI.
The Chinese patent application with publication number of CN114843524A discloses a negative electrode-free sodium metal battery, wherein a carbon material embedded with sodium-philic particles is used as a carrier of metal sodium, the metal sodium is deposited inside pyrolytic carbon black, the conductivity of the pyrolytic carbon black is far lower than that of metal and metal oxide, and the deposition effect of the metal sodium is affected when the pyrolytic carbon black is coated on the surface of the metal particles.
Therefore, the problem of sodium precipitation on the surface of a pole piece under the abusive condition of high-rate charging is needed to be solved in the conventional sodium ion battery at present.
Disclosure of Invention
The application aims to solve the problems and provides a composite negative electrode of a sodium ion battery.
Another object of the present application is to provide a sodium ion battery that addresses the above problems.
It is a further object of the present application to address the above problems by providing an application of a cobalt crosslinked two-dimensional nanoplatelet conductive composite.
The application creatively provides a composite negative electrode of a sodium ion battery, which comprises a current collector, wherein a sodium-philic layer is coated on the current collector, and the sodium-philic layer contains sodium-philic substances.
The current collector is one of copper foil, composite copper foil, aluminum foil and composite aluminum foil.
Through coating the sodium-philic layer on the current collector of the composite negative electrode of the sodium ion battery, redundant sodium ions which cannot be timely embedded by hard carbon nucleate on the sodium-philic layer to form sodium metal clusters, and sodium dendrites are prevented from being formed on the surface of the pole piece, so that the diaphragm is pierced or dead sodium is formed.
In the sodium ion battery composite anode, the sodium-philic layer comprises 60-90 wt% of sodium-philic substance, 0-20 wt% of conductive agent and 0-20 wt% of binder.
As an alternative, the sodium-philic substance is 60wt%, the conductive agent is 20wt%, and the binder is 20%.
As an alternative, the sodium-philic substance is 70wt%, the conductive agent is 15wt%, and the binder is 15%.
As an alternative, the sodium-philic substance is 80wt%, the conductive agent is 10wt%, and the binder is 10%.
As an alternative, the sodium-philic substance is 90wt%, the conductive agent is 5wt% and the binder is 5%.
The sodium-philic layer controls the duty ratio of the conductive agent and ensures the storage performance of the conductive agent through the cooperation of sodium-philic substances, the conductive agent and the adhesive.
In the sodium-philic layer of the composite negative electrode of the sodium ion battery, the sodium-philic substance comprises at least one of tin, antimony, zinc, silver, platinum, gold, bismuth, copper, aluminum, tin oxide, antimony oxide, zinc oxide, bismuth oxide, copper oxide and aluminum oxide;
the conductive agent comprises at least one of conductive carbon black, carbon fiber, acetylene black, ketjen black, graphene and carbon nanotubes;
the binder includes at least one of a fluorine-containing resin, a polypropylene resin, a fiber-type binder, a rubber-type binder, and a polyimide-type binder.
In the above-mentioned composite anode of sodium ion battery, the anode active material layer is coated on the sodium-philic layer.
In the sodium ion battery composite anode, the anode active material layer comprises 90-98wt% of active material, 0-5wt% of conductive agent and 0-5wt% of binder.
In the above-mentioned negative electrode active material layer of the sodium ion battery composite negative electrode, the active material is hard carbon, and comprises biomass-based, resin-based and asphalt-based hard carbon;
the conductive agent comprises at least one of conductive carbon black, carbon fiber, acetylene black, ketjen black, graphene and carbon nanotubes;
the binder includes at least one of a fluorine-containing resin, a polypropylene resin, a fiber-type binder, a rubber-type binder, and a polyimide-type binder.
In the sodium ion battery composite anode, the thickness of the sodium-philic layer is 1-10 mu m; the thickness of the negative electrode active material layer is 50 to 100 μm.
Further, the sodium philic layer is 1 μm, 2 μm, 3 μm, 5 μm or 7 μm.
Further, the anode active material layer is 50 μm, 60 μm, 70 μm, 80 μm, 90 μm or 100 μm.
The application creatively provides a sodium ion battery, which comprises a positive plate, an isolating film and electrolyte, wherein the sodium ion battery is a composite negative electrode.
In the sodium ion battery described above, the positive electrode sheet contains an active material, a conductive agent, and a binder.
Specifically, in the positive plate, the active material is at least one of transition metal layered oxide, polyanion compound and Prussian blue compound which can reversibly remove and intercalate sodium. The conductive agent is at least one of conductive carbon black, carbon fiber, acetylene black, ketjen black, graphene and carbon nano tube. The binder is at least one of fluorine-containing resin, polypropylene resin, fiber type binder, rubber type binder and polyimide type binder.
The separator comprises one of polyethylene, polypropylene and glass fiber.
The electrolyte comprises a nonaqueous organic solvent and a sodium salt.
The non-aqueous organic solvent may be at least one selected from the group consisting of a carbonate-based solvent, an ether-based solvent, and a ketone-based solvent.
Further, the nonaqueous organic solvent may be an aprotic organic solvent such as propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, γ -butyrolactone, 1, 2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethyl sulfoxide, 1, 3-dioxolane, formamide, dimethylformamide, dioxolane, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphotriester, trimethoxymethane, dioxolane derivatives, sulfolane, methyl sulfolane, 1, 3-dimethyl-2-imidazolidone, propylene carbonate derivatives, tetrahydrofuran derivatives, ethers, methyl propionate, ethyl propionate, and the like.
The sodium salt is a material that is readily soluble in the non-aqueous organic solvent.
Further, the sodium salts include, but are not limited to NaCl, naBr, naI, naClO 4 、NaBF 4 、NaPF 6 、NaCF 3 SO 3 、NaCF 3 CO 2 、NaAsF 6 、NaSbF 6 、NaAlCl 4 、CH 3 SO 3 Na、(CF 3 SO 2 ) 2 NNa。
The sodium ion battery composite negative electrode has universality, can be matched with electrolyte of sodium salt, does not need to be replaced by NaFSI, and reduces the cost.
The application creatively provides a preparation method of a sodium ion battery composite anode, which comprises the following steps:
dispersing a sodium-philic substance, a conductive agent and a binder in N-methyl pyrrolidone to form sodium-philic layer slurry, coating the sodium-philic layer slurry on two sides of a current collector, and heating and drying to form a sodium-philic layer to obtain the sodium-philic current collector;
dispersing an active material, a conductive agent and a binder in deionized water to form anode active material slurry, coating the anode active material slurry on two surfaces of the sodium-philic current collector, and heating and drying to form an anode active material layer.
Compared with the prior art, the application has the advantages that:
according to the application, the current collector of the composite negative electrode of the sodium ion battery is coated with the sodium-philic layer, so that the contact area with the hard carbon material is increased, the peeling strength of the electrode plate is improved, the conductivity of the negative electrode plate is improved, and the multiplying power performance is improved. And sodium ion deposition can be induced, sodium ions are prevented from being separated out on the surface of the pole piece, and the circulation and safety performance are improved. The problem of the pole piece surface sodium precipitation under the high-power charging condition of conventional sodium ion battery is solved.
The sodium ion battery composite negative electrode has universality, can be matched with electrolyte of sodium salt, does not need to be replaced by NaFSI, and reduces the cost.
Drawings
Fig. 1 is a schematic structural diagram of a composite negative electrode of a sodium ion battery.
FIG. 2 is a graph showing sodium precipitation from the surface of the negative electrode after 500 cycles in example 2.
Fig. 3 is a graph showing sodium precipitation from the surface of the negative electrode after 500 cycles in comparative example 1.
Detailed Description
Further illustrated by the following specific examples;
the application will be further illustrated with reference to specific examples, which are to be understood as illustrative only and are not intended to limit the scope of the application. Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the teachings of the present application, and such equivalents are intended to fall within the scope of the application as defined in the appended claims.
Example 1
A sodium ion battery prepared by the following method.
Preparation of positive plate
NaNi is processed by 0.33 Fe 0.33 MnO 2 The conductive carbon black and polyvinylidene fluoride were dispersed in N-methylpyrrolidone to form a positive electrode active material slurry having a solid content of 65 wt%. Wherein NaNi 0.33 Fe 0.33 MnO 2 Conductive carbon black polyvinylidene fluorideThe ethylene content was 94% to 2%.
The positive electrode active material slurry was coated on both surfaces of a 13 μm aluminum foil, and then dried at 100℃for 10 minutes, and the dried coated double-sided density was 36mg/cm 2 A compacted density of 3.0mg/cm 3 。
Preparation of sodium-philic current collector
Firstly, metallic tin, conductive carbon black and polyvinylidene fluoride are dispersed in N-methyl pyrrolidone to form sodium-philic layer slurry with the solid content of 40 wt%. Wherein the weight ratio of the metal tin to the conductive carbon black to the polyvinylidene fluoride is 60 percent to 20 percent.
The sodium philic layer slurry was coated on both sides of a copper foil having a thickness of 6 μm to a thickness of 5 μm, and then dried at 100 c for 10 minutes.
Preparation of negative plate
Hard carbon, conductive carbon black, hydroxymethyl cellulose and styrene-butadiene rubber were dispersed in deionized water to form a negative electrode active material slurry having a solid content of 53 wt%. Wherein the weight ratio of graphite to conductive carbon black to hydroxymethyl cellulose to styrene-butadiene rubber is 92 percent to 3 percent to 2 percent to 3 percent.
The negative electrode active material slurry was coated on both surfaces of a sodium-philic current collector to a thickness of 50 μm, and then dried at 100 deg.c for 10 minutes to form a negative electrode active material layer. The density of the dried double-sided coating surface is 16.0mg/cm 2 A compacted density of 0.9mg/cm 3 。
The partial structure of the prepared negative plate is shown in figure 1.
Preparation of sodium ion batteries
Winding the positive electrode, the negative electrode and the polyethylene diaphragm into a core bag (with the thickness of 5.5mm, the width of 75.0mm and the height of 89.5 mm) of a sodium ion battery respectively, packaging the core bag in an aluminum plastic film bag, and then packaging the NaPF 6 The resulting solution was dissolved in a mixed solvent of EC/PC/emc=35:5:60 (mass ratio) at a concentration of 1mol/L to form a nonaqueous electrolyte, and the nonaqueous electrolyte was injected into an aluminum plastic film bag in an amount of 6g/Ah and sealed to prepare a battery.
Standing for 24 hr, forming at 45deg.C, vacuum extracting gas, sealing, charging to 3.95V at 0.2C, and constant voltage to current of 3.95V0.05C, and then 0.2C to 1.5V to obtain initial discharge capacity C 0 。
Example 2
The procedure is exactly as in example 1, except that the sodium philic layer composition is changed to 80%:10%: 10%.
Example 3
The procedure is exactly as in example 2, except that the sodium-philic material is changed to SnO 2.
Example 4
The procedure is exactly as in example 2, except that the sodium philic material is changed to Sb.
Example 5
The procedure is exactly as in example 2, except that the sodium philic material is changed to Sb2O 3.
Example 6
The procedure is exactly as in example 2, except that the sodium philic material is changed to Bi2O 3.
Comparative example 1
The procedure is exactly as in example 1, except that no sodium philic layer is present.
Comparative example 2
The sodium philic material instead comprises fumed carbon black particles having embedded metallic tin, wherein the metallic tin comprises 30% of the total mass of the fumed carbon black particles having embedded metallic tin. The remainder was identical to example 2.
The differences between examples 1-6 and comparative example 1 are shown in Table 1 below.
TABLE 1
The negative electrode sheets prepared in examples 1 to 6 and comparative examples 1 and 2 were subjected to a sheet resistance test, and the results are shown in table 2 below;
TABLE 2
Group of Resistivity (mΩ. M)
Example 1 8.4
Example 2 7.5
Example 3 7.2
Example 4 7.9
Example 5 8.2
Example 6 7.4
Comparative example 1 12.7
Comparative example 2 9.8
The result shows that the battery prepared by the application has lower resistivity and more excellent conductivity.
The batteries produced in examples 1 to 6 and comparative examples 1 and 2 were subjected to the following cycle test:
(1) Standing for 5min;
(2) Constant power charging to 3.95V at 1.0P;
(3) Standing for 5min;
(4) Constant power discharge of 1.0P to 1.5V;
(5) Standing for 5min;
(6) Repeating steps 2-5 500 times, 1500 th timeThe discharge capacity was recorded as C 500 ；
Results of the cycle test 1P 500 cycles at 25℃cycle performance is shown in Table 3 below:
TABLE 3 Table 3
Group of Capacity retention rate
Example 1 91.3％
Example 2 92.5％
Example 3 93.2％
Example 4 92.1％
Example 5 91.8％
Example 6 92.8％
Comparative example 1 85.6％
Comparative example 2 88.4％
The results show that the battery prepared by the method has higher capacity retention rate and better cycle performance.
The negative electrode surface sodium precipitation after 500 cycles in example 2 is shown in FIG. 2, and the negative electrode surface sodium precipitation after 500 cycles in comparative example 1 is shown in FIG. 3.
The specific embodiments described herein are offered by way of example only to illustrate the spirit of the application. Those skilled in the art may make various modifications or additions to the described embodiments or substitutions thereof without departing from the spirit of the application or exceeding the scope of the application as defined in the accompanying claims.
Although terms of a sodium ion battery composite anode, a current collector, a sodium philic layer, a sodium philic substance, a conductive agent, a binder, an anode active material layer, an active material, conductive carbon black, carbon fiber, acetylene black, ketjen black, graphene, carbon nanotubes, fluorine-containing resin, polypropylene resin, a fibrous binder, a rubber type binder, a polyimide type binder, a positive electrode sheet, a separator, an electrolyte, polyethylene, polypropylene, glass fiber, a sodium ion battery, and the like are used more herein. These terms are only used to more conveniently describe and explain the nature of the application and should be construed in a manner consistent with their spirit and scope.

Claims (10)

1. The composite negative electrode of the sodium ion battery comprises a current collector (1), and is characterized in that: the current collector (1) is coated with a sodium philic layer (2), the sodium philic layer (2) comprising a sodium philic substance.
2. A sodium ion battery composite anode as defined in claim 1, wherein: the sodium philic layer (2) comprises 60-90 wt% of sodium philic substance, 0-20 wt% of conductive agent and 0-20 wt% of binder.
3. A composite negative electrode for sodium ion battery as claimed in claim 2, wherein: the sodium-philic substance comprises at least one of tin, antimony, zinc, silver, platinum, gold, bismuth, copper, aluminum, tin oxide, antimony oxide, zinc oxide, bismuth oxide, copper oxide and aluminum oxide;
the conductive agent comprises at least one of conductive carbon black, carbon fiber, acetylene black, ketjen black, graphene and carbon nanotubes;
the binder includes at least one of a fluorine-containing resin, a polypropylene resin, a fiber-type binder, a rubber-type binder, and a polyimide-type binder.
4. A sodium ion battery composite anode as defined in claim 1, wherein: the sodium philic layer (2) is coated with a negative electrode active material layer (3).
5. A sodium ion battery composite anode as defined in claim 4, wherein: the negative electrode active material layer (3) contains 90 to 98wt% of an active material, 0 to 5wt% of a conductive agent, and 0 to 5wt% of a binder.
6. A sodium ion battery composite anode as defined in claim 5, wherein: the active material comprises hard carbon;
the conductive agent comprises at least one of conductive carbon black, carbon fiber, acetylene black, ketjen black, graphene and carbon nanotubes;
the binder includes at least one of a fluorine-containing resin, a polypropylene resin, a fiber-type binder, a rubber-type binder, and a polyimide-type binder.
7. A sodium ion battery composite anode as defined in claim 4, wherein: the thickness of the sodium-philic layer (2) is 1-10 mu m; the negative electrode active material layer (3) has a thickness of 50-100 [ mu ] m.
8. A sodium ion battery comprising a positive plate, a separation membrane and an electrolyte, and further comprising the composite negative electrode of the sodium ion battery as claimed in any one of claims 1 to 7.
9. A sodium ion battery as defined in claim 8, wherein: the positive plate comprises an active material, a conductive agent and an adhesive; the separator comprises one of polyethylene, polypropylene and glass fiber; the electrolyte comprises a nonaqueous organic solvent and a sodium salt.
10. A method for preparing a composite negative electrode of a sodium ion battery according to any one of claims 1 to 7, comprising the steps of:
dispersing a sodium-philic substance, a conductive agent and a binder in N-methyl pyrrolidone to form sodium-philic layer slurry, coating the sodium-philic layer slurry on two sides of a current collector (1), and heating and drying to form a sodium-philic layer (2) to obtain the sodium-philic current collector;
dispersing an active material, a conductive agent and a binder in deionized water to form a negative electrode active material slurry, coating the negative electrode active material slurry on two surfaces of the sodium-philic current collector, and heating and drying to form a negative electrode active material layer (3).
CN202310783459.2A 2023-06-29 2023-06-29 Sodium ion battery composite negative electrode, battery and preparation method of negative electrode Pending CN116825962A (en)

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CN117747847A (en) * 2023-12-22 2024-03-22 中南大学 Composite current collector with sodium-philic interface, preparation thereof and application thereof in negative-electrode-free sodium battery

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117747847A (en) * 2023-12-22 2024-03-22 中南大学 Composite current collector with sodium-philic interface, preparation thereof and application thereof in negative-electrode-free sodium battery

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