CN114420906A - Chemical nickel plating based electrode material with core-shell structure, preparation method thereof and lithium-sulfur battery - Google Patents

Chemical nickel plating based electrode material with core-shell structure, preparation method thereof and lithium-sulfur battery Download PDF

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CN114420906A
CN114420906A CN202210012333.0A CN202210012333A CN114420906A CN 114420906 A CN114420906 A CN 114420906A CN 202210012333 A CN202210012333 A CN 202210012333A CN 114420906 A CN114420906 A CN 114420906A
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sulfur
electrode material
shell structure
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nickel
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胡晓斌
林升炫
肖佳佳
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Shanghai Jiaotong University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01M4/02—Electrodes composed of, or comprising, active material
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract

The invention relates to an electrode material based on a chemical nickel plating core-shell structure, a preparation method thereof and a lithium sulfur battery. Compared with the prior art, the preparation method provided by the invention has the advantages of simple steps, high efficiency and low cost, and solves the problems of non-conductivity, shuttle effect, volume expansion in the charging and discharging processes and the like of elemental sulfur. More importantly, the lithium-sulfur battery prepared by the invention has extremely high active material load and surface capacity and very wide practical application prospect.

Description

Chemical nickel plating based electrode material with core-shell structure, preparation method thereof and lithium-sulfur battery
Technical Field
The invention relates to a material and a preparation method in the technical field of lithium batteries, in particular to an electrode material based on a chemical nickel-plating core-shell structure, a preparation method thereof and a lithium-sulfur battery containing the electrode material of the core-shell structure.
Background
Vehicles mainly comprising automobiles are an important industry of pillars of national economy, and play an important role in the development of the national economy and society. But traditional traffic energy consumption is also one of the main sources causing local environmental pollution and global greenhouse gas emission. Therefore, traffic energy transformation is imperative, and the development of energy-saving automobiles is just an effective measure for promoting energy conservation, emission reduction and carbon neutralization. In addition, for the national conditions of China such as oil shortage and gas shortage and numerous population, the development of new energy industry can not only get rid of the dependence on petroleum, but also realize the opportunity of curve overtaking in the field of automobiles, so the new energy automobile industry is also the strategic industry of China.
The biggest difference between the new energy automobile and the traditional automobile is that the battery is used as power to drive the automobile. Therefore, the power battery is the core of the new energy automobile, and one of the keys for developing the new energy automobile is the development of the power battery. At present, lithium ion power batteries mainly made of lithium iron phosphate and ternary materials are based on a lithium removal-lithium insertion working mechanism, and due to the fact that the number of lithium ions which can be reversibly inserted and removed in structural gaps of electrode materials is limited, the energy stored and released in the electrochemical energy storage process is limited, and therefore the specific capacity and the energy density of the lithium ion batteries are difficult to exceed 300mAh g-1And 400Wh kg-1. The lower battery mass energy density makes the batteries on the electric automobile large and heavy, so that the number of the batteries mounted on each electric automobile is very limited, the endurance mileage of the electric automobile is severely limited, and the battery pack becomes a serious bottleneck problem of the current electric automobile development. Therefore, the search and development of high specific capacity electrode materials different from the conventional intercalation type lithium storage are the key to improve the energy density of the battery.
The lithium metal has extremely high theoretical specific capacity (3860mAh g)-1) And a very low redox potential (-3.04V), which can be matched to almost all positive electrode materials. In the positive electrode material, elements of the sixth main group, such as oxygen, sulfur, selenium and the like, can directly perform a four/two electron transfer chemical reaction with the lithium metal, rather than the traditional lithium deintercalation reaction, and the self weight is light, so that the lithium metal battery has the theoretical specific capacity and the energy density far higher than those of the lithium ion battery. From the prior art, the lithium metal battery mainly comprising the lithium-sulfur battery can well meet the power requirement of the electric automobile, improve the endurance mileage of the electric automobile and is most promisingThe lithium ion battery is replaced, and becomes the first choice power battery of the next generation. In addition, the sulfur resource used by the lithium-sulfur battery is rich, the price is low, the structure is simple, the recovery is easy, and the environment is friendly.
Although the lithium sulfur battery has the above-mentioned advantages, it also has a series of problems. First, elemental sulfur, mesophase polysulfide and the final product lithium sulfide have poor electrical conductivity, especially at room temperature, which is only 5X 10-30Scm-1The rate performance of the lithium-sulfur battery is greatly influenced. Secondly, the intermediate phase polysulfide in the electrochemical reaction process is easily dissolved in the electrolyte, so that a remarkable shuttle effect is generated between the anode and the cathode, and the utilization rate of the active substance is reduced. Wherein, the dissolved polysulfide is converted into lithium disulfide or lithium sulfide, and is easy to deposit on the surface of the electrode, thereby hindering the transmission of electrons and ions, and reducing the conductivity, ion transmission rate, coulombic efficiency and cycle life of the electrode. Thirdly, during charging and discharging, the lithium sulfide is powdered and separated from the electrode due to huge volume expansion caused by lithiation of sulfur, so that the active material on the electrode is reduced and the capacity is attenuated. Finally, lithium dendrites and volume expansion are easily generated in the lithium metal negative electrode in the circulation process, and the lithium metal negative electrode is likely to pierce a diaphragm to cause short circuit of the battery, so that potential safety hazards are brought to the battery.
In order to solve the problems of the above-mentioned lithium sulfur batteries, researchers have made many studies. For modification of the positive active material sulfur, on one hand, the elemental sulfur is compounded with a matrix material which has good conductivity and a specific porous structure, so that the high-performance sulfur-based composite positive material is obtained. There are three main categories of selection of matrix materials in sulfur-based composites. The first type of matrix material is most studied and most common carbon-based material, and includes activated carbon, mesoporous carbon, conductive carbon black, carbon nanofibers, multiwalled carbon nanotubes, graphene, and the like. The second kind of matrix material is composite sulfur-base composite positive electrode material prepared with nanometer metal oxide and simple substance sulfur and includes nanometer La2O3Nano V, nano2O5And nano TiO2And the like. The third kind of matrix material isThe conductive polymer is used as a matrix material. For the modification of the positive electrode material sulfur, on the other hand, an organic sulfide is used as an active material. The purpose of releasing and storing energy is achieved by repeated breakage and bonding of S-S bonds mainly in electrochemical reaction of the organic sulfide. For modification of the negative active material metal lithium, on one hand, a stable solid electrolyte interface film can be formed on the surface of the negative electrode by regulating and controlling the components of the electrolyte, or a stable artificial interface layer is inserted between the diaphragm and the negative electrode, so that lithium dendrites are prevented from puncturing the diaphragm. On the other hand, the lithium is stored by utilizing a porous host material, and the volume expansion of the lithium metal negative electrode is relieved while the growth of lithium dendrites is inhibited.
Research shows that the existing technology modifies the sulfur elementary substance of the active material based on an outside-in method, namely, after synthesizing various porous materials, the elementary sulfur is filled into micro-nano holes of the porous materials. For example, the group of the Arumugam Manthiram project uses foamed nickel as a current collector, and sulfur simple substance is filled in the gap of the foamed nickel, so that the electron conductivity and the ion transmission rate of the sulfur positive electrode are improved to a certain extent. The discharge capacity at 0.2C multiplying power is larger than 900mAhg-1. See in particular (Sheng-Heng Chung, Arumugam Manthird. Lithium-sulfurr batters with super spore cycle viability by injecting pore current collectors. Electrochimica Acta 107(2013) 569-. However, in the prior art, elemental sulfur is difficult to fill up the micro-nano pores of the porous material, so that the prepared lithium sulfur battery has low sulfur surface density and is difficult to meet the requirement of a power battery on a high-load active material.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide an electrode material based on a chemical nickel plating core-shell structure, a preparation method thereof and a lithium sulfur battery.
The purpose of the invention can be realized by the following technical scheme: a preparation method of an electrode material based on a chemical nickel-plating core-shell structure comprises the following steps:
(1) dispersing sulfur powder into deionized water, and then performing ultrasonic dispersion to ensure that sulfur particles are fine and monodisperse;
(2) putting the sulfur particles obtained in the step (1) after ultrasonic dispersion into a sensitizing solution for sensitizing treatment;
(3) putting the sensitized sulfur particles into an activating solution for activating;
(4) and (3) placing the activated sulfur particles into a nickel plating solution for chemical plating, so that the surface of the elemental sulfur particles is uniformly coated with a layer of highly conductive metal nickel, and the electrode material with the nickel-sulfur core-shell structure is obtained.
Further, the preparation process of the sensitizing solution comprises the steps of firstly dissolving stannous chloride into concentrated hydrochloric acid, and then adding deionized water for dilution, so that the concentration of the stannous chloride in the sensitizing solution is 5-50g/L, the concentration of the concentrated hydrochloric acid is 5-50mL/L, and the time of sensitizing treatment is 10-30 min. The dispersed stannous ions are easily and uniformly attached to the surface of the sulfur particles, and provide a solid foundation for the next step of sensitizing ion exchange.
Furthermore, the adding amount of the sulfur particles in the step (2) in the sensitizing solution is 0.1g-500 g/L.
Further, the preparation process of the activation solution comprises the steps of dissolving palladium chloride into concentrated hydrochloric acid, and then adding deionized water for dilution, so that the mass concentration of the palladium chloride in the activation solution is 0.2-2g/L, and the concentration of the concentrated hydrochloric acid is 0.5-50 mL/L. The activation treatment time is 10-30 min. The palladium ions in the activation liquid are converted into palladium simple substances to be attached to the surfaces of the sulfur particles after being sensitized in the previous step, and a catalytic action is provided for the subsequent reduction of the nickel ions.
Furthermore, the adding amount of the sulfur particles in the step (3) in the activating solution is 0.1g-500 g/L.
Further, the solute of the nickel plating solution is as follows: 10-50g/L of nickel sulfate hexahydrate, 10-50g/L of sodium hypophosphite, 1-20g/L of sodium citrate, 1-20g/L of sodium acetate, 1-10g/L of ammonium sulfate, 0.1-1g/L of ammonium chloride, 0.1-1g/L of thiourea, 0.3-3g/L of potassium pyrosulfate, and the solvent is deionized water. Wherein, nickel sulfate provides a nickel source, sodium hypophosphite is used as a reducing agent to provide chemical energy for nickel reduction, and other complexing agents and PH regulators are matched to uniformly reduce nickel ions to the surface of sulfur particles and wrap the sulfur particles to form a nickel-sulfur core-shell structure.
Furthermore, the adding amount of the sulfur particles in the step (4) in the nickel plating solution is 0.1g-500 g/L.
Furthermore, the temperature of the chemical plating process is 30-80 ℃ and the time is 2-30 min.
The invention also provides the core-shell structure electrode material prepared by the method, the surface of the elemental sulfur particles is uniformly coated with a layer of high-conductivity metallic nickel, wherein the particle size of the elemental sulfur particles is 1nm-50um, and the thickness of the coating layer is 1nm-100 nm.
The invention also provides a lithium-sulfur battery which adopts the electrode material with the core-shell structure as an electrode material. In the preparation process of the lithium-sulfur battery based on the chemical nickel-plating core-shell structure, a sensitizing stage provides stannous ions as a reducing agent for reducing palladium ions for an activating stage, and the activating stage provides a palladium simple substance as a catalyst for the chemical plating stage. In the chemical plating stage, nickel ions and a reducing agent sodium hypophosphite uniformly reduce and wrap nickel simple substances to the surfaces of sulfur particles under the action of a palladium catalyst, so that a nickel-sulfur core-shell structure is formed.
Compared with the prior art, the invention has the following beneficial effects:
1. in the lithium-sulfur battery prepared by the invention, the nickel-sulfur composite material with the core-shell structure has high conductivity, so that electrons can be quickly conducted to an interface of an electrochemical reaction, the electrochemical reaction rate is improved, and the release of the battery capacity performance is promoted.
2. The close wrapping of the metal nickel on the elemental sulfur inhibits the dissolution of the intermediate phase polysulfide in the electrolyte and the generation of subsequent shuttle effect in the charging and discharging process. The chemical adsorption of polysulfides by metallic nickel further inhibits polysulfide dissolution. The physical adsorption and the chemical adsorption are cooperated to improve the cycle performance of the lithium-sulfur battery.
3. The electrode prepared from the nickel-sulfur composite material with the core-shell structure does not need other conductive host materials, so that the electrode has high active material load. Higher active material loading, higher areal capacity and energy density are achieved.
Drawings
FIG. 1 is a scanning electron micrograph of the nano nickel-sulfur powder obtained in example 1;
FIG. 2 is a charge-discharge curve of the nickel-sulfur composite material obtained in example 1;
FIG. 3 Rate Properties of the nickel sulphur composite obtained in example 1;
FIG. 4 is a charge-discharge curve of the nickel-sulfur composite material obtained in example 2;
FIG. 5 Rate Properties of the resulting nickel sulfur composite of example 2;
FIG. 6 is a charge-discharge curve of the nickel-sulfur composite material obtained in example 3;
FIG. 7 Rate Performance of the resulting nickel sulfur composite of example 3.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
The preparation method of the lithium-sulfur battery based on the carbon photonic crystal metal coating structure comprises the steps of dispersing sulfur powder into deionized water, and then carrying out ultrasonic dispersion to enable sulfur particles to be fine and monodisperse.
Further, sensitizing solution with certain concentration is used for sensitizing the surfaces of the sulfur particles dispersed by ultrasonic. And (5) after sensitization, washing the mixture to be neutral by using deionized water, and drying the mixture in vacuum. The preparation process of the sensitizing solution comprises the steps of firstly dissolving a certain mass of stannous chloride into concentrated hydrochloric acid, and then adding a proper amount of deionized water for dilution. The concentration of stannous chloride is 5-50g/L, and the concentration of concentrated hydrochloric acid is 5-50 mL/L. The sensitization time is 10-30 min.
Further, activating the surface of the sensitized sulfur particles by using an activating solution with a certain concentration. After activation, the mixture is washed to be neutral by deionized water and dried in vacuum. The preparation process of the activating solution comprises the steps of firstly dissolving a certain mass of palladium chloride into concentrated hydrochloric acid, and then adding a proper amount of deionized water for dilution. The mass concentration of the palladium chloride is 0.2-2g/L, and the concentration of the concentrated hydrochloric acid is 0.5-50 mL/L. The activation time is 10-30 min.
Further, the activated sulfur particles are placed in a nickel plating solution for chemical plating. And after chemical plating, washing the substrate with deionized water to be neutral, and drying the substrate in vacuum. The solute of the nickel plating solution is 10-50g/L of nickel sulfate hexahydrate, 10-50g/L of sodium hypophosphite, 1-20g/L of sodium citrate, 1-20g/L of sodium acetate, 1-10g/L of ammonium sulfate, 0.1-1g/L of ammonium chloride, 0.1-1g/L of thiourea, 0.3-3g/L of potassium pyrosulfate, and the solvent is deionized water. The temperature of the chemical plating process is 30-80 ℃ and the time is 2-30 min.
The following are more detailed embodiments, and the technical solutions and the technical effects obtained by the present invention will be further described by the following embodiments.
Example 1
The preparation method of the electrode material based on the chemical nickel plating core-shell structure comprises the following steps:
(1) the sulfur powder was dispersed into deionized water, followed by ultrasonic dispersion for 1h, so that the sulfur particles were fine and monodisperse.
(2) Sensitizing the surface of the sulfur particles dispersed by ultrasonic by using sensitizing solution with certain concentration. And (5) after sensitization, washing the mixture to be neutral by using deionized water, and drying the mixture in vacuum. The preparation process of the sensitizing solution comprises the steps of firstly dissolving a certain mass of stannous chloride into concentrated hydrochloric acid, and then adding a proper amount of deionized water for dilution. The concentration of stannous chloride is 5g/L, and the concentration of concentrated hydrochloric acid is 5 mL/L. The sensitization time is 30 min.
(3) Activating the surface of the sensitized sulfur particles by using an activating solution with a certain concentration. After activation, the mixture is washed to be neutral by deionized water and dried in vacuum. The preparation process of the activating solution comprises the steps of firstly dissolving a certain mass of palladium chloride into concentrated hydrochloric acid, and then adding a proper amount of deionized water for dilution. The mass concentration of the palladium chloride is 0.2g/L, and the concentration of the concentrated hydrochloric acid is 5 mL/L. The activation time was 30 min.
(4) And placing the activated sulfur particles in a nickel plating solution for chemical plating. And after chemical plating, washing the substrate with deionized water to be neutral, and drying the substrate in vacuum. The solute of the nickel plating solution is 10g/L nickel sulfate hexahydrate, 10g/L sodium hypophosphite, 1g/L sodium citrate, 1g/L sodium acetate, 1g/L ammonium sulfate, 0.1g/L ammonium chloride, 0.1g/L thiourea, 0.3g/L potassium pyrosulfate, and the solvent is deionized water. The temperature of the chemical plating process is 80 ℃, and the time is 30 min.
An electron microscope photograph of the electrode material with the core-shell structure prepared by the method is shown in fig. 1, and it can be seen that a plurality of nickel particles are uniformly attached to the surface of the sulfur particle.
FIG. 2 is a charge-discharge curve of the nickel-sulfur composite material obtained in example 1, and it can be seen that the nickel-sulfur composite material has a specific discharge capacity as high as 1410 mAh/g.
FIG. 3 shows the rate capability of the nickel-sulfur composite material obtained in example 1, which is excellent in rate capability, and the specific discharge capacities at 2C and 5C discharge currents are 805mAh/g and 630mAh/g, respectively.
Example 2
The preparation method of the electrode material based on the chemical nickel plating core-shell structure comprises the following steps:
(1) the sulfur powder was dispersed into deionized water, followed by ultrasonic dispersion for 1h, so that the sulfur particles were fine and monodisperse.
(2) Sensitizing the surface of the sulfur particles dispersed by ultrasonic by using sensitizing solution with certain concentration. And (5) after sensitization, washing the mixture to be neutral by using deionized water, and drying the mixture in vacuum. The preparation process of the sensitizing solution comprises the steps of firstly dissolving a certain mass of stannous chloride into concentrated hydrochloric acid, and then adding a proper amount of deionized water for dilution. The concentration of stannous chloride is 10g/L, and the concentration of concentrated hydrochloric acid is 10 mL/L. The sensitization time is 20 min.
(3) Activating the surface of the sensitized sulfur particles by using an activating solution with a certain concentration. After activation, the mixture is washed to be neutral by deionized water and dried in vacuum. The preparation process of the activating solution comprises the steps of firstly dissolving a certain mass of palladium chloride into concentrated hydrochloric acid, and then adding a proper amount of deionized water for dilution. The mass concentration of the palladium chloride is 0.5g/L, and the concentration of the concentrated hydrochloric acid is 20 mL/L. The activation time was 20 min.
(4) And placing the activated sulfur particles in a nickel plating solution for chemical plating. And after chemical plating, washing the substrate with deionized water to be neutral, and drying the substrate in vacuum. The solute of the nickel plating solution is 20g/L nickel sulfate hexahydrate, 20g/L sodium hypophosphite, 10g/L sodium citrate, 10g/L sodium acetate, 5g/L ammonium sulfate, 0.2g/L ammonium chloride, 0.1g/L thiourea, 0.3g/L potassium pyrosulfate, and the solvent is deionized water. The temperature of the chemical plating process is 50 ℃ and the time is 10 min.
FIG. 4 shows the charge and discharge curves of the nickel-sulfur composite material obtained in example 2, and it can be seen that the nickel-sulfur composite material has a specific discharge capacity as high as 1360 mAh/g.
Fig. 5 shows the rate capability of the nickel-sulfur composite material obtained in example 2, and it can be seen from the graph that the nickel-sulfur composite material has excellent rate capability, and the specific discharge capacities under 2C and 5C discharge currents are 785mAh/g and 580mAh/g, respectively.
Example 3
The preparation method of the electrode material based on the chemical nickel plating core-shell structure comprises the following steps:
(1) the sulfur powder was dispersed into deionized water, followed by ultrasonic dispersion for 1h, so that the sulfur particles were fine and monodisperse.
Sensitizing the surface of the sulfur particles dispersed by ultrasonic by using sensitizing solution with certain concentration. And (5) after sensitization, washing the mixture to be neutral by using deionized water, and drying the mixture in vacuum. The preparation process of the sensitizing solution comprises the steps of firstly dissolving a certain mass of stannous chloride into concentrated hydrochloric acid, and then adding a proper amount of deionized water for dilution. The concentration of stannous chloride is 20g/L, and the concentration of concentrated hydrochloric acid is 20 mL/L. The sensitization time is 10 min.
(4) Activating the surface of the sensitized sulfur particles by using an activating solution with a certain concentration. After activation, the mixture is washed to be neutral by deionized water and dried in vacuum. The preparation process of the activating solution comprises the steps of firstly dissolving a certain mass of palladium chloride into concentrated hydrochloric acid, and then adding a proper amount of deionized water for dilution. The mass concentration of the palladium chloride is 1g/L, and the concentration of the concentrated hydrochloric acid is 20 mL/L. The activation time was 10 min.
(5) And placing the activated sulfur particles in a nickel plating solution for chemical plating. And after chemical plating, washing the substrate with deionized water to be neutral, and drying the substrate in vacuum. The solute of the nickel plating solution is 30g/L nickel sulfate hexahydrate, 30g/L sodium hypophosphite, 20g/L sodium citrate, 15g/L sodium acetate, 10g/L ammonium sulfate, 0.5g/L ammonium chloride, 0.3g/L thiourea, 0.9g/L potassium pyrosulfate, and the solvent is deionized water. The temperature of the chemical plating process is 30 ℃ and the time is 10 min.
FIG. 6 is a charge-discharge curve of the nickel-sulfur composite material obtained in example 3, and it can be seen that the nickel-sulfur composite material has a specific discharge capacity as high as 1290 mAh/g.
Fig. 7 shows the rate capability of the nickel-sulfur composite material obtained in example 3, and it can be seen from the graph that the nickel-sulfur composite material has excellent rate capability, and the specific discharge capacities under 2C and 5C discharge currents are 705mAh/g and 530mAh/g, respectively.
The electrode materials of the core-shell structure obtained in examples 1 to 3 above were used as positive electrodes of lithium sulfur batteries. Mixing and grinding the electrode active material, the conductive agent and the adhesive according to the mass ratio of 80%, 10% and 10%, adding a proper amount of N-methyl pyrrolidone solution, ultrasonically stirring to form slurry, then coating the slurry on an aluminum foil to obtain a lithium-selenium battery positive plate, and assembling the battery by taking the lithium plate as a counter electrode.
The lithium-sulfur battery assembled by the method is subjected to performance detection, and the detection method comprises the following steps:
specific capacity: and (3) placing the assembled battery on a battery tester, setting a charging and discharging voltage interval and constant current parameters, testing the battery capacity in a constant current charging and discharging mode, and calculating the specific capacity of the battery according to the quality of the electrode active material.
Energy density: and placing the assembled battery on a battery tester, setting a charging and discharging voltage interval and constant current parameters, testing the energy of the battery in a constant current charging and discharging mode, and calculating the energy density according to the mass of the battery.
Electron conductivity: the assembled cell was placed on an electrochemical workstation, the frequency was set, and the electrochemical impedance of the cell was tested. And performing equivalent circuit fitting on the impedance to obtain each partial resistance, thereby judging the electron conductivity.
Ion transmission rate: and (3) placing the assembled battery on an electrochemical workstation, setting a voltage interval and a voltage sweeping speed, and testing cyclic voltammetry curves of the battery at different sweeping speeds. And calculating the ion transmission rate of the battery according to the cyclic voltammetry curve result.
Rate capability: and placing the assembled battery on a battery tester, setting a charging and discharging voltage interval, setting gradually-increased current parameters, and obtaining the multiplying power performance of the battery according to the charging and discharging capacity and the electrode active material quality under different charging and discharging currents.
Comparative example a lithium sulphur cell was made as a comparative example using sulphur powder and graphite powder mixed by a method as disclosed in CN202110945500.2, and the results are shown in the following table:
Figure BDA0003459444870000081
Figure BDA0003459444870000091
compared with a comparative example (a core-shell structure is not formed), the nickel-sulfur composite material with the core-shell structure prepared by the method has high conductivity, so that electrons can be quickly conducted to an electrochemical reaction interface, the electrochemical reaction rate is improved, and the release of the battery capacity performance is promoted.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The embodiments described above are intended to facilitate the understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (10)

1. A preparation method of an electrode material based on a chemical nickel-plating core-shell structure is characterized by comprising the following steps:
(1) dispersing sulfur powder into deionized water, and then performing ultrasonic dispersion to ensure that sulfur particles are fine and monodisperse;
(2) putting the sulfur particles obtained in the step (1) after ultrasonic dispersion into a sensitizing solution for sensitizing treatment;
(3) putting the sensitized sulfur particles into an activating solution for activating;
(4) and (3) placing the activated sulfur particles into a nickel plating solution for chemical plating, so that the surface of the elemental sulfur particles is uniformly coated with a layer of highly conductive metal nickel, and the electrode material with the nickel-sulfur core-shell structure is obtained.
2. The preparation method of the electrode material based on the chemical nickel-plating core-shell structure according to claim 1, wherein the preparation process of the sensitizing solution comprises the steps of dissolving stannous chloride into concentrated hydrochloric acid, and then adding deionized water for dilution, so that the concentration of the stannous chloride in the sensitizing solution is 5-50g/L, the concentration of the concentrated hydrochloric acid is 5-50mL/L, and the time for sensitizing treatment is 10-30 min.
3. The preparation method of the electrode material based on the electroless nickel plating core-shell structure, according to claim 1, is characterized in that the addition amount of the sulfur particles in the step (2) in the sensitizing solution is 0.1g-500 g/L.
4. The method for preparing an electrode material based on a chemical nickel plating core-shell structure according to claim 1, wherein the preparation process of the activation solution comprises the steps of dissolving palladium chloride into concentrated hydrochloric acid, and then adding deionized water for dilution, so that the mass concentration of the palladium chloride in the activation solution is 0.2-2g/L, and the concentration of the concentrated hydrochloric acid is 0.5-50 mL/L. The activation treatment time is 10-30 min.
5. The preparation method of the electrode material based on the electroless nickel plating core-shell structure, according to claim 1, is characterized in that the addition amount of the sulfur particles in the activation solution in the step (3) is 0.1g-500 g/L.
6. The method for preparing the electrode material based on the chemical nickel plating core-shell structure according to claim 1, wherein the nickel plating solution comprises the following solutes: 10-50g/L of nickel sulfate hexahydrate, 10-50g/L of sodium hypophosphite, 1-20g/L of sodium citrate, 1-20g/L of sodium acetate, 1-10g/L of ammonium sulfate, 0.1-1g/L of ammonium chloride, 0.1-1g/L of thiourea, 0.3-3g/L of potassium pyrosulfate, and the solvent is deionized water.
7. The method for preparing the electrode material based on the chemical nickel plating core-shell structure according to the claim 1, characterized in that the adding amount of the sulfur particles in the step (4) in the nickel plating solution is 0.1g-500 g/L.
8. The method for preparing the electrode material based on the chemical nickel plating core-shell structure according to the claim 1, wherein the temperature of the chemical plating process is 30-80 ℃ and the time is 2-30 min.
9. An electrode material of core-shell structure prepared by the method according to any one of claims 1 to 8.
10. A lithium-sulfur battery, characterized in that it employs the core-shell structure electrode material of claim 9 as an electrode material.
CN202210012333.0A 2022-01-07 2022-01-07 Chemical nickel plating based electrode material with core-shell structure, preparation method thereof and lithium-sulfur battery Pending CN114420906A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103035879A (en) * 2012-12-07 2013-04-10 湘潭大学 Positive pole piece for lithium-sulfur batteries and preparation method thereof
CN104835946A (en) * 2015-05-30 2015-08-12 田东 Tin and carbon composite cathode material of lithium ion battery and preparation method of tin and carbon composite cathode material
CN108123167A (en) * 2016-11-28 2018-06-05 中国科学院大连化学物理研究所 A kind of lithium-sulfur cell electrode and its preparation and the lithium-sulfur cell structure for including it
CN108118315A (en) * 2018-02-24 2018-06-05 唐山师范学院 A kind of method of the uniform and stable silicon carbide powder chemical nickel plating on surface of coating
CN111224076A (en) * 2018-11-26 2020-06-02 中国科学院大连化学物理研究所 Electrode for inhibiting polysulfide ion shuttle in lithium-sulfur battery, preparation and application

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103035879A (en) * 2012-12-07 2013-04-10 湘潭大学 Positive pole piece for lithium-sulfur batteries and preparation method thereof
CN104835946A (en) * 2015-05-30 2015-08-12 田东 Tin and carbon composite cathode material of lithium ion battery and preparation method of tin and carbon composite cathode material
CN108123167A (en) * 2016-11-28 2018-06-05 中国科学院大连化学物理研究所 A kind of lithium-sulfur cell electrode and its preparation and the lithium-sulfur cell structure for including it
CN108118315A (en) * 2018-02-24 2018-06-05 唐山师范学院 A kind of method of the uniform and stable silicon carbide powder chemical nickel plating on surface of coating
CN111224076A (en) * 2018-11-26 2020-06-02 中国科学院大连化学物理研究所 Electrode for inhibiting polysulfide ion shuttle in lithium-sulfur battery, preparation and application

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