CN108123167B - Electrode for lithium-sulfur battery, preparation method of electrode and lithium-sulfur battery structure comprising electrode - Google Patents

Electrode for lithium-sulfur battery, preparation method of electrode and lithium-sulfur battery structure comprising electrode Download PDF

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CN108123167B
CN108123167B CN201611062786.5A CN201611062786A CN108123167B CN 108123167 B CN108123167 B CN 108123167B CN 201611062786 A CN201611062786 A CN 201611062786A CN 108123167 B CN108123167 B CN 108123167B
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electrode
nickel
lithium
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sulfur
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CN108123167A (en
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勾剑
张华民
张洪章
李先锋
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Dalian Institute of Chemical Physics of CAS
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • 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
    • 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
    • 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
    • H01M4/621—Binders
    • 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
    • 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 discloses an electrode for a lithium-sulfur battery, wherein a metal nickel layer is deposited on the surfaces of two sides of an electrode substrate through chemical in-situ deposition of the electrode substrate, metal nickel is deposited in the electrode substrate, and the thickness of the metal nickel layer on the surface of the electrode is 0.2-4 mu m; the electrode is applied to the lithium-sulfur battery, can obviously improve the performance and the energy density of the lithium-sulfur battery, has simple operation process of the chemical plating in-situ deposition technology, mild experimental conditions and lower experimental cost, and has great potential for realizing future industrialized large-scale production.

Description

Electrode for lithium-sulfur battery, preparation method of electrode and lithium-sulfur battery structure comprising electrode
Technical Field
The invention relates to the field of lithium-sulfur batteries, in particular to a flexible electrode of a lithium-sulfur battery.
Background
In recent years, with the increasing global energy and environmental crisis, lithium ion batteries have become the first choice power source for various electronic products, such as notebook computers, electric bicycles, and other electronic devices. However, with the development of flexible electronics, there is an increasing demand for flexible and wearable media devices, such as OLED flexible smart phones, implantable devices, and the like, and these high performance portable electronic devices also require a high performance battery with good flexibility as a power output in addition to good mechanical flexibility. Although the lithium ion battery has the advantages of high working voltage, long cycle life and the like, the energy density is relatively low, and the poor mechanical property is a major bottleneck restricting the development of the lithium ion battery in the field of flexible batteries. For example, for a lithium ion secondary battery, the specific discharge energy is usually 100-200 Wh-kg-1. When the battery is used as a power supply of an electric automobile, the single charge and discharge can only meet the requirement that the single charge and discharge mileage reaches 500km, which is provided by the United States Advanced Battery Council (USABC).
Lithium-sulfur batteries stand out in numerous secondary battery systems not only because of their low sulfur price, environmental friendliness and abundant reserves as the positive active material, but also because of their practical specific energy in combination with metallic lithium electrodes of more than 500 Wh-kg-1. Therefore, the lithium sulfur battery is considered as one of novel secondary batteries which can replace the lithium ion battery, and the flexible lithium sulfur battery has good application prospect.
However, in the development process of the lithium-sulfur flexible battery, many problems need to be solved. Firstly, the commercialization process of lithium-sulfur batteries is seriously hindered by the problems of poor rate performance, poor cycle stability, low utilization rate of active substances and the like of the lithium-sulfur batteries. The "shuttle effect" of lithium polysulfide, which is an intermediate product in discharge, is one of the main reasons for influencing the performance of lithium-sulfur batteries. In order to solve the "shuttle effect" problem of polysulfide, the existing common solution uses a hierarchical porous carbon material as a carrier of active substance sulfur, which not only can load high-load active substance sulfur due to its large pore volume and high specific surface area, but also has a good physical adsorption effect on the discharge product polysulfide, thereby slowing down the shuttle effect of polysulfide. The carbon materials used as the sulfur-carrying materials generally include porous carbon materials, carbon nanotube nanofiber materials, hollow carbon materials, graphene materials, carbon materials compounded with each other, and the like, but the carbon materials have weak adsorption force on polysulfides due to the nonpolar characteristics of the carbon materials, so that the effect of reducing the "shuttle effect" of the polysulfides is not very obvious.
Secondly, in the preparation of a flexible electrode of a lithium-sulfur battery, an electrode slurry generally comprises an active material, a binder, and a conductive agent, and in order to improve the flexibility and mechanical properties of the battery, the proportion of the binder is greatly increased, so that the electrical conductivity of the electrode is reduced. The problems that the internal electron transport network of the electrode is discontinuous and the utilization rate of the active material is low due to the non-conductivity of the active material and the discharge product existing in the original lithium-sulfur battery are more acute. Meanwhile, in the process of preparing the electrode material, the prepared electrode slurry is usually coated on a metal film, the thickness of the electrode slurry is usually about 25 μm, the metal film not only occupies a certain electrode weight as a current collector, but also can only be used as an inactive substance in the electrode material so as to reduce the volume and mass energy density, and in a flexible device, the electrode material faces the problem that the active substance is peeled off from the film in the bending process of the battery so as to influence the performance of the battery. The existing method for preparing the flexible electrode mainly comprises the steps of using a material with light weight, good mechanical property and excellent conductivity, such as a graphene coating to replace a metal film as a current collector, or adding conductive agents such as graphene, carbon nanotubes and the like into electrode slurry to improve the conductivity inside the electrode, and the methods have the problems of high manufacturing cost and complex process firstly, and the problem that the discontinuous conductive network inside the electrode caused by the overhigh addition ratio of a binder cannot be solved by adding the conductive agent graphene or the carbon nanotubes into the electrode slurry.
The chemical plating is used as an autocatalytic reaction, and the coating deposited by the method has the characteristics of uniform thickness, high deposition speed and the like. Electroless plating technology has been used to coat the interior walls of pipes in the second war, after which a series of electroless coatings such as Ni-W, Ni-P, Ni-B and the like began to develop and apply rapidly. In recent decades, electroless coatings have been commonly used in the fields of aviation, petrochemical industry, medical devices, etc. in the form of alloy coatings, composite coatings, metal coatings, etc., and among them, 95% of industrial electroless coatings use Ni-P, Ni-B-based alloy coatings, and especially Ni-P-based alloy coatings and composite coatings have been widely used in recent 10 years.
The invention content is as follows:
the invention aims to apply an electrode with a nickel layer deposited on the surface to a lithium-sulfur battery, and the step of preparing the electrode with the nickel layer deposited on the surface by a chemical plating method comprises the following steps: firstly, carrying out activation pretreatment on an electrode material matrix needing chemical in-situ deposition. Secondly, the pretreated electrode material is placed in a chemical plating solution for internal and surface chemical in-situ deposition modification.
The electrode is deposited with a metal nickel layer on the two side surfaces of the electrode matrix through chemical in-situ deposition, the metal nickel is deposited in the electrode matrix, and the thickness of the metal nickel layer on the surface of the electrode is 0.2-4 mu m; the electrode matrix comprises a carbon material, sulfur and a binder, wherein the mass content of the sulfur is 40-50%, the mass content of the binder is 20-35%, and the mass content of metal nickel in the electrode matrix accounts for 0.01-2 wt% of the electrode.
The carbon material comprises one or more than two of carbon nano tubes, graphene, carbon nano fibers, BP2000, KB600, KB300 and Super-P.
The binder is one or two of polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), polyvinylidene fluoride (PVDF) and polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP).
The specific operation process is as follows:
1) pretreatment of an electrode substrate: dissolving nickel salt in a solution of sulfuric acid, hydrochloric acid or nitric acid with the pH value of 2.0-5.0, wherein the solution adopts one or more of water, ethanol, DMSO and sulfolane as a solvent, the nickel salt is one or more of nickel sulfate, nickel chloride, nickel acetate and nickel nitrate, and the mass concentration of the pretreatment solution is 180-;
the activation pretreatment solution is used as electrolyte, the electrode matrix and the nickel sheet are respectively used as a negative electrode and a positive electrode, and the surface area of the electrode matrix is 0.01-20mA/cm2Activating for 1-10 minutes under the current density of (1);
2) carrying out chemical Ni plating modification: the chemical plating solution comprises an aqueous solution consisting of nickel salt, a reducing agent, a complexing agent and a buffer, wherein the nickel salt is one or more than two of nickel chloride, nickel sulfate, nickel phosphate and nickel acetate, and the mass concentration of the nickel salt is 10-50 g/L; the reducing agent is one or more than two of sodium hypophosphite, hydrazine hydrate and sodium borohydride, and the mass concentration is 10-50 g/L; the complexing agent is one or more than two of EDTA, EGTA, sodium tartrate and sodium citrate, and the mass concentration is 10-50 g/L; the buffer is one or more than two of sodium acetate, ammonium acetate and ammonium chloride, and the mass concentration is 10-50 g/L; solutions ofPH is between 4.0 and 5.0 or between 8.0 and 9.5; the temperature is controlled between 60 ℃ and 90 ℃ and the time is controlled between 15 minutes and 8 hours in the chemical plating process.
The chemical plating solution also comprises a stabilizer which is one or more than two of sodium thiosulfate, potassium iodide and thiourea, and the mass concentration is 0.01-0.1 g/L;
the pH regulator is 100-400g/L hydrochloric acid or sulfuric acid solution; 40-160g/L sodium hydroxide or potassium hydroxide solution.
The nickel salt in the chemical plating solution is preferably sodium phosphate, and the reducing agent is preferably sodium hypophosphite.
The electrode is used as a positive electrode in a lithium-sulfur battery, and the lithium-sulfur battery consists of the positive electrode, a membrane and a lithium negative electrode.
The beneficial results of the invention are:
the invention can realize the control of the indexes of the thickness, the appearance, the components and the like of the chemical plating Ni coating coated on the surface of the anode material by adjusting the current density and the activation time in the chemical plating pretreatment process and adjusting and controlling the components, the pH value and the time of the chemical plating solution. Therefore, the chemical plating coating can be used as a physical barrier to slow down the diffusion of lithium polysulfide, and simultaneously can change the nonpolar characteristic of the original carbon material of the sulfur carrier in the aspect of chemical polar bond energy to enhance the adsorption of the lithium polysulfide, thereby improving the utilization rate of active substances of the lithium sulfur battery and prolonging the cycle life of the lithium sulfur battery. In addition, surface layer and internal nickel plating modification is carried out on two sides of the sulfur/carbon positive electrode matrix by applying a chemical in-situ deposition technology, and the construction of an electronic transmission network inside and on the surface layer of the electrode can be completed, so that the problem that the electronic transmission network inside and on the interface of the electrode is discontinuous due to the addition of too much binder in the preparation of the lithium-sulfur flexible positive electrode material is effectively solved, the traditional current collector metal film and the conductive agent are replaced, the flexibility of the electrode is increased, and the performance of the lithium-sulfur battery is improved. The chemical plating modification process is simple to operate, mild in experimental conditions and low in experimental cost, and has great potential for realizing future industrial large-scale production.
Drawings
FIG. 1: photographs of the electrode of comparative example 1 (left panel) and the electrode of example 2 (right panel);
FIG. 2: example 2 surface SEM (left) and cross-sectional SEM images (right);
FIG. 3: rate performance discharge curves at 0.1C-1C rate for lithium sulfur batteries assembled as comparative example 1, comparative example 2, example 1 and 2;
FIG. 4: cycle stability testing of lithium sulfur batteries assembled with comparative example 1, comparative example 2, examples 1 and 2;
fig. 5 ac impedance test of assembled lithium sulfur batteries with comparative example 1, comparative example 2, examples 1 and 2.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to limit the scope of the present invention.
COMPARATIVE EXAMPLE 1 (without nickel plating)
20g of commercial KB600 was placed in a tube furnace under Ar protection at 5 ℃ for min-1Heating to 900 deg.C, introducing steam for activation for 1.5h, wherein the flow rate of steam is 600mL min-1The activated carbon material was designated A-KB 600. Mixing 10g A-KB600 and 20g S, heating to 155 deg.C in a tube furnace at a heating rate of 1 deg.C for min-1Keeping the temperature constant for 20 hours, and recording the obtained product as S/A-KB600, wherein the sulfur filling amount is 75 percent. Dissolving 2g of PVDF-HFP binder in 40g N-methylpyrrolidone (NMP), stirring for 1h, adding 4g S/A-KB600, stirring for 4h, adjusting a scraper to 300 mu m, blade-coating an aluminum film to form a film, quickly immersing the film in water for 10min, taking out the film, drying the film at 65 ℃ overnight, shearing the film into small round pieces with the diameter of 10mm, weighing the small round pieces, drying the small round pieces in vacuum at 60 ℃ for 24h, and taking the small round pieces coated with the S/A-KB600 as a positive electrode (the sulfur loading of each round piece is about 2.2mg cm)-2) Lithium sheet as negative electrode, celgard 2325 as diaphragm, 1M lithium bis (trifluoromethylsulfonyl) imide solution (LiTFSI) plus 5% LiNO3The electrolyte solution was a mixed solution of 1, 3-Dioxolane (DOL) and ethylene glycol dimethyl ether (DME) (volume ratio v/v 1:1), the cell was assembled, and the cell cycle performance test was performed at 0.1C rate and the rate performance test was performed at 0.1C-1C rate.
The specific discharge capacity of the first circle under the multiplying power of 0.1C is 1205mAh g-1The specific capacity is maintained to be 786mAh g after 100 cycles-1(ii) a When the multiplying power is increased to 1C, the specific discharge capacity is 504mAh g-1。
Comparative example 2 (without nickel plating, electrode with conductive agent)
Dissolving 1.4g of PVDF-HFP binder in 40g N-methylpyrrolidone (NMP), stirring for 1h, adding 0.6g of conductive agent KB600 and 4g S/A-KB600 (the sulfur charging amount is 75%), stirring for 4h, adjusting a scraper to 300 mu m, coating an aluminum film to form a film, quickly immersing the film into water, taking out the film after 10min, drying the film at 65 ℃ overnight, shearing the film into small round pieces with the diameter of 10mm, weighing the round pieces, and drying the round pieces in vacuum at 60 ℃ for 24 h. Subsequent cell assembly was the same as comparative example. The assembled battery is subjected to a battery cycle performance test at a rate of 0.1C, and a rate performance test at a rate of 0.1C-1C.
The specific discharge capacity of the first ring is 1340mAh g-1Capacity after 100 cycles was maintained at 819mA hr g-1(ii) a When the multiplying power is improved to 1C, the specific discharge capacity is 789mAh g-1。
Example 1
Dissolving 2g of PVDF-HFP binder in 40g N-methylpyrrolidone (NMP), stirring for 1h, adding 4g S/A-KB600 (with 75% of sulfur charge), stirring for 4h, adjusting a scraper to 300 mu m, blade-coating a film on a glass plate (without using a metal film as a current collector), quickly immersing the glass plate and the electrode coating blade-coated on the glass plate in water for 10min, taking the electrode coating off the glass plate and taking out the electrode coating, drying at 65 ℃ overnight, taking an activation pretreatment solution as an electrolyte, taking an electrode substrate and a nickel sheet as a negative electrode and a positive electrode respectively, and drying the electrode substrate surface area at 10mA/cm2Activated for 4 minutes at the current density of (1). The component of the activation pretreatment solution is hydrochloric acid aqueous solution with pH value of 3 and containing nickel chloride with concentration of 240 g/L; and (3) placing the electrode substrate subjected to activation pretreatment in a chemical plating solution at 90 ℃ for 25 minutes to carry out chemical in-situ deposition of metallic nickel. The chemical plating solution comprises 20g/L of nickel sulfate; 24g/L sodium hypophosphite; 15g/L sodium citrate; 0.01g/L thiourea; 15g/L sodium acetate; the solution PH was 9, and the thickness of the surface-deposited nickel layer obtained by electroless plating modification was about 0.5 μm. And drying the electrode with the deposited nickel layer at 65 ℃ overnight, cutting the electrode into small wafers with the diameter of 10mm, weighing the wafers, and performing vacuum drying at 60 ℃ for 24 hours. Subsequent cell assembly was the same as comparative example. The assembled battery is subjected to a battery cycle performance test at a rate of 0.1C, and a rate performance test at a rate of 0.1C-1C.
The specific discharge capacity of the first coil is 1501mAhg -1100 post cycle capacity dimensionSustain at 954mAhg-1(ii) a When the multiplying power is increased to 1C, the specific discharge capacity is 970mAh g-1。
Example 2
The operation processes of preparing the electrode substrate and modifying the chemical plating are the same as the operation process of the embodiment 1, the modulation parameters are that the chemical plating time is 50 minutes, the thickness of the nickel layer deposited on the surface of the electrode is about 1.0 mu m, the assembled battery is subjected to a battery cycle performance test at a multiplying power of 0.1C, and a multiplying power performance test at a multiplying power of 0.1C-1C.
The specific discharge capacity of the first ring is 1625mAh g-1Capacity after 100 cycles was maintained at 1124mAh g-1(ii) a When the multiplying power is increased to 1C, the specific discharge capacity is 1070mAh g-1。
As shown in figure 1, the surface of the lithium sulfur cathode material modified by electroless Ni plating is deposited with a nickel layer with metallic luster, the nickel layer has the function of inhibiting polysulfide shuttle flying, as shown in figure 2, the surface of the nickel layer is dense, the plating layer is uniformly deposited on the surface of an electrode, and the thickness of the nickel layer is about 1 μm.
As shown in fig. 3, the batteries using comparative example 2 and comparative example 1 as positive electrode materials have higher specific discharge capacity at 0.1C-1C rate in the case of containing electrode current collectors than comparative example 1 because the continuity of the electron conductive network inside the electrode is improved and thus the rate capability of the battery is improved in the comparative example 2 compared to comparative example 1 in which a certain amount of conductive agent is added. Examples 1 and 2 showed better battery rate performance at 0.1C-1C rate than comparative example 1 and comparative example 2 without current collector and conductive agent, because one side of the nickel layer deposited on the two surfaces of the electrode substrate acts as a current collector, and the other side can inhibit the shuttle effect of polysulfide, thereby improving the specific discharge capacity of the battery. Meanwhile, through chemical plating modification, discontinuous electronic conductive networks in the electrodes can be connected, so that the electrodes can have better battery performance under high rate. Example 2 is the optimum electrode in the rate performance test of lithium-sulfur battery, and the thickness of the nickel layer deposited on the surface of the electrode is about 1.0 μm.
As shown in fig. 4, in the 0.1C battery cycle performance test, examples 1 and 2 also exhibited better cycle performance than comparative example 2 and comparative example 1, and both the specific discharge capacity at the first cycle and the battery capacity after 100 cycles were greater than those of comparative example 1 and comparative example 2. The reason is also that the nickel layer deposited on the surface of the electrode can well inhibit the shuttle effect of polysulfide, the utilization rate of active substances is improved, and meanwhile, a discontinuous electronic conductive network in the electrode can be improved in the chemical plating modification process. Example 2 is the optimum electrode in the cycle performance test of the lithium sulfur battery, and the thickness of the nickel layer deposited on the surface of the electrode is 1.0 μm.
As can be seen from fig. 5, comparative example 2, example 1 and example 2 exhibited a smaller electrochemical resistance than comparative example 1 due to the addition of the conductive agent and the electroless nickel-modified electrode surface layer and the interior, and the electron transport network of the electrode surface and the interior, which was constructed by electroless nickel plating, of examples 1 and 2 exhibited a smaller electrochemical resistance than that of comparative example 2 with the addition of the conductive agent. Example 2 exhibited the least resistance performance because the electroless plating time was longer than that of example 1. Ac impedance comparison fig. 5 explains why modification of the electrode by electroless nickel plating has a significant improvement in battery performance of lithium sulfur batteries from an electrochemical impedance perspective.

Claims (6)

1. A method for preparing an electrode for a lithium-sulfur battery, comprising:
1) pretreatment of an electrode substrate: dissolving nickel salt in a solution of sulfuric acid, hydrochloric acid or nitric acid with the pH value of 2.0-5.0, wherein the solution adopts one or more of water, ethanol, DMSO and sulfolane as a solvent, the nickel salt is one or more of nickel sulfate, nickel chloride, nickel acetate and nickel nitrate, and the mass concentration of the pretreatment solution is 180-;
the activation pretreatment solution is used as electrolyte, the electrode matrix and the nickel sheet are respectively used as a negative electrode and a positive electrode, and the surface area of the electrode matrix is 0.01-20mA/cm2Activating for 1-10 minutes under the current density of (1);
2) carrying out chemical Ni plating modification: the chemical plating solution comprises nickel salt, a reducing agent, a complexing agent and a buffering agentThe water solution is composed of nickel salt which is one or more than two of nickel chloride, nickel sulfate, nickel phosphate and nickel acetate, and the mass concentration is 10-50 g/L; the reducing agent is one or more than two of sodium hypophosphite, hydrazine hydrate and sodium borohydride, and the mass concentration is 10-50 g/L; the complexing agent is one or more than two of EDTA, EGTA, sodium tartrate and sodium citrate, and the mass concentration is 10-50 g/L; the buffer is one or more than two of sodium acetate, ammonium acetate and ammonium chloride, and the mass concentration is 10-50 g/L; solutions ofPH is between 4.0 and 5.0 or between 8.0 and 9.5; the temperature is controlled between 60 ℃ and 90 ℃ and the time is controlled between 15 minutes and 8 hours in the chemical plating process;
the prepared electrode is characterized in that metal nickel layers are deposited on the surfaces of two sides of the electrode substrate through chemical in-situ deposition, metal nickel is deposited in the electrode substrate, and the thickness of the metal nickel layers on the surface of the electrode is 0.2-4 mu m; the electrode matrix comprises a carbon material, sulfur and a binder, wherein the mass content of the sulfur is 40-50%, the mass content of the binder is 20-35%, and the mass content of metal nickel in the electrode matrix accounts for 0.01-2 wt% of the electrode.
2. The method according to claim 1, wherein the electroless plating solution further comprises a stabilizer selected from the group consisting of sodium thiosulfate, potassium iodide and thiourea, and the mass concentration of the stabilizer is 0.01 to 0.1 g/L.
3. The method according to claim 1, wherein the pH adjusting agent is a hydrochloric acid or sulfuric acid solution having a concentration of 100-400 g/L; 40-160g/L sodium hydroxide or potassium hydroxide solution.
4. The method of claim 1, wherein: the carbon material comprises one or more than two of carbon nano tubes, graphene, carbon nano fibers, BP2000, KB600, KB300 and Super-P.
5. The method of claim 1, wherein: the binder is one or more of polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), polyvinylidene fluoride (PVDF), and polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP).
6. The production method according to claim 1, wherein the electrode produced by the production method is used as a positive electrode in a lithium-sulfur battery, and the lithium-sulfur battery consists of the positive electrode, a membrane and a lithium negative electrode.
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CN109994721B (en) * 2019-03-26 2020-07-10 湘潭大学 S-Ni-O-C bonding enhancement-based lithium-sulfur battery composite positive electrode material and preparation method thereof
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1354529A (en) * 2000-11-22 2002-06-19 三星Sdi株式会社 Positive electrode of lithium-sulfur cell and lithium-sulfur cell including said positive electrode
CN102983312A (en) * 2012-11-28 2013-03-20 武汉工程大学 Preparation method of composite fiber anode material of lithium-sulfur battery
CN103035879A (en) * 2012-12-07 2013-04-10 湘潭大学 Positive pole piece for lithium-sulfur batteries and preparation method thereof
CN103066255A (en) * 2012-12-26 2013-04-24 浙江工业大学 A nano-metal coated sulfur composite material and applications thereof
CN103326003A (en) * 2013-06-08 2013-09-25 苏州诺信创新能源有限公司 Preparation method of nickel fiber tube used in lithium-sulfur battery
CN103730632A (en) * 2013-12-18 2014-04-16 湘潭大学 Bergmeal-based lithium sulphur battery cathode material as well as preparation and application methods thereof
CN103779543A (en) * 2013-12-18 2014-05-07 湘潭大学 Lithium sulphur battery positive electrode material based on sepiolite, preparation method and application method of lithium sulphur battery positive electrode material
CN104253276A (en) * 2014-10-14 2014-12-31 湘潭大学 High-energy-density lithium sulfur battery cathode and preparation method thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100239914A1 (en) * 2009-03-19 2010-09-23 Sion Power Corporation Cathode for lithium battery
US9172086B2 (en) * 2008-12-05 2015-10-27 Samsung Sdi Co., Ltd. Cathode and lithium battery using the same

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1354529A (en) * 2000-11-22 2002-06-19 三星Sdi株式会社 Positive electrode of lithium-sulfur cell and lithium-sulfur cell including said positive electrode
CN102983312A (en) * 2012-11-28 2013-03-20 武汉工程大学 Preparation method of composite fiber anode material of lithium-sulfur battery
CN103035879A (en) * 2012-12-07 2013-04-10 湘潭大学 Positive pole piece for lithium-sulfur batteries and preparation method thereof
CN103066255A (en) * 2012-12-26 2013-04-24 浙江工业大学 A nano-metal coated sulfur composite material and applications thereof
CN103326003A (en) * 2013-06-08 2013-09-25 苏州诺信创新能源有限公司 Preparation method of nickel fiber tube used in lithium-sulfur battery
CN103730632A (en) * 2013-12-18 2014-04-16 湘潭大学 Bergmeal-based lithium sulphur battery cathode material as well as preparation and application methods thereof
CN103779543A (en) * 2013-12-18 2014-05-07 湘潭大学 Lithium sulphur battery positive electrode material based on sepiolite, preparation method and application method of lithium sulphur battery positive electrode material
CN104253276A (en) * 2014-10-14 2014-12-31 湘潭大学 High-energy-density lithium sulfur battery cathode and preparation method thereof

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