CN108123167A - A kind of lithium-sulfur cell electrode and its preparation and the lithium-sulfur cell structure for including it - Google Patents

A kind of lithium-sulfur cell electrode and its preparation and the lithium-sulfur cell structure for including it Download PDF

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CN108123167A
CN108123167A CN201611062786.5A CN201611062786A CN108123167A CN 108123167 A CN108123167 A CN 108123167A CN 201611062786 A CN201611062786 A CN 201611062786A CN 108123167 A CN108123167 A CN 108123167A
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electrode
nickel
lithium
sulfur cell
solution
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CN108123167B (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

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  • Battery Electrode And Active Subsutance (AREA)
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Abstract

The invention discloses a kind of lithium-sulfur cell electrode, electrode is made by chemical in situ depositing electrode matrix secondly side surface has deposited metal nickel layer, and deposition has metallic nickel, 0.2 μm 4 μm of electrode surface metal nickel layer thickness inside electrode matrix；This application of electrode can significantly improve the effect of lithium-sulfur cell performance and energy density in lithium-sulfur cell, and chemical plating in-situ deposition technical operating procedure is simple, and experiment condition is mild, and experimental cost is relatively low, have the great potential for realizing futurity industryization large-scale production.

Description

A kind of lithium-sulfur cell electrode and its preparation and the lithium-sulfur cell structure for including it
Technical field
The present invention relates to lithium-sulfur cell fields, more particularly to lithium-sulfur cell flexible electrode.
Background technology
In recent years, with the getting worse of global energy environmental crisis, lithium ion battery has become all kinds of electronic product ratios Such as preferred power supply of laptop, electric bicycle electronic equipment.However as the development of flexible electronic, people are to soft Property, the demand of wearable media device increasingly increases, such as OLED flexible intelligent mobile phones, implantable equipment etc., these are high For performance portable electric appts in addition to needing to have good mechanical flexibility, similary demand has good flexible high property Energy battery is exported as power supply.Although lithium ion battery has many advantages, such as that operating voltage is high, has extended cycle life, energy density Relatively low, poor mechanical performance is always the main bottleneck for restricting it in the development of flexible battery field.Such as lithium ion Secondary cell, electric discharge are more usual than energy in 100-200Whkg-1.When it is as electric car power supply, single charge and discharge General-utility car traveling 160km can only be met, it is difficult in the single charge and discharge for meeting advanced battery federation of the U.S. (USABC) proposition Journey reaches the requirement of 500km.
Lithium-sulfur cell is shown one's talent in numerous secondary cell systems, and reason is not only in that its positive electrode active materials sulphur price Cheap, environmental-friendly and rich reserves, while it is combined its reality with metal lithium electrode and is higher than 500Whkg than energy-1.Cause This, lithium-sulfur cell is considered as one of new secondary battery of alternative lithium ion battery, and it is good to have flexible lithium sulphur battery Good application prospect.
However in the R＆D process of lithium sulphur flexible battery, there are many problems demands to solve.First existing for lithium-sulfur cell The problems such as high rate performance is poor, cyclical stability is poor, active material utilization is low seriously hinder its commercialization process.In wherein discharging Between " the shuttle effect " of the more lithium sulfides of product be to influence one of the main reason for lithium-sulfur cell performance plays.In order to solve vulcanize more " shuttle effect " problem of object, existing relatively conventional solution method are using classifying porous carbon material as active material sulphur Carrier not only because its larger pore volume and high-specific surface area can load the active material sulphur of high load amount, and produces electric discharge Object polysulfide has preferable physisorption, so as to slow down the shuttle effect of polysulfide.These are used as sulfur loaded Carbon material generally includes porous carbon materials, carbon nano tube nano fiber material, hollow carbon material, grapheme material and mutually answers Carbon material of conjunction etc., but its non-polar character because of carbon material in itself, it is weaker to the adsorption capacity of polysulfide, thus for slowing down The effect of " the shuttle effect " of polysulfide is not fairly obvious.
Secondly in terms of lithium-sulfur cell flexible electrode preparation, usual electrode slurry includes active material, binding agent and conduction Agent, and in order to improve the flexility of battery and mechanical performance, the ratio regular meeting of wherein binding agent greatly improves, so that electrode Electrical conductivity declines.This makes the electrode interior caused by active material and discharging product are non-conductive that script lithium-sulfur cell there is The problem of electron-transport network is discontinuous, active material utilization is low becomes more sharp.Preparing the mistake of electrode material simultaneously Prepared electrode slurry is usually coated on metallic film by Cheng Zhong, and thickness is usually 25 μm or so, this layer of metallic film is made For a kind of collector not only occupy certain electrode weight and also in electrode material can only be used as a kind of inert matter from And volume and mass energy density are reduced, and electrode material is faced with the active matter in battery bending process in flexible apparatus The problem of matter is peeled off from this layer film is so as to influencing battery performance.The existing method for preparing flexible electrode mainly includes the use of The excellent material of lighter weight, satisfactory mechanical property, electric conductivity such as graphite ene coatings carry out substituted metal film as afflux Body or by electrode slurry the middle addition conductive agents such as graphene and carbon nanotubes improve the electric conductivity of electrode interior, And these methods there are the problem of be first cost height, the process is more complicated, secondly conductive agent is added in electrode slurry Graphene or carbon nanotubes can not still solve caused by binding agent additional proportion is excessively high electrode interior conductive network not The problem of continuous.
" chemical plating " is used as a kind of self-catalyzed reaction, and the coating of this method deposition has thickness is uniform, deposition velocity is fast etc. Feature.Electroless plating technology is risen in World War II, is once used to do coating modification for inner-walls of duct, and hereafter, a series of chemical platings apply The beginnings such as layer such as Ni-W, Ni-P, Ni-B quickly development and application.Nearest decades, chemical plating coating are usually applied with alloy The forms such as layer, composite coating and metal coating are applied in fields such as aviation, petrochemical industry, medical instruments, wherein 95% industry Chemical plating coating uses the alloy coat based on Ni-P, Ni-B, and especially in the past 10 years, the alloy based on Ni-P applies Layer and composite coating are even more to be widely used.
The content of the invention：
Present invention aims at by the application of electrode of surface deposited nickel layer, in lithium-sulfur cell, electroless plating method prepares surface and sinks Product nickel layer electrode the step of be：One, activating pretreatment is carried out to the electrode material matrix that chemical in situ is needed to deposit.Two, it will be pre- Processed electrode material, which is placed in chemical plating solution, carries out internal and surface layer chemical in situ deposition modification.
Electrode is made by chemical in situ depositing electrode matrix secondly side surface has deposited metal nickel layer, in electrode matrix Portion's deposition has metallic nickel, 0.2 μm -4 μm of electrode surface metal nickel layer thickness；Electrode matrix includes carbon material, sulphur, binding agent, The mass content 40-50% of middle sulphur, the mass content 20-35% of binding agent, electrode matrix interior metal nickel mass content account for electricity The 0.01-2wt% of pole.
The carbon material is included in carbon nanotubes, graphene, carbon nano-fiber, BP2000, KB600, KB300, Super-P One or more.
The binding agent is polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), Kynoar (PVDF), poly- inclined fluorine One or both of ethylene-hexafluoropropylene copolymer (PVDF-HFP).
Specific operating process is as follows：
1) electrode matrix pre-processes：Activating pretreatment solution is prepared, and is that nickel salt is dissolved in sulphur of the pH value between 2.0-5.0 Acid, hydrochloric acid or nitric acid solution in, solvent which uses be one or both of water, ethyl alcohol, DMSO, sulfolane with On, nickel salt is more than one or both of nickel sulfate, nickel chloride, nickel acetate, nickel nitrate, in the mass concentration of preprocessing solution 180-400g/L；
Using activating pretreatment solution as electrolyte, using electrode matrix and nickel sheet as cathode and anode, compared with Electrode matrix surface area is 0.01-20mA/cm2Current density under activate 1-10 minutes；
2) Electroless Plating Ni modification is carried out：Chemical plating bath includes the water-soluble of nickel salt, reducing agent, complexing agent and buffer composition Liquid, nickel salt is nickel chloride, the one or two or more kinds in nickel sulfate, nickel phosphate, nickel acetate, mass concentration 10-50g/L；Reduction Agent is more than one or both of sodium hypophosphite, hydrazine hydrate, sodium borohydride mass concentration 10-50g/L；Complexing agent by EDTA, It is more than one or both of EGTA, sodium tartrate, sodium citrate, mass concentration 10-50g/L；Buffer is sodium acetate, acetic acid It is more than one or both of ammonium, ammonium chloride, mass concentration 10-50g/L；SolutionPH is between 4.0-5.0 or 8.0-9.5；Change The control of plating process medium temperature degree is learned between 60-90 DEG C, time control 15 minutes -8 it is small when between.
Chemical plating bath further includes stabilizer, and stabilizer is sodium thiosulfate, potassium iodide, one or both of thiocarbamide with On, mass concentration 0.01-0.1g/L；
The PH conditioning agents used for 100-400g/L concentration hydrochloric acid or sulfuric acid solution；The hydroxide of 40-160g/L concentration Sodium or potassium hydroxide solution.
The preferred sodium hypophosphite combination of the preferred sodium phosphate of nickel salt, reducing agent in chemical plating bath.
This electrode is applied to as anode in lithium-sulfur cell, and lithium-sulfur cell is made of anode, film, cathode of lithium.
The present invention beneficial outcomes be：
The present invention by current density in chemical plating preprocessing process, the adjusting of soak time and to chemical plating solution into Point, solution pH value, the regulation and control of time can realize the thickness to the surface coated Electroless Plating Ni coating of positive electrode, pattern, into The control for index of grading.So that chemical plating coating can not only slow down the diffusion of more lithium sulfides as physical barriers, while can To change absorption of the non-polar character of the original sulfur-donor carbon material enhancing to more lithium sulfides in terms of chemical polarity bond energy, improve The active material utilization and cycle life of lithium-sulfur cell.In addition by using chemical in situ deposition technique to sulphur/carbon anode base Two side of body carries out surface layer and internal nickel plating is modified, and can complete the structure of the electron-transport network to electrode interior and surface layer, so as to It is effective to solve the electrode interior caused by adding in excessive binding agent and interface electronics biography in lithium sulphur flexibility positive electrode is prepared The defeated discontinuous problem of network plays the traditional collector metallic film of substitution and conductive agent, increases the flexibility of electrode, improve lithium The effect of sulphur battery performance.The chemical plating modification is easy to operate, and experiment condition is mild, and experimental cost is relatively low, has and realizes The great potential of futurity industryization large-scale production.
Description of the drawings
Fig. 1：1 electrode of comparative example (left figure) and 2 electrode of embodiment (right figure) photo；
Fig. 2：2 surface SEM (left figure) of embodiment and section SEM schemes (right figure)；
Fig. 3：It is put with high rate performance under comparative example 1, comparative example 2, the 0.1C-1C multiplying powers of Examples 1 and 2 assembling lithium-sulfur cell Electric curve；
Fig. 4：It is tested with the cyclical stability of comparative example 1, comparative example 2, Examples 1 and 2 assembling lithium-sulfur cell；
Fig. 5 assembles the ac impedance measurement of lithium-sulfur cell with comparative example 1, comparative example 2, Examples 1 and 2.
Specific embodiment
The following examples are the further explanations to the present invention rather than limit the scope of the invention.
Comparative example 1 (does not have nickel plating)
20g commercializations KB600 is placed in tube furnace, under Ar protections, with 5 DEG C of min-1After being warming up to 900 DEG C, water is passed through Steam activation 1.5h, vapor flow are 600mL min-1, the carbon material after activation is denoted as A-KB600.Take 10g A-KB600 with 20g S uniformly after mixing, are placed in tube furnace, are warming up to 155 DEG C, heating rate is 1 DEG C of min-1, constant temperature 20h, obtained product S/A-KB600 is denoted as, fills sulfur content for 75%.2g binding agents PVDF-HFP is taken to be dissolved in 40g N-Methyl pyrrolidones (NMP) In, 1h is stirred, adds in 4g S/A-KB600, stirs 4h, adjusts scraper to 300 μm, film forming is scratched in aluminum laminated films, and it is quick It is immersed into water, is taken out after 10min, after 65 DEG C of dryings overnight, cut into after a diameter of 10mm sequins weigh, 60 DEG C of vacuum are done It is dry for 24 hours after, to scribble the sequin of S/A-KB600, as anode, (it is about 2.2mg cm that monolithic, which carries sulfur content,-2), lithium piece is cathode, Celgard 2325 is membrane, with double (trifluoromethyl semi-annular jade pendant acyl) the imine lithium solution (LiTFSI) of 1M plus 5%LiNO3It is molten for electrolyte Liquid, solvent are 1,3-dioxolane (DOL) and mixed liquor (the volume ratio v/v=1 of glycol dimethyl ether (DME):1), assembling electricity Pond carries out cycle performance of battery test under 0.1C multiplying powers, high rate performance test is carried out under 0.1C-1C multiplying powers.
First circle specific discharge capacity is 1205mAh g under 0.1C multiplying powers-1, 100 cycle after specific capacity maintain 786mAh g-1；When multiplying power is promoted to 1C, specific discharge capacity is 504mAh g-1。
Comparative example 2 (without nickel plating, electrode contains conductive agent)
1.4g binding agents PVDF-HFP is taken to be dissolved in 40g N-Methyl pyrrolidones (NMP), stirs 1h, 0.6g is added in and leads Electric agent KB600,4g S/A-KB600 (fill sulfur content 75%), stir 4h, adjust scraper to 300 μm, in aluminum laminated films blade coating into Film is quickly immersed into water, after taking out 65 DEG C of dryings overnight after 10min, cuts into a diameter of 10mm sequins, after weighing, 60 DEG C vacuum drying for 24 hours.Further battery assembles same comparative example.The battery of assembling carries out cycle performance of battery survey under 0.1C multiplying powers It tries, high rate performance test is carried out under 0.1C-1C multiplying powers.
First circle specific discharge capacity is 1340mAh g-1, 100 cycle after capacity maintain 819mA h g-1；When multiplying power carries When being raised to 1C, specific discharge capacity is 789mAh g-1。
Embodiment 1
2g binding agents PVDF-HFP is taken to be dissolved in 40g N-Methyl pyrrolidones (NMP), stirs 1h, adds in 4g S/A- KB600 (fills sulfur content 75%), stir 4h, adjust scraper to 300 μm, on a glass blade coating film forming (and be not used metallic film As collector), then glass plate is quickly immersed into water together with the electrode coating scratched above, electrode coating after 10min It comes off and takes out on a glass, after 65 DEG C of dryings overnight, using activating pretreatment solution as electrolyte, with electrode matrix and nickel sheet It is being 10mA/cm compared with electrode matrix surface area respectively as cathode and anode2Current density under activate 4 minutes.Activation Preprocessing solution ingredient is the aqueous hydrochloric acid solution containing the PH=3 that concentration is 240g/L nickel chlorides；By the electricity after activating pretreatment Pole matrix is placed in 25 minutes in 90 DEG C of chemical plating fluids and carries out chemical in situ deposited metal nickel.Chemical plating fluid ingredient is 20g/L sulfuric acid Nickel；24g/L sodium hypophosphites；15g/L sodium citrates；0.01g/L thiocarbamides；15g/L sodium acetates；Solution PH=9 are modified through chemical plating Obtained surface deposited nickel layer thickness is about 0.5 μm.The electrode of deposited nickel layer is cut into diameter through 65 DEG C of dryings overnight again For 10mm sequins, it is dried in vacuo for 24 hours for 60 DEG C after weighing.Further battery assembles same comparative example.The battery of assembling is in 0.1C multiplying powers It is lower to carry out cycle performance of battery test, carry out high rate performance test under 0.1C-1C multiplying powers.
First circle specific discharge capacity is 1501mAhg-1, 100 cycle after capacity maintain 954mAhg-1；When multiplying power promotion is arrived During 1C, specific discharge capacity is 970mAh g-1。
Embodiment 2
Electrode matrix preparation and chemical plating modification operating process are identical with 1 operating process of embodiment, and the parameter of modulation is change It is 50 minutes to learn the plating time, and electrode surface deposited nickel layer thickness is about 1.0 μm, and the battery of assembling carries out battery under 0.1C multiplying powers Cycle performance is tested, and high rate performance test is carried out under 0.1C-1C multiplying powers.
First circle specific discharge capacity is 1625mAh g-1, 100 cycle after capacity maintain 1124mAh g-1；When multiplying power carries When being raised to 1C, specific discharge capacity is 1070mAh g-1。
As shown in Figure 1, the lithium sulphur positive electrode modified by Electroless Plating Ni, surface, which can deposit one layer, has metallic luster Nickel layer, the nickel layer play an important role of inhibit polysulfide shuttle, as shown in Figure 2, the nickel layer surface compact, coating uniformly sinks For product in electrode surface, thickness is about 1 μm.
As shown in Figure 3, using comparative example 2 and comparative example 1 as the battery of positive electrode, in the situation containing electrode current collecting body Under, comparative example 2 has higher specific discharge capacity under 0.1C-1C multiplying powers than comparative example 1, and reason is compared to comparative example 1, a certain amount of conductive agent is added in comparative example 2, the continuity of electrode interior electronic conduction network is improved, so as to improve battery High rate performance.Embodiment 1,2 is not in the case where no collector adds conductive agent, than comparison under 0.1C-1C multiplying powers Example 1 and comparative example 2 illustrate better battery high rate performance, and reason is the nickel layer that surface deposition is surveyed in electrode matrix two Play the role of collector on one side, another side can inhibit the shuttle effect of polysulfide, so as to improve the electric discharge of battery Specific capacity.It is modified simultaneously by chemical plating, the discontinuous electronic conduction network connection of electrode interior can be got up, make it in height Also there can be preferable battery performance under multiplying power.Embodiment 2 is the optimal electrode in the test of lithium-sulfur cell high rate performance, electric Pole surface deposited nickel layer thickness is about 1.0 μm.
As shown in Figure 4, in the test of 0.1C cycle performance of battery, embodiment 1,2 is equally opened up than comparative example 2 and comparative example 1 Show better cycle performance, the battery capacity after first circle specific discharge capacity and 100 cycles is all higher than comparative example 1 and right Ratio 2.Its reason is equally because the nickel layer of electrode surface deposition can be good at inhibiting the shuttle effect of polysulfide, is improved The utilization rate of active material, while electrode interior discontinuous electronic conduction network can obtain during chemical plating is modified To improvement.Embodiment 2 is the optimal electrode in the test of lithium-sulfur cell cycle performance, and electrode surface deposited nickel layer thickness is 1.0μm。
As seen from Figure 5, the addition due to conductive agent and chemical nickel plating modified electrode surface layer and inside, comparative example 2, Example 1 and embodiment 2 show smaller electrochemical impedance than comparative example 1, and Examples 1 and 2 are constructed by chemical nickel plating Electrode surface and internal electron-transport network compared with comparative example 2 adds in conductive agent, illustrate smaller electrochemistry resistance It is anti-.Embodiment 2 is because its electroless plating time is longer than embodiment 1, therefore shows minimum impedance behavior.AC impedance comparison diagram 5 are significantly improved by chemically coated nickel method modified electrode from electrochemical impedance interpretation for the battery performance of lithium-sulfur cell The reason for.

Claims (7)

1. a kind of lithium-sulfur cell electrode, it is characterised in that：The electrode is made by chemical in situ depositing electrode matrix secondly side Surface has deposited metal nickel layer, and deposition has metallic nickel, 0.2 μm of -4 μ of electrode surface metal nickel layer thickness inside electrode matrix m；Electrode matrix includes carbon material, sulphur, the mass content 40-50% of binding agent, wherein sulphur, the mass content 20- of binding agent 35%, electrode matrix interior metal nickel mass content accounts for the 0.01-2wt% of electrode.
2. according to electrode described in claim 1, it is characterised in that：The carbon material includes carbon nanotubes, graphene, carbon Nanowire It is more than one or both of dimension, BP2000, KB600, KB300, Super-P.
3. according to electrode described in claim 1, it is characterised in that：The binding agent is polyvinylpyrrolidone (PVP), poly- second two One or both of alcohol (PEG), Kynoar (PVDF), Kynoar-hexafluoropropylene copolymer (PVDF-HFP) with On.
4. a kind of preparation method of any electrodes of claim 1-3, it is characterised in that:
1) electrode matrix pre-processes：Activating pretreatment solution is prepared, be by nickel salt be dissolved in sulfuric acid of the pH value between 2.0-5.0, In the solution of hydrochloric acid or nitric acid, solvent which uses for one or both of water, ethyl alcohol, DMSO, sulfolane more than, nickel Salt is more than one or both of nickel sulfate, nickel chloride, nickel acetate, nickel nitrate, in the mass concentration 180- of preprocessing solution 400g/L；
Using activating pretreatment solution as electrolyte, using electrode matrix and nickel sheet as cathode and anode, compared with electrode Surface of the base body is 0.01-20mA/cm2Current density under activate 1-10 minutes；
2) Electroless Plating Ni modification is carried out：Chemical plating bath includes the aqueous solution of nickel salt, reducing agent, complexing agent and buffer composition, Nickel salt is nickel chloride, the one or two or more kinds in nickel sulfate, nickel phosphate, nickel acetate, mass concentration 10-50g/L；Reducing agent is It is more than one or both of sodium hypophosphite, hydrazine hydrate, sodium borohydride, mass concentration 10-50g/L；Complexing agent by EDTA, It is more than one or both of EGTA, sodium tartrate, sodium citrate, mass concentration 10-50g/L；Buffer is sodium acetate, acetic acid It is more than one or both of ammonium, ammonium chloride, mass concentration 10-50g/L；SolutionPH is between 4.0-5.0 or 8.0-9.5；Change The control of plating process medium temperature degree is learned between 60-90 DEG C, time control 15 minutes -8 it is small when between.
5. according to the preparation method described in claim 4, it is characterised in that:Chemical plating bath further includes stabilizer, and stabilizer is It is more than one or both of sodium thiosulfate, potassium iodide, thiocarbamide, mass concentration 0.01-0.1g/L.
6. according to the preparation method described in claim 4, it is characterised in that:The PH conditioning agents used is 100-400g/L concentration Hydrochloric acid or sulfuric acid solution；The sodium hydroxide or potassium hydroxide solution of 40-160g/L concentration.
7. a kind of lithium-sulfur cell structure for including electrode described in claim 1, the electrode is applied to lithium sulphur electricity as anode Chi Zhong, lithium-sulfur cell are made of anode, film and cathode of lithium.
CN201611062786.5A 2016-11-28 2016-11-28 Electrode for lithium-sulfur battery, preparation method of electrode and lithium-sulfur battery structure comprising electrode Active CN108123167B (en)

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CN109994721A (en) * 2019-03-26 2019-07-09 湘潭大学 A kind of lithium-sulfur battery composite cathode material and preparation method thereof based on S-Ni-O-C bonding enhancing
CN110098374A (en) * 2019-04-26 2019-08-06 中国航发北京航空材料研究院 A kind of flexible electrode film and the preparation method and application thereof
CN110504457A (en) * 2019-08-21 2019-11-26 中国华能集团清洁能源技术研究院有限公司 A kind of nickel base electrode antiseptic property optimization method
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
CN112421042A (en) * 2020-11-20 2021-02-26 北京理工大学重庆创新中心 Composite binder for lithium-sulfur battery and preparation method and application thereof
CN114420906A (en) * 2022-01-07 2022-04-29 上海交通大学 Chemical nickel plating based electrode material with core-shell structure, preparation method thereof and lithium-sulfur battery

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