CN109473640A - Silicon substrate molecular sieve/carbon pipe carries sulphur composite positive pole and its preparation method and application - Google Patents

Silicon substrate molecular sieve/carbon pipe carries sulphur composite positive pole and its preparation method and application Download PDF

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Publication number
CN109473640A
CN109473640A CN201811165709.1A CN201811165709A CN109473640A CN 109473640 A CN109473640 A CN 109473640A CN 201811165709 A CN201811165709 A CN 201811165709A CN 109473640 A CN109473640 A CN 109473640A
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molecular sieve
carbon pipe
silicon substrate
positive pole
sulphur composite
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Inventor
聂华贵
禅丹
杨植
赖玉崇
丁欣慰
周苏雅
张永贵
林鸣
林一鸣
黄少铭
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Wenzhou University
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Wenzhou University
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • H01M4/364Composites as mixtures
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The present invention provides silicon substrate molecular sieve/carbon pipes to carry sulphur composite positive pole and its preparation method and application, and technical solution is that CS is added in carbon pipe and sulphur simple substance mixed grinding2It is dried after being sufficiently stirred and carbon pipe load sulphur composite material is made;Carbon pipe is carried sulphur composite material to mix with carbon black, Kynoar by certain mass ratio, then N-Methyl pyrrolidone is added, and simultaneously ultrasonic disperse is uniform for the stirring of silicon substrate molecular sieve, viscosity is controlled in 1000-10000cps, obtain slurry, gained slurry is coated uniformly in current collector aluminum foil with the thickness of 150-400mm, aluminium foil is then transferred to 40-60 DEG C of drying in oven, silicon substrate molecular sieve/carbon pipe is obtained and carries sulphur composite positive pole;Preparation method of the invention, it is easy to operate, it is easy to be mass produced;Silicon substrate molecular sieve obtained/carbon pipe carries sulphur composite positive pole for can solve dissolution of more sulphions in liquid electrolyte in lithium-sulfur cell charge and discharge process in lithium-sulfur cell, effectively inhibits shuttle effect, improves the coulombic efficiency and cyclical stability of lithium-sulfur cell.

Description

Silicon substrate molecular sieve/carbon pipe carries sulphur composite positive pole and its preparation method and application
Technical field
The invention belongs to nanocomposite research fields, in particular to a kind of to improve its electrochemistry for lithium-sulfur cell Silicon substrate molecular sieve/carbon pipe of can and inhibit polysulfide shuttle effect etc. carries sulphur composite positive pole and preparation method thereof And the application in lithium-sulfur cell.
Background technique
With the progress of rapid economic development and people life style, demand of the people to the energy is growing, however The exhaustion increasingly of environmental pollution and its reserves caused by fossil fuel, so that demand of the people to novel alternative energy source is more and more tighter Compel.New energy, especially chemical energy source have the characteristics that clean and environmental protection and safe and efficient, meet human kind sustainable development strategy It is required that and gaining great popularity.Currently, installing solar panel and wind power plant in global range, but to make full use of These intermittent energy sources, chargeable cell system are vital a part.Since lithium ion battery is commercialized since 1991, By development in more than 20 years, the performance of the positive and negative pole material of conventional lithium ion battery had been approached its theoretical limit, but in face of more It is still unsatisfactory to carry out huger energy-storage system.Lithium-sulfur cell is 1675mAhg due to its theoretical specific capacity‐1, be traditional lithium from 10 times of sub- battery, and the rich reserves of sulphur, cheap, the low toxicity advantages such as nuisanceless cause the extensive concern of people. However, lithium-sulfur cell is easy to produce volume expansion and lithium metal in shuttle effect and charge and discharge process in charge and discharge process Corrosion the problems such as make the problems such as lithium-sulfur cell active material utilization is low, coulombic efficiency is low, poor circulation, become lithium Obstruction of sulphur battery during business application.
In order to solve these problems, its large-scale use is realized, it is necessary to design and develop novel electrode structure, develop Easy and low-cost preparation method improves the chemical property of lithium-sulfur cell, to promote the practical application of lithium-sulfur cell Prospect.
Summary of the invention
The present invention in order to overcome the disadvantages and deficiencies of the prior art, and provides a kind of silicon substrate molecular sieve/carbon pipe to carry sulphur compound The preparation method of positive electrode, the present invention there is the silicon substrate molecular sieve of absorption and catalyzed conversion effect to be used for lithium sulphur polysulfide In cell positive material, and slurry is made and is coated on traditional sulphur lithium battery aluminum foil material, improves leading for sulphur lithium battery anode The problems such as electrical and polysulfide shuttle effect, excellent cyclical stability is shown, there is the advantage of large-scale production.
The present invention adopts the following technical scheme:
(1) carbon pipe carries the preparation of sulfur materials:
After carbon pipe is mixed with elemental sulfur and is ground uniformly, it is added to CS2In be stirred, then to CS2Volatilization is complete Afterwards, surplus materials keeps the temperature 8-12h in 120-160 DEG C, is cooled to room temperature carries sulfur materials to get carbon pipe later;
(2) silicon substrate molecular sieve/carbon pipe carries the preparation of sulphur composite positive pole:
Carbon pipe obtained by step (1) is carried sulfur materials to mix with conductive additive, binder, N- crassitude is then added Ketone, simultaneously ultrasonic disperse is uniform for the stirring of silicon substrate molecular sieve, controls viscosity in 1000-10000cps, obtains slurry, gained slurry is dried It is dry to carry sulphur composite positive pole to get silicon substrate molecular sieve/carbon pipe.
It is 1:1-2, the carbon Guan Yudan that further setting, which is the mass ratio of carbon pipe described in step (1) and elemental sulfur, The gross mass and CS of matter sulphur2Mass ratio be 1:10-12.
It is 10-30 DEG C that further setting, which is the room temperature,.
It is carbon black that further setting, which is conductive additive described in step (2), and binder is Kynoar, described Silicon substrate molecular sieve is titanium-silicon molecular sieve TS-1 or porous silicon KIT-6 molecular sieve.
Further setting be the carbon pipe carry sulfur materials, conductive additive, binder, silicon substrate molecular sieve mass ratio be (300-400): (15-50): (15-50): (15-50).
The present invention also provides a kind of silicon substrate molecular sieve/carbon pipes such as preparation method preparation to carry sulphur composite positive pole.
The present invention also provides a kind of silicon substrate molecular sieve as mentioned/carbon pipes to carry sulphur composite positive pole in lithium-sulfur cell Silicon substrate molecular sieve/carbon pipe is carried the slurry before the drying of sulphur composite positive pole, is uniformly being coated in lithium-sulfur cell just by application method In the current collector aluminum foil of pole, then current collector aluminum foil is transferred at 40~60 DEG C and is dried to get compound in current collector aluminum foil Silicon substrate molecular sieve and the negative sulphur composite positive pole of carbon pipe.
Further setting is 30 μm of thickness of the current collector aluminum foil, the coating thickness ratio of the slurry are as follows: 150- 400mm。
Further setting is that the current collector aluminum foil uses N-Methyl pyrrolidone and alcohol washes before coating slurry, with Remove surface oxide layer and impurity.
Influence test of the silicon substrate molecular sieve/carbon pipe composite positive pole of the present invention to lithium-sulfur cell performance:
(1) assembling of battery: silicon substrate molecular sieve produced by the present invention/carbon pipe is carried into sulphur composite positive pole, is cut into diameter It for the circular piece of 14mm, weighs under dry environment, and deducts blank aluminium flake quality, it is stand-by that anode pole piece is made;As right It according to the facts tests, it is stand-by that control anode pole piece is also made in the carbon pipe load sulphur composite positive pole without silicon substrate molecular sieve in the same way;
It is being full of argon gas, water and oxygen content are respectively less than the assembling that battery is carried out in the glove box of lppm: with commercial metals Lithium piece is for reference electrode and to electrode, using the 1,3-dioxolane (DOL) of double trifluoromethanesulfonimide lithium structures, ethylene glycol Dimethyl ether (DME) LiTFSI/DOL.DME (1:1) and the liquid electrolyte dissolved with 1%LiNO3, diaphragm use Celgard2400, It is assembled into after CR2025 button cell, stands for 24 hours, then carry out charge-discharge test;
(2) battery charging and discharging test is carried out under different multiplying using the new prestige battery test system of blue electric structure, tested Condition is room temperature environment, window voltage 1.5-3.0V;
The beneficial effects of the present invention are:
(1) stronger as the adsorbent adsorption capacity of polysulfide using silicon substrate molecular sieve;
(2) the silicon substrate molecular sieve and carbon pipe prepared carries sulphur composite positive pole, can be additionally provided the ion of electronic structure Pathway reduces the internal resistance of cell, greatly enhances the discharge capacity and stable circulation performance of battery;
(3) composite positive pole of siliceous based molecular sieve can enhance accelerates to chemically react with the reactivity of polysulfide Dynamics improves lithium-sulfur cell performance to inhibit shuttle effect;
(4) carrier porous carbon provide storage sulphur space, and can limit polysulfide, lithium sulfide diffusion and transport;
In summary, on the one hand, the present invention provides the preparation sides that silicon substrate molecular sieve/carbon pipe carries sulphur composite positive pole Method, it is easy to operate, it is not related to high temperature and pressure, can be completed at room temperature, is easy to be mass produced;On the other hand, it obtained will be somebody's turn to do Composite positive pole is in lithium-sulfur cell, can solve in lithium-sulfur cell charge and discharge process more sulphions in liquid electrolyte Dissolution, effectively inhibit shuttle effect, improve the coulombic efficiency and cyclical stability of lithium-sulfur cell.
Detailed description of the invention
Titanium-silicon molecular sieve TS-1 made from Fig. 1 embodiment of the present invention 1 and carbon pipe carry sulphur composite positive pole for lithium sulphur electricity Charge and discharge platform comparison diagram of the pond with the lithium-sulfur cell without titanium-silicon molecular sieve TS-1 material at 0.2C;
Different proportion titanium-silicon molecular sieve TS-1 made from Fig. 2 embodiment of the present invention 1 and carbon pipe carry sulphur composite positive pole and use In the high rate performance comparison diagram of lithium-sulfur cell and the lithium-sulfur cell without titanium-silicon molecular sieve TS-1 material;
Titanium-silicon molecular sieve TS-1 made from Fig. 3 embodiment of the present invention 1 and carbon pipe graphite composite positive pole are for lithium sulphur electricity Cycle performance figure when pond;
Porous silicon KIT-6 molecular sieve and carbon pipe graphite composite positive pole is made for lithium sulphur electricity in Fig. 4 embodiment of the present invention 2 The battery high rate performance comparison diagram in pond.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, the present invention is made into one below in conjunction with attached drawing Step ground detailed description.
Embodiment 1
Titanium-silicon molecular sieve TS-1 carries the preparation of sulphur composite positive pole with carbon pipe and applies in lithium-sulfur cell
(1) carbon pipe carries the preparation of sulphur composite material: the carbon pipe and 200mg elemental sulfur for taking 200mg in mortar, by porous carbon and Sulphur is fully ground uniformly, and gained mixture is transferred in 25ml weighing bottle, and 3.2mL CS is added2It is sufficiently stirred, to CS2It waves It distributes entirely, mixture is transferred to 120 DEG C of baking ovens heat preservation 12h, is cooled to room temperature later, is collected products therefrom up to carbon pipe and carry sulphur Composite material;
(2) titanium-silicon molecular sieve TS-1 carbon pipe carry sulphur composite positive pole preparation: by carbon pipe carry sulphur composite material 300mg with Conductive additive carbon black 15mg, the mixing of bonding agent Kynoar 15mg, 10-20mg titanium-silicon molecular sieve TS-1, are then added 2.5mL NMP and ultrasonic disperse are sufficiently stirred, and control the viscosity of slurry in 10000cps, then with 150mm or 400mm Thickness be coated in current collector aluminum foil (aluminium foil NMP and twice of alcohol washes, to remove surface oxide layer and miscellaneous with scraper Matter, natural air drying, aluminum foil thickness are 30 μm).Then aluminium foil is transferred in 40 DEG C of baking ovens, is dried to get required positive material is arrived Material;
(3) assembling of battery: by combination electrode material made from step (2), it is cut into the circular piece that diameter is 14mm, dry It weighs under dry environment, and deducts blank aluminium flake quality, anode pole piece is made, for use.As control experiment, not titaniferous silicon molecule It is stand-by that control anode pole piece is also made in the carbon pipe load sulphur composite positive pole of sieve TS-1 in the same way;Be full of argon gas, water and Oxygen content is respectively less than the assembling that battery is carried out in the glove box of lppm.Using commercial metals lithium piece as reference electrode and to electrode, Using LiTFSI/DOL.DME (1:1) and dissolved with 1%LiNO3Liquid electrolyte, diaphragm use Celgard2400, be assembled into After CR2025 button cell, stands for 24 hours, then carry out charge-discharge test;
(4) new prestige battery test system carries out battery charging and discharging test under different multiplying, and test condition is room temperature environment, Window starting voltage is 1.5V, final voltage 3.0V;
Fig. 1 is the load sulphur composite positive pole of titanium-silicon molecular sieve TS-1 carbon pipe made from the present embodiment for lithium-sulfur cell and does not have There is charge and discharge platform comparison diagram of the lithium-sulfur cell of addition titanium-silicon molecular sieve TS-1 at 0.2C, it can be seen from the figure that having The carbon pipe of titanium-silicon molecular sieve TS-1 carries the lithium-sulfur cell capacity of sulphur composite material and acquisition rate is substantially better than and does not add titanium silicon point The battery of son sieve TS-1.
Titanium-silicon molecular sieve TS-1 carbon pipe made from Fig. 2 the present embodiment carries sulphur composite positive pole and is used for lithium-sulfur cell and is free of The lithium-sulfur cell high rate performance comparison diagram of titanium-silicon molecular sieve TS-1, from the graph, it is apparent that containing titanium-silicon molecular sieve TS-1 The lithium-sulfur cell of positive electrode higher discharge capacity is owned by under each multiplying power.
Fig. 3 is the load sulphur composite positive pole of titanium-silicon molecular sieve TS-1 carbon pipe made from the present embodiment for lithium-sulfur cell and does not have There is circulation comparison diagram of the lithium-sulfur cell of addition titanium-silicon molecular sieve TS-1 at 1C, it can be seen from the figure that having titanium silicon molecule The lithium-sulfur cell capacity and cyclical stability for sieving TS-1 are substantially better than the battery for not adding titanium-silicon molecular sieve TS-1.
Embodiment 2
Porous silicon KIT-6 molecular sieve carries the preparation of sulphur composite positive pole with carbon pipe and applies in lithium-sulfur cell
(1) carbon pipe carries the preparation of sulphur composite material: taking the above-mentioned resulting carbon pipe composite material of 200mg and 400mg elemental sulfur In mortar, porous carbon and sulphur are fully ground uniformly, gained mixture is transferred in 25ml weighing bottle, and 6mL CS is added2 It is sufficiently stirred, to CS2Volatilization is transferred to 150 DEG C of baking oven heat preservation 10h completely, by mixture, is cooled to room temperature later, collects gained Product carries sulphur composite material up to carbon pipe;
(2) porous silicon KIT-6 molecular-sieve carbon pipe carries the preparation of sulphur composite positive pole: carbon pipe is carried sulphur composite material 400mg is mixed with conductive additive carbon black 50mg, bonding agent Kynoar 50mg, 5-10mg porous silicon KIT-6 molecular sieve, so 3.5mL NMP and ultrasonic disperse are added afterwards, is sufficiently stirred, controls the viscosity of slurry in 6000cps, then with the thickness of 150mm Degree with scraper be coated in current collector aluminum foil on (aluminium foil NMP and twice of alcohol washes, to remove surface oxide layer and impurity, from It so air-dries, aluminum foil thickness 30um).Then aluminium foil is transferred in 50 DEG C of baking ovens, is dried to get required positive electrode is arrived;
(3) assembling of battery: by combination electrode material made from step (2), it is cut into the circular piece that diameter is 14mm, dry It weighs under dry environment, and deducts blank aluminium flake quality, anode pole piece is made, for use.As control experiment, porous silicon is free of It is stand-by that control anode pole piece is also made in the carbon pipe load sulphur composite positive pole of KIT-6 molecular sieve in the same way;It is being full of argon gas, Water and oxygen content are respectively less than the assembling that battery is carried out in the glove box of lppm.Using commercial metals lithium piece as reference electrode and to electricity Pole, using LiTFSI/DOL.DME (1:1) and dissolved with 1%LiNO3Liquid electrolyte, diaphragm use Celgard2400, assembling After CR2025 button cell, stands for 24 hours, then carry out charge-discharge test;
(4) new prestige battery test system carries out battery charging and discharging test under different multiplying, and test condition is room temperature environment, Window starting voltage is 1.5V, final voltage 3.0V;
Porous silicon KIT-6 molecular-sieve carbon pipe made from Fig. 4 the present embodiment carry sulphur composite positive pole for lithium-sulfur cell with Lithium-sulfur cell high rate performance comparison diagram without porous silicon KIT-6 molecular screen material, from the graph, it is apparent that containing porous The lithium-sulfur cell of the positive electrode of silicon KIT-6 molecular sieve is owned by higher discharge capacity under each multiplying power.
The above disclosure is only the preferred embodiments of the present invention, cannot limit the right model of the present invention with this certainly It encloses, therefore equivalent changes made in accordance with the claims of the present invention, is still within the scope of the present invention.

Claims (9)

1. the preparation method that a kind of silicon substrate molecular sieve/carbon pipe carries sulphur composite positive pole, which is characterized in that the positive electrode is used for The anode of lithium-sulfur cell, preparation method include the following steps:
(1) carbon pipe carries the preparation of sulfur materials:
After carbon pipe is mixed with elemental sulfur and is ground uniformly, it is added to CS2In be stirred, then to CS2After volatilization completely, remain Excess matter keeps the temperature 8-12h in 120-160 DEG C, is cooled to room temperature carries sulfur materials to get carbon pipe later;
(2) silicon substrate molecular sieve/carbon pipe carries the preparation of sulphur composite positive pole:
Carbon pipe obtained by step (1) is carried sulfur materials mix with conductive additive, binder, then addition N-Methyl pyrrolidone with Simultaneously ultrasonic disperse is uniform for the stirring of silicon substrate molecular sieve, controls viscosity in 1000-10000cps, obtains slurry, gained slurry is dried, Sulphur composite positive pole is carried up to silicon substrate molecular sieve/carbon pipe.
2. silicon substrate molecular sieve according to claim 1/carbon pipe carries the preparation method of sulphur composite positive pole, feature exists In: the mass ratio of carbon pipe described in step (1) and elemental sulfur is 1:1-2, the gross mass and CS of the carbon pipe and elemental sulfur2 Mass ratio be 1:10-12.
3. silicon substrate molecular sieve according to claim 1/carbon pipe carries the preparation method of sulphur composite positive pole, feature exists In: the room temperature is 10-30 DEG C.
4. silicon substrate molecular sieve according to claim 1/carbon pipe carries the preparation method of sulphur composite positive pole, feature exists In: conductive additive described in step (2) is carbon black, and binder is Kynoar, and the silicon substrate molecular sieve is titanium silicon Molecular sieve TS-1 or porous silicon KIT-6 molecular sieve.
5. silicon substrate molecular sieve according to claim 4/carbon pipe carries the preparation method of sulphur composite positive pole, feature exists In: the carbon pipe carry sulfur materials, conductive additive, binder, silicon substrate molecular sieve mass ratio be (300-400): (15- 50): (15-50): (15-50).
6. a kind of silicon substrate molecular sieve/carbon pipe such as any one of claim 1-5 preparation method preparation carries sulphur composite positive pole.
7. a kind of silicon substrate molecular sieve as claimed in claim 6/carbon pipe carries application of the sulphur composite positive pole in lithium-sulfur cell Method, it is characterised in that: silicon substrate molecular sieve/carbon pipe is carried into the slurry before the drying of sulphur composite positive pole, is uniformly coated in lithium In the current collector aluminum foil of sulphur cell positive electrode, then current collector aluminum foil is transferred at 40~60 DEG C and is dried to get in collector aluminium Comprehensive silicon based molecular sieve and the negative sulphur composite positive pole of carbon pipe on foil.
8. application method according to claim 7, it is characterised in that: 30 μm of the thickness of the current collector aluminum foil, it is described The coating thickness ratio of slurry are as follows: 150-400mm.
9. application method according to claim 7, it is characterised in that: the current collector aluminum foil uses N- before coating slurry Methyl pyrrolidone and alcohol washes, to remove surface oxide layer and impurity.
CN201811165709.1A 2018-09-30 2018-09-30 Silicon substrate molecular sieve/carbon pipe carries sulphur composite positive pole and its preparation method and application Pending CN109473640A (en)

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Application publication date: 20190315