CN105609720B - A kind of preparation method of NiPC@CNTs/S composites and application - Google Patents

A kind of preparation method of NiPC@CNTs/S composites and application Download PDF

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CN105609720B
CN105609720B CN201511004178.4A CN201511004178A CN105609720B CN 105609720 B CN105609720 B CN 105609720B CN 201511004178 A CN201511004178 A CN 201511004178A CN 105609720 B CN105609720 B CN 105609720B
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cnts
nipc
lithium
dissolved
composites
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CN105609720A (en
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左朋建
张瀚
尹鸽平
高云智
杜春雨
程新群
马玉林
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Harbin Institute of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • 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
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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 a kind of preparation method of NiPC@CNTs/S composites and application, methods described step are as follows：First, nickel salt is dissolved in solvent, while 2 methylimidazoles is dissolved in solvent, until completely dissolved, two solution are well mixed, filtered, clean after shelving 0.5~100 hour, drying, obtaining the metal organic frame containing metallic nickel ions；2nd, metal organic frame is obtained into NiPC@CNTs in protection gas high temperature pyrolysis, a step；3rd, NiPC@CNTs are mixed with elemental sulfur, is heated to 120~158 DEG C, kept for 2~48 hours, cooling obtains NiPC@CNTs/S composites, and it can be used for the positive pole material of lithium-sulfur cell.The lithium-sulphur cell positive electrode active material prepared using this method has preferable electric conductivity and electrochemical stability, has stronger adsorption capacity to more sulphions, beneficial to the coulombic efficiency and cyclical stability for improving lithium-sulfur cell.

Description

A kind of preparation method of NiPC@CNTs/S composites and application
Technical field
The invention belongs to field of chemical power source, is related to preparation method and the application of a kind of lithium-sulphur cell positive electrode active material.
Background technology
Commercialized lithium ion battery plus-negative plate material is mainly based upon insertion reaction at this stage, and specific energy is relatively low, So that the energy density of lithium ion battery is difficult to break through 300Wh/kg.High-energy-density causes lithium with cheap positive electrode Sulphur battery turns into a kind of next battery eliminator of great potential.Using sulphur as positive active material, theoretical specific capacity is up to lithium-sulfur cell 1675mAh/g, and negative pole is then directly using lithium metal as active material, therefore the theoretical energy density of lithium-sulfur cell is up to 2600Wh/ Kg, and the report of 400Wh/kg lithium-sulfur cell groups has been had more than at present, but the cycle performance of battery still needs to further be lifted. Current lithium-sulfur cell still suffers from some problems：First, elemental sulfur is insulator, it is impossible to directly as electrode material；It is second, in-between Product dissolves in electrolyte, and this, which can make battery pair, influences serious " shuttle effect ", causes the charge efficiency of battery extremely low.
To solve the problems, such as that conductivity problems and the more sulphions of intermediate product are easily soluble in electrolyte, researchers are carried out Substantial amounts of experiment, devises numerous schemes：1）Lived using the organic conductive macromolecule material such as polyaniline, polypyrrole clad anode Property material, this is advantageous to lift electrode conductivuty and reduce more sulphions and must dissolve, and is also beneficial to be lifted the multiplying power of positive electrode Performance.2）Using micro-pore carbon material, because the duct of micro-pore carbon material is thinner, the absorption affinity that sulphur is subject in the duct of carbon is more By force, thus more lithium sulfides be difficult to dissolving in the electrolytic solution.3）Strengthen the absorption to more sulphions using silica, in preparation It is mingled with porous silica inside carbon material, or coats nano silicon outside sulphur carbon composite and can effectively increase By force to the absorption of more sulphions.
The content of the invention
It is non-conductive for elemental sulfur in current lithium-sulfur cell, while the more lithium sulfides of positive active material intermediate product are soluble Cause the defects such as cycle performance of battery is poor, coulombic efficiency is low in electrolyte, the invention provides a kind of electrochemistry combination property The preparation method of good NiPC@CNTs/S composites and application.The lithium-sulphur cell positive electrode active matter prepared using this method Matter has preferable electric conductivity and electrochemical stability, has stronger adsorption capacity to more sulphions, beneficial to raising lithium sulphur The coulombic efficiency and cyclical stability of battery.
The purpose of the present invention is achieved through the following technical solutions：
A kind of NiPC@CNTs/S preparation method, is comprised the following steps that：
The first, nickel salt is dissolved in the solution that 0.001 ~ 0.2mol/L is obtained in solvent, while 2-methylimidazole is dissolved in 0.005 ~ 2mol/L solution is obtained in solvent, until completely dissolved, by two solution with nickel ion and 2-methylimidazole with mole Than 1：0.1 ~ 100 ratio is well mixed, and is filtered, is cleaned after shelving 0.5 ~ 100 hour, drying, obtaining containing metallic nickel ions Metal organic frame.
2nd, by metal organic frame in protection gas high temperature pyrolysis, a step obtains NiPC@CNTs, and control pyrolysis temperature exists Between 500 ~ 1500 DEG C, pyrolysis time is between 0.5 ~ 30 hour.Wherein, it is reduced to metal during the pyrolysis of nickel ion Nickel, and metallic nickel grows the catalyst of CNT simultaneously.
3rd, by NiPC@CNTs and elemental sulfur with 2 ~ 6:4 ~ 8 mass ratio mixing, is heated to 120 ~ 158 DEG C, keeps 2 ~ 48 Hour, cooling obtains NiPC@CNTs/S composites, and Ni represents metallic nickel；PC represents porous carbon；CNTs represents CNT；S Represent element sulphur.
Above-mentioned NiPC@CNTs/S composites can be used for the positive electrode of lithium-sulfur cell.
In the present invention, solvent can be water, ethanol, methanol, dimethylformamide, one kind in N NMFs or more Kind.
In the present invention, protection gas can be the one or more in nitrogen, argon gas, helium, hydrogen.
Compared to prior art, the present invention has advantages below：
1st, step pyrolysis obtains the NiPC@CNTs materials containing metallic nickel, porous carbon and CNT simultaneously.
2nd, NiPC@CNTs are applied in lithium-sulfur cell, there are some researches show metallic nickel is advantageous to lift lithium-sulphur cell positive electrode The performance of material（BabuG., AbabtainK, etal.ElectrocatalysisofLithiumPolysulfides: CurrentCollectorsasElectrodesinLi/SBatteryConfiguration[J].ScientificReports, 2015,5,8763）, while CNT can improve the electric conductivity of positive electrode, lift material high rate performance；And porous carbon Because its pore volume is larger, the elemental sulfur of high level can be loaded.
3rd, the synthesis technique it is simple, can be with mass production.
4th, the positive electrode of present invention gained in the growth of porous carbon surface in situ because having CNT, therefore its electric conductivity is good Good, high rate performance is excellent；Metallic nickel has stronger interaction with electric discharge intermediate product simultaneously, effectively can extenuate in discharge and recharge Between product dissolving, lift the coulombic efficiency and cyclical stability of lithium-sulfur cell.
Brief description of the drawings
Fig. 1 is the gained NiPC@CNTs of embodiment 1 electron scanning micrograph；
Fig. 2 is stable circulation linearity curve of the gained NiPC CNTs/S composites of embodiment 1 in 1C；
Fig. 3 is the gained NiPC@CNTs of embodiment 2 electron scanning micrograph；
Fig. 4 is first charge-discharge curve of the gained NiPC@CNTs/S composites of embodiment 3 in 0.2C.
Embodiment
Technical scheme is further described below in conjunction with the accompanying drawings, but is not limited thereto, it is every to this Inventive technique scheme is modified or equivalent substitution, without departing from the spirit and scope of technical solution of the present invention, all should cover In protection scope of the present invention.
Embodiment 1：
（1）13.72 grams of nickel acetate tetrahydrates are dissolved in 5 liters of distilled water, 51.31 grams of 2-methylimidazoles are dissolved in 5 liters Distilled water；By well mixed standing 2 days afterwards of two solution.Above-mentioned solution is filtered, cleaned, back and forth three times, 70 DEG C of bakings It is dry to obtain nickeliferous metal organic frame.
（2）By nickeliferous metal organic frame under argon gas protection, 1000 DEG C are pyrolyzed 6 hours, and step pyrolysis is i.e. available NiPC@CNTs。
（3）By NiPC@CNTs and elemental sulfur with 4：6 mass ratio is well mixed, and is heated to 155 DEG C, is kept for 24 hours, cold But NiPC@CNTs/S composites are obtained afterwards.
（4）By NiPC@CNTs/S composites, conductive black and Kynoar with 8：1：1 mass ratio is scattered in NMP Middle formation slurry is evenly applied to aluminium foil.Anode pole piece is obtained after 50 degrees Celsius of drying in 12 hours, the use of lithium piece is negative pole, 1,2- cyclopentane epoxides/ethylene glycol dimethyl ether solution of the double trifluoromethanesulfonimide lithiums of 1mol/L（Volume ratio 1：1）For electrolysis Liquid, Celgard2400 barrier films are assembled into lithium-sulfur cell, carry out electrochemical property test.
Electron scanning micrograph as shown in Figure 1 can be seen that under the technique, the life of NiPC@CNTs material surfaces With CNT.Stable circulation linearity curve of the lithium-sulfur cell as shown in Figure 2 in 1C understands that discharge capacity is reachable first 891mAh/g, discharge capacity also has 715mAh/g after 20 circulations, has preferable stability.
Embodiment 2：
（1）13.72 grams of nickel acetate tetrahydrates are dissolved in 2.5 liters of methanol；25.65 grams of 2-methylimidazoles are dissolved in 2.5 The methanol risen.By well mixed standing 1 day afterwards of two solution.Above-mentioned solution is filtered, cleaned, back and forth three times, 50 DEG C true Sky drying obtains nickeliferous metal organic frame.
（2）By nickeliferous metal organic frame under nitrogen protection, 1100 DEG C are pyrolyzed 5 hours, and a step is pyrolyzed to obtain NiPC CNTs。
（3）By NiPC@CNTs and elemental sulfur with 3：7 mass ratio is well mixed, and is heated to 155 DEG C, is kept for 24 hours, cold But NiPC@CNTs/S composites are obtained afterwards.
Electron scanning micrograph as shown in Figure 3 understands that the NiPC@CNTs material surfaces obtained under the technique grow There is substantial amounts of CNT.
Embodiment 3：
The present embodiment is protected in the hydrogen containing 10% volume fraction as different from Example 1, by nickeliferous metal organic frame Under shield, 950 DEG C are pyrolyzed 6 hours.One step is pyrolyzed to obtain NiPC CNTs.
The first charge-discharge curve in 0.2C of lithium-sulfur cell as shown in Figure 4 understands that discharge capacity reaches first 1069mAh/g, initial charge capacity are 1041mAh/g.

Claims (4)

1. a kind of NiPC@CNTs/S preparation method, wherein, Ni represents metallic nickel, and PC represents porous carbon, it is characterised in that described Method comprises the following steps that：
First, nickel salt is dissolved in solvent, while 2-methylimidazole is dissolved in solvent, until completely dissolved, by two solution Well mixed, it is 1 to control the mol ratio of nickel ion and 2-methylimidazole：0.1 ~ 100, filtered after shelving 0.5 ~ 100 hour, be clear Wash, dry, obtain the metal organic frame containing metallic nickel ions；
2nd, metal organic frame is obtained into NiPC@CNTs in protection gas high temperature pyrolysis, a step, control pyrolysis temperature 500 ~ Between 1500 DEG C, pyrolysis time is between 0.5 ~ 30 hour；
3rd, by NiPC@CNTs and elemental sulfur with 2 ~ 6:4 ~ 8 mass ratio mixing, is heated to 120 ~ 158 DEG C, is kept for 2 ~ 48 hours, Cooling obtains NiPC@CNTs/S composites.
2. NiPC@CNTs/S according to claim 1 preparation method, it is characterised in that the solvent is water, ethanol, first One or more in alcohol, dimethylformamide, N NMFs.
3. NiPC@CNTs/S according to claim 1 preparation method, it is characterised in that the protection gas is nitrogen, argon One or more in gas, helium, hydrogen.
4. NiPC@CNTs/S composites prepared by a kind of claim 1-3 any claims methods described are used for lithium sulphur electricity The positive electrode in pond.
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CN107123810B (en) * 2017-05-17 2019-04-30 哈尔滨工业大学 A kind of preparation method and applications based on nickel phosphide skeleton structure composite material
CN107134572B (en) * 2017-05-17 2019-04-30 哈尔滨工业大学 A kind of preparation method and application based on nickel phosphide hollow structure composite material
CN109097788B (en) * 2018-08-10 2020-05-12 复旦大学 Double-carbon coupling transition metal nickel-based quantum dot electrocatalyst and preparation method thereof
CN109461903A (en) * 2018-09-29 2019-03-12 昆明理工大学 A kind of preparation method of lithium-sulfur battery composite cathode material
CN109244417B (en) * 2018-09-29 2021-06-18 昆明理工大学 Preparation method of composite positive electrode material of lithium-sulfur battery with nanosheet layered structure
CN109461906B (en) * 2018-09-30 2021-08-20 昆明理工大学 Preparation method of lithium-sulfur battery positive electrode material
CN109802124A (en) * 2019-02-14 2019-05-24 西南大学 Metal atom doped porous carbon nano-composite material of one kind and its preparation method and application
CN112897497A (en) * 2021-01-18 2021-06-04 广东技术师范大学 Sulfur reduction reaction catalytic material and preparation method and application thereof

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