CN108598390A - A kind of preparation method and lithium-sulfur cell of positive material for lithium-sulfur battery - Google Patents

A kind of preparation method and lithium-sulfur cell of positive material for lithium-sulfur battery Download PDF

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CN108598390A
CN108598390A CN201810272543.7A CN201810272543A CN108598390A CN 108598390 A CN108598390 A CN 108598390A CN 201810272543 A CN201810272543 A CN 201810272543A CN 108598390 A CN108598390 A CN 108598390A
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lithium
sulfur
positive material
sulfur battery
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CN108598390B (en
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曹元成
程时杰
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Wuhan New Energy Research Institute Co Ltd
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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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • 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
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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 present invention relates to a kind of preparation methods of positive material for lithium-sulfur battery, include the following steps：Cobalt nitrate and 2 methylimidazoles are dissolved in solvent and are stood, centrifugal drying, ZIF 67 is obtained；ZIF 67 is carbonized under indifferent gas atmosphere, is cooled to room temperature, Co N C are obtained；Co N C and dicyandiamide are carbonized under indifferent gas atmosphere, are cooled to room temperature, CNT Co N C are obtained.A kind of lithium-sulfur cell includes the positive electrode for being used as the lithium-sulfur cell by positive material for lithium-sulfur battery.The beneficial effects of the invention are as follows：Specific surface area and electric conductivity are improved compared to individual metal organic framework compound based composites, it being capable of more effective sulfur loaded, and more effectively inhibit the shuttle effect of polysulfide during cell reaction, it is assembled into battery and carries out constant-current discharge test, the results showed that the chemical property of the growth in situ composite material of carbon nanotube is more excellent.

Description

A kind of preparation method and lithium-sulfur cell of positive material for lithium-sulfur battery
Technical field
The present invention relates to technical field of energy storage more particularly to the preparation methods and lithium sulphur of a kind of positive material for lithium-sulfur battery Battery.
Background technology
With the successful commercialization application of graphite cathode, lithium ion battery is portable in smart mobile phone, laptop etc. It has been widely used in electronic equipment.By development in more than 20 years, the existing lithium-ion electric based on lithium intercalation compound anode Pond has been approached its theoretical capacity, but still cannot meet wanting for the industries such as the electronics industry of high speed development and emerging electric vehicle It asks, it is extremely urgent to find the battery system with higher energy density.Such as, lithium-sulfur cell is the elemental sulfur using lithium metal as cathode For the lithium rechargeable battery of new generation of positive active material, wherein lithium metal is density minimum (0.53g/ in nature cm3), normal potential minimum (- 3.04Vvs.SHE), electrochemical equivalent minimum (0.26g/Ah), theoretical specific capacity highest The metallic element of (3861mAh/g), therefore lithium metal has very high energy density, is assembled as negative material by it Lithium metal battery have higher energy density and operating voltage.Elemental sulfur is widely distributed in nature, utilizes Li2S and S Between inverible transform, theoretical specific capacity 1672mAh/g calculates by average voltage 2.1V, and theoretical energy density is 2600Wh/kg.Lithium-sulphur combination is the highest solid state electrode combination of energy density in all known chemical bilateral systems.
Although compared with conventional lithium ion battery, lithium-sulfur cell has such as above-mentioned obvious advantage, but still there is activity Material utilization is low, poor circulation, the problems such as coulombic efficiency is low, self-discharge rate is high, the paces for having delayed it practical.Dissolving In the Li of organic electrolyte2Sn(4≤n≤8) are electrochemical in electrolyte near anode in the presence of concentration gradient Be oxidized to the relatively long long-chain polysulfide lithium Li of chain length2Sn(6≤n≤8) are spread by diaphragm to cathode of lithium, and directly It reacts with lithium metal, generates the relatively short short chain polysulfide lithium Li of chain length2Sn(4≤n≤6)、Li2S2And Li2S, Eventually lead to the decline of lithium-sulfur cell coulombic efficiency.
Invention content
Technical problem to be solved by the invention is to provide a kind of preparation method of positive material for lithium-sulfur battery and lithium sulphur Battery, to overcome above-mentioned deficiency in the prior art.
The technical solution that the present invention solves above-mentioned technical problem is as follows：A kind of preparation side of positive material for lithium-sulfur battery Method includes the following steps：
S100, cobalt nitrate and 2-methylimidazole are dissolved in solvent, after reaction, obtain ZIF-67；
S200, ZIF-67 is carbonized under indifferent gas atmosphere, obtains Co-N-C；
S300, Co-N-C and dicyandiamide are carbonized under indifferent gas atmosphere, obtain CNT Co-N-C.
The beneficial effects of the invention are as follows：It is improved compared to individual metal organic framework compound based composites and compares table Area and electric conductivity, can more effective sulfur loaded, and more effectively inhibit during cell reaction the shuttle of polysulfide Effect.
Based on the above technical solution, the present invention can also be improved as follows.
Further, ZIF-67 is prepared in the S100 to be as follows：
Cobalt nitrate and 2-methylimidazole are dissolved in methanol, 6h-12h is stood, is then centrifuged for drying, drying temperature 60 DEG C -80 DEG C, time 12h, after, obtain ZIF-67.
Further, Co-N-C is prepared in the S200 to be as follows：
ZIF-67 is carbonized under argon atmosphere, carburizing temperature is 700 DEG C -900 DEG C, obtains Co-N-C.
Further, the specific preparation process of the Co-N-C is as follows：
ZIF-67 is carbonized with the heating rate of 5 DEG C/min at 700 DEG C -900 DEG C under argon atmosphere, carbonization time It for 2h, is cooled to room temperature, obtains Co-N-C.
It is further had the beneficial effect that using above-mentioned：It can effectively ensure that rapid reaction, fully carry out.
Further, CNT@Co-N-C are prepared in the S300 to be as follows：
Co-N-C and dicyandiamide are carbonized under argon atmosphere, carburizing temperature is 700 DEG C -900 DEG C, obtains CNT@ Co-N-C。
Further, the specific preparation process of the CNT@Co-N-C is as follows：
Co-N-C and dicyandiamide are carbonized with the heating rate of 5 DEG C/min at 700 DEG C -900 DEG C under argon atmosphere, Carbonization time is 2h, is cooled to room temperature, and Co-N-C is obtained.
It is further had the beneficial effect that using above-mentioned：It can effectively ensure that rapid reaction, fully carry out.
Further, the mass fraction of dicyandiamide is 1%-50%.
A kind of lithium-sulfur cell includes the positive electrode for being used as the lithium-sulfur cell by positive material for lithium-sulfur battery.
It is further had the beneficial effect that using above-mentioned：Battery capacity improves：Battery is under the big multiplying power of 5C under normal temperature condition Still keep the specific capacity of 670mAh/g；Battery cycle life is long：The circle of charge-discharge cycle 500 still has 79.8% under the multiplying power of 0.2C Capacity retention ratio.
Further, according to active material：Acetylene black：PVDF=7：2：1 proportioning makes positive plate, active material by sulphur and After positive material for lithium-sulfur battery mixed grinding in reaction kettle obtained by 155 DEG C of -158 DEG C of heating 6h-10h；It is negative with lithium piece Pole, is assembled into lithium-sulfur cell in the glove box full of argon gas, and electrolyte is the LITFSI and 1%LiNO of 1mol/L3Mixing Liquid.
Description of the drawings
Fig. 1 is that heretofore described positive material for lithium-sulfur battery synthesizes schematic diagram；
Fig. 2 is SEM figure of the heretofore described positive material for lithium-sulfur battery at 500nm；
Fig. 3 is SEM figure of the heretofore described positive material for lithium-sulfur battery at 500nm；
Fig. 4 is the crystalline structure characteristic peak for the different materials that X-ray diffraction is measured；
Fig. 5 is the charge-discharge performance figure in different multiplying condition lower electrode material；
Fig. 6 is the long circulating charge-discharge performance figure of the CNT@Co-N-C/S electrode materials under the conditions of multiplying power of 0.2C.
Specific implementation mode
The principles and features of the present invention are described below, and the given examples are served only to explain the present invention, is not intended to limit Determine the scope of the present invention.
A kind of preparation method of positive material for lithium-sulfur battery, detailed process is as shown in Figure 1, be mainly concerned with organic frame 4 committed steps such as macromolecular architecture, metal complex, element doping and nanotube growth.Detail following steps：
S100, by cobalt nitrate and 2-methylimidazole according to 1：4 ratio is dissolved in methanol, and stands 6h-12h, after centrifugation 60 DEG C of -80 DEG C of drying, drying time 12h in vacuum drying chamber, wherein dry standard is to remove methanol and micro Water obtains ZIF-67；Shown in scanning electron microscope result figure 2, crystal structure is square.
S200, by ZIF-67 under the indifferent gas atmosphere that argon gas is constituted with the heating rate of 5 DEG C/min at 700 DEG C -900 It DEG C is carbonized, carbonization time 2h is cooled to room temperature, obtains Co-N-C；
S300, by the dicyandiamide that Co-N-C and volume fraction are 1%-50% be placed in tube furnace under indifferent gas atmosphere with The heating rate of 5 DEG C/min is carbonized at 700 DEG C -900 DEG C, and carbonization time 2h is cooled to room temperature, and obtains CNT@Co-N- C。
Shown in result figure 3, cube face covers carbon nanotube, and homogeneity is good.X-ray diffraction result such as Fig. 4 institutes Show, prepared product matches well with standard diagram.
In this preparation method, there are stringent limit in cobalt nitrate, the addition sequence of 2-methylimidazole and dicyandiamide and addition time Dicyandiamide cannot be added before first time is carbonized in system, because cobalt nitrate will produce simple substance cobalt in carbonization, and utilize simple substance cobalt React generation carbon nanotube with the dicyandiamide being subsequently added as catalyst (makes dicyandiamide decompose and react with chemical catalysis method Generate carbon nanotube), finally ensure that carbon nanotube is grown on Co-N-C materials, is integrated, this is for electrode material It is to have very great meaning, if dicyandiamide is added before generating simple substance cobalt, dicyandiamide can decompose before 700 DEG C, and Cobalt nitrate is not calcined also and is decomposed into simple substance cobalt so that final products therefrom is unable to reach corresponding effect.A kind of lithium-sulfur cell, is pressed According to active material：Acetylene black：PVDF (Kynoar)=7：2：1 proportioning makes positive plate, wherein active material by sulphur and Positive material for lithium-sulfur battery presses 4：After 1 ratio mixed grinding in reaction kettle obtained by 155 DEG C of -158 DEG C of heating 6h-10h； Using lithium piece as cathode, lithium-sulfur cell is assembled into the glove box full of argon gas, electrolyte uses the LITFSI and 1% of 1mol/L LiNO3And dimethoxymethane and dioxolanes, dimethoxymethane：Dioxolanes volume fraction percent is 1：1 it is mixed Close liquid.
Assembled battery is placed on blue electric battery test system, test results are shown in figure 5 for high rate performance, as a result table The bright active material can carry out charge and discharge cycles under different multiplying, and capacity retention ratio is good.Further, with the multiplying power of 0.2C Carry out constant current charge-discharge test, obtain the chemical property of battery material, shown in Fig. 6, the result shows that cycle 500 times when institute The product capacity retention ratio of preparation is optimal.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned Embodiment is changed, changes, replacing and modification.

Claims (9)

1. a kind of preparation method of positive material for lithium-sulfur battery, which is characterized in that include the following steps：
S100, cobalt nitrate and 2-methylimidazole are dissolved in solvent, after reaction, obtain ZIF-67；
S200, ZIF-67 is carbonized under indifferent gas atmosphere, obtains Co-N-C；
S300, Co-N-C and dicyandiamide are carbonized under indifferent gas atmosphere, obtain CNT Co-N-C.
2. a kind of positive material for lithium-sulfur battery according to claim 1, which is characterized in that prepare ZIF- in the S100 67 are as follows：
Cobalt nitrate and 2-methylimidazole are dissolved in methanol, 6h-12h is stood, is then centrifuged for drying, drying temperature is 60 DEG C -80 DEG C, time 12h, after, obtain ZIF-67.
3. a kind of preparation of positive material for lithium-sulfur battery according to claim 2, which is characterized in that made in the S200 Standby Co-N-C is as follows：
ZIF-67 is carbonized under argon atmosphere, carburizing temperature is 700 DEG C -900 DEG C, obtains Co-N-C.
4. a kind of preparation method of positive material for lithium-sulfur battery according to claim 3, which is characterized in that the Co- The specific preparation process of N-C is as follows：
ZIF-67 is carbonized with the heating rate of 5 DEG C/min at 700 DEG C -900 DEG C under argon atmosphere, carbonization time is 2h is cooled to room temperature, and obtains Co-N-C.
5. a kind of preparation method of positive material for lithium-sulfur battery according to claim 1, which is characterized in that the S300 The middle CNT@Co-N-C that prepare are as follows：
Co-N-C and dicyandiamide are carbonized under argon atmosphere, carburizing temperature is 700 DEG C -900 DEG C, obtains CNT@Co-N- C。
6. a kind of preparation method of positive material for lithium-sulfur battery according to claim 5, which is characterized in that the CNT@ The specific preparation process of Co-N-C is as follows：
Co-N-C and dicyandiamide are carbonized with the heating rate of 5 DEG C/min at 700 DEG C -900 DEG C under argon atmosphere, are carbonized Time is 2h, is cooled to room temperature, and Co-N-C is obtained.
7. a kind of preparation method of positive material for lithium-sulfur battery according to claim 1 or 5 or 6, which is characterized in that institute It states in S300, the mass fraction of dicyandiamide is 1%-50%.
8. a kind of lithium-sulfur cell, which is characterized in that including by being produced according to claim 1-7 any one of them preparation methods Positive electrode of the positive material for lithium-sulfur battery as the lithium-sulfur cell.
9. lithium-sulfur cell according to claim 8, which is characterized in that according to active material：Acetylene black：PVDF=7：2：1 Proportioning make positive plate, active material by after sulphur and positive material for lithium-sulfur battery mixed grinding 155 DEG C in reaction kettle- Obtained by 158 DEG C of heating 6h-10h；Using lithium piece as cathode, lithium-sulfur cell, electrolyte are assembled into the glove box full of argon gas For the LITFSI and 1%LiNO of 1mol/L3Mixed liquor.
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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
CN109768237A (en) * 2018-12-24 2019-05-17 肇庆市华师大光电产业研究院 A kind of novel lithium sulfur battery anode material, preparation method and application
CN109524678A (en) * 2019-01-23 2019-03-26 中南大学 A kind of analysis oxygen ferrocobalt-cobalt ferrite/nitrogen-doped nanometer carbon pipe composite catalyst and its preparation method and application
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