CN110148735A - A kind of preparation method of self-supporting graphite phase carbon nitride/conducting polymer composite sulfur positive electrode - Google Patents

A kind of preparation method of self-supporting graphite phase carbon nitride/conducting polymer composite sulfur positive electrode Download PDF

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CN110148735A
CN110148735A CN201910474394.7A CN201910474394A CN110148735A CN 110148735 A CN110148735 A CN 110148735A CN 201910474394 A CN201910474394 A CN 201910474394A CN 110148735 A CN110148735 A CN 110148735A
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self
conducting polymer
carbon nitride
graphite phase
phase carbon
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CN110148735B (en
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李欢欢
陈会芹
张玉婷
薛艳
白光月
王玉洁
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Henan Normal University
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Henan Normal University
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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
    • H01M4/362—Composites
    • 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
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • 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 self-supporting graphite phase carbon nitride/conducting polymer composite sulfur positive electrode preparation methods, belong to lithium sulfur battery anode material technical field.Simple substance sulphur granule is uniformly anchored on the carbon cloth through graphite phase carbon nitride modified by the present invention, conducting polymer is uniformly coated on S particle with infusion method to further enhance its electric charge transfer rate and structural stability by the later period, the high conductivity of the height ratio capacity of sulphur, the flexibility of CC and CP is closely combined together by the system, to obtain CP@S@g-C of an example with self supporting structure and function admirable3N4/ CC combination electrode material.Preparation process of the present invention is simple, and prepared material has outstanding lithium-sulfur cell performance, is expected to be applied in flexible, wearable electronic as self-supporting electrode material.

Description

A kind of system of self-supporting graphite phase carbon nitride/conducting polymer composite sulfur positive electrode Preparation Method
Technical field
The invention belongs to lithium sulfur battery anode material technical fields, and in particular to a kind of self-supporting graphite phase carbon nitride/lead The preparation method of electric macromolecule composite sulfur positive electrode.
Background technique
With the clean and effective energy utilization technology that lithium-sulfur cell (LSB) is representative be solve the energy crisis that is on the rise with And one of effective way for the problem that reduces environmental pollution.LSB is anode with sulphur simple substance, and lithium metal is cathode, its operating voltage About 2.15 V, theoretical energy density is up to 2567 Wh/kg, much higher than commercialized lithium ion battery at this stage.In addition sulphur itself Also there are the advantages such as material source is extensive, at low cost, environmental-friendly, therefore LSB has wide application in extensive energy storage field Prospect.
LSB is mainly faced with following problem in science in actual application at present: (1) poorly conductive, sulphur is in room Electronic conductivity under temperature only has 5 × 10-30 S cm-1, this greatly hinders the transfer rate and sulphur of charge in charge and discharge process Effective rate of utilization；(2) volume expansion of sulphur anode is more serious, and there are the changes of 80% volume in charge and discharge process for sulphur simple substance Change, causes electrode material to fall off or be cracked from collector, cause battery capacity sharp-decay；(3) intermediate state vulcanizes more Object (LiPSs) has " shuttle effect ", and the intermediate discharging product for being embodied in sulphur anode is more lithium sulfide (Li2S x ,x=4 ~ 8), They can further be reduced into Li across diaphragm2S, is deposited on lithium anode in solid form, and shuttle effect will lead to electricity Pond internal resistance significantly increases and causes the irreversible loss of active material and capacity.
To avoid shuttle effect, core strategy is that LiPSs is limited in sulphur anode side as far as possible, and it is negative with lithium to shield it The direct contact of pole.Based on this, researchers at home and abroad are set out from different perspectives, in diaphragm modification, introduce intercalation, Novel electric Many fruitful work have been carried out in design and the cathode of lithium protection etc. for solving liquid system (including solid electrolyte).But It is well known that the superiority and inferiority of electrode material is to determine the primary factor of battery performance quality.In addition, exploitation has self-supporting in recent years The flexible electrode material of structure, being applied to is also a new research hotspot in wearable electronic device.Therefore, it is based on sulphur The flexible structure of positive host material designs, and solves the electric conductivity that sulphur is just very poor in LSB, serious volume expansion and LiPSs's The problems such as shuttle effect is the key that LSB is pushed to apply in flexible wearable equipment.
Summary of the invention
Simple and excellent material performance the self-supporting stone the technical problem to be solved by the present invention is to provide a kind of preparation process Black phase carbon nitride/conducting polymer composite sulfur positive electrode preparation method.
The present invention adopts the following technical scheme that solve above-mentioned technical problem, a kind of self-supporting graphite phase carbon nitride/conduction The preparation method of macromolecule composite sulfur positive electrode, it is characterised in that specific steps are as follows:
Step S1: the carbon cloth cut is immersed in saturation aqueous solution of urea, is taken out after sufficiently impregnating dry in 60 DEG C of vacuum Sample after drying, is then placed in tube furnace by dry 2 h, and obtaining product in 550 DEG C of 3 h of heat treatment in a nitrogen atmosphere has The g-C of self supporting structure3N4/CC；
Step S2: 150 mg sublimed sulfurs are dissolved in 15 mL ethylenediamine solutions, then by g-C obtained by step S13N4/ CC ultrasound It is scattered in 200 mL dilute hydrochloric acid solutions, the ethylenediamine solution of sulphur is added drop-wise to g-C under intense agitation3N4The dispersion of/CC In liquid, 30 min are persistently stirred in room temperature after being added dropwise, to after reaction respectively be rushed carbon cloth with deionized water and ethyl alcohol It washes repeatedly, finally obtains product S@g-C in 60 DEG C of 12 h of vacuum drying3N4/CC；
Step S3: by S@g-C obtained by step S23N4/ CC is immersed in poly- (3,4- Ethylenedioxy Thiophene)-poly- (styrene sulfonic acid Sodium) in conductive polymer solution, taken out after infiltrating it sufficiently, then obtained after being dried in vacuo with self supporting structure and performance it is excellent Different CP@S@g-C3N4/ CC combination electrode material.
The invention has the following advantages: the system is by the flexibility and the poly- (Asia 3,4- second two of the height ratio capacity of sulphur, CC Oxygroup thiophene) high conductivity of-poly(sodium styrene sulfonate) (CP) is closely combined together, thus obtain an example have from The CP@S@g-C of support construction and function admirable3N4/ CC combination electrode material.Lithium sulfur battery anode material is used as to be filled When discharge test, which shows excellent chemical property, the electric discharge for the first time, charging capacity under 0.2 C point Not up to 1202.4 mAh/g and 1176.6 mAh/g, still there are 880 mAh/g or so through 25 circulation volumes under 0.2 C.This hair Bright preparation process is simple, and prepared material has outstanding lithium-sulfur cell performance, is expected to as self-supporting electrode material application In flexible, wearable electronic.
Detailed description of the invention
Fig. 1 is gained g-C3N4The SEM of/CC schemes；
Fig. 2 is gained CP@S@g-C3N4The SEM of/CC schemes；
Fig. 3 is CP@S@g-C3N4Charging and discharging curve of/the CC under 0.2 C multiplying power；
Fig. 4 is CP@S@g-C3N4Cycle performance of/the CC under 0.2 C multiplying power.
Specific embodiment
Above content of the invention is described in further details by the following examples, but this should not be interpreted as to this The range for inventing above-mentioned theme is only limitted to embodiment below, and all technologies realized based on above content of the present invention belong to this hair Bright range.
Embodiment
Step S1: the carbon cloth cut is immersed in saturation aqueous solution of urea, is taken out after sufficiently impregnating true in 60 DEG C Sample after drying, is then placed in tube furnace, obtains product in 550 DEG C of 3 h of heat treatment in a nitrogen atmosphere by dry 2 h of sky G-C with self supporting structure3N4/CC；
Step S2: 150 mg sublimed sulfurs are dissolved in 15 mL ethylenediamine solutions, then by g-C obtained by step S13N4/ CC ultrasound It is scattered in 200 mL dilute hydrochloric acid solutions, the ethylenediamine solution of sulphur is added drop-wise to g-C under intense agitation3N4The dispersion of/CC In liquid, 30 min are persistently stirred in room temperature after being added dropwise, to after reaction respectively be rushed carbon cloth with deionized water and ethyl alcohol It washes repeatedly, finally obtains product S@g-C in 60 DEG C of 12 h of vacuum drying3N4/CC；
Step S3: by S@g-C obtained by step S23N4/ CC is immersed in poly- (3,4- Ethylenedioxy Thiophene)-poly- (styrene sulfonic acid Sodium) in conductive polymer solution, taken out after infiltrating it sufficiently, then obtained after being dried in vacuo with self supporting structure and performance it is excellent Different CP@S@g-C3N4/ CC combination electrode material.
The high conductivity of the height ratio capacity of sulphur, the flexibility of CC and CP is closely combined together by the present invention, to obtain Obtained CP@S@g-C of an example with self supporting structure and function admirable3N4/ CC combination electrode material.It is used as lithium-sulfur cell When positive electrode carries out charge-discharge test, which goes out excellent chemical property, and electric discharge for the first time under 0.2 C is filled Capacitance still has 880 mAh/g left under 0.2 C respectively up to 1202.4 mAh/g and 1176.6 mAh/g through 25 circulation volumes It is right.
Embodiment above describes basic principles and main features of the invention and advantage, the technical staff of the industry should Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe originals of the invention Reason, under the range for not departing from the principle of the invention, various changes and improvements may be made to the invention, these changes and improvements are each fallen within In the scope of protection of the invention.

Claims (2)

1. a kind of self-supporting graphite phase carbon nitride/conducting polymer composite sulfur positive electrode preparation method, it is characterised in that tool Body step are as follows:
Step S1: the carbon cloth cut is immersed in saturation aqueous solution of urea, is taken out after sufficiently impregnating dry in 60 DEG C of vacuum Sample after drying, is then placed in tube furnace by dry 2 h, and obtaining product in 550 DEG C of 3 h of heat treatment in a nitrogen atmosphere has The g-C of self supporting structure3N4/CC；
Step S2: 150 mg sublimed sulfurs are dissolved in 15 mL ethylenediamine solutions, then by g-C obtained by step S13N4/ CC ultrasound point It dissipates in 200 mL dilute hydrochloric acid solutions, the ethylenediamine solution of sulphur is added drop-wise to g-C under intense agitation3N4The dispersion liquid of/CC In, 30 min are persistently stirred in room temperature after being added dropwise, to after reaction respectively be rinsed carbon cloth with deionized water and ethyl alcohol Repeatedly, product S@g-C finally is obtained in 60 DEG C of 12 h of vacuum drying3N4/CC；
Step S3: by S@g-C obtained by step S23N4/ CC is immersed in poly- (3,4- Ethylenedioxy Thiophene)-poly- (styrene sulfonic acid Sodium) in conductive polymer solution, taken out after infiltrating it sufficiently, then obtained after being dried in vacuo with self supporting structure and performance it is excellent Different CP@S@g-C3N4/ CC combination electrode material.
2. self-supporting graphite phase carbon nitride according to claim 1/conducting polymer composite sulfur positive electrode preparation side Method, it is characterised in that: the CP@S@g-C3N4/ CC combination electrode material is by the height ratio capacity of sulphur, the height of the flexibility of CC and CP Electric conductivity is combined closely, and when being used as lithium sulfur battery anode material progress charge-discharge test, which is shown Excellent chemical property, the electric discharge for the first time, charging capacity under 0.2 C are respectively up to 1202.4 mAh/g and 1176.6 mAh/ Still there are 880 mAh/g through 25 circulation volumes under g, 0.2 C.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112038620A (en) * 2020-09-28 2020-12-04 中航锂电技术研究院有限公司 Lithium-sulfur battery positive electrode material and lithium-sulfur battery
CN112186153A (en) * 2020-09-23 2021-01-05 长沙矿冶研究院有限责任公司 Lithium cathode with interface nanosheet protective layer and preparation method thereof
CN114256449A (en) * 2020-09-25 2022-03-29 上海交通大学 Sulfur-loaded carbon nitride/carbon fiber composite material and preparation method and application thereof
CN114551895A (en) * 2021-07-08 2022-05-27 万向一二三股份公司 Manufacturing method of flexible lithium metal battery cathode

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CN106602023A (en) * 2016-12-26 2017-04-26 武汉理工大学 Method for in-situ synthesis of graphite phase carbon nitride-copper oxide composite material
CN106684396A (en) * 2016-12-21 2017-05-17 北京化工大学 Method for preparing bifunctional catalyst from peanut hull
CN109286021A (en) * 2018-07-24 2019-01-29 南京航空航天大学 Two-dimentional g-C3N4/WO3/ carbon cloth combination electrode and its preparation method and application

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105126895A (en) * 2015-09-18 2015-12-09 清华大学深圳研究生院 Graphite-phase carbon nitride sheet material and preparation method thereof
CN106684396A (en) * 2016-12-21 2017-05-17 北京化工大学 Method for preparing bifunctional catalyst from peanut hull
CN106602023A (en) * 2016-12-26 2017-04-26 武汉理工大学 Method for in-situ synthesis of graphite phase carbon nitride-copper oxide composite material
CN109286021A (en) * 2018-07-24 2019-01-29 南京航空航天大学 Two-dimentional g-C3N4/WO3/ carbon cloth combination electrode and its preparation method and application

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112186153A (en) * 2020-09-23 2021-01-05 长沙矿冶研究院有限责任公司 Lithium cathode with interface nanosheet protective layer and preparation method thereof
CN112186153B (en) * 2020-09-23 2022-05-20 长沙矿冶研究院有限责任公司 Lithium cathode with interface nanosheet protective layer and preparation method thereof
CN114256449A (en) * 2020-09-25 2022-03-29 上海交通大学 Sulfur-loaded carbon nitride/carbon fiber composite material and preparation method and application thereof
CN112038620A (en) * 2020-09-28 2020-12-04 中航锂电技术研究院有限公司 Lithium-sulfur battery positive electrode material and lithium-sulfur battery
CN114551895A (en) * 2021-07-08 2022-05-27 万向一二三股份公司 Manufacturing method of flexible lithium metal battery cathode
CN114551895B (en) * 2021-07-08 2023-10-03 万向一二三股份公司 Manufacturing method of flexible lithium metal battery negative electrode

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