CN106981633A - A kind of poly- anthraquinone thioether/Ti3C2Tx/ sulphur composite - Google Patents

A kind of poly- anthraquinone thioether/Ti3C2Tx/ sulphur composite Download PDF

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Publication number
CN106981633A
CN106981633A CN201710230127.6A CN201710230127A CN106981633A CN 106981633 A CN106981633 A CN 106981633A CN 201710230127 A CN201710230127 A CN 201710230127A CN 106981633 A CN106981633 A CN 106981633A
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sulphur
composite
poly
anthraquinone
thioether
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CN201710230127.6A
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钟玲珑
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Shenzhen Pei Cheng Technology Co Ltd
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Shenzhen Pei Cheng Technology 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
    • H01M4/366—Composites as layered products
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/62—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 provides a kind of poly- anthraquinone thioether/Ti3C2Tx/ sulphur composite, the composite is by sulphur, sheet Ti3C2TxWith poly- anthraquinone thioether composition, internal layer is sulphur and Ti3C2TxComposite, outer layer is cladding sulphur and Ti3C2TxThe poly- anthraquinone thioether of composite, its poly- anthraquinone thioether：Ti3C2Tx：The mass ratio of sulphur is 0.05 0.2:0.05‑0.2:1.Strata anthraquinone thioether is coated in composite can carry out physical protection to sulfenyl material, and the polysulfide that limitation charge and discharge process is produced is inside poly- anthraquinone thioether, so as to reduce shuttle effect；The composite limits the movement of polysulfide, the effective life-span for improving lithium-sulfur cell simultaneously in terms of physics confinement and chemisorbed two.

Description

A kind of poly- anthraquinone thioether/Ti3C2Tx/ sulphur composite
Technical field
The present invention relates to nano material synthesis, more particularly to a kind of preparation method of lithium sulfur battery anode material.
Background technology
Lithium-sulfur cell is that, using lithium metal as negative pole, elemental sulfur is the battery system of positive pole.Lithium-sulfur cell have two put Level platform（About 2.4 V and 2.1 V）, but its electrochemical reaction mechanism is more complicated.Lithium-sulfur cell has specific energy high （2600 Wh/kg）, specific capacity it is high（1675 mAh/g）, low cost and other advantages, it is considered to be very promising a new generation's electricity Pond.But at present the problems such as there is low active material utilization, low cycle life and poor security, this seriously governs lithium The development of sulphur battery.Causing the main cause of above mentioned problem has the following aspects：（1）Elemental sulfur is electronics and ion insulation Body, room-temperature conductivity is low（5×10-30S·cm-1）, because the sulphur without ionic state is present, thus it is tired as positive electrode activation It is difficult；（2）The high poly- many lithium sulfide Li of state produced in electrode process2Sn（8 ＞ n >=4）It is soluble in electrolyte, positive and negative Concentration difference is formed between pole, negative pole is moved in the presence of concentration gradient, the high poly- many lithium sulfides of state are reduced into low by lithium metal The poly- many lithium sulfides of state.The progress of reaction more than, the oligomeric many lithium sulfides of state are assembled in negative pole, finally formed between electrodes Concentration difference, moves to positive pole and is oxidized to the high many lithium sulfides of poly- state again.This phenomenon is referred to as shuttle effect, reduces sulphur activity The utilization rate of material.While insoluble Li2S and Li2S2Cathode of lithium surface is deposited on, lithium-sulfur cell is further degrading Performance；（3）React final product Li2S is equally electronic body, can be deposited on sulfur electrode, and lithium ion vulcanizes in solid-state Migration velocity is slow in lithium, makes electrochemical reaction kinetic rate slack-off；（4）Sulphur and final product Li2S density is different, works as sulphur Rear volumetric expansion about 79% is lithiated, Li is easily caused2S efflorescence, causes the safety problem of lithium-sulfur cell.Above-mentioned not enough restriction The development of lithium-sulfur cell, this is also the Important Problems that current lithium-sulfur cell research needs to solve.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of poly- anthraquinone thioether/Ti3C2Tx/ sulphur composite, the composite wood Expect material by sulphur, sheet Ti3C2TxConstituted with the poly- anthraquinone thioether of external sheath, the outer layer that is coated on of poly- anthraquinone thioether limits sulphur Sill is moved freely, sheet Ti3C2TxTitanium can adsorb the dissolving of discharging product polysulfide, improve the electrochemistry of material Energy.
The present invention provides a kind of poly- anthraquinone thioether/Ti3C2Tx/ sulphur composite, the composite is by sulphur, sheet Ti3C2Tx With poly- anthraquinone thioether composition, internal layer is sulphur and Ti3C2TxComposite, outer layer is cladding sulphur and Ti3C2TxThe poly- anthracene of composite Quinone thioether, its poly- anthraquinone thioether：Ti3C2Tx：The mass ratio of sulphur is 0.05-0.2:0.05-0.2:1.
The present invention provides a kind of poly- anthraquinone thioether/Ti3C2TxThe preparation method of/sulphur composite is as follows：
（1）By Ti3AlC2Ceramic powders, which are put into hydrofluoric acid, to be corroded, and solution adds deionized water and carries out centrifugal treating after corrosion, Then sediment is dried, obtains the lamellar Ti of stacking3C2TxPowder；
（2）By Ti3C2TxPowder and elemental sulfur in proportion 1:1 uniform mixing, is positioned in sealed reactor, in nitrogen Heating response is to 155 °C in atmosphere, and constant temperature 5-12h is cooled to room temperature after the completion of reaction, obtains Ti3C2Tx/ sulphur composite wood Material；
（3）By obtained Ti3C2Tx/ sulphur composite is added in 1-METHYLPYRROLIDONE and stirred, and is added 1,5- dichloroanthraquinones and is stirred Mix, then add initiator ammonium persulfate, stirring, standing, filtering, vacuum drying obtain poly- anthraquinone thioether/Ti3C2Tx/ sulphur is multiple Condensation material.
Step（1）The concentration of middle hydrofluoric acid is 20%-50%, and the time of corrosion is 4-24 hours;
Step（2）Middle Ti3C2TxThe mass ratio of powder and elemental sulfur is 0.05-0.2:1, heating response temperature is 155-165 DEG C, Time is 5-12 hours;
Step（3）The ratio of middle 1,5- dichloroanthraquinones and elemental sulfur is 0.05-0.2:1；The ratio of initiator and 1,5- dichloroanthraquinones Example is 1：0.01-0.1, one kind that initiator is selected in azodiisobutyronitrile, dibenzoyl peroxide, ammonium persulfate；
The present invention has the advantages that：Poly- anthraquinone thioether/Ti3C2TxTi in/sulphur composite3C2TxOn T be-F bases Group or-OH groups, are highly polar group, strong chemisorbed, energy can be formed to the polysulfide formed in charge and discharge process It is effective to prevent polysulfide from reaching negative pole through barrier film；Cladding strata anthraquinone thioether can be to sulfenyl material in composite simultaneously Physical protection is carried out, the polysulfide that limitation charge and discharge process is produced is inside poly- anthraquinone thioether, so as to reduce shuttle effect；Should Composite limits the movement of polysulfide simultaneously in terms of physics confinement and chemisorbed two, effectively improves lithium-sulfur cell Life-span.
Brief description of the drawings
Fig. 1 is the process chart of the present invention.
Fig. 2 is the charge-discharge performance figure of composite of the present invention.
Embodiment
Below in conjunction with the accompanying drawings, the preferably embodiment to the present invention is described in further detail：
Embodiment 1
（1）By Ti3AlC2Ceramic powders, which are put into the hydrofluoric acid that mass concentration is 20%, corrodes solution addition after 24h, corrosion Deionized water carries out centrifugal treating, then dries sediment, obtains the lamellar Ti of stacking3C2TxPowder；
（2）By 0.5g Ti3C2TxPowder is uniformly mixed with 10g elemental sulfurs, is positioned in sealed reactor, in the atmosphere of nitrogen Middle heating response is to 155 °C, and constant temperature 12h is cooled to room temperature after the completion of reaction, obtains Ti3C2Tx/ sulphur composite；
（3）By obtained Ti3C2Tx/ sulphur composite is added in 1-METHYLPYRROLIDONE and stirred, and adds 0.5g 1,5- dichloros Anthraquinone is stirred, and then adds 0.05g initiator azodiisobutyronitriles, stirring, standing, filtering, vacuum drying obtain poly- anthraquinone sulphur Ether/Ti3C2Tx/ sulphur composite.
Embodiment 2
（1）By Ti3AlC2Ceramic powders are put into mass concentration and gone to corrode solution addition after 4h, corrosion in 50% hydrofluoric acid Ionized water carries out centrifugal treating, then dries sediment, obtains the lamellar Ti of stacking3C2TxPowder；
（2）By 2g Ti3C2TxPowder is uniformly mixed with 10g elemental sulfurs, is positioned in sealed reactor, in the atmosphere of nitrogen Heating response is to 165 °C, and constant temperature 5h is cooled to room temperature after the completion of reaction, obtains Ti3C2Tx/ sulphur composite；
（3）By obtained Ti3C2Tx/ sulphur composite is added in 1-METHYLPYRROLIDONE and stirred, and adds 2g 1, the chrloroanthracenes of 5- bis- Quinone is stirred, and then adds 0.02g initiator dibenzoyl peroxides, stirring, standing, filtering, vacuum drying obtain poly- anthraquinone sulphur Ether/Ti3C2Tx/ sulphur composite.
Embodiment 3
（1）By Ti3AlC2Ceramic powders, which are put into the hydrofluoric acid that mass concentration is 30%, corrodes solution addition after 20h, corrosion Deionized water carries out centrifugal treating, then dries sediment, obtains the lamellar Ti of stacking3C2TxPowder；
（2）By 1g Ti3C2TxPowder is uniformly mixed with 10g elemental sulfurs, is positioned in sealed reactor, in the atmosphere of nitrogen Heating response is to 160 °C, and constant temperature 10h is cooled to room temperature after the completion of reaction, obtains Ti3C2Tx/ sulphur composite；
（3）By obtained Ti3C2Tx/ sulphur composite is added in 1-METHYLPYRROLIDONE and stirred, and adds 1g 1, the chrloroanthracenes of 5- bis- Quinone is stirred, and then adds 0.05g initiator ammonium persulfates, stirring, stand, filtering, vacuum drying, obtain poly- anthraquinone thioether/ Ti3C2Tx/ sulphur composite.
Embodiment 4
（1）By Ti3AlC2Ceramic powders, which are put into the hydrofluoric acid that mass concentration is 40%, corrodes solution addition after 15h, corrosion Deionized water carries out centrifugal treating, then dries sediment, obtains the lamellar Ti of stacking3C2TxPowder；
（2）By 1.5g Ti3C2TxPowder is uniformly mixed with 10g elemental sulfurs, is positioned in sealed reactor, in the atmosphere of nitrogen Middle heating response is to 162 °C, and constant temperature 8h is cooled to room temperature after the completion of reaction, obtains Ti3C2Tx/ sulphur composite；
（3）By obtained Ti3C2Tx/ sulphur composite is added in 1-METHYLPYRROLIDONE and stirred, and adds 1.5g 1,5- dichloros Anthraquinone is stirred, and then adds 0.08g initiator azodiisobutyronitriles, stirring, standing, filtering, vacuum drying obtain poly- anthraquinone sulphur Ether/Ti3C2Tx/ sulphur composite.
Embodiment 5
（1）By Ti3AlC2Ceramic powders, which are put into the hydrofluoric acid that mass concentration is 35%, corrodes solution addition after 13h, corrosion Deionized water carries out centrifugal treating, then dries sediment, obtains the lamellar Ti of stacking3C2TxPowder；
（2）By 0.8g Ti3C2TxPowder is uniformly mixed with 10g elemental sulfurs, is positioned in sealed reactor, in the atmosphere of nitrogen Middle heating response is to 157 °C, and constant temperature 9h is cooled to room temperature after the completion of reaction, obtains Ti3C2Tx/ sulphur composite；
（3）By obtained Ti3C2Tx/ sulphur composite is added in 1-METHYLPYRROLIDONE and stirred, and adds 0.8g 1,5- dichloros Anthraquinone is stirred, and then adds 0.03g initiator dibenzoyl peroxides, stirring, standing, filtering, vacuum drying obtain poly- anthraquinone Thioether/Ti3C2Tx/ sulphur composite.
The preparation and performance test of electrode；By composite, acetylene black and PVDF in mass ratio 80：10：10 in NMP Mixing, it is electrode film to be coated on aluminium foil, and metal lithium sheet is that, to electrode, CELGARD 2400 is barrier film, 1mol/L LiTFSI/ DOL-DME (volume ratios 1:1) it is electrolyte, 1mol/L LiNO3 is additive, button electricity is assembled into full of Ar glove boxes Pond, constant current charge-discharge test is carried out using Land battery test systems.Charging/discharging voltage scope is 1-3V, and current density is 0.2C, performance is as shown in table 1.
Table 1
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5
First discharge specific capacity（mAh/g） 1053 1047 1055 1038 1046
Fig. 2 is the charge-discharge performance figure that the composite of the embodiment of the present invention 1 is prepared into lithium-sulfur cell.As can be seen from the figure charge and discharge Electrical efficiency can reach more than 98%, and first charge-discharge capacity is 1052 mAh/g, and efficiency for charge-discharge is 98.1%, 500 charge and discharges After electricity circulation, capacity still possesses 65%, illustrates the structure of the composite and can effectively suppress shuttle effect, improves sulphur battery Life-span.
Above content is to combine specific preferred embodiment further description made for the present invention, it is impossible to assert The specific implementation of the present invention is confined to these explanations.For general technical staff of the technical field of the invention, On the premise of not departing from present inventive concept, some simple deduction or replace can also be made, should all be considered as belonging to the present invention's Protection domain.

Claims (5)

1. a kind of poly- anthraquinone thioether/Ti3C2Tx/ sulphur composite, it is characterised in that the composite is by sulphur, sheet Ti3C2TxWith Poly- anthraquinone thioether composition, internal layer is sulphur and Ti3C2TxComposite, outer layer is cladding sulphur and Ti3C2TxThe poly- anthraquinone of composite Thioether, its poly- anthraquinone thioether：Ti3C2Tx：The mass ratio of sulphur is 0.05-0.2:0.05-0.2:1.
2. one kind prepares poly- anthraquinone thioether/Ti as claimed in claim 13C2TxThe method of/sulphur composite, it is characterised in that Including following several steps：
Step（1）：By Ti3AlC2Ceramic powders, which are put into hydrofluoric acid, to be corroded, and solution adds deionized water and centrifuged after corrosion Processing, then sediment is dried, obtain the lamellar Ti of stacking3C2TxPowder；
Step（2）：By Ti3C2TxPowder is uniformly mixed in proportion with elemental sulfur, is positioned in sealed reactor, in nitrogen Room temperature is cooled to after the completion of heating response in atmosphere, constant temperature, reaction, Ti is obtained3C2Tx/ sulphur composite；
Step（3）：By obtained Ti3C2Tx/ sulphur composite is added in 1-METHYLPYRROLIDONE and stirred, and adds 1,5- dichloros Anthraquinone is stirred, and then adds initiator ammonium persulfate, stirring, stand, filtering, vacuum drying, obtain poly- anthraquinone thioether/ Ti3C2Tx/ sulphur composite.
3. method as claimed in claim 2, it is characterised in that the step（1）The concentration of middle hydrofluoric acid is 20%-50%, rotten The time of erosion is 4-24 hours.
4. method as claimed in claim 2, it is characterised in that the step（2）Middle Ti3C2TxThe quality of powder and elemental sulfur Than for 0.05-0.2:1, heating response temperature is 155-165 DEG C, and the time is 5-12 hours.
5. method as claimed in claim 2, it is characterised in that the step（3）The ratio of middle 1,5- dichloroanthraquinones and elemental sulfur Example is 0.05-0.2:1；The ratio of initiator and 1,5- dichloroanthraquinones is 1：0.01-0.1, initiator from azodiisobutyronitrile, One kind in dibenzoyl peroxide, ammonium persulfate.
CN201710230127.6A 2017-04-10 2017-04-10 A kind of poly- anthraquinone thioether/Ti3C2Tx/ sulphur composite Withdrawn CN106981633A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104817083A (en) * 2015-05-25 2015-08-05 哈尔滨工业大学 Rapid-heating-assisted ultrasonic stripping method for two-dimensional nanometer Ti3C2 lamella
CN105098162A (en) * 2015-09-14 2015-11-25 哈尔滨工业大学 Preparation method for titanium carbide nanosheet/graphene composite material capable of being used as anode of lithium ion battery
CN105702928A (en) * 2016-02-18 2016-06-22 钟玲珑 Preparation method of graphene/poly-anthraquinone thioether/sulphur composite cathode material
CN106450205A (en) * 2016-11-02 2017-02-22 南京工业大学 Two-dimensional transition metal carbide (nitride) and nano sulfur particulate composite as well as preparation and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104817083A (en) * 2015-05-25 2015-08-05 哈尔滨工业大学 Rapid-heating-assisted ultrasonic stripping method for two-dimensional nanometer Ti3C2 lamella
CN105098162A (en) * 2015-09-14 2015-11-25 哈尔滨工业大学 Preparation method for titanium carbide nanosheet/graphene composite material capable of being used as anode of lithium ion battery
CN105702928A (en) * 2016-02-18 2016-06-22 钟玲珑 Preparation method of graphene/poly-anthraquinone thioether/sulphur composite cathode material
CN106450205A (en) * 2016-11-02 2017-02-22 南京工业大学 Two-dimensional transition metal carbide (nitride) and nano sulfur particulate composite as well as preparation and application thereof

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