CN107768638A - A kind of lithium sulfur battery anode material and the lithium-sulfur cell using the positive electrode - Google Patents

A kind of lithium sulfur battery anode material and the lithium-sulfur cell using the positive electrode Download PDF

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CN107768638A
CN107768638A CN201710978717.7A CN201710978717A CN107768638A CN 107768638 A CN107768638 A CN 107768638A CN 201710978717 A CN201710978717 A CN 201710978717A CN 107768638 A CN107768638 A CN 107768638A
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lithium
iron
porous carbon
sulfur cell
nitrogen
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杨文�
刘珍珍
张小玲
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Beijing Institute of Technology BIT
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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
    • 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
    • H01M4/62—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

A kind of lithium-sulfur cell the invention discloses lithium sulfur battery anode material and using the positive electrode.Iron and nitrogen are collectively incorporated into by the present invention using doping method in situ, while the porous carbon materials of iron nitrogen exotic atom codope are prepared using hard template method.The method of the invention is：Prepare presoma, catalyst, polymer early stage of hard template；Polymer early stage is calcined to obtain solid；Solid through over etching, clean, be dried to obtain carbon material of the present invention.The carbon material of preparation is well mixed with sulphur powder, carbon sulphur composite is thermally formed under argon atmosphere and is applied to lithium-sulfur cell.Gained carbon material nitrogen, iron content are higher, and specific surface area and yield are higher, and preparation process is simple to operation.Preferable applied to chemical property in lithium-sulfur cell, performance is obviously improved compared with not iron content carbon material, and the addition of iron catalyst, which can fix sulphur well and suppress polysulfide, shuttles, and accelerates kinetics, so as to improve the cyclical stability of lithium-sulfur cell.

Description

A kind of lithium sulfur battery anode material and the lithium-sulfur cell using the positive electrode
Technical field
The present invention relates to a kind of iron nitrogen exotic atom codope porous carbon positive electrode for lithium-sulfur cell；It is directed to use with The lithium-sulfur cell of the carbonaceous positive electrode.
Background technology
With very high theoretical specific capacity (1675m Ah g when elemental sulfur is as lithium sulfur battery anode material-1) and theoretical ratio Energy (2600Wh kg-1), it is considered to be one of optimal selection of high-energy density secondary battery of future generation.In addition, elemental sulfur stores up Abundant, cheap, safe, the environment-friendly characteristic of amount makes the system great commercial value again.But lithium-sulfur cell Still suffer from some problems：First, elemental sulfur causes active material utilization low with its reduzate lithium sulfide poorly conductive；Two It is that the dissolving diffusion of intermediate product causes the loss of active material, the generation of this " shuttle effect ", seriously constrains lithium sulphur electricity The cyclical stability in pond.In consideration of it, my invention has the iron nitrogen exotic atom codope porous carbon of high-specific surface area, Ran Houtong The method of Overheating Treatment pours into elemental sulfur in porous carbon.Porous carbon with good conductivity alleviates elemental sulfur and its product Li2S Nonconducting problem, and polysulfide control is played a role in carbon pores road to suppressing polysulfide shuttle, it is another The addition of aspect iron catalyst further suppress polysulfide dissolving and shuttle, and kinetics be accelerated, so as to improve lithium The cyclical stability of sulphur battery.
The content of the invention
The present invention is intended to provide a kind of iron nitrogen exotic atom codope porous carbon positive electrode as lithium-sulfur cell and making With the lithium-sulfur cell of the carbonaceous positive electrode.The preparation method of the present invention, step are as follows：
(1) by o-phenylenediamine monomer ultrasonic dissolution in acid flux material, treat that monomer dissolves, iron is added under ultrasound condition and is urged Agent, then by nano silicon-based hard template under ultrasound condition, it is added in above-mentioned solution, adds and trigger after 0.5~2h of ultrasound The oxidant of o-phenylenediamine monomer polymerization, at 0~15 DEG C, stirring polymerization obtains polymer early stage.
(2) above-mentioned polymer early stage centrifugal drying is obtained into solid 1, under atmosphere of inert gases, solid 1 is subjected to high temperature Calcining, is specially warming up to 600~1000 DEG C with 1~10 DEG C/min speed, keeps 0~2h, room to be dropped at this temperature Wen Hou, take out, obtain solid 2.
(3) by after the grind into powder of solid 2, it is added in the etching agent ammonium acid fluoride aqueous solution of silicon substrate hard template, 1~48h is reacted at 25 DEG C, is cleaned up with water, after centrifugal drying, it is porous to obtain iron nitrogen exotic atom codope of the present invention Carbon material 3.
(4) by after iron nitrogen exotic atom codope porous carbon materials 3 and elemental sulfur mixed grinding, under inert atmosphere conditions 160~200 DEG C of heat treatments, obtain carbon sulphur composite 4.
(5) by above-mentioned resulting iron nitrogen exotic atom codope porous carbon sulphur composite 4 and acetylene black, PVDF mixing shapes Into uniform slurries, coated in aluminum foil current collector, dried under the conditions of 50~80 DEG C, it is standby to give over to electrode slice.
In step (1), the silicon substrate hard template is in silica nanosphere and mesoporous silica molecular sieve material It is a kind of.
In step (1), the mass ratio of the presoma o-phenylenediamine monomer and silicon substrate hard template is 1:(0.5~10).
In step (1), the acid medium is H2SO4One kind in solution and HCl solution.
In step (1), the mol ratio of the o-phenylenediamine monomer and acid flux material is 1：(1~20).
In step (1), the concentration range of the acid flux material is 0.1~5mol/L.
In step (1), the iron catalyst is one kind in FePC and ferric nitrate.
In step (1), the mass ratio of the o-phenylenediamine monomer and iron catalyst is 1：(0.1~1).
In step (1), the oxidant (NH for triggering the polymerization of o-phenylenediamine monomer4)2S2O8Solution and FeCl3In solution It is a kind of.
In step (1), the o-phenylenediamine monomer and the mol ratio for triggering its oxidant polymerizeing are 1：(1~6).
In step (2), the atmosphere of inert gases is one kind in nitrogen and argon gas.
In step (3), the mass content of the ammonium acid fluoride aqueous solution of addition is 1~65%.
In step (4), the mass ratio of the iron nitrogen exotic atom codope porous carbon and elemental sulfur is 3:7.
In step (6), the iron nitrogen exotic atom codope porous carbon sulphur composite and conductive agent acetylene black, bonding agent PVDF mass ratio is 8:1:1.
Beneficial effect：
The method synthesis iron nitrogen exotic atom codope that the present invention is combined using doping in situ and nano silicon-based hard template is more The addition of hole carbon material, wherein iron catalyst, which can fix sulphur well and suppress polysulfide, shuttles, and accelerates kinetics； Hard template method containing micropore, mesoporous, macropore, and duct to connect in the iron nitrogen exotic atom codope porous carbon materials of synthesis again Lead to, have higher specific surface area, apply and be advantageous to electronics in lithium-sulfur cell and ion quickly transmits, improve battery performance, And good conductive porous carbon base body alleviates elemental sulfur and product Li2The non-conductive problems of S, and polysulfide is controlled in carbon Certain effect is served to suppressing polysulfide shuttle in duct, so as to improve the cyclical stability of lithium-sulfur cell.
Brief description of the drawings
Fig. 1 is the transmission electron microscope picture of the iron nitrogen exotic atom codope porous carbon materials prepared in embodiment 2.
Fig. 2 is the adsorption isotherm of the iron nitrogen exotic atom codope porous carbon materials prepared in embodiment 3.
Fig. 3 is the graph of pore diameter distribution of the iron nitrogen exotic atom codope porous carbon materials prepared in embodiment 3.
Fig. 4 is the electrode material prepared in embodiment 3 battery charging and discharging cyclic curve under the conditions of 0.1C.
Embodiment
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, But not limited to this.
Embodiment 1
(1) by 2g o-phenylenediamine monomer ultrasonic dissolutions in 2mol/L hydrochloric acid solution, treat that monomer dissolves, in ultrasound condition Lower addition 0.0849g FePCs, are then added to above-mentioned solution by 5g nanometer titanium dioxide silicon ball hard templates under ultrasound condition In, addition 20mL 1mol/L FeCl after ultrasonic 0.5h3The aqueous solution, the stirring polymerization 24h under the conditions of 0 DEG C.
(2) reactant centrifugal drying obtained above is obtained into solid product, under nitrogen atmosphere, with 10 DEG C/min speed Degree is warming up to 900 DEG C, keeps 1h at this temperature, after being down to room temperature naturally, takes out.
(3) solid abrasive is added in the 4mol/L ammonium acid fluoride aqueous solution to etch away nano-silicon into after powder Ball, etching 24h is stirred at room temperature, is cleaned up with deionized water, 24h is dried at 60 DEG C, obtains iron nitrogen exotic atom codope Porous carbon materials.
(4) by iron nitrogen exotic atom codope porous carbon materials and elemental sulfur with mass ratio 3:After 7 mixed grindings, in argon atmospher Lower 160 DEG C of heat treatment 12h is enclosed, obtains carbon sulphur composite.
(5) by above-mentioned resulting iron nitrogen exotic atom codope porous carbon sulphur composite and acetylene black, PVDF according to matter Measure ratio 8:1:1 is mixed to form uniform slurries, coated in aluminum foil current collector, is dried under the conditions of 60 DEG C, it is standby to give over to electrode slice.
Embodiment 2
(1) by 2g o-phenylenediamine monomer ultrasonic dissolutions in 2mol/L hydrochloric acid solution, treat that monomer dissolves, in ultrasound condition Lower addition 0.1773g FePCs, are then added to above-mentioned solution by 5g nanometer titanium dioxide silicon ball hard templates under ultrasound condition In, 20mL 1mol/L ammonium persulfate aqueous solution is added after ultrasonic 0.5h, polymerization 24h is stirred under the conditions of 0 DEG C.
(2) reactant centrifugal drying obtained above is obtained into solid product, under nitrogen atmosphere, with 5 DEG C/min speed Degree is warming up to 900 DEG C, keeps 2h at this temperature, after being down to room temperature naturally, takes out.
(3) solid abrasive is added in the 4mol/L ammonium acid fluoride aqueous solution to etch away nano-silicon into after powder Ball, etching 24h is stirred at room temperature, is cleaned up with deionized water, 24h is dried at 60 DEG C, obtains iron nitrogen exotic atom codope Porous carbon materials.
(4) by iron nitrogen exotic atom codope porous carbon materials and elemental sulfur with mass ratio 3:After 7 mixed grindings, in argon atmospher Lower 155 DEG C of heat treatment 12h is enclosed, obtains carbon sulphur composite.
(5) by above-mentioned resulting iron nitrogen exotic atom codope porous carbon sulphur composite and acetylene black, PVDF is according to matter Measure ratio 8:1:1 is mixed to form uniform slurries, coated in aluminum foil current collector, is dried under the conditions of 60 DEG C, it is standby to give over to electrode slice.
Embodiment 3
(1) by 2g o-phenylenediamine monomer ultrasonic dissolutions in 2mol/L hydrochloric acid solution, treat that monomer dissolves, in ultrasound condition Lower addition 0.1773g FePCs, are then added to above-mentioned solution by 5g nanometer titanium dioxide silicon ball hard templates under ultrasound condition In, addition 40mL 1mol/L FeCl after ultrasonic 0.5h3The aqueous solution, the stirring polymerization 24h under the conditions of 0 DEG C.
(2) reactant centrifugal drying obtained above is obtained into solid product, under nitrogen atmosphere, with 5 DEG C/min speed Degree is warming up to 900 DEG C, keeps 1h at this temperature, after being down to room temperature naturally, takes out.
(3) solid abrasive is added in the 4mol/L ammonium acid fluoride aqueous solution to etch away nano-silicon into after powder Ball, etching 24h is stirred at room temperature, is cleaned up with deionized water, 24h is dried at 60 DEG C, obtains iron nitrogen exotic atom codope Porous carbon materials.
(4) by iron nitrogen exotic atom codope porous carbon materials and elemental sulfur with mass ratio 3:After 7 mixed grindings, in argon atmospher Lower 155 DEG C of heat treatment 24h is enclosed, obtains carbon sulphur composite.
(5) by above-mentioned resulting iron nitrogen exotic atom codope porous carbon sulphur composite and acetylene black, PVDF is according to matter Measure ratio 8:1:1 is mixed to form uniform slurries, coated in aluminum foil current collector, is dried under the conditions of 60 DEG C, it is standby to give over to electrode slice.
Embodiment 4
(1) by 2g o-phenylenediamine monomer ultrasonic dissolutions in 2mol/L hydrochloric acid solution, treat that monomer dissolves, in ultrasound condition Lower addition 0.1773g FePCs, are then added to above-mentioned solution by 10g nanometer titanium dioxide silicon ball hard templates under ultrasound condition In, addition 40mL 1mol/L FeCl after ultrasonic 0.5h3The aqueous solution, the stirring polymerization 24h under the conditions of 0 DEG C.
(2) reactant centrifugal drying obtained above is obtained into solid product, under nitrogen atmosphere, with 10 DEG C/min speed Degree is warming up to 800 DEG C, keeps 1h at this temperature, after being down to room temperature naturally, takes out.
(3) solid abrasive is added in the 4mol/L ammonium acid fluoride aqueous solution to etch away nano-silicon into after powder Ball, etching 24h is stirred at room temperature, is cleaned up with deionized water, 24h is dried at 60 DEG C, obtains iron nitrogen exotic atom codope Porous carbon materials.
(4) by iron nitrogen exotic atom codope porous carbon materials and elemental sulfur with mass ratio 3:After 7 mixed grindings, in argon atmospher Lower 160 DEG C of heat treatment 12h is enclosed, obtains carbon sulphur composite.
(5) by above-mentioned resulting iron nitrogen exotic atom codope porous carbon sulphur composite and acetylene black, PVDF according to matter Measure ratio 8:1:1 is mixed to form uniform slurries, coated in aluminum foil current collector, is dried under the conditions of 60 DEG C, it is standby to give over to electrode slice.
The assembling of battery
In glove box, the above-mentioned positive plate made is combined into together with negative pole, barrier film, electrolyte, battery case 2025 button cells, 24 hours are stood, is then tested, wherein negative pole is lithium piece, and electrolyte is bis trifluoromethyl sulfonic acid acyl The glycol dimethyl ether and DOX solution (containing the lithium nitrate that concentration is 1mol/L) of imine lithium, bis trifluoromethyl sulfonic acid The concentration of imide li is 1mol/L, is 1 as the glycol dimethyl ether of solvent and the volume ratio of 1,3- dioxolanes:1, barrier film For lithium ion battery separator celgrad 2300.
Performance test
Charge-discharge test is carried out to the lithium-sulfur cell assembled using Land test systems, discharge and recharge section is 1.5- 3.0V, the current density of discharge and recharge is 0.1C.

Claims (3)

1. a kind of iron nitrogen exotic atom codope porous carbon positive electrode as lithium-sulfur cell and use the carbonaceous positive electrode Lithium-sulfur cell, it is characterised in that described iron nitrogen exotic atom codope porous carbon materials be by original position doping and nano-silicon The method synthesis that base hard template is combined.Wherein the addition of iron catalyst can fix sulphur well and suppress polysulfide and wear Shuttle, accelerate kinetics, so as to improve the cyclical stability of lithium-sulfur cell.
2. a kind of iron nitrogen exotic atom codope porous carbon positive electrode as lithium-sulfur cell and use the carbonaceous positive electrode Lithium-sulfur cell, comprise the following steps：
(1) by o-phenylenediamine monomer ultrasonic dissolution in acid flux material, treat that monomer dissolves, iron catalysis is added under ultrasound condition Agent, then by nano silicon-based hard template under ultrasound condition, it is added in above-mentioned solution, in stirring condition after 0.5~2h of ultrasound Lower to add the oxidant for triggering the polymerization of o-phenylenediamine monomer, at 0~15 DEG C, stirring polymerization obtains polymer early stage.
(2) above-mentioned polymer early stage centrifugal drying is obtained into solid 1, under atmosphere of inert gases, solid 1 is subjected to high temperature and forged Burn, be specially warming up to 600~1000 DEG C with 1~10 DEG C/min speed, keep 0~2h at this temperature, treat that temperature drops to After room temperature, take out, obtain solid 2.
(3) by after the grind into powder of solid 2, it is added in the etching agent ammonium acid fluoride aqueous solution of silicon substrate hard template, at 25 DEG C 1~48h of lower reaction, is cleaned up with water, after centrifugal drying, obtains iron nitrogen exotic atom codope porous carbon of the present invention Material 3.
(4) by after iron nitrogen exotic atom codope porous carbon materials 3 and elemental sulfur mixed grinding, under inert atmosphere conditions in 160 ~200 DEG C of heat treatments, obtain iron nitrogen exotic atom codope porous carbon sulphur composite 4.
(5) above-mentioned resulting iron nitrogen exotic atom codope porous carbon sulphur composite 4 and acetylene black, PVDF are mixed to form Even slurries, coated in aluminum foil current collector, dried at 50~80 DEG C, it is standby to give over to electrode slice.
3. iron nitrogen exotic atom codope porous carbon positive electrode and use according to claim 2 as lithium-sulfur cell The lithium-sulfur cell of the carbonaceous positive electrode, it is characterised in that:
In step (1), the silicon substrate hard template is one in silica nanosphere and mesoporous silica molecular sieve material Kind, the mass ratio of the presoma o-phenylenediamine monomer and silicon substrate hard template is 1:(0.5~10).
In step (1), the acid medium is H2SO4One kind in solution and HCl solution, o-phenylenediamine monomer and acidity are molten The mol ratio of agent is 1：(1~20), the concentration range of acid flux material is 0.1~5mol/L.
In step (1), the iron catalyst is one kind in FePC and ferric nitrate, o-phenylenediamine monomer and iron catalyst Mass ratio is 1：(0.1~1).
In step (1), the oxidant for triggering o-phenylenediamine monomer to polymerize is (NH4)2S2O8Solution and FeCl3In solution One kind, o-phenylenediamine monomer and the mol ratio for triggering its oxidant polymerizeing are 1：(1~6).
In step (2), the atmosphere of inert gases is one kind in nitrogen and argon gas.
In step (3), the mass content of the ammonium acid fluoride aqueous solution of addition is 1~65%.
In step (4), the mass ratio of the iron nitrogen exotic atom codope porous carbon and elemental sulfur is 3:7.
In step (6), the iron nitrogen exotic atom codope porous carbon sulphur composite and conductive agent acetylene black, bonding agent PVDF Mass ratio be 8:1:1.
CN201710978717.7A 2017-10-19 2017-10-19 A kind of lithium sulfur battery anode material and the lithium-sulfur cell using the positive electrode Pending CN107768638A (en)

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CN109728297A (en) * 2018-12-11 2019-05-07 温州大学 Metal phthalocyanine/carbon pipe composite material preparation method and its application in lithium-sulphur cell positive electrode
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CN109713287A (en) * 2019-01-02 2019-05-03 齐鲁工业大学 A kind of preparation method of the derivative sulfur doping carbon anode material of lithium-ion battery of polythiophene
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CN112913075B (en) * 2019-05-03 2023-02-14 株式会社Lg新能源 Functional separator having catalytic site introduced therein, method of manufacturing the same, and lithium secondary battery comprising the same
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