CN113745474A - PANI @ CN/SnS lithium ion battery anode material and preparation method thereof - Google Patents
PANI @ CN/SnS lithium ion battery anode material and preparation method thereof Download PDFInfo
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- CN113745474A CN113745474A CN202110929731.4A CN202110929731A CN113745474A CN 113745474 A CN113745474 A CN 113745474A CN 202110929731 A CN202110929731 A CN 202110929731A CN 113745474 A CN113745474 A CN 113745474A
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- 229920000767 polyaniline Polymers 0.000 title claims abstract description 96
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000010405 anode material Substances 0.000 title claims description 24
- 239000010406 cathode material Substances 0.000 claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 22
- 239000007773 negative electrode material Substances 0.000 claims abstract description 14
- 239000002135 nanosheet Substances 0.000 claims abstract description 10
- 239000002131 composite material Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 38
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 22
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 17
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 15
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 11
- 239000003999 initiator Substances 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 239000011593 sulfur Substances 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000011065 in-situ storage Methods 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 6
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 6
- 238000003763 carbonization Methods 0.000 claims description 5
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000010000 carbonizing Methods 0.000 claims description 3
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 claims description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000001351 cycling effect Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 3
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 239000002057 nanoflower Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 description 1
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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
- H01M4/58—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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- 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
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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
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- 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
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- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- 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
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Abstract
The invention belongs to the technical field of lithium ion batteries, and particularly discloses a PANI @ CN/SnS lithium ion battery cathode material and a preparation method thereof3N4The composite nano sheet is constructed, and the carbon layer is coated on the surface of the composite nano sheet, wherein the carbon layer is made of polyaniline; in the negative electrode material, the mass fraction of the carbon element is 30-40%. The PANI @ CN/SnS lithium ion battery cathode material has excellent electrochemical performance, the specific capacity of the PANI @ CN/SnS lithium ion battery cathode material can still maintain about 760mAh/g after being circulated for 100 circles under the current density of 200mA/g, and the preparation method is simple and feasible, and is suitable for popularization and application.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a PANI @ CN/SnS lithium ion battery cathode material and a preparation method thereof.
Background
Lithium ion batteries have attracted attention in recent years as secondary rechargeable batteries because of their high energy density, wide operating voltage range, long operating life, and environmental friendliness. The synthetic elements of SnS are abundant in storage on earth, and are non-toxic and low in cost. Due to its great potential in batteries, it has received increasing attention as an energy storage material in the last decades. Due to its unique 2D layered structure and semiconductor properties, SnS materials typically have excellent chemical stability and high theoretical specific capacity and reversibility. As a promising matrix material for storing different alkali metal ions through alloying/dealloying reactions, SnS has broad electrochemical prospects in batteries. However, the volume expansion of tin-based sulfides during ion deintercalation can lead to poor cycling stability of the battery, which limits its development as a negative electrode material for lithium ion batteries.
g-C3N4Is composed of a structural unit triazine ring (C)3N3) The structure of the graphite-like laminated planar structure formed by N connection has particularity, and g-C is carried out under the high temperature condition of more than 550 DEG C3N4Cracking occurs, a porous structure is generated, the surface area is large, and the porous structure can serve as a soft template and shorten a path for diffusion of ions and electrons. Chinese patent CN109286009A discloses a preparation method of a nano-sheet self-assembled three-dimensional nano-flower tin sulfide/graphitized carbon nitride lithium ion battery cathode material, wherein g C of the prepared lithium ion battery cathode material is coated on the surface of stannous sulfide3N4Can relieve SnS2Volume change during charging and discharging. Chinese patent document CN110311119A discloses a preparation method of a lithium ion battery cathode material SnS/ND-CN, the SnS/ND-CN prepared by the method realizes SnS nanocrystallization, forms SnS/ND-CN with a nano sheet structure, has larger specific surface area, increases the contact chance and the reaction active site with electrolyte,is beneficial to the migration of lithium ions and relieves the volume change in the charging and discharging process.
However, CN-SnS as negative electrode material of lithium ion battery, g-C3N4The conductivity of the tin-based sulfide is slightly weak, and the tin-based sulfide still has larger volume strain, so that the cycling stability of the lithium ion battery is poor.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a PANI @ CN/SnS lithium ion battery anode material and a preparation method thereof, wherein high-conductivity polyaniline is coated on C3N4SnS electrode material surface, intended to solve the existing C3N4SnS electrode material due to g-C3N4Poor conductivity and poor electrochemical performance of the battery caused by large volume expansion of SnS in the charge and discharge processes.
In order to realize the purpose, the invention provides a PANI @ CN/SnS lithium ion battery cathode material which comprises SnS and g-C3N4The composite nano sheet is constructed, and the carbon layer is coated on the surface of the composite nano sheet, wherein the carbon layer is made of polyaniline; in the negative electrode material, the mass fraction of the carbon element is 30-40%.
According to another aspect of the present invention, there is also provided a method for preparing a PANI @ CN/SnS lithium ion battery anode material, comprising the steps of:
s1, preparation g-C3N4；
S2, g-C prepared by step S13N4Directly mixing and stirring the polyaniline and a tin source and a sulfur source for reaction, and then adding protonic acid, an aniline monomer and an initiator to synthesize polyaniline in situ under an acidic condition to obtain a PANI @ CN/SnS precursor;
s3, heating and preserving the PANI @ CN/SnS precursor prepared in the step S2, then carbonizing at high temperature in a protective atmosphere, and cooling to obtain the PANI @ CN/SnS lithium ion battery negative electrode material.
Preferably, in step S1, g-C is prepared3N4The specific process is as follows: heating the raw materials to 500-600 ℃ at a heating rate of 3-5 ℃/min, and calcining for 2-4 h to obtain the final productTo g-C3N4(ii) a Wherein the raw material is at least one of dicyandiamide, urea, melamine and thiourea.
Preferably, in step S2, the sulfur source is at least one of thioacetamide and thiourea.
Preferably, in step S2, the Sn source and the S source are mixed in a molar ratio of Sn element to S element of 1 (1-2).
Preferably, in step S2, the protonic acid is at least one of hydrochloric acid and sulfuric acid, and the initiator is at least one of persulfate, dichromate, and hydrogen peroxide.
Preferably, the protonic acid is hydrochloric acid, the initiator is ammonium persulfate, and the molar ratio of the hydrochloric acid to the aniline monomer to the ammonium persulfate is (1-1.5):1 (1-3).
Preferably, in step S2, the temperature during the synthesis of polyaniline is controlled below 5 ℃, and the reaction time is 10h-14 h.
Preferably, in step S3, the PANI @ CN/SnS precursor is heated and preserved for 10h to 12h in an oil bath, and the temperature of the oil bath is 60 ℃ to 85 ℃.
Preferably, in step S3, the protective atmosphere is argon-hydrogen mixed gas, and the high-temperature carbonization process is performed at a temperature rise rate of 5 ℃/min to 10 ℃/min, and after the temperature is raised to 700 ℃ to 900 ℃, the temperature is maintained for 2h to 4 h.
Generally, compared with the prior art, the above technical solution conceived by the present invention has the following beneficial effects:
(1) the invention coats C by using polyaniline with high conductivity as a carbon layer3N4The negative electrode material of the lithium ion battery is obtained by the SnS compound, the volume expansion of the material in the SnS charge and discharge process can be effectively relieved by the porous lamellar structure of the material, more active sites are exposed, and the transmission path of ions and electrons is shortened, so that the material has higher specific capacity and excellent cycling stability, the specific capacity can still be maintained at about 760mAh/g after being cycled for 100 circles under the current density of 200mA/g, and the material has important reference value for the practical application of lithium ion energy storage equipment with excellent electrochemical performance.
(2) At present, g-C is generally3N4Preparing C with a tin source and a sulfur source by a hydrothermal method3N4SnS complex, but the hydrothermal method requires high temperature and pressure steps, making it more dependent on production equipment; and the hydrothermal method has poor experimental repeatability and is not convenient to be amplified into batch experiments due to the lack of deep research on the control of influencing factors in the crystal nucleus forming process and the crystal growth process of the hydrothermal method. The method utilizes the one-step method of solution to prepare the high-conductivity PANI-coated C in situ3N4The SnS electrode material has the advantages of simple operation steps, good repeatability, high yield of the obtained product, uniform dispersion of components and excellent electrochemical performance.
(3) The preparation method has the advantages of abundant available synthetic raw materials, no strict limitation, no pollution, simple equipment, low energy consumption and low cost.
(4) The preparation method of the invention strictly controls the concentration of reactants for polymerizing the polyaniline and the reaction temperature to be C3N4And a polyaniline carbon layer with uniform shape and high conductivity is formed on the surface of the SnS composite, so that the performance of the battery cathode material is improved.
Drawings
FIG. 1 is a process flow diagram of the present invention for preparing PANI @ CN/SnS lithium ion battery anode material;
FIG. 2 is an SEM image of the PANI @ CN/SnS lithium ion battery anode material prepared in example 1 of the present invention under the scale of 500 nm;
FIG. 3 is an SEM image of the PANI @ CN/SnS lithium ion battery anode material prepared in example 1 of the present invention at a scale of 200 nm;
FIG. 4 is an X-ray diffraction pattern of the PANI @ CN/SnS lithium ion battery anode material prepared in example 1 of the present invention;
FIG. 5 is a charge-discharge curve diagram of the PANI @ CN/SnS lithium ion battery anode material prepared in example 1 of the present invention;
FIG. 6 is a graph of the cycling performance of the PANI @ CN/SnS lithium ion battery anode material prepared in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a PANI @ CN/SnS lithium ion battery cathode material which comprises SnS and g-C3N4The composite nano sheet is constructed, and the carbon layer is coated on the surface of the composite nano sheet, wherein the carbon layer is made of polyaniline; in the negative electrode material, the mass fraction of the carbon element is 30-40%.
Polyaniline (PANI) has the characteristics of high specific capacity, good redox reversibility, high conductivity, simple synthesis method, low cost and the like, and is used as C3N4The coating carbon layer of the SnS precursor can improve the electrode conductivity and well relieve the volume expansion of the SnS in the charge-discharge reaction process. g-C3N4And in combination with the polyaniline carbon layer, nitrogen atoms can be doped in the PANI crystal lattice, and the nitrogen-doped carbon matrix can further reduce the energy barrier of lithium ion penetration and promote the rapid diffusion of lithium ions and electrons. Meanwhile, the polyaniline carbon layer and SnS can form a C-S-C heterocyclic configuration, and the reaction kinetics of the material are improved.
By utilizing thermogravimetric analysis and battery performance tests, a large number of experiments prove that if the content of carbon in the negative electrode material is too high, the specific discharge capacity of the material is low; if the content of the carbon element is too low, the capacity fading is fast. The PANI @ CN/SnS lithium ion battery cathode material provided by the invention has excellent electrochemical performance, and the specific capacity of the PANI @ CN/SnS lithium ion battery cathode material can still maintain about 760mAh/g after being cycled for 100 circles under the current density of 200 mA/g.
As shown in fig. 1, the preparation method of the PANI @ CN/SnS lithium ion battery anode material provided by the present invention comprises the following steps:
s1, preparation g-C3N4；
S2, g-C prepared by step S13N4Directly mixing and stirring the polyaniline and a tin source and a sulfur source for reaction, and then adding protonic acid, an aniline monomer and an initiator to synthesize polyaniline in situ under an acidic condition to obtain a PANI @ CN/SnS precursor;
s3, heating and preserving the PANI @ CN/SnS precursor prepared in the step S2, then carbonizing at high temperature in a protective atmosphere, and cooling to obtain the PANI @ CN/SnS lithium ion battery negative electrode material.
In some embodiments, step S1 uses a calcination process to prepare g-C3N4The preparation raw materials can be selected from various nitrogen-rich precursors, and the preparation method has the characteristics of short process flow, less used equipment, low requirement on equipment, short preparation time and the like. The raw material can be at least one of dicyandiamide, urea, melamine and thiourea. The specific preparation process comprises heating the raw materials to 500-600 deg.C at a heating rate of 3-5 deg.C/min, calcining for 2-4 h, and naturally cooling to room temperature to obtain g-C3N4。
In some embodiments, in step S2, the tin source may be stannous chloride dihydrate, and the sulfur source may be at least one of thioacetamide and thiourea. The tin source and the sulfur source are mixed according to the molar ratio 1 (1-2) of the Sn element to the S element.
The invention adopts a chemical oxidative polymerization method to synthesize polyaniline, and uses an initiator to perform oxidative polymerization on aniline monomers under an acidic condition. Protonic acid is an important factor influencing the oxidative polymerization of aniline, and on the one hand, provides the pH value required by the reaction medium; on the other hand, the polyaniline skeleton is endowed with certain conductivity in the form of a dopant. The polymerization is carried out simultaneously with in-situ doping, and the polymerization and doping are completed simultaneously. The synthesis reaction is influenced by the type and concentration of protonic acid, the type and concentration of initiator, the concentration of aniline monomer, the reaction temperature, the reaction time and other factors. The protonic acid used for synthesizing polyaniline is at least one of hydrochloric acid and sulfuric acid, and the initiator is at least one of persulfate, dichromate and hydrogen peroxide, so that the reaction temperature is controlled to be C3N4The surface of the SnS compound is used for synthesizing polyaniline more uniformly, and a surfactant can be added in the synthesis process, wherein the surfactant can adopt at least one of polyvinylpyrrolidone (PVP), dodecylbenzene sulfonic acid (DBSA) and sodium dodecylbenzene sulfonate (SDBS). Because the polyaniline of the coating layer is synthesized in situ in the cathode material, the reaction environment is complicated, and the method is used for preparing the polyaniline in C3N4The SnS compound has uniform surface formation form, high conductivity and air spaceThe invention discloses a polyaniline carbon skeleton with a stable core structure, which is characterized in that a large number of experiments are carried out to screen out a preferred embodiment, wherein, hydrochloric acid is selected as protonic acid, ammonium persulfate is selected as initiator, and the molar ratio of hydrochloric acid to aniline monomer to ammonium persulfate is (1-1.5) to (1-3); the temperature is controlled below 5 ℃ in the synthesis process, and the reaction time is 10-14 h. If the reaction temperature is too high, side reactions during the production of polyaniline may increase, and more by-products may be produced.
In some embodiments, in step S3, the PANI @ CN/SnS precursor is heated and held in an oil bath at a temperature of 60 ℃ to 85 ℃ for 10h to 12 h. The PANI @ CN/SnS precursor is heated more uniformly by the oil bath, and water vapor is not generated in the heating process, so that better crystallization of SnS is facilitated. The protective atmosphere in the carbonization process is argon-hydrogen mixed gas, the temperature is raised to 700-900 ℃ at the temperature raising rate of 5-10 ℃/min, and then the temperature is kept for 2-4 h. Ar/H2The carbon skeleton with uniform appearance and large specific surface area can be obtained by controlling proper carbonization temperature in the reducing atmosphere of gas, and the electrical property and specific capacity of the battery cathode material can be effectively improved by carbonization treatment.
The above technical solution is described in detail below with reference to specific examples.
Example 1
The embodiment provides a PANI @ CN/SnS lithium ion battery cathode material, and the preparation method comprises the following steps:
(1)g-C3N4the preparation of (1): heating urea to 550 ℃ at the heating rate of 5 ℃/min, carrying out heat preservation and calcination for 2h, and naturally cooling to room temperature to obtain g-C3N4。
(2) Preparation of PANI @ CN/SnS precursor: adding 0.5 mmol-C into 50mL of ethanol3N4Ultrasonic dispersing, then adding 1mmol SnCl2·2H2And performing O ultrasonic treatment for 2h, then adding 1mmol thioacetamide, and stirring for reaction for 2 h. And adding 0.1mmol PVP, 0.5mmol hydrochloric acid and 0.5mmol aniline monomer into the original system, slowly adding 0.5mmol ammonium persulfate, and carrying out polymerization reaction in an ice bath environment for 12 hours to obtain a PANI @ CN/SnS precursor.
(3) Preparing a PANI @ CN/SnS lithium ion battery anode material: polymerizing the polymer prepared in the step (2)The latter system was reacted for 12h with stirring directly in a 65 ℃ oil bath. Then placed in a tube furnace at Ar/H2And (3) heating to 800 ℃ at a heating rate of 5 ℃/min in a gas atmosphere, calcining at a constant temperature for 2h, and cooling to obtain the PANI @ CN/SnS lithium ion battery negative electrode material.
The PANI @ CN/SnS lithium ion battery anode material prepared in this example was observed with a scanning electron microscope, and as can be seen from fig. 2 and 3, the material as a whole showed a lamellar structure with holes visible on the surface. The lamellar structure can provide convenience for lithium ion de-intercalation and can relieve volume expansion in the SnS charge-discharge process; the surface defects expose more active sites, and shorten the transmission path of ions and electrons, so that the material as a lithium ion negative electrode shows excellent electrochemical performance. An X-ray diffraction pattern (XRD) is shown in figure 4, and the lithium ion battery cathode material has obvious characteristic peaks of SnS besides obvious carbon peaks, which indicates that the carbon layer successfully coats SnS.
Electrochemical tests are carried out on the lithium ion battery cathode material of the embodiment, as can be seen from fig. 5, the charge and discharge curves of the cycle 2 nd circle and the cycle 10 th circle almost coincide, which indicates that the electrode has high reversibility; as can be seen from FIG. 6, the specific discharge capacity of the PANI @ CN/SnS electrode is maintained to be stable under the current density of 200mA/g, and 760mAh/g can be maintained after 100 cycles.
Example 2
The embodiment provides a PANI @ CN/SnS lithium ion battery cathode material, and the preparation method comprises the following steps:
(1)g-C3N4the preparation of (1): heating melamine to 500 ℃ at the heating rate of 5 ℃/min, carrying out heat preservation and calcination for 4h, and naturally cooling to room temperature to obtain g-C3N4。
(2) Preparation of PANI @ CN/SnS precursor: adding 0.5 mmol-C into 50mL of ethanol3N4Ultrasonic dispersing, then adding 1mmol SnCl2·2H2And performing O ultrasonic treatment for 2 hours, then adding 1.5mmol thioacetamide, and stirring for reaction for 2 hours. And adding 0.75mmol of hydrochloric acid and 0.5mmol of aniline monomer into the original system, slowly adding 1mmol of ammonium persulfate, and carrying out polymerization reaction in an ice bath environment for 10 hours to obtain a PANI @ CN/SnS precursor.
(3) Step (3) of this example is the same as step (3) of example 1.
Through detection, the PANI @ CN/SnS lithium ion battery cathode material prepared by the embodiment has excellent electrochemical performance, the discharge capacity of the PANI @ CN/SnS lithium ion battery cathode material is maintained at 760mAh/g after 100 cycles of circulation at a current density of 200 mA/g.
Example 3
The embodiment provides a PANI @ CN/SnS lithium ion battery cathode material, and the preparation method comprises the following steps:
(1)g-C3N4the preparation of (1): heating thiourea to 600 ℃ at the heating rate of 3 ℃/min, carrying out heat preservation and calcination for 2h, and naturally cooling to room temperature to obtain g-C3N4。
(2) Step (2) of this example is the same as step (2) of example 1;
(3) preparing a PANI @ CN/SnS lithium ion battery anode material: and (3) directly stirring the polymerized system prepared in the step (2) in an oil bath kettle at the temperature of 75 ℃ for reaction for 10 hours. Then placed in a tube furnace at Ar/H2And (3) heating to 800 ℃ at a heating rate of 10 ℃/min in a gas atmosphere, calcining at a constant temperature for 3h, and cooling to obtain the PANI @ CN/SnS lithium ion battery negative electrode material.
Through detection, the PANI @ CN/SnS lithium ion battery cathode material prepared by the embodiment has excellent electrochemical performance, the discharge capacity of the PANI @ CN/SnS lithium ion battery cathode material is maintained at 758mAh/g after 100 cycles of circulation under the current density of 200 mA/g.
Example 4
The embodiment provides a PANI @ CN/SnS lithium ion battery cathode material, and the preparation method comprises the following steps:
(1)g-C3N4the preparation of (1): step (1) of this example is the same as step (1) of example 1.
(2) Preparation of PANI @ CN/SnS precursor: 50mL of ethanol was added with 0.5mmol of C3N4Ultrasonic dispersing, then adding 1mmol SnCl2·2H2And performing O ultrasonic treatment for 1h, then adding 2mmol thioacetamide, and stirring for reaction for 2 h. Adding into the original strain0.1mmol of PVP, 0.5mmol of hydrochloric acid and 0.5mmol of aniline monomer, then slowly adding 1.5mmol of ammonium persulfate, and carrying out polymerization reaction in an ice bath environment for 14 hours to obtain a PANI @ CN/SnS precursor.
(3) Preparing a PANI @ CN/SnS lithium ion battery anode material: and (3) directly stirring the polymerized system prepared in the step (2) in an oil bath kettle at 65 ℃ for reaction for 12 hours. Then placed in a tube furnace at Ar/H2And (3) heating to 700 ℃ at a heating rate of 8 ℃/min in a gas atmosphere, calcining at a constant temperature for 4h, and cooling to obtain the PANI @ CN/SnS lithium ion battery negative electrode material.
Through detection, the PANI @ CN/SnS lithium ion battery cathode material prepared by the embodiment has excellent electrochemical performance, the discharge capacity of the PANI @ CN/SnS lithium ion battery cathode material is maintained at 778mAh/g after 100 cycles of circulation at a current density of 200 mA/g.
The embodiments show that the PANI @ CN/SnS lithium ion battery cathode material prepared by the invention has excellent electrochemical performance, high specific capacity and good cycling stability.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A PANI @ CN/SnS lithium ion battery cathode material is characterized in that: comprising SnS and g-C3N4The composite nano sheet is constructed, and the carbon layer is coated on the surface of the composite nano sheet, wherein the carbon layer is made of polyaniline; in the negative electrode material, the mass fraction of the carbon element is 30-40%.
2. The preparation method of the PANI @ CN/SnS lithium ion battery anode material of claim 1, which is characterized by comprising the following steps:
s1, preparation g-C3N4；
S2, g-C prepared by step S13N4Mixing with tin source and sulfur source directlyStirring for reaction, and then adding protonic acid, aniline monomer and initiator to synthesize polyaniline in situ under an acidic condition to obtain a PANI @ CN/SnS precursor;
s3, heating and preserving the PANI @ CN/SnS precursor prepared in the step S2, then carbonizing at high temperature in a protective atmosphere, and cooling to obtain the PANI @ CN/SnS lithium ion battery negative electrode material.
3. The method for preparing the PANI @ CN/SnS lithium ion battery anode material according to claim 2, wherein in step S1, g-C is prepared3N4The specific process is as follows: heating the raw materials to 500-600 ℃ at a heating rate of 3-5 ℃/min, and calcining for 2-4 h to obtain g-C3N4(ii) a Wherein the raw material is at least one of dicyandiamide, urea, melamine and thiourea.
4. The method for preparing the PANI @ CN/SnS lithium ion battery anode material according to claim 2, wherein the method comprises the following steps: in step S2, the sulfur source is at least one of thioacetamide and thiourea.
5. The method for preparing the PANI @ CN/SnS lithium ion battery anode material according to claim 2, wherein the method comprises the following steps: in step S2, the Sn source and the S source are mixed in a molar ratio of Sn element to S element of 1 (1-2).
6. The method for preparing the PANI @ CN/SnS lithium ion battery anode material according to claim 2, wherein the method comprises the following steps: in step S2, the protonic acid is at least one of hydrochloric acid and sulfuric acid, and the initiator is at least one of persulfate, dichromate, and hydrogen peroxide.
7. The method for preparing the PANI @ CN/SnS lithium ion battery anode material according to claim 6, wherein the method comprises the following steps: the protonic acid is hydrochloric acid, the initiator is ammonium persulfate, and the molar ratio of the hydrochloric acid to aniline monomer to the ammonium persulfate is (1-1.5) to 1 (1-3).
8. The method for preparing the PANI @ CN/SnS lithium ion battery anode material according to claim 2, wherein the method comprises the following steps: in step S2, the temperature is controlled below 5 ℃ in the process of synthesizing polyaniline, and the reaction time is 10-14 h.
9. The method for preparing the PANI @ CN/SnS lithium ion battery anode material according to claim 2, wherein the method comprises the following steps: in the step S3, the PANI @ CN/SnS precursor is heated and insulated for 10h-12h in an oil bath, and the temperature of the oil bath is 60 ℃ to 85 ℃.
10. The method for preparing the PANI @ CN/SnS lithium ion battery anode material according to claim 2, wherein the method comprises the following steps: in the step S3, the protective atmosphere is argon-hydrogen mixed gas, and the high-temperature carbonization process is performed at a temperature rise rate of 5-10 ℃/min until the temperature rises to 700-900 ℃, and then the temperature is kept for 2-4 h.
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